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Title: organic chemistry - I - notes and questions
Description: this file contain organic chemistry test banks SN1 and SN2 E1 E2
Description: this file contain organic chemistry test banks SN1 and SN2 E1 E2
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Chapter 1
MULTIPLE CHOICE QUESTIONS
Topic: Atomic Orbitals
1
...
a place where Ψ is positive
...
a place where Ψ2 is large
...
Ans: C
Topic: Atomic Orbitals, Molecular Orbitals
2
...
Which principle(s) or rule must be used to determine the correct electronic configuration
for carbon in its ground state?
A) Aufbau Principle
B) Hund's Rule
C) Pauli Exclusion Principle
D) (A) and (B) only
E) All three
Ans: E
1
Chapter 1
Topic: Atomic Orbitals, Bonding
4
...
A)
B)
C)
D)
E)
According to molecular orbital theory, which molecule could not exist?
H2
He2
Li2
F2
N2
Ans: B
Topic: Atomic Orbitals, Molecular Orbitals
6
...
The following electron configuration represents _______
...
the sp3 hybridized state of carbon
...
the ground state of carbon
...
Ans: C
Topic: Atomic Orbitals, Molecular Orbitals
8
...
A) σ bonding MO
B) π bonding MO
C) σ* antibonding MO
D) π* antibonding MO
E) π* bonding MO
Ans: B
Topic: Atomic Orbitals, Hybridization
9
...
(2sp2, 2sp2)
(2sp3, 2sp3)
(2sp, 2sp)
(2p, 2p)
(2sp, 1s)
Ans: C
3
Chapter 1
Topic: Lewis Structures, Formal Charges
10
...
All
valence electrons are shown; however, electrical charges have been omitted deliberately
...
H:N:H
...
H:N:H
...
H:O:H
...
H:B:H
...
What is the formal charge on oxygen in the following structure?
...
In which structure(s) below does the oxygen have a formal charge of +1?
...
...
H
II
...
Which structure(s) contain(s) an oxygen that bears a formal charge of +1?
...
:O
:O
...
...
: O C O:
H C
H3C
O
H
H3C
O
CH3
C
: O
...
: : O
...
...
CH3
H
I
II
III
IV
V
A)
B)
C)
D)
E)
I and II
III and IV
V
II
I and V
Ans: B
5
Chapter 1
Topic: Lewis Structures, Formal Charges
14
...
)
...
N
...
N
H
D) H3C
H
CH3
...
In which structure(s) below does nitrogen have a formal charge of +1?
H3C
N
CH2
H3C
...
H
...
OH
...
H3C
NH2
H
I
A)
B)
C)
D)
E)
...
Which of the following is an ion with a single negative charge?
...
B) : O N O :
...
C)
: O:
...
:
...
Which of these is a correct electron-dot representation of the nitrite ion, NO2-?
...
...
...
:O:N::O
O
:O::N:O:
...
...
...
:O:N:O:
...
IV
A)
B)
C)
D)
E)
...
V
I
II
III
IV
V
Ans: A
7
Chapter 1
Topic: Lewis Structures, Formal Charges
18
...
A) H N F :
...
O
...
F:
...
O
...
O
H
...
H
...
Listed below are electron dot formulas for several simple molecules and ions
...
H : Be : H
H
...
H
...
H
H
...
I
A)
B)
C)
D)
E)
H
...
H
II
III
IV
V
Which of the structures is negatively charged?
I
II
III
IV
V
Ans: B
8
Chapter 1
Topic: Lewis Structures, Formal Charges
20
...
Considering Lewis structures, which of these compounds possesses a single unpaired
electron?
A) N2
B) N2O
C) NO
D) N2O4
E) O2
Ans: C
Topic: Lewis Structures
...
Z
Y
A)
B)
C)
D)
E)
...
In which of these cases does the central atom have a zero formal charge?
A) HFH
H
B)
C)
H3C O
F
F
B
CH3
F
F
H
D)
H3C
N
CH3
H
CH3
E)
H3C
C
CH3
CH3
Ans: E
Topic: Lewis Structures, Formal Charges
24
...
ExpAns:ion of the valence shell to accommodate more than eight electrons is possible
with:
A) Fluorine
B) Nitrogen
C) Carbon
D) Sulfur
E) Beryllium
Ans: D
10
Chapter 1
Topic: Lewis Structures, Molecular Geometry
26
...
A)
B)
C)
D)
E)
VSEPR theory predicts an identical shape for all of the following, except:
NH3
H3O+
BH3
CH3All have the same geometry
Ans: C
Topic: Lewis Structures, Molecular Geometry
28
...
Which of the structures below would be trigonal planar (a planar triangle)? (Electrical
charges have been deliberately omitted
...
...
...
:
...
...
F
H
F
F
H
...
...
...
...
I
A)
B)
C)
D)
E)
II
IV
III
I
II
III
IV
I and IV
Ans: A
Topic: Lewis Structures, Molecular Geometry
30
...
A)
B)
C)
D)
E)
What bond angle is associated with a tetrahedral molecule?
120°
109
...
A)
B)
C)
D)
E)
What would be the spatial arrangement of the atoms of the methyl anion, :CH3-?
Octahedral
Tetrahedral
Trigonal planar
Linear
Trigonal pyramidal
Ans: E
Topic: Lewis Structures, Molecular Geometry
33
...
Which molecule would be linear? (In each case you should write a Lewis structure
before deciding
...
A)
B)
C)
D)
E)
The bond angles in PH3 would be expected to be approximately:
60°
90°
105°
109°
120°
Ans: C
13
Chapter 1
Topic: Periodic Properties, Electronegativity
36
...
H
O
N
B
C
Ans: N
Topic: Atomic Orbitals, Hybridization
37
...
I
A)
B)
C)
D)
E)
II
III
IV
V
I
II
III
IV
V
Ans: C
Topic: Atomic Orbitals, Hybridization
38
...
A)
B)
C)
D)
E)
In which molecule is the central atom sp3 hybridized?
CH4
NH3
H2O
All of these
None of these
Ans: D
Topic: Atomic Orbitals, Hybridization
40
...
A)
B)
C)
D)
E)
Which compound has the shortest carbon-carbon bond(s)?
CH3CH3
CH2=CH2
HC≡CH
CH3CH2CH3
All carbon-carbon bonds are the same length
...
A)
B)
C)
D)
E)
Which of the following contains an sp2-hybridized carbon?
CH4
CH3:−
CH3CH3
CH3+
HC≡CH
Ans: D
15
Chapter 1
Topic: Atomic Orbitals, Hybridization
43
...
A)
B)
C)
D)
E)
How many sigma (1s-2sp3) bonds are there in ethane?
7
6
5
3
1
Ans: B
Topic: Atomic Orbitals, Bonding
45
...
A)
B)
C)
D)
E)
The greatest degree of ionic character is anticipated for the bond between:
H and C
H and Cl
C and Cl
H and Br
Br and Cl
Ans: B
Topic: Atomic Orbitals, Hybridization
47
...
Which of the structures below is not expected to contribute to the CO2 resonance
hybrid?
A)
O
B)
C
O
O
C
C
O
O
C) O
D)
E)
O
O
C
C
O
O
Ans: D
17
Chapter 1
Topic: Atomic orbitals, Lewis structures, resonance
...
49
...
...
H
O
...
...
:
...
...
:
...
O
...
Which of the following pairs are NOT resonance structures?
A)
and
H3C O N O :
H3C O N O :
:
...
O
...
...
...
:
...
E) None of these pairs represents resonance structures
...
How many resonance structures can be written for the NO3- ion in which the nitrogen
atom bears a formal charge of +1?
A) 1
B) 2
C) 3
D) 4
E) 5
Ans: C
Topic: Empirical and Molecular Formulas
52
...
)
CH
CH2
C2H4
C6H6
C2H2
Ans: B
Topic: Empirical and Molecular Formulas
53
...
Its molecular weight is 285 +/- 5
...
A compound consists only of carbon, hydrogen and oxygen
...
5%, H, 13
...
The molecular weight of the compound was found to be 103 +/- 3
...
Which of the following is a set of constitutional isomers?
Br
Br
I
A)
B)
C)
D)
E)
Br
II
Br
III
IV
I and II
II and III
I, II, and III
II, III, and IV
I, III, and IV
Ans: E
Topic: General
56
...
A)
B)
C)
D)
E)
CH3CH2OCH2CH3 and CH3CH2CH2CH2OH are examples of what are now termed:
Structural isomers
Resonance structures
Functional isomers
Empirical isomers
Constitutional isomers
Ans: E
20
Chapter 1
Topic: Hybridization
58
...
What is the approximate hybridization state of the oxygen molecule in trimethylamine,
(CH3)3N?
A) sp
B) sp2
C) sp3
D) p3
E) d2sp3
Ans: C
Topic: Lewis structures, Hybridization
60
...
e
...
Which of the following structures represent compounds that are constitutional isomers
of each other?
I
A)
B)
C)
D)
E)
II
III
IV
I and II
I and III
I, II, and III
I, II, III, and IV
II and III
Ans: C
Topic: Isomerism
62
...
Ans: A
22
IV
Chapter 1
Topic: Isomerism
63
...
Consider the following:
CH3CH2CH2CH=CHCH2CH2CH3
I
CH3CH2CH=CHCH2CH2CH2CH3
III
A)
B)
C)
D)
E)
CH3CH2CH2CH2CH2CH2CH=CH2
II
CH2=CHCH2CH2CH2CH2CH2CH3
IV
Which structures can exist as cis-trAns: isomers?
I and II
I and III
I and IV
II and III
I alone
Ans: B
23
Chapter 1
Topic: Isomerism
65
...
Which of the following represent pairs of constitutional isomers?
OH
O
A)
O
and
Br
H
Br
CH3
H
and Br
H
CH2
C)
O
CH3
CH3
B)
H
Br
H
and H
CH3
D) More than one of these pairs
E) All of these pairs
Ans: D
Topic: Isomerism
67
...
When the 1s orbitals of two hydrogen atoms combine to form a hydrogen molecule,
how are the electrons distributed in the resulting molecular orbitals?
A) 2 electrons in the bonding molecular orbital
B) 1 electron in the bonding molecular orbital, 1 electron in the non-bonding molecular
orbital
C) 1 electron in the bonding molecular orbital, 1 electron in the antibonding molecular
orbital
D) 2 electrons in the non-bonding molecular orbital
E) 2 electrons in the antibonding molecular orbital
Ans: A
Topic: Atomic Orbitals, Electron Configuration, Hybridization
69
...
Identify the atomic orbitals involved in the C-2---C-3 sigma bond (indicated by an
arrow) in the following molecule:
1
4
2
6
7
A)
B)
C)
D)
E)
5
2
3
2
sp , sp
sp2, sp
sp2, sp3
sp3, sp2
sp, sp2
Ans: E
25
Chapter 1
Topic: Lewis Structures
71
...
Based on the VSEPR theory, which of the following would have a tetrahedral
arrangement of electrons around the central atom?
A) BH3
B) NO2 −
C) SiH4
D) CO3 2−
E) SO3
Ans: C
Topic: Molecular Geometry
73
...
A)
B)
C)
D)
E)
Select the least electronegative element
P
N
Mg
Si
K
Ans: E
26
Chapter 1
Topic: Atomic Orbitals, Hybridization
75
...
Which molecule has the shortest carbon-carbon single bond?
I
II
III
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: E
Topic: Atomic Orbitals, Hybridization
77
...
How many s-sp3 bonds are there in the following substance?
A)
B)
C)
D)
E)
3
8
12
13
16
Ans: D
Topic: Resonance
79
...
Organic compounds were originally defined as compounds obtained from __________
...
The modern definition of organic chemistry is _________________
...
Different compounds with the same molecular formula are referred to as __________
...
Constitutional isomers differ in the _________________
...
The bond that results when two atoms share a pair of electrons is called a
_________________
...
Define an orbital
...
An orbital is defined as a region of space where the probability of _________________
is high
...
There are three fundamental rules that we use in writing electronic configurations for
atoms and molecules
...
Which one?
1s
2s
2p
2p
Ans: Pauli exclusion principle
2p
Topic: Molecular orbitals
88
...
Ans: antibonding
Topic: Molecular orbitals
89
...
Ans: bonding
29
Chapter 1
Topic: Lewis Structures
90
...
Ans:
O
...
O
...
...
N
...
...
O
...
O
...
Draw all the isomers of C4H9Br, using bond-line formulas
...
Draw all the isomers of C4H10O, using bond-line formulas
...
Draw all isomers of C4H8, using bond-line formulas
...
...
Draw the Lewis structure of acetic acid, CH3CO2H, clearly indicating all non-bonding
pairs of electrons
...
O
...
Which compound would you expect to have the lowest boiling point?
NH2
A)
B)
NH2
C)
H
N
D)
N
E)
NH2
Ans: D
:
Topic: Molecular geometry, dipole moment
2
...
e
...
A)
B)
C)
D)
Which of these compounds would have the highest boiling point?
CH3OCH2CH2CH2OCH3
CH3CH2OCH2CH2OCH3
CH3CH2OCH2OCH2CH3
CH3OCH2CHOCH3
CH3
E) HOCH2CH2CH2CH2CH2OH
Ans: E
Topic: Intermolecular forces
4
...
A)
B)
C)
D)
E)
Which compound would have the highest boiling point?
CH3CH2CH2CH2CH2CH3
CH3CH2OCH2CH2CH3
CH3CH2CH2CH2CH2OH
CH3CH2OCH(CH3)2
CH3OCH2CH2CH2CH3
Ans: C
Topic: Intermolecular forces
6
...
Which compound would you expect to have the lowest boiling point?
O
A)
NH2
H
N
B)
O
O
C)
N
D)
NH2
O
E)
O
N
H
Ans: C
Topic: Intermolecular forces
8
...
Which of the following would have no net dipole moment
(μ = 0 D)?
A) CBr4
B) cis-1,2-Dibromoethene
C) trAns:-1,2-Dibromoethene
D) 1,1-Dibromoethene
E) More than one of these
Ans: E
34
Chapter 2
Topic: Molecular geometry, dipole moment
10
...
A)
B)
C)
D)
E)
The strongest of attractive forces is which type?
van der Waals
Ion-dipole
Dipole-dipole
Cation-anion
Hydrogen bonds
Ans: D
Topic: Intermolecular forces
12
...
This alkane is predicted to have the highest melting point of those shown:
A) CH3CH2CH2CH3
B) CH3CHCH3
CH3
C) CH3CH2CH2CH2CH3
D) CH3CHCH2CH3
E)
CH3
CH3
CH3CCH3
CH3
Ans: E
Topic: Intermolecular forces
14
...
Which compound would have the lowest boiling point?
OH
OH
O
I
II
III
OH
OH
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: A
Topic: Molecular geometry, Polarity
16
...
A)
B)
C)
D)
E)
Which molecule has a zero dipole moment?
SO2
CO2
CO
CHCl3
None of these
Ans: B
Topic: Molecular geometry, polarity
18
...
A)
B)
C)
D)
E)
Which molecule would have a dipole moment greater than zero?
BeCl2
BCl3
CO2
H2O
CCl4
Ans: D
Topic: Molecular geometry, polarity
20
...
A) Three or more atoms in the molecule
B) Presence of one or more polar bonds
C) A non-linear structure
D) Presence of oxygen or fluorine
E) Absence of a carbon-carbon double or triple bond
Ans: B
38
Chapter 2
Topic: Molecular geometry, polarity
21
...
A)
B)
C)
D)
E)
Which of these is the weakest of the intermolecular attractive forces?
Ion-ion
van der Waals
Dipole-dipole
Covalent bonding
Hydrogen bonding
Ans: B
Topic: Functional groups
23
...
Which compound is a secondary amine?
A) CH3CH2CH2NH2
B) CH3CHCH3
NH2
C) CH3CH2NH
CH3
D) H3C N CH3
CH3
E) CH3CH2CHNH2
CH3
Ans: C
Topic: Functional groups
25
...
Which compound is a ketone?
A) O
C OH
H
O
B)
CH3CCH2CH3
C) O
HCOCH3
D) O
C H
H
E) H3C
CH OH
H3C
Ans: B
Topic: Functional groups
27
...
The compound shown below is a synthetic estrogen
...
OH
O
A)
B)
C)
D)
E)
In addition to an alkane (actually cycloalkane) skeleton, the Enovid molecule also
contains the following functional groups:
Ether, alcohol, alkyne
...
Alcohol, carboxylic acid, alkene, alkyne
...
Amine, alkene, ether, alkyne
...
Which is a 3° alkyl halide?
F
Br
Cl
I
II
III
I
Br
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: B
42
Chapter 2
Topic: Functional groups
30
...
Which functional group is not contained in prostaglandin E1?
O
O
HO
H
A)
B)
C)
D)
E)
H
H
OH
H OH
Prostaglandin E1
Ketone
2° alcohol
3° alcohol
Carboxylic acid
Alkene
Ans: C
43
Chapter 2
Topic: Functional groups
32
...
Which functional
group is not present in cortisone?
OH
O
O
OH
O
A)
B)
C)
D)
E)
1° alcohol
2° alcohol
3° alcohol
Ketone
Alkene
Ans: B
Topic: Functional groups
33
...
Which functional groups are present in the molecule of capsaicin?
O
N
H
O
OH
A)
B)
C)
D)
E)
Capsaicin
Alkene, ketone, amine, alcohol, ester
Alkene, ketone, alcohol, ether
Alkene, amine, phenol, ether
Ether, phenol, alkene, amide
Ester, phenol, alkene, amide
Ans: D
44
Chapter 2
Topic: Functional groups
34
...
Which of the following functional groups is NOT in
atropine?
N
O
O
OH
Atropine
A)
B)
C)
D)
E)
Amine
Ester
Alcohol
Benzene Ring
Ketone
Ans: E
Topic: Functional groups
35
...
OH
O
O
A)
B)
C)
D)
E)
In addition to a cycloalkane skeleton, testosterone also contains the following functional
groups:
Alkene, ester, tertiary alcohol
...
Alkene, ketone, secondary alcohol
...
Alkene, ketone, tertiary alcohol
...
Which is a carboxylic acid?
OH
O
OH
O
O
I
O
II
III
O
O
O
OH
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: E
Topic: Functional groups
37
...
Which compound is a primary amine with the formula C5H13N?
H2N
NH
H2N
I
II
III
N
NH2
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: C
Topic: Functional groups
39
...
A)
B)
C)
D)
E)
The C–O–C bond angle in diethyl ether is predicted to be approximately:
90º
105º
110º
120º
180º
Ans: C
Topic: Functional groups
41
...
The number of unique open-chain structures corresponding to the molecular formula
C3H5Cl is:
A) 2
B) 3
C) 4
D) 5
E) 6
Ans: C
48
Chapter 2
Topic: General, Bonding
43
...
An example of a tertiary amine is:
H
N
NH2
I
II
NH2
IV
A)
B)
C)
D)
E)
H2N
III
N
V
I
II
III
IV
V
Ans: E
49
Chapter 2
Topic: Functional groups
45
...
A)
B)
C)
D)
E)
How many constitutional isomers are possible with the formula C4H10O?
3
4
5
6
7
Ans: E
Topic: Functional groups
47
...
Which of these compounds is a secondary alkyl chloride?
A) CH3CH2CH2CH2CH2Cl
CH3
B)
CH3CCH2CH3
Cl
C) CH3CHCH2CH2CH3
Cl
D) CH3CH2CHCl
CH2CH3
E) Two of these
Ans: E
Topic: Functional groups, Isomerism
49
...
Many organic compounds contain more than one functional group
...
An oxygen-containing compound shows strong IR absorption at 1630-1780 cm-1 and
3200-3550 cm-1
...
The absorption band for the O-H stretch in the IR spectrum of an alcohol is sharp and
narrow in the case of:
A) a Nujol mull of the alcohol
...
C) a gas phase spectrum of the alcohol
...
A split peak for the IR absorption due to bond stretching is observed for the carbonyl
group in which of these compounds?
O
A)
CH3CH2CH2COH
O
B)
CH3CH2CCl
O
C)
ca
CH3CH2CNH2
O
D)
CH3CH2COCH2CH3
O O
E)
CH3CH2COCCH2CH3
Ans: E
Topic: IR Spectroscopy
54
...
The IR stretching frequency can be expected to occur at the lowest frequency for which
of these bonds?
A) C–H
B) O–H
C) N–H
D) S–H
E) Difficult to predict
Ans: D
53
Chapter 2
Topic: IR Spectroscopy
56
...
A)
B)
C)
D)
E)
An anticipated IR absorption band may not be observed because:
it occurs outside the range of the instrument used
...
the absorption band is eclipsed by another
...
All of these
Ans: E
Topic: IR Spectroscopy
58
...
The IR absorption due to the stretching of which of these carbon-hydrogen bonds occurs
at the highest frequency?
H
H
H
I
II
III
H
IV
A)
B)
C)
D)
E)
H
V
I
II
III
IV
V
Ans: E
Topic: IR Spectroscopy
60
...
The IR spectrum of which type of compound generally exhibits evidence of hydrogen
bonding?
A) Aldehyde
B) Carboxylic acid
C) Alkene
D) Ester
E) Ketone
Ans: B
55
Chapter 2
Topic: Intermolecular forces
62
...
A)
B)
C)
D)
E)
The IR stretching frequency occurs at the lowest frequency for which of these bonds?
B–H
O-H
N-H
S-H
Difficult to predict
Ans: D
Topic: IR Spectroscopy
64
...
The IR spectrum of which of the following substances is likely to show a small, but
sharp peak at 2200 cm-1?
OH
O
N
H
II
I
IV
A)
B)
C)
D)
E)
III
V
I
II
III
IV
V
Ans: E
SHORT ANSWER QUESTIONS
Topic: Functional Groups
66
...
Ans: alkenes
Topic: Functional Groups, IR Spectroscopy
67
...
What functional group is
present in the molecule?
Ans: A terminal alkyne
Topic: Functional Groups
68
...
Ans: carbonyl
57
Chapter 2
Topic: Functional Groups, IR Spectroscopy
69
...
What functional group is
present in the molecule?
Ans: an alkene
Topic: Functional Groups, IR Spectroscopy
70
...
Which oxygen
containing functional group is present in P?
Ans: aldehyde
Topic: Functional Groups, IR Spectroscopy
58
Chapter 2
71
...
Which oxygen
containing functional group is present in P?
Ans: alcohol
Topic: General
72
...
Ans: delocalized
Topic: General
73
...
Ans: not shared equally
Topic: Functional Groups
74
...
Ans: functional groups
Topic: Functional Groups
75
...
Ans: Pi bonds
Topic: Bonding, Solubility
76
...
Why?
Ans: Sodium chloride, which is an ionic substance, is soluble in a polar solvent such as
water, but not in a non-polar solvent such as hexane
...
Draw all tertiary amine isomers of C6H15N
...
Draw all isomers of C6H14
...
Draw a structural formula for C8H18 , in which there are two quaternary carbons
...
Draw all isomers of C5H10O that are ketones
...
Draw all isomers of C3H8O and classify each according to functional group
OH
Ans:
C3H8O
OH
O
primary alcohol
secondary alcohol
ether
Topic: Isomers, Functional Groups
82
...
Ans:
O
O
O
O
O
O
O
Topic: Isomers, Functional Groups
83
...
The IR absorption frequencies of the C-H bond in alkanes, alkenes and alkynes are
measurably different
...
Ans: IR absorption frequency depends on bond strength; the bond strength of C-H
bonds in alkanes, alkenes and alkynes is different because different atomic
orbitals (hybridized) of carbon are involved in the bond: the C-H bond in alkanes
is described as (sp3-s), that in alkenes is (sp2-s) and in alkynes, it is (sp-s)
...
% p character of the hybrid orbitals of carbon would indicate
different bond lengths /bond strengths for alkanes, alkenes and alkynes, with the
bond length / bond strength being the longest/weakest respectively
...
Topic: Molecular Geometry, Dipole Moment
85
...
Briefly explain why, using relevant diagrams as appropriate to illustrate
your Ans:wer
...
In some molecules containing bonds of identical
polarity, the molecular geometry may result in a net cancellation of the overall
dipole forces
...
...
: O C O:
Topic: Intermolecular Forces
86
...
Briefly explain why
...
No hydrogen bonding is possible between molecules of propane,
resulting in a lower boiling point compared with ethanol
...
Ethanol, C2H5OH, and dimethyl ether, CH3OCH3, have the same molar mass, yet,
ethanol has a much higher boiling point
...
Ans: Strong hydrogen bonding between molecules of ethanol leads to elevation in
boiling point
...
61
Chapter 2
Topic: IR Spectroscopy
88
...
However, IR spectra of gaseous
samples show sharp peaks
...
Ans: Broad signals of alcohols are due to hydrogen bonding associated with the O-H
group
...
62
Chapter 3
MULTIPLE CHOICE QUESTIONS
Topic: Acid-Base Definitions
1
...
B) Electron pair donor
...
D) Hydrogen ion donor
...
Ans: B
Topic: Acid-Base Definitions
2
...
Which of the following is not a conjugate acid - conjugate base pair (in that order)?
A) H3PO4, H2PO4−
B) HBF4, BF4−
C) CH3CH2OH, CH3CH2O−
D) H3O+, H2O
E) HPO4−, H2PO4−
Ans: E
Topic: Acid-Base Definitions
4
...
Consider the equilibrium
PO43− +
H2O ⇄
ΗPΟ42− +
ΟΗ−
Which are the Bronsted-Lowry bases?
A) PO43− and HPO42−
B) PO43− and OH−
C) PO43− and H2O
D) H2O and OH−
E) H2O and HPO42−
Ans: B
Topic: Acid-Base Definitions
6
...
B) All Lewis acids contain hydrogen
...
D) All Lewis acids are electron deficient
...
Ans: B
Topic: Acid-Base Definitions
7
...
Which of the following is not a Lewis base?
A) NH3
B) H−
C) BF3
D) H2O
E) H3C−
Ans: C
Topic: Acid-Base Definitions
9
...
The reaction between which combination of substances below cannot be classified as a
Bronsted-Lowry acid-base reaction?
A) CH3Li + C2H5OH
B) H2SO4 + CH3CO2Na
C) BF3 + NH3
D) H3O+ + CH3NHE) two of the above
Ans: C
Topic: Acid-Base Definitions
11
...
This species is a carbon-based Lewis acid:
A) CH4
B) HCCl3
C) CH3+
D) :CH3−
E) ·CH3
Ans: C
Topic: Acid-Base Definitions
13
...
Which of the acids below would have the strongest conjugate base?
A) CH3CH2OH pKa = 18
B) CH3CO2H pKa = 4
...
81
D) Cl2CHCO2H pKa = 1
...
66
Ans: A
Topic: Acid-Base Definitions
15
...
Adding sodium hydride to ethanol would produce:
D) CH3CH2Na + NaOH
A) CH3CH2OCH2CH3 + H2
B) CH3CH2OCH2CH3 + NaOH
E) CH3CH3 + NaOH
C) CH3CH2ONa + H2
D)CH3CH2Na + NaOH
E) CH3CH3 + NaOH
Ans: C
Topic: Acid-Base Reactions
17
...
Which acid-base reaction would not take place as written?
A) CH3Li + CH3CH2OH ⎯⎯⎯⎯→ CH4 + CH3CH2OLi
B) HC≡CH + NaOH ⎯⎯⎯⎯→ HC≡CNa + H2O
C) HC≡CNa + H2O ⎯⎯⎯⎯→ HC≡CH + NaOH
D) CH3OH + NaH ⎯⎯⎯⎯→ CH3ONa + H2
E) CH3CO2H + CH3ONa ⎯⎯⎯⎯→ CH3CO2Na + CH3OH
Ans: E
Topic: Acid-Base Reactions
19
...
Which acid-base reaction would not take place as written?
A) CH3Li + CH3CH2OH ⎯⎯⎯⎯→ CH4 + CH3CH2OLi
B) H2C=CH2 + NaOH ⎯⎯⎯⎯→ H2C=CHNa + H2O
C) CH3C≡CNa + H2O ⎯⎯⎯⎯→ CH3C≡CH + NaOH
D) (CH3)2CHOH + NaH ⎯⎯⎯⎯→ (CH3)2CHONa + H2
E) CH3CO2H + CH3ONa ⎯⎯⎯⎯→ CH3CO2Na + CH3OH
Ans: B
Topic: Acid-Base Reactions
21
...
Acetic acid dissociates most completely in:
A) CCl4
B) Cl2C=CCl2
C) H2O
D) (CH3CH2)2O
E) the gas phase
...
Which pair of species are both bases in the following reaction?
HCN and H2O ⇄
A)
B)
C)
D)
E)
H3O+ and CN−
H2O and CN−
H3O+ and H2O
HCN and H3O+
HCN and CN−
H3O+ and CN−
Ans: A
68
Chapter 3
Topic: Acid-Base Reactions
24
...
Ans: E
Topic: Acid-Base Reactions
25
...
NH3 + ethanol
E) NaC2H3O2 (aq) + HI
Ans: B
Topic: Acid-Base Reactions
26
...
Which reaction of these potential acids and bases does not occur to any appreciable
degree due to an unfavorable equilibrium?
A) NaNH2 + CH3CH2CH2CH2CH2OH
B) CH3CH2CO2H + NaCl
C) NaHCO3 + CH3CH2CO2H
D) NaH + CH3CH2CH2CH2CH2NH2
E) all of the above will occur due to a favorable equilibrium
Ans: E
69
Chapter 3
Topic: Acid-Base Reactions
28
...
Which combination of reagents is effective in generating sodium ethoxide,
CH3CH2ONa?
A) CH3CH2OH + KH
B) CH3CH2OH + NaNH2
C) CH3CH2OH + Na
D) Two of the above
E) All of the above
Ans: E
Topic: Acid-Base Reactions
30
...
In the reaction, Na+NH2− + CH3OH ⎯⎯⎯⎯→ CH3O−Na+ + NH3, the stronger
base is:
A) NaNH2
B) CH3OH
C) CH3ONa
D) NH3
E) This is not an acid-base reaction
...
Which sequence is the best one to use to prepare CH3C≡CD?
D2O
A) CH C CH NaH
3
B) CH C CH
3
C)
CH3C
CH
NaOH
D2O
CH3ONa
D2O
D) CH C CH DOH
3
E) None of these will be successful
...
Adding sodium hydride, NaH, to water produces:
A) H2 and NaOH(aq)
B) H-(aq) + Na+(aq)
C) H3O+(aq) + Na+(aq)
D) H3O−(aq) + Na+(aq)
E) Na2O + H2
Ans: A
Topic: Acid-Base Reactions
34
...
Which reaction will yield CH3CH2-D?
A) CH3CH3 + D2O
B) CH3CH2Li + D2O
C) CH3CH2OLi + D2O
D) CH3CH2OH + D2O
E) More than one of these
Ans: B
71
Chapter 3
Topic: Acid-Base Reactions, isotope labeling
36
...
The compounds ethane, ethene, and ethyne exhibit this order of increasing acidity:
A) Ethyne < ethene < ethane
B) Ethene < ethyne < ethane
C) Ethane < ethyne < ethene
D) Ethane < ethene < ethyne
E) Ethene < ethane < ethyne
Ans: D
Topic: Relative acid/base strength
38
...
B) PH3 is a weaker base than NH3
...
D) OH− is a stronger base than OR−
...
Ans: D
Topic: Relative acid/base strength
39
...
Which is a protic solvent?
A) CCl4
B) HCCl3
C) CH3OH
D) CH3(CH2)4CH3
E) CH3CH2OCH2CH3
Ans: C
Topic: Solvent effects
41
...
Which of the following classes of substances cannot be used as protic solvents?
A) esters
B) aldehydes
C) ketones
D) carboxylic acids
E) two of the above
Ans: D
73
Chapter 3
Topic: Acid constants
43
...
01 M solution of a weak acid has a pH of 4
...
0
B) 8
...
0
D) 4
...
0
Ans: C
Topic: General
44
...
B) The conjugate base of a strong acid is a strong base
...
D) Strong acids can have negative pKa values
...
Ans: D
Topic: Relative acid/base strengths
45
...
A particular acid has Ka = 2
...
The evaluation of which of
these expressions gives the value for pKa?
A) 10-14/2
...
0 x 10-5)
C) 5 – log 2
...
0
E) 2
...
As a consequence of the "leveling effect," the strongest acid which can exist in
appreciable concentration in aqueous solution is:
A) H3O+
B) H2SO4
C) HClO4
D) HCl
E) HNO3
Ans: A
Topic: Relative acid/base strengths
48
...
An acid, HA, has the following thermodynamic values for its dissociation in water at
27º C: ΔH = -8
...
The ΔG for the process is:
A) +29 kJ mol-1
B) +13 kJ mol-1
C) -6
...
Which of these bases is the strongest one which can be used (and retains its basic
character) in aqueous solution?
A) OCH3−
B) F−
C) OH−
D) C2H3O2−
E) HSO4−
Ans: C
75
Chapter 3
Topic: Acidity constant- thermodynamic principles
51
...
B) The two terms are identical numerically
...
D) Ka is the reciprocal of Keq
...
Ans: E
Topic: Acids/bases-general principles
52
...
B) The stronger an acid, the weaker its conjugate base
...
D) Comparison of the acidity of strong acids in solution requires the use of a solvent
less basic than water
...
Ans: E
Topic: Acid-base reactions
53
...
B) the weaker acid and the stronger base
...
D) the stronger acid and the stronger base
...
Ans: A
Topic: Relative acid-base strengths
54
...
The compound aniline, C6H5NH2, has weakly basic properties in aqueous solution
...
A) CH3OH
B) CH3CH2OH
C) CF3CO2H
D) Liquid NH3
E) CH3(CH2)4CH3
Ans: C
Topic: Relative acid-base strengths
56
...
Which is the strongest acid?
A) CH3CH2OH
B) CH3CO2H
C) HC≡CH
D) CH2=CH2
E) CH3CH3
Ans: B
Topic: Relative acid-base strengths
58
...
A)
B)
C)
D)
E)
Which is the strongest acid?
CH3CH2CH2CH2CHFCO2H
CH3CHBrCH2CH2CH2CO2H
CH3CH2CH2CHClCH2CO2H
CH3CH2CH2CHFCH2CO2H
CH3CH2CH2CHICH2CO2H
Ans: A
Topic: Relative acid-base strengths
60
...
A)
B)
C)
D)
E)
Which of the following substances has a hydrogen atom with pKa ≈25?
CH3CH2CH2CH2CO2H
CH3CHCH2C≡CCH3
CH3CH2CH2C≡CH
CH3CH2CH2CH2CH=CH2
CH3CH2CH2CH2NH2
Ans: C
78
Chapter 3
Topic: Relative acid-base strengths
62
...
Ans: A
Topic: Relative acid-base strengths
63
...
Select the strongest base
...
A group of acids arranged in order of decreasing acidity is:
HNO3 > CH3COOH > C6H5OH > H2O > HC≡CH
What is the arrangement of the conjugate bases of these compounds in decreasing order
of basicity?
A) NO3− > CH3COO− > C6H5O− > OH− > HC≡C−
B) CH3COO− > C6H5O− > NO3− > OH− > HC≡C−
C) C6H5O− > NO3− > HC≡C− > OH− > CH3COO−
D) HC≡C− > OH− > C6H5O− > CH3COO− > NO3−
E) No prediction of relative base strength is possible
...
What prediction can be made of the relative strengths of the conjugate bases of: H2S,
HCl, SiH4, PH3?
A) PH2− > SiH3− > HS− > Cl−
B) SiH3− > PH2− > HS− > Cl−
C) Cl− > HS− > PH2− > SiH3−
D) HS− > Cl− > SiH3− > PH2−
E) Cl− > PH2− > SiH3− > HS−
Ans: B
Topic: Acids/bases- general
67
...
Which of these phosphorus-based acids is dibasic?
O
A)
P
HO
OH
OH
O
B)
HO
P
OH
H
O
C)
H
P
H
OH
O
D)
HO
P
O
O
OH
O O
E)
HO
P
P
P
OH
OH
OH
OH OH
Ans: B
Topic: Acids/bases- general
69
...
B) A more basic solvent than H2O must be used
...
D) These oxidizing acids cause redox reactions to occur
...
Ans: C
Topic: Acids/bases- general
70
...
Which set contains non-equivalent members?
A) Enthalpy and heat content
B) Endothermic reaction and +ΔH
C) Exothermic reaction and -ΔH
D) Kinetic energy and energy of motion
E) High energy and high stability
Ans: E
SHORT-ANSWER QUESTIONS:
Topic: General Reactivity
72
...
Ans: multiple bonds
Topic: Reaction Types
73
...
Ans: substitution, addition, elimination, rearrangement
Topic: Reaction Mechanisms
74
...
Ans: homolysis
Topic: Reaction Mechanisms
75
...
Ans: charged fragments/ions
Topic: Acids and Bases
76
...
Ans: donate a proton
Topic: Acids and Bases
77
...
Ans: donate a lone pair of electrons
82
Chapter 3
Topic: Acids and Bases
78
...
Ans: conjugate base
Topic: Nucleophiles and Electrophiles
79
...
Ans: nucleophiles
Topic: Acids and Bases
80
...
Ans: base; Lewis
Topic: Curved Arrow Notation
81
...
The curved arrow
begins with ______________ and points toward ______________
...
Why do water-insoluble carboxylic acids dissolve in aqueous sodium hydroxide?
Ans: Because they are converted to water-soluble salts
...
Bond polarization that takes place through space and through the bonds of the molecule
is called the _____________
...
What are the two fundamental types of energy?
Ans: potential energy and kinetic energy
Topic: Types of Solvents
85
...
Ans: one that has a hydrogen atom attached to a strongly electronegative element such as
oxygen
83
Chapter 3
Topic: Relative acid strength
86
...
Ans: The greater acidity of the –OH hydrogen in acetic acid is due primarily to two
factors: resonance and inductive effects
...
Also,
comparison of the respective conjugate bases shows that, unlike the ethoxide ion, the
acetate ion is stabilized by resonance
...
O
O
H
O
(- H+)
O
Inductive effect:
electron withdrawing
O
O
H
O
resonance stabilized anion
(- H+)
O
84
Chapter 3
Topic: Relative acid strength, isotope labeling
87
...
How will you
selectively deuterate the specified hydrogen atom, indicated by an arrow, in the
following compound? Use equations to clarify your answer and briefly explain your
rationale
...
By using an appropriate strong
base, such as NaH or NaNH2, the acetylenic hydrogen is selectively removed; adding
D2O then replaces the lost hydrogen atom with a deuterium atom
...
Write an equation to show the reaction between ethanol, C2H5OH and methyllithium,
CH3Li
...
Ans:
...
...
: CH3 Li+
+
CH4
Topic: Acid-base reactions, solvent selection
89
...
You also need to choose an appropriate solvent for carrying out the
reaction
...
Ans: No, ethanol would be unsuitable for carrying out the reaction between propyne and
methyllithium
...
Typically, the
selected solvent should be chemically inert toward all substances used in the reaction, so
that it does not interfere with the desired reaction
...
You are planning to purify an impure sample of benzoic acid, known to be contaminated
with naphthalene
...
Ans: Benzoic acid reacts with aqueous NaOH to form a water soluble salt, while
naphthalene, which is not soluble in water to any appreciable extent, does not react with
NaOH
...
After filtration, HCl is added to the filtrate to regenerate benzoic acid, which
precipitates as almost pure crystals
...
Alternatively, before beginning the reaction with aqueous NaOH, the impure
sample is first dissolved in diethyl ether (benzoic acid and naphthalene are both
soluble in ether) and placed in a separatory funnel
...
The rest of the procedure is as described earlier
...
A)
B)
C)
D)
E)
The IUPAC name for
6-Ethyl-3,4-dimethylheptane
2-Ethyl-4,5-dimethylheptane
3,4,6-Trimethyloctane
3,5,6-Trimethyloctane
2-(1-Methylpropyl)-4-methylhexane
Ans: C
is:
Topic: Nomenclature
2
...
A correct IUPAC name for the following compound is:
A)
B)
C)
D)
E)
2,5-Dimethyl-3-propylheptane
3,6-Dimethyl-5-propylheptane
6-Methyl-4-(1-methylethyl)octane
2-Methyl-3-(2-methylbutyl)hexane
3-Methyl-5-(1-methylethyl)octane
Ans: E
87
Chapter 4
Topic: Nomenclature
4
...
A)
B)
C)
D)
E)
Which of the following pairs of compounds represent pairs of constitutional isomers?
2-Methylbutane and pentane
2-Chlorohexane and 3-chlorohexane
sec-Butyl bromide and tert-butyl bromide
Propyl chloride and isopropyl chloride
All of the above
Ans: E
88
Chapter 4
Topic: Nomenclature
6
...
2
...
Select the systematic name for
Cl
H
A)
B)
C)
D)
E)
H
Cl
cis-1,3-Dichlorocyclopentane
trans-1,4-Dichlorocyclopentane
cis-1,2-Dichlorocyclopentane
trans-1,3-Dichlorocyclopentane
1,1-Dichlorocyclopentane
Ans: D
89
Chapter 4
Topic: Nomenclature
8
...
A)
B)
C)
D)
E)
Which isomer of C5H10 would you expect to have the smallest heat of combustion?
Cyclopentane
Methylcyclobutane
1,1-Dimethylcyclopropane
cis-1,2-Dimethylcyclopropane
trans-1,2-Dimethylcyclopropane
Ans: A
Topic: Nomenclature
10
...
2
...
2
...
2
...
2
...
What is the name of this compound?
A)
B)
C)
D)
E)
Bicyclo[2
...
2]octane
Bicyclo[3
...
1]octane
Bicyclo[4
...
1]octane
Bicyclo[4
...
0]octane
Bicyclo[3
...
0]octane
Ans: D
Topic: Nomenclature
12
...
A correct IUPAC name for the following compound is:
Br
A)
B)
C)
D)
E)
Ans:
3,6,7-trimethyl-4-bromo-1-octene
4-bromo-3-methyl-6-isopropyl-1-heptene
4-bromo-3,6,7-trimethyl-1-octene
4-bromo-6-isopropyl-3-methyl-1-heptene
4-bromo-6-isopropyl-3,6-dimethyl-1-hexene
C
91
Chapter 4
Topic: Nomenclature
14
...
3
...
3
...
3
...
3
...
3
...
A)
B)
C)
D)
E)
III
V
Which of the above is bicyclo[3
...
1]nonane?
I
II
III
IV
V
Ans: D
Topic: Nomenclature
16
...
2
...
A)
B)
C)
D)
E)
Which of the above is bicyclo[4
...
0]nonane?
I
II
III
IV
V
Ans: A
Topic: Nomenclature
Use the following to answer questions 18-19:
Br
H
H
Br
Br
H
H
I
Br
Br
H
Br
H
II
III
Topic: Nomenclature
18
...
A)
B)
C)
D)
E)
cis-1,2-Dibromocyclohexane is represented by structure(s):
I
II
III
II and III
I and II
Ans: A
93
Chapter 4
Topic: Nomenclature
20
...
A)
B)
C)
D)
E)
CH3CHCH2−
CH2CH3 is:
An IUPAC name for the group
Isopentyl
Isoamyl
sec-Butylmethyl
2-Methylbutyl
2-Ethylpropyl
Ans: D
Topic: Nomenclature
22
...
A)
B)
C)
D)
E)
Br
Cl is:
The correct IUPAC name for
2-Bromo-4-chloro-4-isopropylpentane
4-Bromo-2-chloro-2-isopropylpentane
5-Bromo-3-chloro-2,3-dimethylhexane
2-Bromo-4-chloro-4,5-dimethylhexane
2-(2-Bromopropyl)-2-chloro-3-methylbutane
Ans: C
Topic: Nomenclature
24
...
The correct IUPAC name for the following compound is:
OH
A)
B)
C)
D)
E)
1-Hydroxy-3-sec-butylcyclopentane
3-sec-Butyl-1-cyclopentanol
1-sec-Butyl-3-cyclopentanol
4-sec-Butyl-1-cyclopentanol
3-Isobutyl-1-cyclopentanol
Ans: B
95
Chapter 4
Topic: Nomenclature
26
...
What is the correct name of the following compound?
Cl
A)
B)
C)
D)
E)
1-Chlorobicyclo[4
...
1]octane
2-Chlorobicyclo[4
...
0]octane
2-Chlorobicyclo[4
...
1]octane
2-Chlorobicyclo[4
...
1]heptane
5-Chlorobicyclo[4
...
1]octane
Ans: C
Topic: Nomenclature
28
...
Which of the following structures represents bicyclo[3
...
1]octane?
I
II
IV
A)
B)
C)
D)
E)
III
V
I
II
III
IV
V
Ans: E
Topic: Nomenclature
30
...
Neglecting stereochemistry, which of these common group names is ambiguous, i
...
,
does not refer to one specific group?
A) Butyl
B) sec-Butyl
C) tert-Pentyl
D) Neopentyl
E) sec-Pentyl
Ans: E
97
Chapter 4
Topic: Nomenclature
32
...
Isopentyl is the common name for which alkyl group?
A) CH3CH2CH2CH
CH3
B) CH3CH2CHCH2
CH3
CH3CHCH2CH2
C)
CH3
D) CH3CH2CH
CH2CH3
E)
CH3
CH3CCH2
CH3
Ans: C
98
Chapter 4
Topic: Nomenclature
34
...
An IUPAC name for the following compound is:
A)
B)
C)
D)
E)
4-Isobutyl-3,4-dimethylheptane
4-sec-Butyl-2,4-dimethylheptane
2,4,5-Trimethyl-4-propylheptane
3,4,6-Trimethyl-4-propylheptane
4-Isobutyl-4,5-dimethylheptane
Ans: C
Topic: Nomenclature
36
...
What is the correct IUPAC name for the following compound?
OH
F
A)
B)
C)
D)
E)
5-Ethyl-3-fluorohexanol
5-Ethyl-3-fluoro-1-hexanol
2-Ethyl-4-fluoro-6-hexanol
3-fluoro-5-methyl-7-heptanol
3-fluoro-5-methyl-1-heptanol
Ans: E
Topic: Nomenclature
38
...
3
...
3
...
3
...
3
...
3
...
A correct name for the following compound is:
Br
A)
B)
C)
D)
E)
4-bromo-3,8-dimethylbicyclo[5
...
2]nonane
3,8-dimethyl-4-bromo-bicyclo[5
...
0]nonane
4-bromo-3,8-dimethylbicyclo[5
...
1]decane
7-bromo-2,6-dimethylbicyclo[5
...
0]nonane
4-bromo-3,8-dimethylbicyclo[5
...
0]nonane
Ans: E
100
Chapter 4
Topic: Conformational Analysis
40
...
A)
B)
C)
D)
E)
The preferred conformation of cis-3-tert-butyl-1-methylcyclohexane is the one in which:
the tert-butyl group is axial and the methyl group is equatorial
...
both groups are axial
...
the molecule exists in a boat conformation
...
What structure represents the most stable conformation of cis-1,3-dimethylcyclohexane?
CH3
H
H
H
CH3
H3C
H
CH3
H
H3C
I
H
II
III
H
H
CH3
H3C
CH3
H3C
H
H
V
IV
A)
B)
C)
D)
E)
CH3
I
II
III
IV
V
Ans: B
Topic: Ring Strain
43
...
Which cycloalkane has the lowest heat of combustion per CH2 group?
I
II
IV
A)
B)
C)
D)
E)
III
V
I
II
III
IV
V
Ans: D
Topic: Ring Strain
45
...
Ans: A
Topic: Ring Strain
46
...
A)
B)
C)
D)
E)
Which cycloalkane has the greatest ring strain?
Cyclopropane
Cyclobutane
Cyclopentane
Cyclohexane
Cycloheptane
Ans: A
Topic: Conformational Analysis
48
...
The most stable conformation of 1,2-dibromoethane is:
H
Br
H
Br
H
H
H
H
Br
Br
H
H
H
I
H
Br
H
H
II
III
H
Br
H
Br
Br
Br
H
H
H
H
H
H
IV
A)
B)
C)
D)
E)
Br
V
I
II
III
IV
V
Ans: C
105
Chapter 4
Topic: Conformational Analysis
50
...
The most stable conformation of 3-bromo-2-methylpentane, viewed through the
C-3—C-4 bond (i
...
, C-3 in the front, C-4 in the back):
CH3
Br
H
H
Br
H
H
CH3
CH(CH3)2
H
H
H
CH(CH3)2
I
H
Br
H
CH3
CH(CH3)2
II
III
CH3
H
Br
CH(CH3)2
H
H
Br
H
CH3
CH3
H
IV
A)
B)
C)
D)
E)
CH2CH3
V
I
II
III
IV
V
Ans: A
107
Chapter 4
Topic: Conformational Analysis
52
...
e
...
The most stable conformation of 2,3-dimethylpentane, viewed through the
C-2—C-3 bond (i
...
, C-2 in the front, C-3 in the back):
CH3
CH3
CH3
H
H
CH3
H
CH2CH3
CH3
CH3
H
CH2CH3
H
H
H3C
I
H
H
CH(CH3)2
II
III
CH3
CH3
H
CH3
H
H3C
CH3
CH3
CH(CH3)2
IV
V
H3CH2C
A)
B)
C)
D)
E)
H
H
I
II
III
IV
V
Ans: D
Topic: Ring Strain
54
...
The most stable conformation of cis-1-tert-butyl-2-methylcyclohexane is the one in
which:
A) the tert-butyl group is axial and the methyl group is equatorial
...
C) both groups are axial
...
E) the twist boat conformation is adopted
...
The most stable conformation of trans-1-tert-butyl-2-methylcyclohexane is the one in
which:
A) the tert-butyl group is axial and the methyl group is equatorial
...
C) both groups are axial
...
E) the molecule is in the half chair conformation
...
The most stable conformation of trans-1-tert-butyl-3-methylcyclohexane is the one in
which:
A) the tert-butyl group is axial and the methyl group is equatorial
...
C) both groups are axial
...
E) the twist boat conformation is adopted
...
A)
B)
C)
D)
E)
In the most stable conformation of cis-1,4-dimethylcyclohexane, the methyl groups are:
one axial, one equatorial
...
both equatorial
...
None of the above
Ans: A
110
Chapter 4
Topic: Conformational Analysis
59
...
It is
the most stable conformation because:
H
H
OH
H
OH
H
A)
B)
C)
D)
E)
this corresponds to an anti conformation
...
it is stabilized by intramolecular hydrogen bonding
...
it has the highest energy of all the possibilities
...
The graph below is a plot of the relative energies of the various conformations of:
0o
60o 120o 180o 240o 300o 360o
Angle of rotation
A)
B)
C)
D)
E)
Ethane
Propane
Chloroethane
1-Chloropropane (C1-C2 rotation)
Butane (C1-C2 rotation)
Ans: D
111
Chapter 4
Topic: Conformational Analysis
Relative energy
61
...
Consider the graph below, which is a plot of the relative energies of the various
conformations of hexane, viewed through the C2-C3 bond
...
Consider the graph below, which is a plot of the relative energies of the various
conformations of 2,3-dimethylbutane, viewed through the C2-C3 bond
...
Which conformation of trans-1-isopropyl-3-methylcyclohexane would be present in
greatest amount at equilibrium?
A) The conformation with the methyl group equatorial and the isopropyl group axial
B) The conformation with the methyl group axial and the isopropyl group equatorial
C) The conformation with both groups axial
D) The conformation with both groups equatorial
E) The twist boat conformation
...
Which conformation represents the most stable conformation of trans-1-bromo-4methylcyclohexane?
CH3
Br
Br
Br
CH3
CH3
I
II
III
CH3
Br
H3C
Br
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: A
Topic: Cis-Trans Isomers
66
...
Ans: B
114
Chapter 4
Topic: Cis-Trans Isomers
67
...
Ans: C
Topic: Conformational Analysis
68
...
Ans: E
115
Chapter 4
Topic: Conformational Analysis
69
...
twist boat
...
half-chair
...
Ans: D
Topic: Conformational Analysis
70
...
CH3
CH3
H3C
H3C
I
A)
B)
C)
D)
E)
II
I is more stable than II by 7
...
I is more stable than II by 15 kJ mol-1
...
5 kJ mol-1
...
The two are equal in stability
...
A)
B)
C)
D)
E)
The twist boat conformation is the preferred conformation for this compound
...
Which of these C10H18 isomers is predicted to be the most stable?
I
II
III
H
H
H
IV
A)
B)
C)
D)
E)
H
V
I
II
III
IV
V
Ans: E
Topic: Alkane Synthesis
73
...
H2 and Ni
H2O
Heat
Zn, H3O+
Light
Ans: A
Topic: Alkane Synthesis
74
...
Zn, H3O+
CuI
H2O
H3O+
OHAns: A
117
Chapter 4
Topic: General
75
...
How many compounds with the formula C7H16 (heptanes) contain a single 3° carbon
atom?
A) 2
B) 3
C) 4
D) 5
E) 6
Ans: C
Topic: Alkane Synthesis, Nomenclature
77
...
The synthesis of an alkyne precursor to 2,2-dimethylheptane is accomplished most
effectively by the reaction between these two reagents:
A) CH3CH2CH2C≡CNa and (CH3)3CBr
B) CH3CH2C≡CNa and (CH3)3CCH2Br
C) (CH3)3CC≡CNa and CH3CH2CH2Br
D) (CH3)3CCH2CH2C≡CH and CH3CH2I
E) HC≡CNa and (CH3)3CCH2CH2Br
Ans: C
118
Chapter 4
Topic: Alkane Synthesis, Nomenclature
79
...
What is the simplest alkane, i
...
, the one with the smallest molecular weight, which
possesses primary, secondary and tertiary carbon atoms?
A) 2-Methylpropane
B) 2-Methylbutane
C) 2-Methylpentane
D) 3-Methylpentane
E) 2,2-Dimethylbutane
Ans: B
Topic: General
81
...
To determine the parent name for an alkane, we begin by finding the
___________________________
...
When more than one substituent is present on the parent chain, how do we organize the
names of the substituents in the name of the compound?
___________________________
...
A compound containing two fused or bridged rings is referred to as a
___________________________
...
A compound containing a triple bond between the first two carbons in the chain is called
a ___________________________
...
When non-bonded atoms/groups are closely positioned, the repulsive interactions
between their electron clouds are referred to as ___________________________
...
_____________________ have the same molecular formula and connectivity but
different arrangements of atoms in three-dimensional space
...
Alkanes in which some or all of the carbon atoms are arranged in a ring are called
___________________________
...
What is the fundamental principle of the IUPAC system of nomenclature for organic
compounds?
Ans: Each different compound should have an unambiguous name
...
What are the four possible parts of a IUPAC name?
Ans: locant, prefix, parent name, suffix
Topic: General
91
...
Ans: bridgeheads
Topic: Nomenclature
92
...
Br
OH
Ans: 5-bromo-6-cyclopentyl-2-hexanol
Topic: Nomenclature
93
...
Give the IUPAC name corresponding to the following structure:
Br
F
Ans: trans-1-bromo-2-fluorocyclohexane
Topic: Nomenclature
95
...
Draw the bond-line structural formula corresponding to the most stable conformation of
the following substance: trans-1-bromo-3-(1-methylpropyl)cyclohexane
Br
Ans:
Topic: Nomenclature
97
...
Draw the Newman projection formula for the gauche conformation of the C2-C3 bond
in pentane
...
Draw the Newman projection formula for the most stable conformation of the C2-C3
bond in 3-methylpentane
...
Complete the following reaction sequence, giving structural details of A, B and C
...
Which of the following is the enantiomer of the following substance?
H
H
Br
H
CH3
CH3
Br
H
Br
H
H
CH3
I
A)
B)
C)
D)
E)
Ans:
CH3
H
Br
H
II
III
I
II
III
It does not have a non-superposable enantiomer
...
Which of the following molecules is achiral?
CO2H
H
H
H3C
C C
H
C
OH
HO2C
CH3
Br
H
H
Cl
OH
I
II
III
CO2H
H
OH
HO
H
CO2H
IV
A)
B)
C)
D)
E)
Ans:
F
CH3
Br
HO
CH2CH3
V
I
II
III
IV
V
B
123
Chapter 5
Topic: Identifications and Comparisons
3
...
B) stereoisomers
...
D) constitutional isomers
...
I and II are:
CH2CH3
H3C
Cl
CH2Cl
H
H
H
I
A)
B)
C)
D)
E)
Ans:
CH2CH3
II
constitutional isomers
...
non-superposable mirror images
...
not isomeric
...
Pairs of enantiomers are:
CH3
H3C
H
CH3
Cl
Cl
CH3
H3C
Cl
CH2CH2CH3
CH2CH2CH3
CH2CH2CH3
I
II
III
CH2Cl
CH2CH2CH3
H3C
H
Cl
CH2CH2CH3
H
A)
B)
C)
D)
E)
Ans:
H
IV
I, II and III, IV
I, II
III, IV
IV, V
None of the structures
C
V
Topic: Identifications and Comparisons
6
...
The molecules shown are:
H
H
H
OH
H
H
Br
Br
H
CH3
CH3
A)
B)
C)
D)
E)
Ans:
OH
constitutional isomers
...
diastereomers
...
None of these
B
Topic: Identifications and Comparisons
The
8
...
diastereomers
...
two conformations of the same molecule
...
B
Topic: Identifications and Comparisons
9
...
enantiomers
...
identical
...
The molecules below are:
F
H
H
H
F
H
F
F
A)
B)
C)
D)
E)
Ans:
constitutional isomers
...
diastereomers
...
stereoisomers
...
The molecules shown are:
H
CH3
Cl
H
Cl
CH3
H
Cl
Cl
H
CH3
A)
B)
C)
D)
E)
Ans:
CH3
enantiomers
...
constitutional isomers
...
not isomeric
...
The molecules shown are:
H
CH3
OH
H
OH
H
H
CH3
A)
B)
C)
D)
E)
Ans:
constitutional isomers
...
diastereomers
...
None of these
B
127
Chapter 5
Topic: Identifications and Comparisons
13
...
enantiomers
...
identical
...
The molecules below are:
CH3
H
H
H
H
CH3
CH3
CH3
A)
B)
C)
D)
E)
Ans:
structural isomers
...
diastereomers
...
None of these
C
Topic: Identifications and Comparisons
15
...
B) enantiomers
...
D) constitutional isomers
...
The molecules below are:
Cl
CH3
Cl
Br
F
F
Br
I
A)
B)
C)
D)
E)
Ans:
CH3
II
constitutional isomers
...
diastereomers
...
None of these
D
Topic: Identifications and Comparisons
17
...
enantiomers
...
identical
...
The molecules shown are:
H
F
A)
B)
C)
D)
E)
Ans:
CH3
F
constitutional isomers
...
diastereomers
...
None of these
A
129
Chapter 5
Topic: Identifications and Comparisons
19
...
enantiomers
...
identical
...
The molecules below are:
H
H
H
H
CH3
Cl
A)
B)
C)
D)
E)
Ans:
Cl
CH3
constitutional isomers
...
diastereomers
...
None of these
B
130
Chapter 5
Topic: Identifications and Comparisons
21
...
Which molecule is achiral?
H
Br
Br
H
Br
Cl
H
Cl
H
H
Br
Cl
Br
Br
Cl
Cl
H
H
I
II
III
A)
B)
C)
D)
E)
Ans:
I
II
III
More than one of the above
None of the above
C
131
Chapter 5
Topic: Identifications and Comparisons
23
...
enantiomers
...
identical
...
The structures
H
CH3
CH3
CH3
H
H
H
CH3
represent:
A) a single compound
...
C) meso forms
...
E) conformational isomers
...
Which pair of structures represents the same compound?
CH3
OH
H
H
H
CH3
OH
H
H
HO
H
HO
CH3
CH3
H
HO
H
HO
H
OH
CH3
CH3
OH
H
OH
H
HO
H
CH3
II
OH
OH
CH3
CH3
H
OH
H
HO
OH
H
CH3
III
IV
V
I
A)
B)
C)
D)
E)
Ans:
I and II
II and III
III and IV
III and V
IV and V
D
Topic: Identifications and Comparisons
26
...
The two compounds shown below are:
Br
Cl
H
F
H
Br
F
A)
B)
C)
D)
E)
Ans:
Cl
enantiomers
...
constitutional isomers
...
different but not isomeric
...
The two compounds shown below are:
Br
Br
H
H
A)
B)
C)
D)
E)
Ans:
Br
H
and
H
Br
are:
identical
...
diastereomers
...
meso forms
...
(2R,4S) –2,4–Dichloropentane and (2S,4R)-2,4-dichloropentane are:
A) enantiomers
B) diastereomers
C) identical
D) conformational isomers
E) constitutional isomers
Ans: C
134
Chapter 5
Topic: Meso compounds
30
...
Which of the following is(are) meso compound(s)?
CH3
H
CH3
Cl
CH3
Cl
H
H
Cl
H
Cl
H
Cl
H
Cl
CH3
CH3
CH3
I
II
III
A)
B)
C)
D)
E)
Ans:
I
II
III
Both II and III
Both I and III
E
135
Chapter 5
Topic: Meso compounds
32
...
Which of the following is(are) meso?
Br
Br
H
H
Br
H
Br
Br
I
II
A)
B)
C)
D)
E)
Ans:
Br
Br
H
H
III
Topic: Meso compounds
34
...
Which molecule has a plane of symmetry?
H
CH2CH3
CH3
HO
H
HO
CH3
I
A)
B)
C)
D)
E)
Ans:
H
F
CH3
H
F
II
III
I
II
III
More than one of these
None of these
D
Topic: Meso compounds
36
...
Which molecule is a meso compound?
H
H
CH3
H
Br
H
Br
OH
H3C
H
H3C
F
H
F
CH3
CH3
OH
CH3
I
II
III
A)
B)
C)
D)
E)
Ans:
I
II
III
More than one of the above
None of the above
D
Topic: Meso compounds
38
...
Which of the following substances is achiral ?
Cl
H
H
F
H
H
CH3
F
H
Br
I
A)
B)
C)
D)
E)
Ans:
II
CH3
Br
H
III
HO
IV
I
II
III
IV
More than one of these
E
Topic: Meso compounds
40
...
B) There are one or more planes of symmetry
...
D) More than one stereogenic center must be present
...
Ans: E
Topic: Meso compounds
41
...
(R)-2-Chlorobutane is represented by:
H3C
Cl
H
CH3
CH3
Cl
CH3
H3C
CH2Cl
CH2CH3
Cl
H3C
Cl
H
H
CH2CH3
CH2CH3
H
CH2CH3
I
A)
B)
C)
D)
E)
Ans:
CH2CH3
II
III
IV
V
CH3
CH2CH3
I
II
III
IV
V
C
Topic: Specific names
43
...
Which structure represents (S)-1-chloro-1-fluoroethane?
Cl
CH3
F
F
H
H
Cl
H
Cl
CH3
CH3
F
I
II
III
A)
B)
C)
D)
E)
Ans:
I
II
III
More than one of the above
None of the above
D
Topic: Specific names
45
...
Which structure represents (S)-2-bromobutane?
H
H
CH3
CH3
Br
Br
H
H3C
Br
CH2CH3
CH2CH3
CH2CH3
I
II
III
A)
B)
C)
D)
E)
Ans:
I
II
III
More than one of the above
None of the above
A
Topic: Specific names
CH2CH3
47
...
The Cahn-Ingold-Prelog stereochemical designations used for the following substance
are:
H
Cl
Cl
H
Cl
A)
B)
C)
D)
E)
Ans:
Cl
2R,4S
2S,4R
2R,4R
2S,4S
The “R,S” terminology doesn't apply in this case
...
Which of these is not a correct Fischer projection formula of the (S) form of
3-bromo-1,1-dichloro-2-propanol ?
CHCl2
H
OH
CH2Br
I
A)
B)
C)
D)
E)
Ans:
CH2Br
HO
H
CHCl2
II
H
Cl2HC
CH2Br
OH
OH
CHCl2
H
CH2Br
IV
III
OH
CHCl2
BrH2C
H
V
I
II
III
IV
V
D
Topic: Optical activity
50
...
52º,
D
and (R)-(-)-2-butanol,[α] 25 = -13
...
76º?
D
D
A) 75%(R) 25%(S)
B) 25%(R) 75%(S)
C) 50%(R) 50%(S)
D) 67%(R) 33%(S)
E) 33%(R) 67%(S)
Ans: B
143
Chapter 5
Topic: Optical activity
51
...
The compounds whose molecules are shown below would have:
CH2CH3
CH3
H
F
H
F
CH2CH3
CH3
I
II
A)
B)
C)
D)
E)
Ans:
the same melting point
...
equal but opposite optical rotations
...
The compounds whose molecules are shown below would have:
CH3
CH3
H
F
H
CH3
F
A)
B)
C)
D)
E)
Ans:
F
H
H3C
F
H
the same melting point
...
equal but opposite optical rotations
...
The compounds whose molecules are shown below would have:
H
H
H
OH
OH
A)
B)
C)
D)
E)
Ans:
the same melting point
...
equal but opposite optical rotations
...
The compounds whose structures are shown below would have:
CH3
Br
CH3
Br
Br
CH3
Br
A)
B)
C)
D)
E)
Ans:
the same melting point
...
equal but opposite optical rotations
...
A solution of which of these allenes will rotate plane-polarized light?
H
H
C
C
H
H
C
H
C
H
C
Cl
I
H
C
C
H
H
C
C
Cl
Cl
Cl
Cl
C
C
Cl
C
Cl
V
IV
A)
B)
C)
D)
E)
Ans:
C
III
C
Cl
C
Cl
II
Cl
H
I
II
III
IV
V
C
Topic: Optical activity
57
...
Which of these is a comparatively insignificant factor affecting the magnitude of
specific optical rotation?
A) Concentration of the substance of interest
B) Purity of the sample
C) Temperature of the measurement
D) Length of the sample tube
E) All of the above are equally significant
...
What can be said with certainty if a compound has [α] 25 = -9
...
B) The compound has the (R) configuration
...
D) The compound possesses only one stereogenic center
...
Ans: C
Topic: Optical activity
60
...
In the absence of specific data, it can only be said that (R)–2–bromopentane is:
A) dextrorotatory (+)
...
C) optically inactive
...
E) analogous in absolute configuration to (R)–2–chloropentane
...
If a solution of a compound (30
...
5º
E) +4
...
Which compound would show optical activity?
A) cis 1,4- Dimethylcyclohexane
B) trans 1,4- Dimethylcyclohexane
C) cis 1,4- Dimethylcycloheptane
D) trans 1,4- Dimethylcycloheptane
E) More than one of these
Ans: D
Topic: Optical activity
64
...
Which of the following is true about any (R)-enantiomer?
A) It is dextrorotatory
...
C) It is an equal mixture of + and -
...
E) (R) indicates a racemic mixture
...
Which of the following is true of any (S)-enantiomer?
A) It rotates plane-polarized light to the right
...
C) It is a racemic form
...
E) It has the highest priority group on the left
...
Enantiomers are:
A) molecules that have a mirror image
...
C) non-superposable molecules
...
E) non-superposable molecules that are mirror images of each other
...
Which of the following is NOT true of enantiomers? They have the same:
A) boiling point
...
C) specific rotation
...
E) chemical reactivity toward achiral reagents
...
Which statement is true of 1,3-dimethylcyclobutane?
A) Only one form of the compound is possible
...
C) Two sets of enantiomers are possible
...
E) None of the previous statements is true
...
In which of the following reactions is the absolute configuration of the product likely to
be the same as that of the reactant?
Br
Br
A)
PBr3
(R)
OH
Br
O
B)
Br
(R)
OH
Br
OH
O
HA
O
Br
C)
OH
H2O
OH
(R)
D) All of the above
E) Answers A) and B) only
Ans: E
OH
Topic: Reaction Stereochemistry
71
...
Which reaction must take place with retention of configuration at the stereogenic
center?
OH
Cl
HCl
A)
F
Br
F
OH
B)
F
PCl3
O
C)
F
OH
Br
F
Cl
O
O
F
O
O
D) More than one of the above
E) None of the above
Ans: D
Topic: Reaction stereochemistry
73
...
B) (R)-2-methyl-5-heptanol
C) (S)-6-methyl-3-heptanol
D) (R,S)-6-methyl-3-heptanol
E) Achiral 6,6-dimethyl-3-hexanol
Ans: D
Topic: General stereochemistry
74
...
For the generalized structure BrCH2CHClCH2CHClCH2Br there exists what number of
stereoisomers?
A) 2
B) 3
C) 4
D) 6
E) 8
Ans: B
Topic: General stereochemistry
76
...
What is the molecular formula for the alkane of smallest molecular weight which
possesses a stereogenic center?
A) C4H10
B) C5H12
C) C6H14
D) C7H16
E) C8H18
Ans: D
Topic: General stereochemistry
78
...
How many different compounds are there which correspond to the general name "3-(1methylbutyl)cyclobutanol”?
A) 2
B) 4
C) 6
D) 8
E) None of the above
Ans: B
Topic: General stereochemistry
80
...
What is the total number of compounds, stereoisomers included, designated by the
general name "dichlorocyclopentane"?
A) 4
B) 5
C) 7
D) 8
E) 9
Ans: C
153
Chapter 5
Use the following to answer questions 82-85:
Consider the following compounds:
H
CH2OH
H
OH
H
H
CH3
HO
CH3
HO
H
H
CH3
HO
CH3
CH3
OH
H
H3C
H
CH3
OH
H
OH
I
II
III
IV
Topic: General stereochemistry
82
...
Which compound above (I-IV) is a meso compound?
A) I
B) II
C) III
D) IV
E) None of these
Ans: D
Topic: General stereochemistry
84
...
Which compounds above (I-IV) form a set of stereoisomers?
A) I, II and III
B) II, III and IV
C) II and III
D) I, III and IV
E) I, II, III and IV
Ans: B
SHORT ANSWER QUESTIONS
Topic: General stereochemistry
86
...
Ans: all parts of each object must coincide
Topic: General stereochemistry
87
...
Ans: superposable
Topic: General stereochemistry
88
...
Ans: nonsuperposable mirror images
Topic: General stereochemistry
89
...
Ans: nonsuperposable
Topic: General stereochemistry
90
...
Ans: two or more, superposable
155
Chapter 5
Topic: General stereochemistry
91
...
O
O
HO
HN
O
H2N
O
Aspartame
Ans: two
Topic: General stereochemistry
92
...
Ans: achiral
Topic: General stereochemistry
93
...
Ans: atomic number
Topic: General stereochemistry
94
...
Ans: identical
Topic: General stereochemistry
95
...
Ans: polarimeter
Topic: General stereochemistry
96
...
A) True
B) False
Ans: B
156
Chapter 5
Topic: General stereochemistry
97
...
Ans: racemic mixture
Topic: General stereochemistry
98
...
Ans: meso compound
Topic: General stereochemistry
99
...
Ans: diastereomers
Topic: Nomenclature
100
...
Draw a dash-wedge structure for (1R)-1-bromo-1,3,3-trimethylcyclohexane
Ans:
Br
Topic: Nomenclature
102
...
Draw a dash-wedge structure for (1S,3R)-1-ethyl-1,3-dimethylcyclopentane
CH3
Ans:
C2H5
H
CH3
Topic: Nomenclature
104
...
)
H
C2H5
H3C
CH3
Ans: (1S)-1-ethyl-1,3,3-trimethylcyclopentane
Topic: Nomenclature
105
...
)
H
OH
H3C
OH
Ans: (1R,3S)-1-methylcyclopentane-1,3-diol
158
Chapter 5
Topic: Fischer projections
106
...
CH3
CH3
CH3
CH3
Ans:
Br
H
H
Br
H
Br
H
H
H
H
H
H
H
Br
H
H
Br
Br
H
H
Br
H
H
H
H
H
H
H
H
H
Br
H
CH3
CH3
CH3
CH3
2R,4S
2S,4R
2S,4S
2R,4R
2,4-dibromohexane
Topic: Stereoisomers
107
...
Ans:
H
H
H
H
Br
1S, 3R
H
Br
H
H
1R, 3S
Br
1S, 3S
1-bromo-3-isopropylcyclohexane
159
Br
H
1R, 3R
Chapter 5
Topic: Fischer projections
108
...
Ans:
CH3
H3C
CH3
H
H
OH
CH3
CH3
H3C
H
H3C
H
HO
H
H
OH
H3C
H
H
CH3
H
CH3
H
H
H
H
H
H
H3C
H
HO
H
H3C
H
H
H
CH3
CH3
CH3
CH3
3S,4S
3R,4R
3S,4R
3R,4S
2,4-dimethyl-3-hexanol
Topic: Fischer projections
109
...
H2C
H
Ans:
*
OH
H
OH
H
H
H
Br
H
CH2Br
(3R)-6-Bromo-1-hexen-3-ol
...
Consider the SN2 reaction of butyl bromide with OH- ion
...
It would double the rate
...
It would increase the rate four times
...
Ans: D
Topic: Reaction kinetics
−
2
...
I
O
O
O
NaI
ONa
Assuming no other changes, what effect on the rate would result from simultaneously
doubling the concentrations of both 2-iodopentane and CH3CO2− ion?
A)
B)
C)
D)
E)
No effect
...
It would triple the rate
...
It would increase the rate six times
...
Consider the SN2 reaction of 1-chloro-5-methylhexane with CN ion
...
It would double the rate
...
It would increase the rate four times
...
Ans: D
Topic: Reaction kinetics
4
...
g
...
Increasing the temperature of a chemical reaction usually increases greatly the rate of
the reaction
...
B) Decreases the probability factor
...
D) Decreases the energy of activation
...
Increasing the temperature of a chemical reaction usually increases greatly the rate of
the reaction
...
B) Increases the total number of collisions between reactants
C) Decreases the rate of the reverse reaction
...
E) None of the above properly explains the observed increase in reaction rates with
increase in temperature
...
The rate equation for a nucleophilic substitution reaction of a tertiary alkyl bromide (RBr) with I− ion would be:
A) Rate = k [RBr]
B) Rate = k [I−]
C) Rate = k [RBr][I−]
D) Rate = k [RBr]2[I−]
E) Rate = k [RBr][I−]2
Ans: A
Topic: Reaction Kinetics
8
...
Consider the reaction of 2-chloro-2-methylpentane with sodium iodide
...
It would triple the rate
...
It would increase the rate five times
...
What would you expect to be the chief organic product(s) when tert-butyl bromide
reacts with sodium acetylide, i
...
,
Br
I
HC
C:
?
Na
II
III
HC
CH
IV
A)
B)
C)
D)
E)
I
II
III
IV
None of these
Ans: D
164
Chapter 6
Topic: Predicting mechanisms, products
11
...
e
...
What product(s) would you expect to obtain from the following SN2 reaction?
H
H
CH3ONa
CH3
Br
H
H
H
OCH3
CH3
OCH3
CH3
H
I
A)
B)
C)
D)
E)
?
CH3OH
CH3O
H
H
Br
II
III
I
II
An equimolar mixture of I and II
...
What major product(s) are likely to be obtained from the following reaction?
H
H
Cl
CH3CH2ONa
CH3CH2OH, 65oC
H
H
O
I
A)
B)
C)
D)
E)
?
O
H
H
H
O
H
Cl
II
III
I, by predominantly SN2
II, by predominantly SN2
An equimolar mixture of I and II, by predominantly SN1
...
Ans: E
Topic: Predicting mechanisms, products
14
...
Treating 1-bromo-1-methylcyclohexane with CH3OH at room temperature would yield:
A)
OCH3
B)
C)
D) All of these
E) None of these
Ans: D
Topic: Predicting products
16
...
Ans: B
167
Chapter 6
Topic: Predicting mechanisms, products
17
...
Which would be formed in the following reaction?
CH3
Br
H3C
O
OH
?
50oC
H
O
CH3 O
O
H3C
O
CH3
H3C
H
H
I
III
A)
B)
C)
D)
E)
II
IV
I
II
III
IV
All of the above
Ans: E
169
Chapter 6
Topic: Predicting mechanisms, products
19
...
When 1,4-diiodo-2,2-dimethylbutane (0
...
10 mol of NaCN in
dimethyl sulfoxide at 30°C, the product formed is:
I
A) NC
B)
CN
I
C) both A) and B)
...
The major product(s) of the following reaction is(are):
H
NaI, CH3CH2OH
H
25oC
Cl
CH3
H
I
H
H
H
H
I
OCH2CH3
H
CH3
CH3
CH3
I
A)
B)
C)
D)
E)
CH3
II
III
IV
I
II
III
IV
Equal amounts of I and II
Ans: A
171
Chapter 6
Topic: Predicting products
22
...
What would be the major product(s) of the following reaction?
CH3
H3C
CH3O− / CH3OH
55oC
Br
H
CH3
H3C
OCH3
H
A)
B)
C)
D)
E)
II
CH3
III
CH3
H
I
H3C
OCH3
H3C
H3C
IV
I
II
III and IV
I and II
All of the above
Ans: C
173
Chapter 6
Topic: Predicting mechanisms, products
24
...
What would be the major product obtained when trans-1-bromo-3-methylcyclopentane
is allowed to react with NaSH at 25oC?
H
H3C
H
SH
H
I
A)
B)
C)
D)
E)
SH H3C
H3C
SH
H3C
H
Br
HS
H
II
III
I
II
III
IV
Equal amounts of I and II
Ans: B
174
H
Br
IV
Chapter 6
Topic: Synthesis, reagent selection
26
...
Which
reagent would you use?
A) HCl, heat
B) NH3(aq), 25oC
C) CH3CO2Na, CH3CO2H, heat
D) CH3CH2ONa, CH3CH2OH, heat
E) CH3CH2OH, heat
Ans: D
Topic: Predicting mechanisms, products
27
...
A)
B)
C)
D)
E)
Reaction of sodium ethoxide with 1-bromopentane at 30°C yields primarily:
CH3CH2CH2CH=CH2
CH3CH2CH=CHCH3
CH3CH2CH2CH2CH3
CH3CH2CH2CH2CH2OH
CH3CH2CH2CH2CH2OCH2CH3
Ans: E
175
Chapter 6
Topic: Predicting mechanisms, products
29
...
If 0
...
20 mol of NaH, 0
...
When 0
...
10 mol of NaOCH3 in CH3OH at
40°C, the major product is:
A) CH3OCH2CH2CH2CH2Cl
B) CH3OCH2CH2CH2CH2I
C) CH3OCH2CH2CH2CH2OCH3
D) CH2=CHCH2CH2Cl
E) CH2=CHCH2CH2I
Ans: A
Topic: Generalities
32
...
by using a high concentration of the nucleophile
...
by the use of weak nucleophiles
...
Ans: B
176
Chapter 6
Topic: Generalities
33
...
B) The rate of an SN1 reaction depends on the concentration of the nucleophile
...
D) Answers A) and C) only are true
...
Ans: D
Topic: Generalities
34
...
B) The rate of an SN1 reaction depends on the concentration of the nucleophile
...
E) Answers A), B) and C) are true
...
A)
B)
C)
D)
E)
SN1 reactions of the type, Nu- + RL ⎯⎯⎯⎯→ Nu–R + L-, are favored:
when tertiary substrates are used
...
when L- is a strong base
...
by none of the above
...
Which of the following statements is (are) true of an SN2 reaction of (R)-2-bromobutane
with hydroxide ion?
A) Doubling the hydroxide ion concentration would double the rate of the reaction
...
)
B) The major product would be (S)-2-butanol
...
(Assume that all other experimental conditions are unchanged
...
SN1 reactions of the following type,
Nu:- + R-X ⎯⎯⎯⎯→ R-Nu + :X-
A)
B)
C)
D)
E)
are favored:
by the use of tertiary substrates (as opposed to primary or secondary substrates)
...
by increasing the polarity of the solvent
...
by more than one of the above
...
SN1 reactions of the following type,
Nu:- + R-X ⎯⎯⎯⎯→ R-Nu + :X-
A)
B)
C)
D)
E)
are favored:
by the use of tertiary substrates (as opposed to primary or secondary substrates)
...
by increasing the polarity of the solvent
...
by more than one of the above
...
A)
B)
C)
D)
E)
A true statement about the transition state(s) of an SN2 reaction is:
the two transition states are of unequal energy
...
the single transition state represents the point of maximum free energy of the reaction
...
the transition state will always have a net charge of -1
...
A)
B)
C)
D)
E)
Elimination reactions are favored over nucleophilic substitution reactions:
at high temperatures
...
when 3° alkyl halides are used as substrates
...
in all of these cases
...
A)
B)
C)
D)
E)
The hybridization state of the charged carbon in a carbocation is
sp4
sp3
sp2
sp
s
Ans: C
Topic: Carbocations
42
...
The p orbital of the charged carbon in the isopropyl cation, (CH3)2CH+, contains how
many electrons?
A) 1
B) 2
C) 3
D) 4
E) 0
Ans: E
179
Chapter 6
Topic: Generalities, solvent effects
44
...
A) Y: + RX ⎯⎯⎯⎯→ RY+ + X:B) Y:- + RX ⎯⎯⎯⎯→ RY + X:C) Y: + RX+ ⎯⎯⎯⎯→ RY+ + X:
D) Y:- + RX+ ⎯⎯⎯⎯→ RY + X:
E) RX+ ⎯⎯⎯⎯→ R+ + X:
Ans: A
Topic: Generalities, solvent effects
45
...
A)
B)
C)
D)
E)
Which is a polar aprotic solvent?
2-methylhexane
CH3CN
NH3(l)
CH3CH2CH2OCH2CH2CH3
2-methyl-2-propanol
Ans: E
180
Chapter 6
Topic: Generalities, nucleophiles
47
...
A)
B)
C)
D)
E)
2 H2O + RX
XH3O+
ROH
H2O
RX
Ans: D
ROH + H3O+ + X−
Topic: Generalities, nucleophiles
48
...
A)
B)
C)
D)
E)
2 R’OH + RX
X−
[ROH2]+
ROR’
R’OH
RX
Ans: D
ROR’ + [ROH2]+ + X−
Topic: Transition State theory
49
...
an increase in the probability factor
...
an increase in the reaction rate
...
Ans: D
181
Chapter 6
Topic: Generalities, leaving group
50
...
S−Na+
S
Na+
I
A)
B)
C)
D)
E)
+
I−
C6H5SNa+
CH3CH2I
C6H5SCH2CH3
IAns: E
Topic: Generalities, solvent effects
51
...
A)
B)
C)
D)
E)
Which is the weakest nucleophile in polar protic solvents?
IBrClFAll of the above are equally strong nucleophiles, regardless of the type of solvent used
Ans: D
Topic: Generalities, leaving group
53
...
A)
B)
C)
D)
E)
Which of the following is not a nucleophile?
H2O
CH3ONH3
NH4+
All are nucleophiles
...
A)
B)
C)
D)
E)
Which ion is the strongest nucleophile in aqueous solution?
FClBrIAll of these are equally strong
...
A)
B)
C)
D)
E)
Which of the following is not a good leaving group?
C2H5O−
Cl−
I−
CH3CO2−
All of these are good leaving groups
Ans: A
Topic: Leaving groups
57
...
Which is the strongest nucleophile?
A) OHB) CH3CH2OC)
D) CH3CH2OH
E) H2O
Ans: B
Topic: Nucleophile, solvent effects
59
...
Ans: A
Topic: Nucleophile, solvent effects
60
...
The relative nucleophilicities of species do not necessarily parallel the relative basicities
of the same species because:
A) not all nucleophiles are bases, and vice versa
...
C) nucleophilicity is a thermodynamic matter; basicity is a matter of kinetics
...
E) Actually, the relative values do parallel one another
...
Ambident nucleophiles are ones which can react with a substrate at either of two
nucleophilic sites
...
...
:OCH2CH2S:
:CN:
:OH
...
...
...
...
...
H
...
A)
B)
C)
D)
E)
Which ion is the strongest nucleophile in an aprotic solvent such as dimethylsulfoxide?
IBrClFThese are all equal
...
A)
B)
C)
D)
E)
Which of the following is a feasible substitution reaction?
CH3CH2Cl + NaBr ⎯⎯⎯⎯→ CH3CH2I + NaCl
CH3CH3 + NaCN ⎯⎯⎯⎯→ CH3CH2CN + NaH
CH3CH2Cl + NaOH ⎯⎯⎯⎯→ CH2=CH2 + H2O + NaCl
More than one of the above
None of the above
Ans: A
Topic: Predicting mechanism, products
65
...
0 M NaOH in a mixture of water and methanol would
yield mainly:
A) (CH3)3COH through an SN1 reaction
...
C) (CH3)3COH through an SN2 reaction
...
E) CH2=C(CH3)2 through an E2 reaction
...
Select the potential energy diagram that represents an exothermic (exergonic) reaction
...
Select the potential energy diagram that represents a single-step endothermic
(endergonic) reaction
...
Select the potential energy diagram that represents a two-step endothermic (endergonic)
reaction
...
The Hammond-Leffler postulate when applied to nucleophilic substitutions and
elimination reactions states that:
A) a negatively-charged nucleophile is stronger than its conjugate acid
...
C) bimolecular nucleophilic substitutions are 2nd order kinetically
...
E) elimination reactions will always compete with nucleophilic substitution reactions
...
A)
B)
C)
D)
E)
Which will be true for any actual or potential nucleophilic substitution reaction?
ΔH° is positive
...
ΔG‡ is positive
...
ΔG° is negative
...
For the typical SN2 reaction
Y- + RX ⎯⎯⎯⎯→ RY + X-
A)
B)
C)
D)
E)
it can be predicted that ΔS‡ will be:
positive
...
negative
...
unpredictable as to algebraic sign
...
The reaction,
CH3Cl + OH−
A)
B)
C)
D)
E)
H2O
CH3OH +
Cl−
has the following thermodynamic values at 27ºC: ΔH = -75
...
4 J K-1 mol-1
...
8 kJ mol-1
-76
...
0 kJ mol-1
+91
...
6 kJ mol-1
Ans: E
190
Chapter 6
Topic: Activation energy
73
...
the fraction of molecules with proper orientation
...
More than one of the above
None of the above
Ans: D
Topic: Free energy diagrams
74
...
Which is a true statement concerning the transition state of the rate-determining step of
an SN1 reaction?
A) Structurally, it closely resembles the carbocation intermediate
...
C) Formation of the transition state is an exothermic reaction
...
E) More than one of the above
Ans: A
Topic: Stereochemistry of SN/E reactions
76
...
Consider the substitution reaction that takes place when (R)-3-bromo-3-methylhexane is
treated with methanol
...
B) The reaction would take place only with retention of configuration at the stereogenic
center
...
D) No reaction would take place
...
Ans: C
Topic: Predicting mechanism, stereochemistry of SN reactions
78
...
Which of the following would be true?
A) An SN2 reaction would take place with inversion of configuration at the stereogenic
center
...
C) An SN1 reaction would take place with racemization of configuration at the stereogenic
center
...
E) An E2 reaction would take place, during which the stereogenic center is lost
...
Consider the substitution reaction that takes place when (R)-3-iodo-3-methylheptane is
treated with sodium acetate (CH3CO2Na)
...
B) An SN1 reaction would take place with retention of configuration at the stereogenic
center
...
D) An SN1 reaction would take place, accompanied by an E1 reaction, affording a complex
mixture of products
...
Ans: D
192
Chapter 6
Topic: Predicting products
80
...
A)
B)
C)
D)
E)
Which SN2 reaction will occur most rapidly in a mixture of water and ethanol?
I- + CH3CH2–Br ⎯⎯⎯⎯→ CH3CH2–I + BrI- + CH3CH2–Cl ⎯⎯⎯⎯→ CH3CH2–I + ClI- + CH3CH2–F ⎯⎯⎯⎯→ CH3CH2–I + FBr- + CH3CH2–Cl ⎯⎯⎯⎯→ CH3CH2–Br + ClBr- + CH3CH2–F ⎯⎯⎯⎯→ CH3CH2–Br + FAns: A
Topic: Predicting mechanism, kinetics
82
...
A) HO- + CH3-Cl ⎯⎯⎯⎯→ CH3OH + ClB) HO- + CH3CH2-Cl ⎯⎯⎯⎯→ CH3CH2OH + ClC) HO- + (CH3)2CH-Cl ⎯⎯⎯⎯→ (CH3)2CHOH + ClD) HO- + (CH3)3C-Cl ⎯⎯⎯⎯→ (CH3)3COH + ClE) HO- + (CH3)3CCH2-Cl ⎯⎯⎯⎯→ (CH3)3CCH2OH + ClAns: A
Topic: Kinetics
83
...
Which SN2 reaction would take place most rapidly?
H2O
A)
OH− + CH3Cl
CH3OH + Cl−
o
25 C
O
O
B)
H2O
−
+ CH3Cl
+ Cl
o
−
25 C
H3C
O
H3CO
CH3
H 2O
C)
H2O + CH3Cl
CH3OH2+ + Cl−
25oC
H
D)
CH3OH
O
CH3OH + CH3Cl
+ Cl−
25oC
H3C
CH3
H2O
E)
SH− + CH3Cl
CH3SH + Cl−
o
25 C
Ans: E
Topic: Leaving groups
85
...
Which nucleophilic substitution reaction would be likely to occur (although probably
not in excellent yield, due to competing elimination) ?
A) HO− + CH3CH2CH2CHICH3 ⎯⎯⎯⎯→ CH3 CH2CH2CHOHCH3 + I−
B) Cl− + CH3CH2CH2CH2–OH ⎯⎯⎯⎯→ CH3CH2CH2CH2–Cl + OH−
C) CH3S− + CH3CH2CH2–OCH3 ⎯⎯⎯⎯→ CH3S–CH2CH2CH3 + OCH3−
D) All of the above are likely to occur
E) None of the above are likely to occur
Ans: B
194
Chapter 6
Topic: Leaving groups
87
...
Ans: A
Topic: Nucleophilicity, leaving groups
88
...
A)
B)
C)
D)
E)
Which nucleophilic substitution reaction is not likely to occur?
I− + CH3CH2–Cl ⎯⎯⎯⎯→ CH3CH2–I + Cl−
I− + CH3CH2–Br ⎯⎯⎯⎯→ CH3CH2–I + Br−
I− + CH3CH2–OH ⎯⎯⎯⎯→ CH3CH2–I + OH−
CH3O− + CH3CH2–Br ⎯⎯⎯⎯→ CH3CH2–OCH3 + Br−
OH− + CH3CH2–Cl ⎯⎯⎯⎯→ CH3CH2–OH + Cl−
Ans: C
195
Chapter 6
Topic: Leaving groups
90
...
Which alkyl chloride, though primary, is essentially unreactive in SN2 reactions?
Cl
A)
B)
Cl
C)
Cl
Cl
D)
E)
Cl
Ans: E
196
Chapter 6
Topic: Kinetics
92
...
Which of these compounds would give the largest E2/SN2 product ratio on reaction with
sodium ethoxide in ethanol at 55°C?
Cl
A)
B)
Cl
C)
Cl
D)
Cl
E)
Cl
Ans: D
197
Chapter 6
Topic: Multistep synthesis, acid-base reactions, SN2
94
...
What final product is likely to be obtained through the following series of reactions?
NaNH2
Cl
A
NH3(l)
B
excess H2
C
Ni
Ans:
Topic: Multistep synthesis, acid-base reactions, SN2
96
...
As we go down Group 7A of the periodic table, the size of the halogen atom increases;
accordingly, the carbon-halogen bond length gets _______________ and the bond
strength gets _______________
...
In the SN2 reaction, the unstable arrangement of atoms in which both the nucleophile
and the leaving group are partially bonded to the same carbon atom is called the
______________________
...
A reaction in which the nucleophile is a molecule of the solvent is referred to as a
______________ reaction
...
The substitution mechanism whose rate depends primarily on the relative stability of the
intermediate carbocation is the _________
...
The substitution mechanism whose rate depends primarily on the degree of steric
hindrance around the leaving group is the _________
...
The stabilizing effect of alkyl substituents on carbocations can be explained through
_____________________
...
Increasing the concentration of either of the reactants of an SN2 reaction increases the
rate of the reaction
...
Ans: the frequency of collisions between reactant species, thereby statistically
increasing the chance encounters between species having the requisite Eactivation
Topic: Activation energy, transition state theory
104
...
Ans: have energy equal/greater than the activation energy, approach with the proper
orientation
...
Draw the potential energy diagram that represents an exothermic reaction between a
tertiary alkyl halide and methanol
...
Ans: The reaction is likely to occur via an SN1 mechanism
...
The second
step is a fast step, where the methanol oxygen acts as a nucleophile, attaching to
the positively charged carbon, forming a protonated ether; the last step is a fast
loss of a proton to form the (uncharged) ether product
...
Give a detailed reaction mechanism for the reaction expected to occur when 2-bromo-2methylpentane is heated with sodium methoxide
...
Also indicate which
step is likely to be rate-determining
...
The first step is the ratedetermining step, leading to the formation of a tertiary carbocation, followed by
base promoted elimination to afford 2 different alkene products
...
: Br :
H
slow
...
H
200
...
fast
Chapter 6
Topic: SN1 kinetics
107
...
The reason for this is that
________________________
...
Since the nucleophile is not
involved in the rate-determining step, changes in its concentration typically have
no impact on the rate of reaction
...
The relative nucleophilicity of the halide ions in polar aprotic solvents is observed to be
markedly different from that in protic solvents
...
Ans: The smaller, more highly electronegative fluoride ion is more effectively solvated
in a protic solvent and is therefore a weaker nucleophile compared to the larger,
less electronegative and more polarizable iodide ion
...
When 5-bromo-1-pentanol is treated with sodium hydride in diethyl ether, the product is
analyzed to be C5H10O
...
Ans: The alcohol is likely to be first deprotonated by the strong base, generating an
alkoxide ion, which can then undergo intramolecular SN2 reaction to afford the
observed product, a cyclic ether
...
OH
...
+
O : Na
...
A correct IUPAC name for the following compound is:
A)
B)
C)
D)
E)
3,3,5-trimethyl-2-hexene
3-isobutyl-3-isopropyl-2-propene
3-isobutyl-4-methyl-2-pentene
3-(1-methylethyl)-5-methyl-2-hexene
None of the above
Ans: D
Topic: Nomenclature
2
...
Give the IUPAC name for
A)
B)
C)
D)
E)
3-Methyl-4-hexyne
4-Methyl-2-hexyne
2-Ethyl-3-pentyne
4-Ethyl-2-pentyne
3-Methyl-2-hexyne
Ans: B
202
Chapter 7
Topic: Nomenclature
4
...
Select the structure of 4–ethyl-2,3-dimethyl-2-heptene
...
Select the structure for cis-3-methyl-6-vinylcyclohexene
...
The correct IUPAC name for the following compound is:
Cl
Br
A)
B)
C)
D)
E)
(E)-2-Bromo-3-chloro-5-methyl-2-hexene
(E)-2-Bromo-3-chloro-5-methyl-3-hexene
(Z)-2-Bromo-3-chloro-5-methyl-3-hexene
(Z)-2-Bromo-3-chloro-5-methyl-2-hexene
(E)-2-Methyl-5-bromo-4-chloro-4-hexene
Ans: A
204
Chapter 7
Topic: Nomenclature
8
...
Which of the following carbocations would NOT be likely to undergo rearrangement?
A) CH3CHCHCH3
CH3
CH3
B)
CH3CHCCH3
C)
CH3
CH3
CH3CCH2CH3
D)
CH3
CH3CHCH2
CH3
E)
CH3CCHCH2CH3
CH3
Ans: C
205
Chapter 7
Topic: Carbocation stability
10
...
A)
B)
C)
D)
E)
Which statement(s) is (are) true of acid-catalyzed alcohol dehydrations?
Protonation of the alcohol is a fast step
...
Rearrangements of less stable carbocations to more stable carbocations are common
...
All of the above
Ans: E
Topic: Carbocation Stability, Rearrangement
12
...
What do carbocations usually do? They may:
A) rearrange to a more stable carbocation
...
C) combine with a nucleophile
...
E) do all of the above
...
Neopentyl alcohol, (CH3)3CCH2OH, cannot be dehydrated to an alkene without
rearrangement
...
A)
B)
C)
D)
E)
Rearrangements are likely to occur in which of the following reaction types?
SN1 reactions
SN2 reactions
E1 reactions
E2 reactions
Both SN1 and E1 reactions
Ans: E
207
Chapter 7
Topic: Alkene Synthesis, Reaction Mechanisms
15
...
Which product(s) would be produced by acid-catalyzed dehydration of 2-methyl-2pentanol?
A)
B)
and
C)
and
D)
E)
O
Ans: B
208
Chapter 7
Topic: Alkene Synthesis, Reaction Mechanisms
17
...
Which would be the major product of the following reaction?
D2, Ni
?
D
CH3
D
D CH3
DD
H CH3
H
D
I
H
II
III
CH3
DH
D
D
CH3
D
H
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: A
209
Chapter 7
Topic: Alkene Synthesis, Reaction Mechanisms
19
...
Which compound would be the major product?
Br
(CH3)3COK
?
(CH3)3COH
heat
O
A)
B)
C)
OH
D)
E)
Ans: E
210
Chapter 7
Topic: Alkene Synthesis, Reaction Mechanisms, Carbocation Rearrangements
21
...
Which alkene would you expect to be the major product of the following dehydration?
H2SO4
?
heat
OH
I
IV
A)
B)
C)
D)
E)
III
II
V
I
II
III
IV
V
Ans: C
212
Chapter 7
Topic: Alkyne Synthesis, Catalytic hydrogenation
23
...
The structure of the product obtained from 2-butyne and Li/C2H5NH2 is:
A)
B)
C)
HN
D)
NH
E)
Ans: A
213
C
Chapter 7
Topic: Catalytic hydrogenation
25
...
A)
B)
C)
D)
E)
Which reaction would yield 2-butyne?
CH3C≡C:− Na+ + CH3Br ⎯⎯⎯⎯→
CH3CH2Br + HC≡C:− Na+ ⎯⎯⎯⎯→
CH3:− Na+ + HC≡CCH3 ⎯⎯⎯⎯→
More than one of these
None of these
Ans: A
Topic: Alkyne Synthesis
27
...
Your task is to convert 2-bromobutane to 1-butene in highest yield
...
Which of the following reactions would yield 3,3-dimethyl-1-butene in a reasonable
percentage yield (i
...
, greater than 50%)?
A)
H2SO4
heat
OH
B)
(CH3)3COK, (CH3)3COH
heat
Br
C)
i) 3 NaNH2, mineral oil, heat
Br
Br
ii) H3O+
D) All of these
E) Answers B) and C) only
Ans: B
215
Chapter 7
Topic: Alkene Synthesis, Reaction Mechanisms
30
...
Dehydrohalogenation of tert-pentyl bromide will produce 2-methyl-1-butene as the
chief product when:
A) CH3COONa is employed as the base
...
C) CH3CH2ONa/CH3CH2OH is employed as the base
...
E) any base is used, as long as the temperature is sufficiently high
...
A)
B)
C)
D)
E)
Which is not a satisfactory procedure for the synthesis of 3-methyl-1-butene?
(CH3)2CHCΗΟΗCH3 + conc
...
NH3
(CH3)2CHCH2CH2Br + CH3ONa/CH3OH
(CH3)2CHCHBrCH3 + (CH3)3COK/(CH3)3COH
(CH3)2CHC≡CH + H2/Ni2B (P-2)
Ans: A
216
Chapter 7
Topic: Alkene Synthesis, Nomenclature, Reaction Mechanisms
33
...
NH3
CH3CH2CHBrCH2CH3 + CH3CH2ONa/CH3CH2OH
Ans: C
Topic: Alkyne Reduction, Nomenclature, Reaction Mechanisms
34
...
None of the above is correct
...
Which of the following reactions would yield 2-pentyne?
I
A)
NaNH2
(1 mol)
NaNH2
B)
Br
(1 mol)
C)
Br
Zn
CH3CO2H
Br
HA
heat
D)
OH
E)
Br
NaOC2H5
C2H5OH
Ans: B
217
Chapter 7
Topic: Alkyne Synthesis, Nomenclature, Reaction Mechanisms
36
...
A)
B)
C)
D)
E)
Compute the index of hydrogen deficiency for the molecule C10H8
...
Which compound has an index of hydrogen deficiency equal to three?
I
II
III
IV
A)
B)
C)
D)
E)
V
I, III
IV, V
V
II
II, V
Ans: E
Topic: Index of Hydrogen Deficiency, Nomenclature
39
...
2
...
Which is a possible structure for a compound with an index of hydrogen deficiency
equal to 3 and which absorbs one molar equivalent of hydrogen when treated with
hydrogen and a platinum catalyst?
A)
B)
C)
D)
E)
I
I
II
III
IV
V
Ans: C
II
III
IV
219
V
Chapter 7
Topic: Index of Hydrogen Deficiency, Catalytic Hydrogenation
41
...
Select a structure for C6H6
...
A compound, C6H10, which reacts with 2 mol of hydrogen over a platinum catalyst and
which shows an IR absorption band at approximately 3300 cm-1 could be:
I
II
IV
A)
B)
C)
D)
E)
III
V
I
II
III
IV
V
Ans: C
220
Chapter 7
Topic: Index of Hydrogen Deficiency, Catalytic Hydrogenation
43
...
Which of the
following is a possible structure for the compound?
I
IV
A)
B)
C)
D)
E)
III
II
V
I
II
III
IV
V
Ans: D
Topic: Index of Hydrogen Deficiency, Catalytic Hydrogenation
44
...
The compound could have:
A) one ring and three double bonds
...
C) two rings and a triple bond
...
E) More than one of the above
Ans: E
Topic: Index of Hydrogen Deficiency, Catalytic Hydrogenation
45
...
no rings and one double bond
...
two rings and no double bonds
...
Ans: C
Y (C8H16)
221
Chapter 7
Topic: Index of Hydrogen Deficiency, Catalytic Hydrogenation
46
...
A compound X with the formula C7H10 undergoes catalytic hydrogenation to produce a
compound Y with the formula C7H14
...
B) X might have two double bonds and one ring
...
D) X might have one double bond and one triple bond
...
Which reaction would you expect to liberate the least heat?
A)
+ 9O2
6CO2 + 6H2O
B)
+ 9O2
+ 9O2
C)
6CO2 + 6H2O
6CO2 + 6H2O
+ 9O2
D)
E)
+ 9O2
6CO2 + 6H2O
6CO2 + 6H2O
Ans: C
222
Chapter 7
Topic: Alkene Stability, Heats of Hydrogenation and Combustion
49
...
Which
would you expect to liberate the LEAST heat?
A) 1-Pentene
B) 2-Pentene
C) 2-Methyl-1-butene
D) 2-Methyl-2-butene
E) 3-Methyl-1-butene
Ans: D
Topic: Alkene Stability, Heats of Hydrogenation and Combustion
50
...
One mole of each of the following alkenes is subjected to complete combustion
...
Which reaction would you expect to liberate the most heat?
A)
+ 9O2
6CO2 + 6H2O
B)
+ 9O2
+ 9O2
C)
6CO2 + 6H2O
6CO2 + 6H2O
+ 9O2
D)
E)
+ 9O2
6CO2 + 6H2O
6CO2 + 6H2O
Ans: C
Topic: Alkene Stability, Heats of Hydrogenation and Combustion
53
...
Which alkene would liberate the most heat per mole when subjected to complete
combustion?
A)
B)
C)
D)
E)
Ans: A
224
Chapter 7
Topic: Alkene Stability, Heats of Hydrogenation and Combustion
55
...
One mole of each of the following alkenes is subjected to complete combustion
...
Which alkene is most stable?
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
V
Ans: A
225
V
Chapter 7
Topic: Alkene Stability, Heats of Hydrogenation and Combustion
58
...
B) In general, the greater the number of alkyl groups attached to the carbon atoms of the
double bond, the greater the stability of the alkene
...
D) trans-Cycloalkenes are always more stable than the cis-isomers
...
Ans: D
Topic: Relative Acidity of Alkenes, Alkynes; Acid-Base Chemistry
59
...
A)
B)
C)
D)
E)
Select the strongest base
...
−
NH2
...
Ans: E
...
A)
B)
C)
D)
...
In the following hydrocarbon, which hydrogen would have the smallest value for pKa?
CH3CH2CH=CHCH2CH2C≡CH
A) CH3CH2CH=CHCH2CH2C CH
B) CH3CH2CH=CHCH2CH2C CH
C) CH3CH2CH=CHCH2CH2C CH
D) CH3CH2CH=CHCH2CH2C CH
E) CH3CH2CH=CHCH2CH2C CH
Ans: E
Topic: Relative Acidity of Alkenes, Alkynes; Bond Lengths
63
...
B) Acetylene is the strongest acid and has the shortest C-H bond length
...
D) Ethene is the strongest acid and has the shortest C-H bond length
...
Ans: B
227
Chapter 7
Topic: Alkene Synthesis; Alcohol Dehydration
64
...
Which mechanistic step in the acid-catalyzed dehydration of 3,3-dimethyl-2-butanol is
the rate determining step?
A) Step 1:
+
H3O+
+
H2O
OH2+
OH
B) Step 2:
+
H2O
OH2+
C) Step 3:
D) Step 4a:
+
H2O
+
H3O+
+
H 2O
+
H3O
E) Step 4b:
Ans: B
228
+
Chapter 7
Topic: Alkene Synthesis; Alcohol Dehydration
66
...
Which alcohol would be most easily dehydrated?
OH
OH
I
OH
II
III
OH
OH
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: B
229
Chapter 7
Topic: Alkene Structure; Stereochemistry
68
...
e
...
Determine the total number of stereoisomers which correspond to this general structure:
Cl
CH3CHCHCH=CHCH3
CH3
A)
B)
C)
D)
E)
4
6
8
10
12
Ans: C
Topic: Alkene Structure; Stereochemistry
70
...
A)
B)
C)
D)
E)
For which of the following is cis-trans isomerism impossible?
2-Hexene
3-Methyl-2-pentene
3-Hexene
2-Methyl-2-butene
2-Pentene
Ans: D
230
Chapter 7
Topic: Alkene Structure; Stereochemistry
72
...
Which of the following compounds can exhibit cis-trans isomerism?
I
...
2-Pentene
III
...
1,2-Dibromoethene
A)
B)
C)
D)
E)
V
...
A)
B)
C)
D)
E)
What is the total number of pentene isomers, including stereoisomers?
2
3
4
5
6
Ans: E
231
Chapter 7
Topic: Nomenclature; Stereochemistry
75
...
While this often also
corresponds to (Z) and (E) descriptions, sometimes it does not
...
The most specific term used to designate the relationship of cis-3-hexene to trans-3hexene is:
A) stereoisomers
...
C) diastereomers
...
E) conformational isomers
...
A)
B)
C)
D)
E)
How many stereoisomers can be predicted for 4–ethyl-2,3-dimethyl-2-heptene?
1
2
3
4
None of the above
Ans: B
232
Chapter 7
Topic: General Information, Bonding
78
...
A)
B)
C)
D)
E)
What characteristic(s) of alkynes would make it difficult to prepare cyclohexyne?
The requirement for linearity at the triple bond center
The large electron density between carbons of a triple bond
The short carbon-carbon triple bond length
The need that the carbon-carbon triple bond be internal in the chain
All of these
Ans: A
Topic: General Information, Nomenclature
80
...
Zaitsev's rule states that:
A) In electrophilic addition of an unsymmetrical reagent to an unsymmetrical alkene, the
more positive portion of the reagent will become attached to the carbon of the double
bond bearing the greater number of hydrogen atoms
...
C) E2 reactions occur only if the β-hydrogen and leaving group can assume an antiperiplanar arrangement
...
E) The order of reactivity of alcohols in dehydration reactions is 3º > 2º > 1º
...
Regarding the use of potassium tert-butoxide as a base in E2 reactions, it is incorrect to
state that:
A) this base is more effective than ethoxide ion, because it (KO-t-Bu) is the more basic of
the two
...
e
...
C) it is more reactive in dimethyl sulfoxide than it is in tert-butyl alcohol
...
E) it will form, predominantly, the more stable alkene
...
When an elimination reaction gives the most stable alkene as the major product, we say
that the elimination follows ________________'s rule
...
When an elimination reaction gives the less substituted alkene as the major product, we
say that the elimination follows ________________'s rule
...
In a dehydration reaction, the leaving group is _______________
...
In hydrogenation reactions, both hydrogen atoms add to the pi system from the same
face of the molecule
...
Ans: syn
Topic: General Information
87
...
Ans: Cis / Z
Topic: General Information
88
...
Ans: strong acid
234
Chapter 7
Topic: General Information
89
...
These options include
reaction with a nucleophile, loss of a beta proton to give an alkene, and
________________
...
Alkynes can be produced from either __________________ or _________________
dihalides
...
Conversion of alkynes to E-alkenes (trans-alkenes) can be accomplished via a
__________________ reaction
...
The number of (s-sp2) bonds in a molecule of 2,3-dimethyl-2,4-heptadiene is _____
...
How will you prepare cis-1,2-dimethylcyclohexane from 1,2-dimethylcyclohexene?
Ans: Catalytic hydrogenation with H2, Ni (or Pt/Pd)
H2, Ni
Topic: Alkyne Reduction
94
...
Na, NH3 (l)
235
Chapter 7
SHORT EXPLANATION / STRUCTURE DRAWING QUESTIONS
Topic: Nomenclature, Stereochemistry
95
...
) as
relevant
...
The ambiguous name dimethylcyclopentene does not clearly distinguish between
several structures
...
b) Indicate which of these is likely to be the most stable, i
...
c) Which of these structures represents an achiral molecule?
Ans: a)
dimethylcyclopentene
I
II
III
IV
V
VI
b) Structure I is likely to be the most stable, because it is a tetra-substituted
alkene: II, IV and V are tri-substituted; III and VI are di-substituted
...
Complete the following reaction sequence, providing a brief rationale for your answer
...
However, since III is a terminal alkyne, it has a hydrogen atom that is labile in
presence of NaNH2; hence, an extra mole equivalent of the base is required to
ensure complete reaction and convert all of the initially formed III into the sodium
alkynide intermediate, II; this, upon acidification, affords the final alkyne product
III
...
Complete the following reaction, giving structural details of all intermediates as well as
the final product
...
What “new”, more stable, carbocation(s) may be formed when the following
carbocation undergoes spontaneous rearrangement?
Ans:
Topic: Nomenclature, Multistep Synthesis
100
...
OH
Ans:
H2
H3O+
+
Ni
heat
Step 1:
Acid-catalyzed dehydration of 5-methyl-2-hexanol to yield an isomeric mixture of
5-methyl-1-hexene and 5-methyl-2-hexene
Step 2:
Catalytic hydrogenation of the double bond with H2, Ni to yield the desired 2methylhexane
Topic: Nomenclature, Multistep Synthesis
101
...
+
Ans:
Na :
NaNH2
CH3CH2Br
NH3 (l)
Li, NH3(l)
Step 1:
Add NaNH2/NH3(l) to selectively deprotonate the alkyne hydrogen
...
Step 3:
Add Na(s)/NH3(l) to give the desired trans-alkene by dissolving metal reduction
...
Provide a mechanistic explanation for the formation of the observed products in the
following reaction
...
The IR spectrum of an unknown substance Q, C9H16, is found to have distinct peaks at
3310 cm-1 and 2140 cm-1
...
Propose a reasonable
structure for Q, based on the above information, briefly explaining your rationale
...
Ans:
excess H2
Ni
IR: 2140, 3310 cm-1
2,3-dimethylheptane
Substance Q:
5,6-dimethyl-1-heptyne
The Index of Hydrogen deficiency of Q is 2 (compared with C9H20)
...
The catalytic hydrogenation data provides further details of the carbon skeleton
...
Thus, the structure given above is
consistent with all of the given information
...
An alkene adds hydrogen in the presence of a catalyst to give 3,4-dimethylhexane
...
The structure of the alkene is:
CH3
A)
CH3CH=C-CHCH2CH3
(cis or trans)
CH3
CH3
B)
CH3CH2C=CCH3
(cis or trans)
CH2CH3
C)
CH3
CH2=CCH2CHCH2CH3
CH3
CH2
D)
CH3CH2CCHCH2CH3
CH3
CH3
E)
CH3CH2CHCHCH=CH2
CH3
Ans: B
241
Chapter 8
Topic: Structure Elucidation
2
...
What is the structure of Z?
O
Z
1) O3
2) Zn, HOAc
O
2HCH + CH3CCH2CH
O
I
II
III
O
H
IV
A)
B)
C)
D)
E)
O
V
I
II
III
IV
V
Ans: B
242
Chapter 8
Topic: Structure Elucidation
3
...
On catalytic hydrogenation, 1 mol of C
absorbs 1 mol of hydrogen and yields a compound with the molecular formula C7H14
...
Compound X has the molecular formula C6H10
...
X also shows IR absorption at about 3300 cm-1
...
The most likely
structure for X is:
A)
B)
C)
D)
E)
Ans: D
243
Chapter 8
Topic: Structure Elucidation
5
...
On oxidation with hot
aqueous potassium permanganate, A yields CH3CH2COOH and (CH3)2CHCOOH
...
Determine a possible structure for an alkene, X, formula C9H14, on the basis of the
following information: X adds one mole of hydrogen on catalytic hydrogenation
...
O
HO
OH
O
A possible structure for X might be:
I
II
IV
A)
B)
C)
D)
E)
III
V
I
II
III
IV
V
Ans: C
Topic: Structure Elucidation
7
...
On catalytic
hydrogenation, Y yields Z(C7H16) and Z is also optically active
...
One mole of an optically active compound, X, with the molecular formula C6H8 reacts
with three moles of hydrogen in the presence of a catalyst to yield an optically inactive
product that cannot be resolved
...
Which is a possible structure for X?
A) (E)-4-hexen-1-yne
B) (Z)-4-hexen-1-yne
C) (E)-2-hexen-4-yne
D) 2-methyl-1-penten-3-yne
E) 3-methyl-1-penten-4-yne
Ans: E
Topic: Structure Elucidation
9
...
The product isolated from these reactions is:
O
O
What is the structure of the alkene?
I
II
III
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: C
246
Chapter 8
Topic: Structure Elucidation
10
...
On catalytic hydrogenation,
A is converted to B (C7H16) and B is also optically active
...
Which substance would undergo the following reaction?
?
A)
B)
C)
D)
E)
i
...
Zn, HOAc
H
O
+
4-Hexen-1-yne
3-methyl-1-hexene
(E)-2-hexene
(Z)-2-hexene
4-methyl-1-hexene
Ans: E
r
247
H
O
Chapter 8
Topic: Structure Elucidation
12
...
An unknown compound, B, has the molecular formula C7H12
...
B has
significant IR absorption band at about 3300 and 2200 cm-1
...
What compound would yield an equimolar mixture of CH3CH2CH2CHO and CH3CHO
upon treatment with O3, followed by Zn/HOAc?
A) 1-Hexene
B) cis-2-Hexene
C) trans-2-Hexene
D) More than one of these
E) None of these
Ans: D
Topic: Structure Elucidation
15
...
The alkene is:
A) 2,2-Dimethyl-2-hexene
B) 2,3-Dimethyl-2-hexene
C) 2,4-Dimethyl-2-hexene
D) 2,4,4-Trimethyl-2-pentene
E) More than one of the above is a possible answer
...
Which of the following would decolorize bromine in carbon tetrachloride and yield a
ketone upon reaction with sulfuric acid in the presence of catalytic amounts of HgSO4?
A) CH3CH=CHCH3
B) CH3CH=CH2
C) CH3CH2C≡CH
D) CH3CH2CH2CH3
E) All of these would give positive results in each test
...
Which of these compounds will react with cold concd
...
Which of the following reagents might serve as the basis for a simple chemical test that
would distinguish between pure 1-pentene and pure pentane?
A) Bromine in carbon tetrachloride
B) Dilute aqueous potassium permanganate
C) Concentrated sulfuric acid
D) All of the above
E) Answers A) and B) only
Ans: D
Topic: Structure Elucidation
19
...
H2SO4
KMnO4,OHNone of these
Ans: B
249
Chapter 8
Topic: Structure Elucidation
20
...
H2SO4
D) Two of the above
E) All of the above
Ans: E
Topic: Structure Elucidation
21
...
A reagent or test that could be used to distinguish between 1-pentene and 1-pentyne
would be:
A) Bromine in carbon tetrachloride
B) Dilute aqueous potassium permanganate
C) CrO3 in H2SO4
D) H2SO4
E) IR examination
Ans: E
Topic: Structure Elucidation
23
...
Treating 1-methylcyclohexene with H3O+ would yield primarily which of these?
HO
HO
HO
I
II
III
HO
OH
IV
A)
B)
C)
D)
E)
V
I and V
II
III and V
IV
I, III and V
Ans: D
Topic: Reaction Products
25
...
Treating 1-methylcyclohexene with HCl would yield primarily which of these?
H3C
Cl
H3C
Cl
H3C
Cl
I
II
H3C
Cl
III
Cl
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: C
Topic: Reaction Products
27
...
The reaction of Br2/CCl4 to cyclohexene would produce the compound(s) represented
by structure(s):
H
H
H
Br
H
Br
A)
B)
C)
D)
E)
Br
Br
I
I alone
II alone
II and III
III alone
I , II and II
Ans: C
Br
H
Br
H
II
III
Topic: Reaction Products
29
...
A)
B)
C)
D)
E)
What is the chief product of the reaction of IBr with 2-methyl-2-pentene?
2-bromo-3-iodo-2-methylpentane
3-bromo-2-iodo-2-methylpentane
1-bromo-2-iodo-2-methylpentane
2-bromo-1-iodo-2-methylpentane
All of the above
Ans: A
Topic: Reaction Products
31
...
What product would result from the following reaction?
KMnO4, H2O
cold, dilute
?
CO2H
O
K
I
OH OH
MnO4
II
III
OH OH
IV
A)
B)
C)
D)
E)
OH OH
V
I
II
III
IV
V
Ans: C
254
Chapter 8
Topic: Reaction Products
33
...
Which of these is not formed when cyclopentene reacts with an aqueous solution of
bromine?
Br
OH
OH
Br
I
A)
B)
C)
D)
E)
Br
Br
Br
II
Br
III
OH
OH
IV
V
I
II
III
IV
V
Ans: E
Topic: Reaction Products
35
...
Addition of hydrogen chloride to the following molecule would produce:
HCl
?
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
I
A)
B)
C)
D)
E)
Cl
II
III
IV
V
I and II
II and III
I and IV
V
All of the above are equally likely to be formed
Ans: A
256
Chapter 8
Topic: Reaction Products
37
...
KMnO4, H2O
H
cold, dilute
ii
...
Select the structure of the major product formed in the following reaction
...
Which of these compounds is not formed when gaseous ethene is bubbled into an
aqueous solution of bromine, sodium chloride and sodium nitrate?
A) BrCH2CH2Br
B) BrCH2CH2Cl
C) BrCH2CH2OH
D) ClCH2CH2OH
E) BrCH2CH2ONO2
Ans: D
258
Chapter 8
Topic: Reaction Products
40
...
2 Cl2
?
Cl
Cl
Cl
Cl
Cl
Cl
Cl
I
II
Cl
III
Cl
Cl
Cl
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: C
259
Chapter 8
Topic: Reaction Products
41
...
What would be the major product of the following reaction?
Br2, CCl4
?
CH3
CH3
H
Br
Br
H
H
Br
Br
H
C3H7
I
A)
B)
C)
D)
E)
CH3
CH3
H
Br
Br
H
Br
H
H
Br
C3H7
C3H7
C3H7
II
III
IV
Equal amounts of I and II
Equal amounts of II and III
Equal amounts of III and IV
I and II as major products, III and IV as minor products
All of the above in equal amounts
Ans: A
260
Chapter 8
Topic: Reaction Products
43
...
Hydroxylation of cis-2-pentene with cold alkaline KMnO4 yields
CH3
CH3
CH3
H
OH
HO
H
H
H
OH
HO
H
HO
C2H5
A)
B)
C)
D)
E)
C2H5
CH3
OH
H
C2H5
HO
H
H
OH
C2H5
I
II
III
IV
Equal amounts of I and II
Equal amounts of II and III
Equal amounts of III and IV
I and II as major products, III and IV as minor products
All of the above in equal amounts
Ans: B
261
Chapter 8
Topic: Reaction Products
45
...
Reaction of trans-2-hexene with a solution of Br2 in CCl4 produces:
H
Br
H
Br
H
Br
Br
H
Br
H
I
H
Br
II
III
Br
H
Br
H
IV
A)
B)
C)
D)
E)
H
Br
H
Br
V
I and II
II and V
III and IV
IV and V
V
Ans: C
262
Chapter 8
Topic: Reaction Products
47
...
What is the major product of the following reaction?
H2SO4, H2O
?
HgSO4
OH
OH
OH
OH
I
II
III
O
O
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: D
Topic: Reaction Products
49
...
Consider the addition of HCl to 3-methyl-1-butene
...
What is the final product of the following synthesis?
2-Butyne
HO
H
H2
Ni2B (P-2)
CH3
OH
H
CH3
I
A)
B)
C)
D)
E)
HO
HO
C4H8
CH3
H
H
CH3
i
...
NaHSO4
HO
H
II
CH3
H
OH
CH3
III
Final Product
H
HO
CH3
OH
H
CH3
IV
I
II
III
IV
An equimolar mixture of III and IV
Ans: B
Topic: Synthetic Strategy
52
...
Which reagent(s) given below could be used to synthesize cis-1,2-cycloheptanediol
from cycloheptene?
A) KMnO4, OH−, 5oC
B) KMnO4, H3O+, 75oC
C) H2SO4, heat
D) All of these
E) None of these
Ans: A
Topic: Synthetic Strategy
54
...
NH3
H3O+, heat; then cold dilute KMnO4
HBr; then NaNH2; then H2, Pt
None of these
Ans: B
Topic: Synthetic Strategy
55
...
A) (1) HBr; (2) NaOC2H5
B) (1) Br2; (2) NaOC2H5
C) (1) Br2; (2) H2O
D) (1) NaNH2; (2) HBr
E) (1) HBr; (2) H2SO4
Ans: B
Topic: Synthetic Strategy
56
...
Assuming syn addition, the
spatial arrangement of the two hydroxyl groups in the product would be:
A) equatorial-axial
B) axial-axial
C) equatorial-equatorial
D) coplanar
E) trans
Ans: A
265
Chapter 8
Topic: Synthetic Strategy
57
...
How many compounds are possible from the addition of bromine to CH2=CHCH2CH3
(counting stereoisomers separately)?
A) One
B) Two
C) Three
D) Four
E) Five
Ans: B
Topic: Reaction Products
59
...
A)
B)
C)
D)
E)
Which reaction of an alkene proceeds with anti addition?
Hydroboration/oxidation
Bromination
Oxidation with cold KMnO4
Hydrogenation
Oxymercuration-demercuration
Ans: B
Topic: Reaction Products
61
...
KMnO4 ⎯⎯⎯⎯→
trans-2-butene + Br2 ⎯⎯⎯⎯→
1-pentene + HCl ⎯⎯⎯⎯→
cis-2-butene + D2/Pt ⎯⎯⎯⎯→
cyclobutene + OsO4, then Na2SO3 ⎯⎯⎯⎯→
Ans: C
Topic: Reaction Products
62
...
3,3-dimethylcyclohexene is subjected to reaction with cold, dilute KMnO4, to give 3,3dimethyl-1,2-cyclohexanediol
...
Cyclohexene reacts with bromine to yield 1,2-dibromocyclohexane
...
B) be a racemic form and, in their most stable conformation, they would have one bromine
atom equatorial and one axial
...
D) be a meso compound and, in its most stable conformation, it would have one bromine
atom equatorial and one axial
...
Ans: A
Topic: Reaction Products
65
...
A)
B)
C)
D)
E)
Which reaction would give a meso compound as the product?
Cyclopentene + Br2/CCl4
Cyclopentene + OsO4, then NaHSO3
Cyclopentene + RCO3H, then H3O+
Cyclopentene + Cl2, H2O
More than one of these
Ans: B
268
Chapter 8
Topic: Reaction Products
67
...
(R)-3-Chloro-1-butene reacts with HCl by Markovnikov addition, and the products are
separated by gas chromatography
...
The interaction of the π bond of an alkene with an electrophile can initially result in the
formation of a species termed a π complex
...
A)
B)
C)
D)
E)
Markovnikov addition of HI to 2-methyl-2-butene involves:
initial attack by an iodide ion
...
isomerization of 2-iodo-2-methylbutene
...
formation of carbocation at C-3
...
Which reaction is NOT stereospecific?
trans-2-Butene
Br2/CCl4
cis-2-Pentene
I
Br2/H2O
II
1-Methylcyclohexene
H2/Pd
III
2-Methyl-2-heptene
dil KMnO4
trans-2-Hexene
5oC
V
IV
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: E
270
HBr
Chapter 8
Topic: Reaction Products
72
...
The thermodynamic parameters at 298 K for the following reaction are given below
...
9 kJ mol-1
ΔSº = -131 J K-1 mol-1
ΔGº = -25
...
B) Neither ΔHº nor ΔSº favors product formation
...
D) The entropy term is favorable but the formation of ethyl chloride is not favored
...
Ans: C
271
Chapter 8
Topic: Reaction Products
74
...
B) steric hindrance favors its formation
...
D) it is the more/most stable product
...
Ans: C
Topic: General Information
75
...
A)
B)
C)
D)
E)
Which alkene would you expect to be most reactive toward acid-catalyzed hydration?
1 pentene
trans-2-pentene
cis-2-pentene
2-methyl-1butene
All of these would be equally reactive
...
A)
B)
C)
D)
E)
The most resistant compound to the action of hot alkaline KMnO4 is:
Pentane
1-Pentene
2-Pentene
2-Pentyne
Cyclopentene
Ans: A
272
Chapter 8
Topic: General Information
78
...
Consider the ozonolysis products obtained from all the unbranched and unsymmetrical
isomers of heptene
...
B) an aldehyde and a ketone
...
D) two different aldehydes
...
Ans: D
SHORT ANSWER QUESTIONS
Topic: General Information
80
...
Ans: Markovnikov's Rule
Topic: General Information
81
...
Ans: regioselective
Topic: General Information
82
...
Ans: stereospecific
273
Chapter 8
Topic: General Information
83
...
Ans: stereoselective
Topic: General Information
84
...
Ans: syn, anti-Markovnikov
Topic: General Information
85
...
Why is that?
Ans: Because alkenes are planar, and the reagent can add from either face
...
The “decolorization” of molecular bromine is often used as a functional group test to
detect the presence of ________________
...
Neutral divalent carbon compounds are called ___________
...
Carbenes are frequently produced by α-elimination reactions
...
Ans: both attached to the same carbon
Topic: General Information
89
...
Ans: electrophiles
274
Chapter 8
Topic: Reaction Sequence
90
...
Provide regiochemical
and stereochemical details as relevant
...
Subsequent hydroboration
oxidation is regioselective (anti-Markovnikov) and stereospecific (syn), resulting in the
formation of racemic (2S,3R & 2R,3S) 3-methyl-2-pentanol
...
Topic: Reaction Products
91
...
Ans:
HCl
Cl
HCl
most stable
carbocation
Both alkenes are unsymmetrically substituted: the major product is a consequence of
regioselective addition to the double bond
...
275
Chapter 8
Topic: Reaction Products
92
...
Br2, H2O
?
Ans:
OH
Br
H
OH
Br
H
+
The reaction takes place with Markovnikov regioselectivity and anti stereospecificity,
giving a racemic mixture of the halohydrin as the major product
...
Draw Fischer projection formula(s) of the major product(s) of the reaction between Z-2-methyl3-hexene and cold, alkaline KMnO4
...
Topic: Reaction Products
94
...
CH2CH3
CH2CH3
Ans:
OH
HO
CH3
cold, dil H3C
+ HO
H
H
OH
KMnO4
C2H5
C2H5
The reaction takes place with syn stereospecificity, giving a racemic mixture of the diol
product
...
Draw Fischer projection formulas of the major product of the reaction between E-2-methyl-3hexene and aqueous Br2
...
Since the alkene is symmetrically
substituted, Markovnikov rule is not applicable, and the reaction is not regioselective
...
Topic: Reaction Products
96
...
What other product(s) might also be obtained? Explain clearly
...
One pathway results in ring expansion to a more stable 5-membered ring
...
The other pathway
is less likely, since ring strain is not relieved; however, this could lead to a minor
product, as shown above
...
Deduce the structure of an unknown compound A, C8H16, from the following data
...
A decolorizes Br2/CCl4, and upon reaction with excess H2/Ni,
affords 1-ethyl-2-methylcyclopentane
...
O
O
Ans: A must be 3-ethyl-4-methylcyclopentene
...
Predict the product(s) of the oxidation of 2,3,4-trimethyl-1,5-heptadiene with hot, alkaline
KMnO4
...
Predict the structure of product obtained when cis-2-hexene is allowed to react with Zn/CH2I2
...
The reaction proceeds with retention of alkene
stereochemistry, resulting in a racemic mixture of the two cis enantiomers
...
Predict the structure of product obtained when 1-hexyne is allowed to react with aqueous
H2SO4 in the presence of catalytic amounts of HgSO4
...
279
Chapter 9
MULTIPLE CHOICE QUESTIONS
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
If all the protons of 1-fluoropentane could be discerned, which would you expect to be
at the lowest field in the 1H NMR spectrum of this compound?
CH3CH2CH2CH2CH2F
A)
B)
C)
D)
E)
V IV III II I
Protons on carbon I
Protons on carbon II
Protons on carbon III
Protons on carbon IV
Protons on carbon V
Ans: A
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
Which proton(s) of the compound below would appear as a septet in the 1H NMR
spectrum?
I
CH3
CH3CH2CH2-O-CH
CH3
V IV III
II
I
A) The protons on carbon I
B) The proton on carbon II
C) The protons on carbon III
D) The protons on carbon IV
E) The protons on carbon V
Ans: B
Page 280
Chapter 9
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
Which proton(s) of the compound below would appear as a doublet in the 1H NMR
spectrum?
I
CH3
CH3CH2CH2-O-CH
CH3
V IV III
II
I
A) The protons on carbon I
B) The protons on carbon II
C) The protons on carbon III
D) The protons on carbon IV
E) The protons on carbon V
Ans: A
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
Which proton(s) of the compound below would appear as a triplet in the 1H NMR
spectrum?
I
CH3
CH3CH2CH2-O-CH
CH3
II
V IV III
I
A) The protons on carbon II
B) The protons on carbon I and V
C) The protons on carbon III and V
D) The protons on carbon III and IV
E) The protons on carbon V
Ans: C
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
How many signals would you expect to find in the 1H NMR spectrum of
CH3OCH2CH2OCH3?
A) 1
B) 2
C) 3
D) 4
E) 5
Ans: B
281
Chapter 9
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
Predict the splitting pattern you would observe for the proton at C3 of 2,3-dimethyl-2phenylbutane
...
7
...
A)
B)
C)
D)
E)
Doublet
Singlet
Quartet
Septet
Octet
Ans: B
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
Predict the splitting pattern you would observe for the proton at C4 of 2,3-dimethyl-2phenylbutane
...
9
...
The signal for the protons on the benzylic carbon would be a doublet
...
The signal for the methyl protons would be a doublet
...
Ans: D
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
A)
B)
C)
D)
E)
How many 1H NMR signals would trans-1,2-dichlorocyclopropane give?
1
2
3
4
5
Ans: B
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
How many 1H NMR signals would the following compound give?
ClCH2CHCH3
A)
B)
C)
D)
E)
Br
1
2
3
4
5
Ans: D
283
Chapter 9
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
A)
B)
C)
D)
E)
How many 1H NMR signals would cis-1,2-dichlorocyclopropane give?
1
2
3
4
5
Ans: C
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
How many 1H NMR signals would you expect from this compound?
OCH3
OCH3
A)
B)
C)
D)
E)
1
2
3
4
5
Ans: B
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
The 1H NMR signal for which of the indicated protons occurs furthest downfield?
III
Cl
H
H
C C C
C CH3
I
H
IV
II
V
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: E
284
Chapter 9
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
The 1H NMR spectrum of which of the compounds below, all of formula C7H12O2,
would consist of two singlets only?
O
O
O
O
O
O
I
II
III
O
O
O
O
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: E
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
The 1H NMR spectrum of which of the compounds below, all of formula C7H12O2,
would consist of three singlets only?
O
O
O
O
O
I
II
III
O
O
O
O
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: B
285
O
Chapter 9
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
The 1H NMR spectrum of which of the compounds below, all of formula C7H12O2,
would consist of a singlet, a doublet and a triplet only?
O
O
O
O
O
O
I
II
III
O
O
O
O
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: D
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
The 1H NMR spectrum of which of these compounds would consist of a triplet, singlet
and quartet only?
A) 2-chloro-4-methylpentane
B) 3-chloro-2-methylpentane
C) 3-chloropentane
D) 1-chloro-2,2-dimethylbutane
E) 3-chloro-3-methylpentane
Ans: E
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
In NMR terminology, protons Ha and Hb are said to be:
H
Cl
Hb
A)
B)
C)
D)
E)
Ha
Identical
Enantiotopic
Diastereotopic
Homotopic
Mesotopic
Ans: C
286
Chapter 9
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
Consider the 1H NMR spectrum of very pure 1-propanol
...
21
...
vicinal protons
...
diastereotopic protons
...
Ans: D
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
In the structure shown, Hb and Hc are classified as:
Hb
A)
B)
C)
D)
E)
Ha
homotopic protons
...
enantiotopic protons
...
isomeric protons
...
23
...
vicinal protons
...
diastereotopic protons
...
Ans: D
Topic: Proton NMR- Chemical Shift, Splitting, Etc
...
In the structure shown, Hb and Hc are classified as:
HO H
Ha H
b
A)
B)
C)
D)
E)
homotopic protons
...
enantiotopic protons
...
isomeric protons
...
25
...
the spectra are determined in a chiral solvent
...
a high amplitude setting is employed
...
Ans: B
288
Chapter 9
Topic: Proton NMR- Unknown Identification
...
A compound with the molecular formula C4H10O gives a 1H NMR spectrum consisting
only of a quartet centered at δ 3
...
1
...
27
...
25
a septet at δ 2
...
25
I
II
III
IV
V
]
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: D
289
Chapter 9
Topic: Proton NMR- Unknown Identification
...
A compound with the molecular formula C10H13Cl gave the following 1H NMR
spectrum:
singlet, δ 1
...
1
multiplet, δ 7
...
29
...
4
quartet, δ 3
...
0 (4H)
There was no evidence of an -OH band in the IR spectrum
...
A compound with the molecular formula C6H15N gave the following 1H NMR spectrum:
triplet, δ 0
...
4
There were no other signals
...
A compound with the molecular formula C8H9ClO gave the following 1H NMR
spectrum:
triplet, δ 3
...
2
multiplet, δ 7
...
The most likely structure
for the compound is:
Cl
O
O
O
Cl
Cl
I
II
III
O
Cl
Cl
IV
A)
B)
C)
D)
E)
O
V
I
II
III
IV
V
Ans: A
291
Chapter 9
Topic: Proton NMR- Unknown Identification
32
...
7 and a quintet centered at δ 2
...
The most likely
structure for the compound is:
A) CH3CH2CHCl2
B) CH3CHClCH2Cl
C) ClCH2CHClCH3
D) ClCH2CH2CH2Cl
E) CH3CCl2CH3
Ans: D
Topic: Proton NMR- Unknown Identification
33
...
2
singlet, δ 2
...
8
multiplet, δ 7
...
A compound C5H10O gave the following spectral data:
1
H NMR spectrum
IR spectrum,
doublet, δ 1
...
10
near 1720 cm-1
septet, δ 2
...
A compound C4H9Br gave the following 1H NMR spectrum:
multiplet, δ 4
...
8; doublet, δ 1
...
0 (3H)
Which is a reasonable structure for the compound?
A) CH3CH2CHBrCH3
B) CH3CH2CH2CH2Br
C) (CH3)2CHCH2Br
D) (CH3)3CBr
Ans: A
293
Chapter 9
Topic: Proton NMR- Unknown Identification
36
...
Its spectral data is as follows:
1
H NMR
IR
-1
triplet, δ 1
...
4
2200 cm (sharp)
singlet, δ 1
...
4
3300 cm-1 (sharp)
quartet, δ 1
...
37
...
Which of these structures could be the correct one for the compound?
CH3
A)
CH3CCH2CH2Cl
CH3
Cl
B)
CH3CH2CCH2CH3
CH3
CH3 CH3
C)
CH3C
CHCH3
Cl
CH3
D)
CH3CHCHCH2CH3
Cl
CH3
E)
CH3C
CHCH3
CH3 Cl
Ans: D
Topic: C-13 NMR- Symmetry, Chemical shift
38
...
How will the methyl carbon appear in the proton off-resonance decoupled 13C spectrum
of toluene?
A)
B)
C)
D)
E)
Singlet
Doublet
Triplet
Quartet
Quintet
Ans: D
Topic: C-13 NMR- Symmetry, Chemical shift
40
...
How many 13C signals would 1,3-dichlorobenzene give?
Cl
Cl
A)
B)
C)
D)
E)
1
2
3
4
5
Ans: D
296
Chapter 9
Topic: C-13 NMR- Symmetry, Chemical shift
42
...
How many 13C signals would you expect from C6H5OCH3?
O
A)
B)
C)
D)
E)
1
2
3
4
5
Ans: E
Topic: C-13 NMR- Symmetry, Chemical shift
44
...
Which of these compounds will not be represented by a singlet only in the 1H NMR
spectrum?
A) Neopentane
B) Hexamethylbenzene
C) Isobutane
D) (Z)-1,2-Dichloroethene
E) (E)-1,2-Dichloroethene
Ans: C
Topic: Proton NMR- Symmetry, Splitting, Chemical shift
46
...
A compound C5H11Cl which exhibits only two singlets in the 1H NMR spectrum must
be:
A) 1-Chloropentane
B) 1-Chloro-2,2-dimethylpropane
C) 1-Chloro-2-methylbutane
D) 3-Chloropentane
E) 1-Chloro-3-methylbutane
Ans: B
298
Chapter 9
Topic: Proton NMR- Symmetry, Splitting, Chemical shift
48
...
Consider the expected splitting of signal “b” in the 1H NMR spectrum of N-methyl-1propanamine, shown below
...
Consider the expected splitting of signal “b” in the 1H NMR spectrum of 1-methoxy-2methylpropane, shown below
...
Consider the expected splitting of signal “b” in the 1H NMR spectrum of 1,1-dichloro-3methylbutane, shown below
...
Consider the expected splitting of signal “b” in the 1H NMR spectrum of 1,2dimethoxypropane, shown below
...
Consider the expected splitting of signal “c” in the 1H NMR spectrum of 2-ethyl-1butanol, shown below
...
Consider the expected splitting of the C2 proton signal in the 1H NMR spectrum of 2ethyl-1,3-propanediol
...
What is the theoretical multiplicity of the C-2 proton signal in the 1H NMR spectrum of
2-hydroxymethyl-1,3-propanediol, shown below?
OH
HO
A)
B)
C)
D)
E)
OH
1
6
7
8
9
Ans: C
Topic: Proton NMR- Symmetry, Splitting, Chemical shift
56
...
Which of
the following is likely to be observed?
A)
B)
C)
D)
E)
7 signals: all singlets
7 signals: 4 singlets, 3 doublets
3 signals: all singlets
3 signals: one singlet, 2 doublets
3 signals: two singlets, one doublet
Ans: E
302
Chapter 9
Topic: Proton NMR- Symmetry, Splitting, Chemical shift
57
...
Which of the
following is likely to be observed?
A)
B)
C)
D)
E)
7 signals: all singlets
4 signals: all singlets
3 signals: all singlets
3 signals: one singlet, 2 doublets
4 signals: two singlets, two doublets
Ans: B
Topic: Proton NMR- Symmetry, Splitting, Chemical shift
58
...
Presuming that the coupling constants for neighboring protons are
sufficiently different, and that the instrument has sufficient resolving power, what is the
theoretical multiplicity of the C2 proton signal?
A) 3
B) 4
C) 5
D) 6
E) 8
Ans: D
303
Chapter 9
Topic: Carbon NMR- Symmetry, Chemical shift
59
...
In 13C NMR spectroscopy, the signal due to this type of carbon occurs furthest
downfield
...
Use the following to answer Q 61-62
Topic: Mass Spectrometry
...
A)
B)
C)
D)
E)
Which is the base peak?
15
29
44
45
100
Ans: B
Topic: Mass Spectrometry
...
A)
B)
C)
D)
E)
Which is the likely molecular ion (M+•)?
15
29
44
45
100
Ans: C
Topic: Mass Spectrometry
...
What is the molecular formula of this compound?
A)
B)
C)
D)
E)
m/z
84 M+•
85
86
C5H10O
C5H8O
C5H24
C6H12
C4H6O2
Ans: B
intensity
10
...
56
0
...
64
...
00
1
3
...
3
Topic: Mass Spectrometry
...
The mass spectra of alkyl bromides and chlorides are characterized by an unusually
intense __________
...
66
...
67
...
CH3CH2CH2CH2CH2CH3
(CH3CH2)2CHCH3
(CH3)3CCH2CH3
(CH3)2CHCH(CH3)2
None of these
Ans: D
Topic: Mass Spectrometry
...
The data below from the molecular ion region of the mass spectrum of a halogencontaining compound are consistent with the presence of what halogen(s) in the original
compound?
intensity
A)
B)
C)
D)
E)
51
...
0
M • +2
+
49
...
69
...
An organic compound absorbs strongly in the IR at 1687 cm-1
...
1 ppm and a multiplet centered at 7
...
Its
mass spectrum shows significant peaks at m/z 120, m/z 105 and m/z 77
...
Which form of electromagnetic radiation possesses the least energy?
Ans: radiofrequency radiation
Topic: General
72
...
Ans: nuclear magnetic resonance
Topic: General; Signal Integration
73
...
Ans: area under the peak
308
Chapter 9
Topic: General; Chemical Shift
74
...
Ans: upfield; downfield
Topic: Reference Compound
75
...
Name two rapid processes that occur in organic molecules
...
In electron impact mass spectrometry, a beam of high-energy electrons initially
dislodges one electron from the compound being studied
...
Ans: molecular ion
Topic: Nitrogen Rule
78
...
If the molecular ion peak is odd, the
molecule must contain an odd number of nitrogen atoms
...
What can be determined from the relative abundance of the M+• +1 peak?
Ans: An approximation for the number of carbon atoms in the molecule
...
What can be determined from the relative abundance of the M+• +2 peak?
Ans: The presence of a number of different elements, including S, Br, and Cl
...
In mass spectrometry, the most intense peak is assigned an intensity of 100%, and is
referred to as the ______________
...
A mass spectrometer sorts ions on the basis of their _______________
...
Briefly explain how you might distinguish between the following substances by
comparing their 1H-NMR spectra:
O
O
O
O
I
II
Ans: The main difference would likely be in the chemical shift of the methine proton of
the isopropyl group
...
5 ppm, while the analogous proton in II is
likely to be found, also as a septet, at about 2
...
O
O
O
O
I
~3
...
3 ppm
310
Chapter 9
Topic: Structure Elucidation
84
...
The methine proton in I is likely to be more deshielded, and produce a signal
(septet) at about 3
...
3 ppm
...
4 ppm, while the analogous proton in II is
likely to be found, also as a triplet, at about 2
...
I
II
O
O
O
O
~3
...
2 ppm
(triplet)
~2
...
4 ppm
(triplet)
311
Chapter 9
Topic: Structure Elucidation
85
...
The methine proton in I is likely to be more deshielded, and produce a signal
(septet) at about 3
...
3 ppm
...
4 ppm, while the analogous proton in II is
likely to be found, also as a triplet, at about 2
...
I
II
O
N
H
~3
...
2 ppm
(triplet)
H
N
O
~2
...
1 ppm
(triplet)
312
Chapter 9
Topic: Structure Elucidation
86
...
Elucidate the structure of A by
scrutinizing its IR, 1H NMR and 13C NMR spectra, shown below
...
An unknown compound, C, has the formula C7H7Br
...
314
Chapter 9
Ans:
Br
4-Bromotoluene
315
Chapter 9
Topic: Structure Elucidation
88
...
Elucidate the structure of E by
scrutinizing its IR, 1H NMR and 13C NMR spectra, shown below
...
An unknown compound, F, has the formula C3H6O2
...
317
Chapter 9
Ans:
O
OH
Propanoic acid
318
Chapter 9
Topic: Structure Elucidation
90
...
Elucidate the structure of I by
scrutinizing its IR, 1H NMR and 13C NMR spectra, shown below
...
An unknown compound, L, has the formula C5H10O2
...
O
Ans:
O
Methyl butyrate
320
Chapter 9
Topic: Structure Elucidation
92
...
Elucidate the structure of U by
scrutinizing its IR, 1H NMR and 13C NMR spectra, shown below
...
An unknown compound, V, has the formula C8H10O
...
323
Chapter 9
Ans:
OH
2,6-dimethylphenol
324
Chapter 9
Topic: Structure Elucidation
94
...
Assign the signals to
the respective hydrogen atoms in the molecule
...
3 ppm
triplet
Ans:
>
>
>
1
...
0 ppm
sextet
Topic: 1H NMR
95
...
9-10 ppm
triplet
Ans:
>
>
Cl
O
4-5 ppm
doublet
325
Chapter 9
Topic: 1H NMR
96
...
Ans: Five
1
2
1'
4
3
OH
5
Topic: 13C NMR, Structure Elucidation
97
...
32 ppm
>
>
33 ppm
>
>
Br
27 ppm
Br
>
Ans:
33 ppm
326
Chapter 9
Topic: 1H NMR
98
...
~1
...
2 ppm
triplet
>
>
~3
...
9 ppm
singlet
>
O
>
O
>
Ans:
~3
...
The bond dissociation energies for the relevant bonds are given below each of the
species involved in the following reaction
...
(CH3)3C-H
+
Cl-Cl
(CH3)3C-Cl
+
H-Cl
ΔHo=400 kJ/mol ΔHo=243 kJ/mol
A)
B)
C)
D)
E)
ΔHo=349 kJ/mol ΔHo=432 kJ/mol
+243 kJ / mol
-138 kJ / mol
+138 kJ / mol
-781 kJ / mol
+781 kJ / mol
Ans: B
Topic: Delta H Calculations and Comparisons
2
...
Calculate the overall ΔH° for the reaction
...
The bond dissociation energies for the relevant bonds are given below each of the
species involved in the following reaction
...
CH3CH2-H
+
Cl-Cl
CH3CH2-Cl
+ H-Cl
ΔH =421 kJ/mol ΔH =243 kJ/mol
o
A)
B)
C)
D)
E)
ΔH =353 kJ/mol ΔH =432 kJ/mol
o
o
o
-121 kJ / mol
+121 kJ / mol
+243 kJ / mol
+664 kJ / mol
-785 kJ / mol
Ans: A
Topic: Delta H Calculations and Comparisons
4
...
Calculate the overall ΔH° for the reaction
...
A)
B)
C)
D)
E)
Which of the reactions listed below would have a value of ΔH° equal to zero?
H–H ⎯⎯⎯⎯→ 2H·
H· + CH3–H ⎯⎯⎯⎯→ CH3–H + H·
CH3· + CH3· ⎯⎯⎯⎯→ CH3–CH3
CH3· + CH3–H ⎯⎯⎯⎯→ CH3–H + CH3·
Reactions (B) and (D)
Ans: E
329
Chapter 10
Topic: Delta H Calculations and Comparisons
6
...
A)
B)
C)
D)
E)
Which of the reactions listed below would be exothermic?
H–H ⎯⎯⎯⎯→ 2H·
H· + CH3–H ⎯⎯⎯⎯→ CH3–H + H·
CH3· + CH3· ⎯⎯⎯⎯→ CH3–CH3
CH3· + CH3–H ⎯⎯⎯⎯→ CH3–H + CH3·
All of the above
Ans: C
Topic: Activation Energies
8
...
A)
B)
C)
D)
E)
Which of the following reactions would have an activation energy equal to zero?
CH3–CH3 ⎯⎯⎯⎯→ 2CH3·
H· + CH3CH3 ⎯⎯⎯⎯→ CH3CH3 + H·
2CH3CH2· ⎯⎯⎯⎯→ CH3CH2CH2CH3
CH3· + CH3CH3 ⎯⎯⎯⎯→ CH3CH3 + CH3·
None of the above
Ans: C
330
Chapter 10
Topic: Activation Energies
10
...
Which of the following reactions would have the smallest energy of activation?
...
+ HBr
B)
+ HBr
...
C)
+ Br
...
E)
+ HBr
...
+ HBr
...
Ans: C
Topic: Activation Energies
12
...
A)
B)
C)
Which of the following reactions should have the smallest energy of activation?
CH4 + Cl· ⎯⎯⎯⎯→ CH3· + HCl
CH3CH3 + Cl· ⎯⎯⎯⎯→ CH3CH2· + HCl
CH3CHCH3
CH3CHCH2
+
+
Cl
CH3
D)
CH3CHCH3
CH3CCH3
+
E)
+
Cl
CH3
CH3
CH3
C
HCl
CH3
HCl
CH3
CH3
CH3
+
CH3
Cl
CH3
C
CH2
+
CH3
Ans: D
Topic: Activation Energies
14
...
A)
B)
C)
D)
E)
An example of a reaction having an Eact = 0 would be:
Br· + Br–Br ⎯⎯⎯⎯→ Br–Br + Br·
F· + CH4 ⎯⎯⎯⎯→ H–F + CH3·
CH3· + Cl· ⎯⎯⎯⎯→ CH3Cl
More than one of these
None of these
Ans: C
332
HCl
Chapter 10
Topic: Activation Energies
16
...
Given the following bond dissociation energies:
ΔH° (kJ mol-1)
CH3CH2–H
H–F
H–Cl
H–Br
H–I
A)
B)
C)
D)
E)
Ans:
421
570
432
366
298
predict which of the following reactions would have the highest energy of activation
...
Given the following bond dissociation energies:
ΔH°(kJ mol-1)
CH3–H
H–F
H–Cl
H–Br
H–I
A)
B)
C)
D)
E)
440
570
432
366
298
predict which of the following reactions would have the highest energy of activation
...
A)
B)
C)
D)
E)
For which of the following gas-phase reactions would the Eact be equal to ΔH°?
Cl–Cl ⎯⎯⎯⎯→ 2Cl·
2 Cl· ⎯⎯⎯⎯→ Cl–Cl
Cl· + CH4 ⎯⎯⎯⎯→ CH3· + H–Cl
CH3· + CH3· ⎯⎯⎯⎯→ CH3–CH3
CH3· + Cl–Cl ⎯⎯⎯⎯→ CH3–Cl + Cl·
Ans: A
Topic: Reaction Products (Isomers)
20
...
How many different monochlorobutanes (including stereoisomers) are formed in the
free radical chlorination of butane?
A) 1
B) 2
C) 3
D) 4
E) 5
Ans: C
Topic: Reaction Products (Isomers)
22
...
The reaction of 2,2-dimethylbutane with chlorine would yield how many monochloro
derivatives? (include stereoisomers)
A) 1
B) 2
C) 3
D) 4
E) 5
Ans: D
Topic: Reaction Products (Isomers)
24
...
A) 2
B) 3
C) 4
D) 5
E) 6
Ans: C
335
Chapter 10
Topic: Reaction Products (Isomers)
25
...
Butane
...
Isopentane
...
Ans: E
Topic: Reaction Products (Isomers)
26
...
More than one monochloro compound can be obtained from the free radical chlorination
of:
A) Cyclopentane
B) Neopentane
C) Isobutane
D) Ethane
E) Methane
Ans: C
Topic: Reaction Products (Isomers)
28
...
A) 4
B) 5
C) 6
D) 7
E) 8
Ans: C
336
Chapter 10
Topic: Reaction Products (Isomers)
29
...
The free radical chlorination of (R)-2-chloropentane forms a mixture of
dichloropentanes which includes:
A) three optically active compounds
B) two achiral compounds
...
D) one pair of diastereomers
...
Ans: B
Topic: Reaction Products (Isomers)
31
...
The free radical chlorination of 3-chloropentane forms a mixture of dichloropentanes
which, on precise fractional distillation, affords these fractions:
A) 4 fractions, none optically active
B) 4 fractions, 2 optically active
C) 7 fractions, 4 optically active
D) 7 fractions, 6 optically active
E) 7 fractions, all optically active
Ans: A
337
Chapter 10
Topic: Reaction Products (Isomers)
33
...
How many fractions (in total) would be obtained and how many of these
fractions would be optically active?
A) Three fractions total; all optically active
B) Four fractions total; three fractions optically active
C) Five fractions total; all optically active
D) Five fractions total; four fractions optically active
E) Five fractions total; three fractions optically active
Ans: E
Topic: Reaction Products
34
...
Ans: B
338
?
Chapter 10
Topic: Reaction Products
35
...
CH3
Br2
?
hν
CH2Br
Br
CH3
CH3
Br
CH3
IV
V
Br
Br
I
A)
B)
C)
D)
E)
II
III
I
II
III
IV
V
Ans: B
Topic: Reaction Products
36
...
In the presence of light at 25°C, isobutane (1 mol) and bromine (1 mol) yield which
monobromo product(s)?
A) 2-Methyl-1-bromopropane (almost exclusively)
B) 2-Methyl-2-bromopropane (almost exclusively)
C) A mixture of 50% (A) and 50% (B)
D) A mixture of 90% (A) and 10% (B)
E) Butyl bromide
Ans: B
Topic: Reaction Products
38
...
In a competition reaction, equimolar amounts of five alkanes compete for a deficiency
of chlorine at 300°C
...
Which of the following combinations of reactants can provide a demonstrable example
of anti-Markovnikov addition?
A) CH2=CHCH3 + HCl + ROOR
B) CH3CH=CH2 + H2O + Cl2
C) CH3CH=CHCH3 + HBr + ROOR
D) CH3CH2CH=CH2 + HBr + ROOR
E) CH3CH2CH=CH2 + Br2 + ROOR
Ans: D
340
Chapter 10
Topic: Reaction Products
41
...
What product would result from the following reaction?
+ HBr
peroxides
?
Br
Br
I
A)
B)
C)
D)
E)
Br
HOO Br
II
III
Br OOH
IV
I
II
III
IV
V
Ans: A
341
V
Chapter 10
Topic: Synthesis
43
...
Ans: B
Topic: Synthesis
44
...
What sequence of reactions could be used to prepare cis-1,2-cyclopentanediol from
cyclopentane?
A) (1) Cl2, hν; (2) t-BuOK/t-BuOH; (3) OsO4; (4) NaHSO3/H2O
B) (1) t-BuOK/t-BuOH; (2) Cl2, hν; (3) NaOH/H2O
C) (1) Cl2, hν; (2) t-BuOK/t-BuOH; (3) H2O2
D) (1) NaOH/H2O; (2) Br2; (3) NaNH2(2eq
...
NH3; (4) KMnO4, NaOH/H2O, 5°C
E) (1) Cl2, hν; (2) t-BuOK/t-BuOH; (3) Hg(OAc)2, H2O (4) NaBH4, H3O+
Ans: A
342
Chapter 10
Topic: Mechanisms
46
...
A)
B)
C)
D)
A chain reaction is one that:
involves a series of steps
...
is one that can be initiated by light
...
E) involves free radicals that have an unusual stability and thereby cause a large quantum
yield
...
Which of the following statements is true when used to compare the reaction of fluorine
with 2-methylhexane and the reaction of bromine with 2-methylhexane?
A) Bromine is the less reactive and the less selective, giving 2-bromo-2-methyl hexane as
one of several products
...
C) Fluorine is the more reactive and less selective, giving 2-fluoro-2-methyl hexane as one
of several products
...
E) More than one of the above statements is true
Ans: C
343
Chapter 10
Topic: Mechanisms
49
...
The probability factor is low
...
One of the chain propagating steps has a very high Eact
...
Ans: D
Topic: Mechanisms
50
...
The transition state of the rate determining step is product-like
...
A) and B)
A), B) and C)
Ans: D
Topic: Mechanisms
51
...
For which of the following reactions would the transition state most resemble the
products? The following bond dissociation energies may be useful
...
Which of the following gas-phase reactions is a possible chain-terminating step in the
light-initiated chlorination of methane?
A) Cl–Cl ⎯⎯⎯⎯→ 2Cl·
B) Cl· + CH4 ⎯⎯⎯⎯→ CH3· + H–Cl
C) CH3· + CH3· ⎯⎯⎯⎯→ CH3–CH3
D) CH3· + Cl–Cl ⎯⎯⎯⎯→ CH3Cl + Cl·
E) More than one of the above
Ans: C
Topic: Mechanisms
54
...
The mechanism for the reaction involves:
A) attack on the alkene by a Br+ ion
...
C) attack on the alkene by a bromine atom, Br·
...
E) isomerization of the 2-bromobutane produced initially
...
The reaction of Cl2 with a methyl radical has a positive ΔH°
...
A)
B)
C)
D)
E)
Ans:
The hybridization state of the carbon of a methyl radical is:
sp
sp2
sp3
sp4
p3
B
Topic: Free Radicals
57
...
Which of the following free radicals is the most stable?
CH2
A)
B)
CH3CHCH2CH3
CH3
C)
CH3CHCH2CH2
CH3
D)
CH2CHCH2CH3
CH3
CH3CHCHCH3
E)
CH3
CH3CCH2CH3
Ans: E
Topic: Free Radicals
59
...
A)
B)
C)
D)
E)
Free radicals can be produced by:
use of high temperatures
...
reaction of a molecule with another free radical
...
all of A), B) and C)
...
The ΔH° value is expected to be least for which indicated C-H bond of isopentane?
A) H CH2CHCH2CH3
B)
C)
CH3
CH3CHCH2CH3
CH2
H
H
CH3CCH2CH3
D)
CH3
H
CH3CHCHCH3
E)
CH3
CH3CHCH2CH2
H
CH3
Ans: C
Topic: Free Radicals
62
...
The process is endothermic
...
ΔH° is positive
...
Ans: C
Topic: Free Radicals
63
...
Thus, monochlorination of isopentane
should produce these percentages of 2-chloro-2-methylbutane (A), combined 1-chloro2-methylbutane and 1-chloro-3-methylbutane (B), and 2-chloro-3-methylbutane (C):
A) 8% A, 75% B, 17% C
B) 25% A, 45% B, 30% C
C) 29% A, 44% B, 18% C
D) 30% A, 35% B, 35% C
E) 36% A, 43% B, 21% C
Ans: B
348
Chapter 10
Topic: Miscellaneous
64
...
e
...
A) F·
B) Cl·
C) O·
D) ClO·
E) FO·
Ans: B
Topic: Miscellaneous
65
...
CH3 CH3
A)
B)
RCH2CHCH2CH
CH3
CH3
C)
RCHCH2CHCH2
CH3
CH3
D)
RCHCH2CH2CH
CH3
RCH2CHCHCH2
CH3
E)
CH3
RCCH2CH
CH3 CH3
Ans: A
Topic: Miscellaneous
66
...
When an alkane in which all hydrogen atoms are not equivalent is monosubstituted, use
of this halogen produces a ratio of isomers which is essentially statistical, i
...
, dependent
only on the number of each type of hydrogen
...
What is the final product, C, obtained via the following reaction sequence?
Br2
hν
A t-BuOK
t-BuOH
heat
OH
A)
B)
C)
D)
E)
I
I
II
III
IV
V
Ans: A
OH
II
B
ii) H2O2, OH
OH
III
i) BH3, THF
−
OH
OH
OH
IV
350
C
V
Chapter 10
Topic: Multistep Reactions
69
...
What is the major product obtained from the following reaction sequence?
Br2
HBr
NaSH
B
D
A t-BuOK
C
peroxides
t-BuOH
hν
heat
SH
SH
A)
B)
C)
D)
E)
I
I
II
III
IV
V
Ans: A
SH
II
SH
III
IV
351
V
Chapter 10
Topic: Multistep Reactions
71
...
What is the major product obtained from the following reaction sequence?
i) BH3, THF
HBr
t-BuOK
B
C
A
peroxides
t-BuOH
ii) H2O2, OH−
heat
OH
OH
OH
I
II
III
HO
OH
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: E
352
Chapter 10
Topic: Multistep Reactions
73
...
Intermediates possessing unpaired electrons are called ______________
...
A covalent bond breaking so that each of the resulting intermediates bears a single
unpaired electron is an example of __________________ bond cleavage
...
Bond formation is an ______________ process, and therefore ΔH° is ____________
...
Although alkyl radicals are uncharged, the carbon bearing the odd electron is electron
___________, and alkyl groups provide a __________________ effect
...
The mechanism for a free-radical reaction consists of three types of steps
...
In a chain-initiating step, radicals are _____________
...
In a chain-terminating step, radicals are ______________
...
In a chain-propagating step, one radical _______________
...
While the electrophilic addition of HBr to an alkene is ionic and follows Markovnikov's
rule, if the reaction is done in the presence of peroxides it becomes a ___________
reaction and is ____________________ in regiochemistry
...
Macromolecules made up of many repeating subunits are called ____________
...
Two radicals that are very important in biological processes are ________________ and
__________________
...
Chlorofluorocarbons, or freons, diffuse into the upper atmosphere
...
Ans: the ozone layer
Topic: General
86
...
Ans: Carbocation; free-radical
Topic: Reaction Products ( Isomers)
87
...
For each structure,
indicate, with an asterisk, any stereocenters that might be present
...
Draw bond-line formulas of all monochloro derivatives that might be formed when 1,1dimethylcyclobutane is allowed to react with Cl2 under UV irradiation
...
Ans:
Cl2, hν Cl
+ Cl *
+ Cl
1,1-dimethylcyclobutane
monochloro derivatives
355
Chapter 10
Topic: Reaction Products ( Isomers)
89
...
For each structure,
indicate, with an asterisk, any stereocenters that might be present
...
Deduce the structure of a substance, C8H18, which gives only a single monochloro
derivative upon reaction with Cl2 under UV irradiation
...
Draw bond-line formulas of all dichloro derivatives that might be formed when 1chloro-2,2,3,3,-tetramethylpentane is allowed to react with Cl2 under UV irradiation
...
Cl
Ans:
Cl
*
Cl
Cl2
Cl
+ Cl
+
hν
Cl
Cl
1-chloro-2,2,3,3tetramethylpentane
Cl
Cl
Cl
+
Cl
dichloro derivatives
356
*
+
Chapter 10
Topic: Reaction Products ( Isomers)
92
...
For each
structure, indicate, with an asterisk, any stereocenters that might be present
...
Complete the following reaction sequence: indicate regiochemical/stereochemical
details as relevant
...
Complete the following reaction sequence: indicate regiochemical/stereochemical
details as relevant
...
Complete the following reaction sequence: indicate regiochemical/stereochemical
details as relevant
...
Suggest a reasonable strategy for the synthesis of 1-bromo-2-methylcyclohexane from
methylcyclohexane
Br2
C2H5ONa
Ans:
HBr
Br
peroxides
C2H5OH
hν
Br
heat
358
O
Chapter 10
Topic: Mechanisms
97
...
Ans: During the free radical bromination of 2-methylbutane, the most stable
intermediate is produced by abstraction of the tertiary hydrogen atom at C2
...
Br2
minor product
hν
+
termination step: radical coupling
Topic: Mechanisms
98
...
Two such
radicals can couple together via a termination step to afford 1,4-dibromo-2,2,3,3teramethylbutane as a minor product
...
HBr
peroxides
Br +
Br
most stable radical intermediate
Br
Br
Br
Br
Br +
Br
Br
termination steps: radical coupling
359
Chapter 10
Topic: Reactivity / Selectivity
99
...
Ans: The energy of activation for the first propagation step in the free radical
mechanism for halogenation of alkanes determines the overall reactivity pattern
for the various halogens
...
I
...
Eact for this step very high: reaction very slow, further steps inhibited
Topic: Reactivity / Selectivity
100
...
However, when the same alkane is allowed
to react with Br2/ hν, there is only one major monobromination product
...
Chlorine is
highly reactive and therefore there is not much differentiation between the
different kinds of hydrogen atoms- as a result, all the possible free radicals are
formed, leading to the formation of all possible constitutional isomers
...
Br
Br2
hν
Cl2, hν
Cl
Cl
Cl
Cl
360
Chapter 11
MULTIPLE CHOICE QUESTIONS
Topic: Nomenclature
1
...
A)
B)
C)
D)
E)
A correct IUPAC name for isobutyl alcohol is:
2-Methyl-1-propanol
2-Methyl-1-butanol
1-Methyl-1-propanol
1,1-Dimethyl-1-ethanol
3-Methyl-1-propanol
Ans: A
Topic: Nomenclature
3
...
CH3CCHCH
A)
B)
C)
D)
E)
The correct IUPAC substitutive name for
4-Penten-2-methyl-2-ol
4-Methyl-1-penten-2-ol
2-Methyl-4-penten-2-ol
4-Methyl-1-penten-4-ol
4-Hydroxy-4-methyl-1-pentene
Ans: C
CH3
CH2
is:
Topic: Nomenclature
5
...
CH2CH3
CH3CH2COH
A)
B)
C)
D)
E)
The IUPAC name of compound
1,1,1-Triethylmethanol
1,1-Diethyl-1-propanol
2-Ethyl-3-pentanol
3-Ethyl-3-pentanol
tert-Heptanol
Ans: D
CH2CH3
362
is:
Chapter 11
Topic: Nomenclature
7
...
Select the structure of benzyl methyl ether
...
OH
OH
A)
B)
C)
D)
E)
is properly named:
cis-1,2-Cyclopentanediol
meso-1,2-Cyclopentanediol
(1R,2R)-1,2-Cyclopentanediol
(1R,2S)-1,2-Cyclopentanediol
(1S,2S)-1,2-Cyclopentanediol
Ans: C
Topic: Nomenclature
10
...
What is the most accurate name for the molecule represented by the following Fischer
projection formula?
H
H3CH2C
A)
B)
C)
D)
E)
OCH3
CH3
sec-Butyl methyl ether
Isobutyl methyl ether
tert-Butyl methyl ether
(R)-2-Methoxybutane
(S)-2-Methoxybutane
Ans: E
364
Chapter 11
Topic: Nomenclature
12
...
A)
B)
C)
D)
E)
Which of these, though commonly used, is an incorrect name for CH3CHOHCH3?
Isopropyl alcohol
sec-Propyl alcohol
2-Propanol
Isopropanol
More than one of these
...
A)
B)
C)
D)
E)
Which of these, though commonly used, is an incorrect name for (CH3)3COH?
tert-Butyl alcohol
tert-Butanol
2-Methyl-2-propanol
More than one is incorrect
...
Ans: B
Topic: Isomerism, Stereoisomers
15
...
A)
B)
C)
D)
E)
What is the total number of pentyl alcohols, including stereoisomers?
7
8
9
10
11
Ans: E
Topic: Isomerism, Stereoisomers
17
...
The number of optically active pentyl alcohols (C5H12OH), i
...
, the total number of
individual enantiomers, is:
A) 0
B) 2
C) 3
D) 4
E) 6
Ans: E
Topic: Alcohol Reactions
19
...
The product(s) of the following reaction
CH2
CH2
excess HBr
CH2
CH2
is/are:
heat
O
CH3CH2OCH2CH3
CH3CH2CH2CH2OH and CH3CH2CH2CH2Br
I
II
CH2
BrCH2CH2CH2CH2OH and BrCH2CH2CH2CH2Br
CH2
CH2
O
III
A)
B)
C)
D)
E)
IV
I
II
III
IV
None of these
Ans: C
367
CHBr
Chapter 11
Topic: Alcohol Synthesis
21
...
BH3-THF
?
2
...
Which would be the best way to carry out the following synthesis?
?
CH3CH2CHCH3
CH3CH2CH2CH2OH
Br
A)
B)
C)
D)
E)
CH2OH
(1) HA, heat; (2) H3O+, H2O, heat
(1) (CH3)3COK / (CH3)3COH; (2) BH3:THF, then H2O2, OH(1) (CH3)3COK / (CH3)3COH; (2) H3O+, then H2O, heat
(1) KOH, C2H5OH; (2) BH3:THF, then H2O2, OH(1) KOH, C2H5OH; (2) HA, heat; (3) H3O+, H2O, heat
Ans: B
368
V
Chapter 11
Topic: Alcohol Synthesis
23
...
CH3
1
...
NaBH4, NaOH
CH3
CH3
CH2OH
HO CH3
OH
CH3
OH
OH
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
V
Ans: D
369
V
Chapter 11
Topic: Alcohol Synthesis, Isotope Labeling
24
...
What product would you expect
from the following reaction?
CH3
1
...
H2O2/NaOH
HO
H
D
H
CH3
+
enantiomer
I
A)
B)
C)
D)
E)
H
D
BD2
CH3
+
enantiomer
II
D
D
CH3
H
+
enantiomer
III
H
OH
CH3
H
D
+
enantiomer
IV
I
II
III
IV
V
Ans: A
Topic: Ether Reactions, Isotope Labeling
25
...
HA
CH3CH
CH2
?
18O
O
H2
18
A) CH3CH2CH2 OH
B) CH3CHCH3
C)
18OH
CH3CHCH2OH
18OH
D) CH3CH
E)
CH2
OH 18OH
CH3CHCH218OH
18OH
Ans: C
370
BD2
CH3
+
enantiomer
V
Chapter 11
Topic: Ether Reactions
26
...
HBr (xs)
C6H5CH2OCH3
A)
B)
C)
D)
E)
?
heat
C6H5Br + CH3OH
C6H5CH2Br + CH3Br
C6H5CH2OH + CH3Br
C6H5CH2Br + CH3OH
C6H5CH2CH2Br
Ans: B
Topic: Ether Synthesis
27
...
A)
B)
C)
D)
E)
Which is the best method to prepare 2-ethoxy-5methylhexane?
C2H5ONa + (CH3)2CHCH2CH2Br
C2H5ONa + (CH3)2CHCH2CH2CH2CH2Br
C2H5ONa + (CH3)2CHCH2CH2CHBrCH3
C2H5Br + (CH3)2CHCH2CH2CH(CH3)ONa
C2H5OH + (CH3)2CHCH2CH2CHOHCH3 + H2SO4, 140°C
Ans: D
Topic: Alcohol Reactions
29
...
A)
B)
C)
D)
E)
Which of the following could not be used to synthesize 2-bromopentane efficiently?
1-Pentene + HBr
2-Pentene + HBr
2-Pentanol + HBr
2-Pentanol + PBr3
All of the above would afford good yields of 2-bromopentane
Ans: B
Topic: Alcohol Reactions
31
...
Which of the following would be a reasonable synthesis of 2-butanol?
A)
H3O+, heat
1-Butene
1
...
H2O2, NaOH
1
...
NaBH4, NaOH
D) More than one of these
E) None of these
Ans: D
372
Chapter 11
Topic: Epoxide Reactions
33
...
Which of the following would be a reasonable synthesis of CH3CH2CH2CH2OH?
A)
H3O+, heat
1-Butene
1
...
H2O2, NaOH
1
...
NaBH4, NaOH
D) More than one of these
E) None of these
Ans: B
Topic: Alcohol Synthesis
35
...
H2SO4; then H2O, heat
D) Hg(OAc)2/THF-H2O; then NaBH4,OHE) HBr; then NaOH/H2O
Ans: D
373
Chapter 11
Topic: Alcohol Reactions
36
...
The
product of this reaction is then heated with KI in methanol
...
Which method would provide the best synthesis of ethyl isopropyl ether?
A) (CH3)2CHONa + CH3CH2Br ⎯⎯⎯⎯⎯→
B) CH3CH2ONa + (CH3)2CHBr ⎯⎯⎯⎯⎯→
C)
H2SO4, 140 oC
CH3CH2OH
+ (CH3)2CHOH
D)
H2SO4, 180 oC
CH3CH2OH
+ (CH3)2CHOH
E) CH3CH2ONa + (CH3)2CHOH ⎯⎯⎯⎯⎯→
Ans: A
Topic: Alcohol Reactions
38
...
Which compound (or compounds) would be produced when trans-2-butene is treated
first with a peroxy acid to form an epoxide, and then the epoxide is subjected to acidcatalyzed hydrolysis?
H
HO
CH3
CH3
HO
CH3
H
H
OH
C
C
C
C
C
C
H
CH3
OH
A)
B)
C)
D)
E)
HO
CH3
H
H3C
H
OH
I
II
An equimolar mixture of I and II
An equimolar mixture of II and III
I alone
II alone
III alone
Ans: E
III
Topic: Ether Reactions
40
...
A)
B)
C)
D)
E)
Which is the best method for the synthesis of tert-butyl methyl ether?
CH3ONa + (CH3)3CBr ⎯⎯⎯⎯→
(CH3)3CONa + CH3I ⎯⎯⎯⎯→
CH3OH + (CH3)3COH + H2SO4 at 140° C ⎯⎯⎯⎯→
(CH3)3CONa + CH3OCH3 ⎯⎯⎯⎯→
CH3ONa + (CH3)3COH ⎯⎯⎯⎯→
Ans: B
375
Chapter 11
Topic: Alcohol Reactions
42
...
cis-3-Methylcyclopentanol is treated with CH3SO2Cl in the presence of a base
...
What is the final
product?
A) trans-1-Iodo-3-methylcyclopentane
B) cis-1-Iodo-3-methylcyclopentane
C) 1-Methylcyclopentene
D) 2-Methylcyclopentene
E) 3-Methylcyclopentene
Ans: A
376
Chapter 11
Topic: Alcohol Reactions
44
...
Which would be the major product of the reaction shown?
CH2CH3
1
...
NaBH4, NaOH
H
OH
OHCH2CH3
H
H
CH2CH3
H
CH2CH3
H CH2CH3
H CH2CH2OH
O
H
H
OH
H
I
A)
B)
C)
D)
E)
H
II
III
IV
V
I
II
III
IV
V
Ans: B
Topic: Alcohol Reactions
46
...
HBr and heat
PBr3
NaBr/H2O and heat
More than one of these
All of these
Ans: D
378
Chapter 11
Topic: Epoxide Reactions
47
...
When 3-methyl-2-pentene is treated with mercuric acetate, Hg(O2CCH3)2, in a THFethanol mixture and the resulting product reacted with NaBH4 in basic solution, the
principal product formed is which of these?
A) 3-methyl-3-pentanol
B) 3-ethoxy-3-methylpentane
C) 3-methyl-2-pentanol
D) 2-ethoxy-3-methylpentane
E) 1-ethoxy-3-methylpentane
Ans: B
Topic: Alcohol Synthesis
49
...
H3C
A)
B)
C)
D)
E)
CH
CH3
CH
CH3
to
H3C
CH
CH
CH3
OH
Br
is best
The conversion of
achieved through use of which of these reagents in a low temperature reaction?
Concd
...
The conversion of 3-methyl-1-octanol to 1-chloro-3-methyloctane is best achieved
through use of which of these reagents?
A) Concd
...
What is the product of the reaction of propyl alcohol with (CH3)3SiCl in the presence of
a tertiary amine?
A) CH3CH2CH2Si(CH3)3
B) (CH3)2CHSi(CH3)3
C) CH3CH2CH2OSi(CH3)3
D) (CH3)2CHOSi(CH3)3
E) (CH3CH2CH2)3SiOH
Ans: C
380
Chapter 11
Topic: Alcohol Synthesis
53
...
What is the major product of the reaction when (R)-3-methylcyclohexene is subjected to
the hydroboration-oxidation sequence?
A) (1R,2R)-2-methylcyclohexanol + (1S,2R)-2-methylcyclohexanol
B) (1S,2R)-2-methylcyclohexanol + (1S,2S)-2-methylcyclohexanol
C) (1R,3R)-3-methylcyclohexanol + (1S,3R)-3-methylcyclohexanol
D) (1S,3R)-3-methylcyclohexanol (1S,3S)-3-methylcyclohexanol
E) Two of the above
Ans: E
381
Chapter 11
Topic: Alcohol Synthesis
55
...
CH3
S
OH,
O
Methanesulfonic acid,
is treated, in turn, with PCl5 and (R)-2-butanol
...
cis-3-Hexene is treated with magnesium monoperoxyphthalate and the product is then
subjected to acid-catalyzed hydrolysis
...
Which of the following reagents might serve as the basis for a simple chemical test that
would distinguish between pure 1-butene and CH3CH2CH2CH2OH?
A) Bromine in carbon tetrachloride
B) Dilute aqueous potassium permanganate
C) Chromic oxide in aqueous sulfuric acid
D) All of these
E) None of these
Ans: D
Topic: Chemical Tests
59
...
H2SO4
KMnO4 in H2O
Ans: D
384
Chapter 11
Topic: Chemical Tests
60
...
Which of the compounds listed below would you expect to have the highest boiling
point? (They all have approximately the same molecular weight
...
A)
B)
C)
D)
E)
Which compound would have the highest boiling point?
CH3CH2CH2CH3
CH3CH2OCH3
CH3CH2CH2OH
(CH3)2CHOH
HOCH2CH2OH
Ans: E
Topic: Physical Properties, Comparison
63
...
Which compound would have the lowest boiling point?
O
I
A)
B)
C)
D)
E)
CH2OH
OH
OH
II
III
IV
OH
V
I
II
III
IV
V
Ans: A
Topic: Physical Properties, Comparison
65
...
A)
B)
C)
D)
E)
Which of the alcohols listed below would you expect to react most rapidly with HBr?
CH3CH2CH2CH2CH2CH2OH
(CH3CH2)2CH2CH2OH
(CH3CH2)2CHOHCH3
CH3CH2CH2CH2CH2OH
(CH3CH2)2C(CH3)OH
Ans: E
386
Chapter 11
Topic: Alcohol Reaction Rates
67
...
Ans: D
Topic: Ether Reaction Rates
68
...
Which of these ethers is least likely to undergo significant cleavage by hot aqueous
H2SO4 ?
CH3OCH3
CH3OCH(CH3)2
(CH3)2CHOCH(CH3)2
I
II
III
(CH3)3COC(CH3)3
IV
A)
B)
C)
D)
E)
O
V
I
II
III
IV
V
Ans: A
387
Chapter 11
Topic: Alcohol Reaction Rates
70
...
The following reaction,
HBr
CH3CH2CH2CH2OH
A)
B)
C)
D)
E)
CH3CH2CH2CH2Br
heat
+
H2 O
is probably:
An SN1-type reaction involving the protonated alcohol as the substrate
...
An E1-type reaction involving the protonated alcohol as the substrate
...
An epoxidation reaction
...
The reaction between 1-pentanol and HBr to yield 1-bromopentanol is probably:
A)
B)
C)
D)
E)
an SN1-type reaction involving the protonated alcohol as the substrate
...
an E1-type reaction involving the protonated alcohol as the substrate
...
an epoxidation reaction
...
The reaction between 2-methyl-2-pentanol and HBr to yield 2-bromo-2-methylpentane
is probably:
A) an SN1-type reaction involving the protonated alcohol as the substrate
...
C) an E1-type reaction involving the protonated alcohol as the substrate
...
E) an epoxidation reaction
...
The reaction between 2-methyl-2-pentanol and HBr to yield 2-methyl-2-pentene is
probably:
A) an SN1-type reaction involving the protonated alcohol as the substrate
...
C) an E1-type reaction involving the protonated alcohol as the substrate
...
E) an epoxidation reaction
...
The reaction between 4-methyl-1-pentanol and HBr to yield 4-methyl-1-pentene is
probably:
A) an SN1-type reaction involving the protonated alcohol as the substrate
...
C) an E1-type reaction involving the protonated alcohol as the substrate
...
E) an epoxidation reaction
...
Which statement is true concerning the formation of alcohols by the hydroborationoxidation sequence?
A) Overall, the process results in syn addition and anti-Markovnikov orientation
...
C) Overall, the process results in syn addition and Markovnikov orientation
...
E) The stereochemistry and orientation are unpredictable
...
What is the electrophilic species involved in the initial step of the reaction below?
Hg(OAc)2
OH
HgOAc
THF, H2O
A)
B)
C)
D)
E)
+
OH
HgOAc
H3O+
THF
the THF/H2O complex
Ans: B
+
Topic: Reaction Mechanisms
78
...
an SN2-type reaction involving the protonated alcohol as the substrate
...
an E2-type reaction involving the protonated alcohol as the substrate
...
Ans: B
Topic: Stereoisomerism
79
...
constitutional isomers
...
diastereomers
...
Ans: D
390
+
H2O
Chapter 11
Topic: Stereoisomerism
80
...
constitutional isomers
...
diastereomers
...
Ans: C
Topic: Ether Reactivity
81
...
B) Ethers generally have lower boiling points than alcohols of a corresponding molecular
weight
...
D) Ethers can generally be cleaved by heating them with strong acids
...
Ans: C
391
Chapter 11
Topic: General
82
...
A)
B)
C)
D)
E)
The major industrial process in use today for the production of methanol is the:
hydration of ethyne
...
hydrogenation of carbon dioxide
...
catalytic reduction of carbon monoxide
...
A)
B)
C)
D)
E)
Today, most industrial ethanol is made in the U
...
by the:
fermentation of grain
...
hydration of ethylene
...
hydration of acetylene
...
Long-term storage of ethers can be dangerous, because most ethers react slowly with
oxygen by a radical process called __________________
...
Ans: autooxidation, explosive
Topic: General, Alcohol Synthesis
86
...
a
...
b
...
c
...
Ans: a
...
oxymercuration-demercuration; c
...
Reactions of alcohols can be broadly categorized into three types
...
Those that utilize the hydroxyl oxygen as a ____________
...
Those that utilize the hydroxyl proton as an _________
...
Those that convert the hydroxyl group into a _____________
...
acid; c
...
Stereochemically speaking, conversion of an alcohol into a tosylate occurs with
_____________ of configuration
...
When an alcohol in which the OH is attached to a stereogenic carbon reacts with thionyl
chloride (SOCl2) in the presence of a 3° amine, the resulting alkyl chloride is produced
with _____________ of configuration
...
The SN2 reaction between an alkoxide and an alkyl halide is commonly referred to as
the _________________ synthesis
...
Three-membered rings containing oxygen are called _______________ or
______________
...
The development of a procedure called __________________ has made the use of
nonpolar solvents possible in reactions involving polar reagents
...
The relationship between a crown ether and the ion it transports is known as the
____________________ relationship
...
A compound or ion that prefers a nonpolar environment to an aqueous one is said to be
______________
...
Draw structures for all possible ethers having the formula C4H10O
O
Ans:
O
O
C4H10O: ethers
Topic: Ether Synthesis
96
...
Which is the best method to prepare ethoxycyclopentane via the Williamson method?
Ans:
O
ONa
+
I
394
Chapter 11
Topic: Alcohol Synthesis
98
...
Ans: The alkene is symmetrically substituted: thus, Markovnikov rule does not apply
...
H3C
H
hydroboration-oxidation
(3R)-3-methylcyclopentene
H3C
H3C
H
H3C
H
H3C
H
H
OH
OH
+
+
+
OH
OH
Topic: Ether Synthesis
99
...
Give the correct IUPAC name corresponding to the following structure:
OH
Ans: 6-cyclohexyl-2,7-dimethyl-3-octanol
395
Chapter 11
Topic: Nomenclature
101
...
Give the correct IUPAC name corresponding to the following structure:
O
O
Ans: 1,3-diethoxyhexane
Topic: Nomenclature
103
...
Provide a reasonable synthetic strategy for the synthesis of a racemic mixture of
(1R,2R) and (1S,2S)-2-bromo-1-methylcyclopentanol from methylcyclohexane
...
Complete the following reaction sequence, giving structural details of all key
intermediates:
i) Li, NH3
?
ii) KMnO4 ,OH−, H2O
Ans:
iii) H3O+
Li
NH3
i) KMnO4 ,OH−, H2O
ii) H3O+
H
H
OH
OH
+
HO
H
HO
2S,3R
H
2R,3S
Topic: Multistep Reactions
106
...
Complete the following reaction sequence, giving structural details of all key
intermediates:
i) Li, NH3
?
ii) MMPP
Ans:
iii) H3O+, H2O
Li
NH3
i) MMPP
ii) H3O+, H2O
H
H
OH
OH
+
H
OH
H
2S, 3S
OH
2R, 3R
398
Chapter 12
MULTIPLE CHOICE QUESTIONS
Topic: General Carbonyl Information
1
...
All are significant contributors
...
When nucleophilic addition to a carbonyl group occurs, the carbon attacked undergoes
this hybridization change:
A) sp2 ⎯⎯⎯⎯→ sp3
B) sp ⎯⎯⎯⎯→ sp2
C) sp ⎯⎯⎯⎯→ sp3
D) sp3 ⎯⎯⎯⎯→ sp2
E) sp2 ⎯⎯⎯⎯→ sp
Ans: A
Topic: Functional Group Tests
3
...
Which reagent(s) will distinguish between 2-methylcyclopentanol and 1methylcyclopentanol?
A) Br2/CCl4
B) KMnO4
C) CrO3/aqueous H2SO4
D) NaOH (aq)
E) B) and C)
Ans: E
Topic: Functional Group Tests
5
...
Which of the reagents listed below would serve as the basis for a simple chemical test to
distinguish between CH3CH=CHCH2OH and CH3CH2CH2CH2OH ?
A) CrO3 in H2SO4
B) Cold conc
...
Which of the reagents listed below would serve as the basis for a simple chemical test to
distinguish between (CH3)2C=CHCH2CH2OH and (CH3)2CHCH2CH2CH2OH ?
A) CrO3 in H2SO4
B) Cold conc
...
Which of the reagents/techniques listed below would serve as the basis for a simple
chemical test to distinguish between 2-methyl-3-hexyn-1-ol and 2-methyl-5-hexyn-1-ol?
A) CrO3 in H2SO4
B) Cold conc
...
Which of the reagents/techniques listed below would serve as the basis for a simple
chemical test to distinguish between 2-methyl-3-hexyn-2-ol and 2-methyl-5-hexyn-1-ol?
A) CrO3 in H2SO4
B) IR spectroscopy
C) Br2 in CCl4
D) A) and B)
E) All of the above
Ans: D
Topic: Functional Group Tests
10
...
Which of the reagents listed below would serve as the basis for a simple chemical test to
distinguish between (CH3)3COH and (CH3)2CHCH2OH ?
A) NaH
B) NaOH/H2O
C) Br2 in CCl4
D) Cold conc
...
CrO3 in H2SO4/H2O will fail to give a positive test with which of these compounds?
A) CH3CH2CH2CH2OH
B) CH3CHCH2CH3
OH
C) (CH3)3COH
H
D)
CH3CH2CH2C
O
E) More than one of these
Ans: C
Topic: Functional Group Tests
13
...
Which reagent will not give a positive test with this compound?
Cold conc
...
The final product, D, in the following reaction sequence,
CH2
CH2
CH3CHOH
PBr3
CH3
A
Mg
ether
A) CH3CHOCH2CH2OH
CH3
CH3CHCH2CH2Br
C)
CH3
CH3CHCH2CH2OH
D)
CH3
CH3CHOCH2CH3
E)
C
H3O+
D
,
would be?
B)
B
O
CH3
CH3CHCH2CH3
CH3
Ans: C
403
Chapter 12
Topic: Reactions and Reaction Sequences
15
...
What is the product, A, that would be obtained from the following reaction sequence?
CH2
CH2
CH3CH2MgBr
C CH
C CCH2CH3
C CCH2CH2OCH2CH3
I
H3O+
O
A
CH3CH2
II
C CCH2CH2OH
III
CH3
C CCH2CH2OCH3
C COCHCH2CH3
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: C
Topic: Reactions and Reaction Sequences
17
...
What would be the product, O, of the following reaction sequence?
CH3CH2CHCH3
Mg
ether
Br
D2O
N
O
A) CH3CH2CH2CH3
B) CH3CH2CHCH3
C)
D
CH3CH2CHCH3
OD
D) CH3CH2CH2CH2OD
E) CH3CH2CH2CH2D
Ans: B
Topic: Reactions and Reaction Sequences
19
...
What is the product, A, that would be obtained from the following reaction sequence?
OH
PBr3
H3O+
heat
(CH3)2C=O
Mg, Et2O
A
OH
OH
I
II
III
HO
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: C
Topic: Reactions and Reaction Sequences
21
...
What is the final product of the following reaction sequence?
O
i)
Mg, Et2O
CH3I
H2CrO4
acetone
+
ii) H3O
A
O
OH
II
III
O
O
I
OH
O
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: E
408
Chapter 12
Topic: Reactions and Reaction Sequences
23
...
What would be the major product of the following reaction?
O
O
i) NaBH4
ii) ethylene oxide, HA
OH
I
HO
HO
O
O
O
III
II
O
A
O
OH
OH
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: A
Topic: Reactions and Reaction Sequences
25
...
What would be the major product of the following reaction?
Cl
A)
B)
C)
D)
E)
Li, Et2O
CuI
H
Br
CH3
A
(R)-3-ethyl-5-methylheptane
(R,S)-3-ethyl-5-methylheptane
(S)-3-ethyl-5-methylheptane
(3R,5S)-5-ethyl-3-methylheptane
(3S,5R)-5-ethyl-3-methylheptane
Ans: C
Topic: Reactions and Reaction Sequences
27
...
What is (are) the principal product(s) formed when 1 mol of ethylmagnesium bromide
reacts with 1 mol of 3-(N-methylamino)cyclopentanone ?
H
N
O
H3C
CH3
BrMgN
O
+ CH4
CH3CH2MgBr
H
N
H
N
CH2CH3
OMgBr
H3C
H
N
CH2CH3
N
OMgBr
O
H3C
IV
V
I
II
III
IV
V
Ans: A
Topic: Reactions and Reaction Sequences
29
...
What is the predominant product from the reaction of 2-hexanol with H2CrO4?
A) CH3CO2H
B) CH3(CH2)3CO2H
O
C)
CH3(CH2)3CCH3
D) CH3(CH2)4CO2H
E) A) and B)
Ans: C
Topic: Synthetic Strategy, Redox
31
...
Which of the reagents listed below would efficiently accomplish the transformation of
CH3CH2CH=CHCH2CH2CHO into CH3CH2CH2CH2CH2CH2CH2OH?
A) KMnO4
B) NaBH4
C) Br2 in CCl4
D) H2, Ni
E) Two of the above
Ans: D
Topic: Synthetic Strategy, Redox
33
...
Which of the reagents listed below would efficiently accomplish the transformation of
CH3CH2CH=CHCH2CH2CH2OH into CH3CH2CH=CHCH2CH2CHO ?
A) KMnO4(aq, alkaline)
B) CrO3 / H2SO4
C) PCC in CH2Cl2
D) Br2, CCl4
E) Two of the above
Ans: C
Topic: Synthetic Strategy
35
...
Which of the reagents listed below would efficiently accomplish the transformation of
3-methyl-3-cyclopentenone into 3-methyl-3-cyclopentenol?
OH
O
?
A)
B)
C)
D)
E)
i) LiAlH4; ii) H2O
NaBH4,H2O
H2, Pd
A) and B)
A), B) and C) of the above
Ans: D
414
Chapter 12
Topic: Synthetic Strategy, Redox
37
...
A)
B)
C)
D)
E)
When 2-pentanol is treated with chromic acid,
The color changes from orange to blue
The color changes from purple to colorless
The color changes from blue to red
The color changes from orange to green
The color changes from green to orange
Ans: D
Topic: Reactions and Reaction Sequences
39
...
A)
B)
C)
D)
E)
When 3-methyl-3-pentanol is treated with chromic acid,
The color changes from orange to blue
The color changes from purple to colorless
The purple color remains unchanged
The color changes from orange to green
The orange color remains unchanged
Ans: E
415
Chapter 12
Topic: Reactions and Reaction Sequences
41
...
NH3
HO
CH3CC
B)
NaNH2
CH
CCH3
CH3
OCH3
CH3CC
CCH3
CH3
OCH3
C)
D)
CH3C COCH2CHCH3
CH3
CH3CC
CONa
CH3
E) None of these
Ans: B
Topic: Reactions and Reaction Sequences
42
...
What product(s) is/are produced in the 1:1 reaction of sec-butylmagnesium bromide
with
OH
H
?
CH3CHCH2CH2C
OH
A)
O
OMgBr
CH3CHCH2CH2CHCCH2CH3
CH3
B)
OMgBr
H
+
CH3CH2CH2CH3
C)
CH3CHCH2CH2C
O
OH
OMgBr
D)
CH3CHCH2CH2CHCH2CH(CH3)2
H
OMgBr
O
E)
CH3CHCH2CH2C
H
CH3CHCH2CH2C
O
+
(CH3)3CH
OCHCH2CH3
CH3
Ans: B
417
Chapter 12
Topic: Reactions and Reaction Sequences
44
...
A)
B)
C)
D)
E)
The reaction of lithium di-sec-butylcuprate with isopentyl bromide yields:
2,5-Dimethylheptane
2,6-Dimethylheptane
3,5-Dimethylheptane
3,4-Dimethylheptane
3,6-Dimethylheptane
Ans: A
Topic: Reactions and Reaction Sequences
46
...
What compound(s) result(s) from the reaction of CH3CH2CH2MgBr with
CH3CH2CH2CH2CO2H (1:1 mole ratio)?
A) (CH3CH2CH2)2CCH2CH2CH2CH3
OH
O
B)
C)
CH3CH2CH2CCH2CH2CH2CH3
O
CH3CH2CH2CH2COCH2CH2CH3
D) CH3CH2CH3 + CH3CH2CH2CH2CO2MgBr
O O
E)
CH3CH2COCCH2CH2CH2CH3
Ans: D
Topic: Synthetic Strategy
C6H5
48
...
Which pairs
of compounds listed below would you choose as starting materials?
O
A)
CH3CH2CH2Br and
B)
C)
CH3CC6H5
O
CH3CH2CH2CH and C6H5Br
O
CH3CH2CHCH3
and
C6H5CH
Br
D) More than one of these
E) None of these
Ans: A
419
Chapter 12
Topic: Synthetic Strategy
49
...
Your task is to synthesize 2-phenyl-2-hexanol through a Grignard synthesis
...
How could the following synthesis be accomplished?
O
OH
CH2CH
A)
O
(1) SOCl2, (2) Mg, ether, (3) CH3CH, then H3O+
B) (1) SOCl2, (2) Li, ether, (3) (CH3CH2)2CuLi, (4) KMnO4, OHO
C)
1) PBr3, (2) Mg, ether, (3) CH2
D) More than one of the above
E) None of the above
Ans: C
CH2, then
420
H3O+ (4) PCC,CH2Cl2
Chapter 12
Topic: Synthetic Strategy, Redox
52
...
Select the correct reagent(s) for the following reaction:
O
OH
CH3CCH2CH2CO2CH3
A)
B)
C)
D)
E)
CH3CHCH2CH2CO2CH3
+
LiAlH4/ether; then H3O
NaBH4; then H3O+
H2 with Pt/C
B) and C)
A), B) and C)
Ans: D
Topic: Synthetic Strategy, Redox
54
...
Which method would give (CH3)2CC CH ?
A) CH3CHCH3
H2CrO4
NH4+
HC CNa
acetic
acid
CH3CH2Li
OH
B) CH3CCH3
C)
O
CH3CC
H3O+
H2CrO4
acetone
CH
2 CH3MgBr
NH4+
O
D) More than one of the above
E) None of the above
Ans: D
Topic: Synthetic Strategy
56
...
Ans: C
Topic: Synthetic Strategy
57
...
Which of these reactions will not produce a 1° alcohol?
1
...
H3O+
CH2
1
...
H3
1
...
H3O+
CH3CH2CH2CH2Li
CH3(CH2)5COOH
1
...
H3O+
1
...
H3O+
Ans: C
423
Chapter 12
Topic: Synthetic Strategy, Stereochemistry
59
...
Et2O
2
...
Et2O
2
...
Et2O
2
...
Which of the following reactions would serve as a reasonable synthesis of the following
racemic alcohol (2-phenyl-2-butanol)?
OH
CH3CC6H5
C2H5
O
A)
+
+
C6H5MgBr
2
...
Et2O
CH3CC6H5
O
C)
CH3MgBr
+
B)
1
...
NH4+
1
...
NH4+
CH3CC2H5
D) Answers A) and B) only
E) Answers A), B) and C)
Ans: E
Topic: Synthetic Strategy, Stereochemistry
61
...
Which reaction leads to an optically active product?
A)
+
NaBH
4
O
O
B)
ClMg
+
C)
H
CO2H
H2, Pt
+
D)
E)
+
H OH
H3C CHO
+
O
O
KMnO4
LiAlH4 / Et2O
(excess)
Ans: C
Topic: Acid/Base
63
...
A)
B)
C)
D)
Which of the following is the strongest base?
RMgX
Mg(OH)X
RH
H2O
Ans: A
Topic: Acid/Base
65
...
A)
B)
C)
D)
E)
Which reaction is an oxidation?
RCHO ⎯⎯⎯⎯→ RCO2H
RCH2OH ⎯⎯⎯⎯→ RCHO
RCH2OH ⎯⎯⎯⎯→ RCO2H
Two of these
All of these
Ans: E
Topic: Synthetic Strategy, Redox
67
...
Which reagent(s) is/are capable of reducing the following ester to a primary alcohol ?
O
O
A)
B)
C)
D)
E)
LiAlH4 / ether
NaBH4 / H2O
Na / C2H5OH
H2 / Ni, atmospheric pressure
All can be used successfully
...
Which reagent(s) is/are capable of reducing the following ester to an aldehyde ?
O
O
A)
B)
C)
D)
E)
LiAlH4 / ether
NaBH4 / H2O
Na / C2H5OH
H2 / Ni, atmospheric pressure
None of the above can be used successfully
...
A)
B)
C)
D)
Which of these transformations cannot be classified as a reduction?
RCH2Cl ⎯⎯⎯⎯→ RCH3
RCH=CH2 ⎯⎯⎯⎯→ RCH2CH3
RCOOH ⎯⎯⎯⎯→ RCH2OH
O
RCH2OH + R'OH
E) All of these are reductions
...
Which of these compounds cannot be reduced by sodium borohydride?
H
A)
B)
(CH3)2CHC
O
C)
O
CH3CH2CCH3
O
C6H5COH
D)
O
CH3(CH2)4COCH3
E) Neither C) nor D) can be reduced
...
A)
B)
C)
D)
E)
In the reaction of carbonyl compounds with LiAlH4, the effective reducing species is:
Li+
Al+3
AlH4AlH3
HAns: E
Topic: Redox, Reaction Mechanisms
73
...
B) the presence of H2SO4 limits the oxidation
...
D) aldehydes are not oxidized by the K2Cr2O7/H2SO4 mixture
...
Ans: C
Topic: Redox, Reaction Mechanisms
74
...
the oxidant isn't in a sufficiently high oxidation state
...
the intermediate chromate ester cannot lose hydrogen
...
Ans: D
429
Chapter 12
Topic: Synthetic Strategy, Redox
75
...
Ans: C
C6H5CCH2CH2CH2CH3
Topic: Synthesis of Grignards and Other Organometallics
76
...
Why is this difference in behavior observed?
A) Steric hindrance in the case of tetrahydrofuran precludes reaction with the Grignard
...
C) The oxirane ring is the more highly strained
...
E) Oxirane is a cyclic ether, while tetrahydrofuran is a hydrocarbon
...
Which of these compounds cannot be used to prepare the corresponding Grignard
reagent?
A) CH3OCH2CH2CH2Br
B) (CH3)3CCl
C) CH2=CHCH2Br
D) (CH3)2NCH2CH2Br
H
E)
O
CCH2CH2I
Ans: E
430
Chapter 12
Topic: Synthesis of Grignards and Other Organometallics
78
...
A)
B)
C)
D)
E)
Which of these is the least reactive type of organometallic compound?
RK
R2Hg
RLi
R2Zn
R3Al
Ans: B
Topic: Synthesis of Grignards and Other Organometallics
80
...
Which of these is most likely to be a successful synthesis of an organometallic
compound?
A) CH3CH2CH2MgBr + LiCl ⎯⎯⎯⎯→ CH3CH2CH2Li + MgBrCl
B) 2 CH3CH2CH2CH2Li + ZnCl2 ⎯⎯⎯⎯→ (CH3CH2CH2CH2)2Zn + 2 LiCl
C) 3 (CH3CH2)2Hg + 2 AlCl3 ⎯⎯⎯⎯→ 2 (CH3CH2)3Al + 3 HgCl2
D) (CH3CH2)3Al + 3 NaCl ⎯⎯⎯⎯→ 3 CH3CH2Na + AlCl3
E) (CH3)2Cu + MgBr2 ⎯⎯⎯⎯→ (CH3)2Mg + CuBr2
Ans: B
SHORT ANSWER QUESTIONS
Topic: General
82
...
Ans: nucleophilic
Topic: General, Redox
83
...
Ans: reduction
Topic: General, Redox
84
...
Ans: oxidation
Topic: General, Redox
85
...
Ans: lithium aluminum hydride
Topic: General, Redox
86
...
Ans: hydride ion
Topic: General, Redox Reagents
87
...
Ans: Jones reagent
432
Chapter 12
Topic: Functional Group Tests
88
...
Ans: orange; green
Topic: General
89
...
Ans: organometallic compounds
Topic: General
90
...
Ans: Grignard reagents
Topic: Synthesis of Grignards and Other Organometallics
91
...
Topic: Reactions of Grignards and Other Organometallics
92
...
Ans: Formaldehyde and ethylene oxide
Topic: Reactivity of Grignards and Other Organometallics
93
...
Ans: percent ionic character
Topic: Reactions of Grignards and Other Organometallics
94
...
Ans: Any aldehyde except formaldehyde
433
Chapter 12
Topic: Reactions of Grignards and Other Organometallics
95
...
Ans: tertiary
Topic: Reactions of Grignards and Other Organometallics
96
...
Ans: t-butyl alcohol: (CH3)3COH
Topic: Reactions of Grignards and Other Organometallics
97
...
OH
Ans:
3-phenyl-3-pentanol:
Topic: Reactions of Grignards and Other Organometallics
98
...
Ans: 3-methyl-3-pentanol CH3CH2C(CH3)(OH)CH2CH3
Topic: Redox Reactions
99
...
In the reaction of carbonyl compounds with NaBH4, the effective reducing species is:
Ans: H− (hydride)
Topic: Grignard Reactions
101
...
Under
strongly acid conditions, a tertiary alcohol product can undergo facile dehydration
to an alkene
...
Diethyl ether, the most commonly used solvent for Grignard reactions, also acts as an
‘internal cooling agent’, preventing the overheating of the reaction mixture: what
specific property of diethyl ether is exploited here and why is it important to prevent the
overheating of the reaction mixture?
Ans: Diethyl ether is very volatile (35-36oC): its low boiling point ensures that
reactions carried out in diethyl ether solvent cannot become overheated (the
maximum temperature cannot exceed the b
...
of the solvent): this is important in
Grignard reactions, because Grignard reagents decompose at higher temperatures
...
Topic: General
102
...
PCC and CrO3 are both Cr(VI) reagents
...
Why?
Ans: Both reagents first oxidize the alcohol to the corresponding aldehyde
...
When the solvent
is non-aqueous, such as CH2Cl2, these key intermediates cannot be formed,
thereby preventing further oxidation of aldehydes (with PCC/CH2Cl2)
...
What would be the major product, A, of the following reaction?
i) NaBH4
ii) NaH, Et2O
iii)
CF3
O
O
S
A
O
OCH2CH3
Ans:
O
435
Chapter 12
Topic: Multistep Synthetic Strategy
105
...
Ans: 3-hexanol- i) PCC; ii) CH3MgBr (or CH3Li); iii) NH4Cl
OH
O
PCC
CH2Cl2
i) CH3MgBr, Et2O
ii) NH4Cl
OH
Topic: Multistep Synthetic Strategy
106
...
Ans: 1-butanol i) PCC; ii) (CH3)2CHMgBr (or (CH3)2CHLi); iii) NH4Cl (H3O+)
HO
PCC
CH2Cl2
i) (CH3)2CHMgBr, Et2O
ii) NH4Cl
O
OH
Topic: Multistep Synthetic Strategy
107
...
Ans: 1-pentene i)MMPP; ii) CH3CH2MgBr (or CH3CH2Li); iii) NH4Cl (H3O+)
MMPP
O
i) CH3CH2MgBr, Et2O
ii) NH4Cl
OH
Topic: Multistep Synthetic Strategy
108
...
Ans: CH3CH2CH2CH2CO2H i)SOCl2; ii) 2 equivalents CH3CH2MgBr (or
CH3CH2Li); iii) NH4Cl (H3O+)
i) CH3CH2MgBr
O
O
OH
SOCl2
(2 equivalents), Et2O
HO
Cl
ii) NH4Cl
436
Chapter 12
Topic: Multistep Reaction Sequence
109
...
1-hexene-----------------i) HBr
ii) Li
iii) (CH3CH2)2C=O
iv) C2H5I
Br
Li
Ans:
HBr
Li
O
OLi
O
C2H5I
Topic: Multistep Reaction Sequence
110
...
2-methyl-1-pentene-----------------i) BH3, THF
ii) H2O2,NaOH
iii) PCC, CH2Cl2
iv) CH3CH2C≡C:−Na+
v) NH4Cl
Ans:
i) BH3,THF
HO
ii) H2O2, NaOH
PCC,
CH2Cl2
i)
HO
:− Na+
O
ii) NH4Cl
437
Chapter 12
Topic: Multistep Reaction Sequence
111
...
4-methyl-1-hexene-----------------i) BH3, THF
ii) H2O2,NaOH
iii) SOCl2
iv) Mg, Et2O
iv) ethylene oxide
v) NH4Cl
Ans:
i) BH3,THF
HO
ii) H2O2, NaOH
SOCl2
Mg
Et2O
ClMg
i)
Cl
O
ii) NH4Cl
HO
438
Chapter 12
Topic: Multistep Reaction Sequence
112
...
Bromocyclohexane-----------------i) Li
ii) CuI
iii) 4-methyl-1-bromohexane
Ans:
Br
Li
Li
CuI
Br
439
CuLi
2
Chapter 13
MULTIPLE CHOICE QUESTIONS
Topic: Nomenclature
1
...
What is an IUPAC name for this triene?
H
CH3CH2
A)
B)
C)
D)
E)
H H
CH3
H
H
H
(2E,4Z,6E)–2,4,6–Nonatriene
(2Z,4E,6Z)–2,4,6–Nonatriene
(2E,4Z,6Z)–2,4,6–Nonatriene
(3Z,5Z,7E)–3,5,7–Nonatriene
(3Z,5E,7E)–3,5,7–Nonatriene
Ans: C
Topic: Nomenclature
3
...
A correct IUPAC name of the compound below is:
Br
A)
B)
C)
D)
E)
1-Bromo-1-methyl-2,5-cyclohexadiene
3-Bromo-3-methyl-1,4-cyclohexadiene
6-Bromo-6-methyl-1,4-cyclohexadiene
2-Bromo-2-methyl-1,3-cyclohexadiene
None of these
Ans: B
Topic: Stability (Alkenes, Cations, Radicals)
5
...
A)
B)
C)
D)
E)
Which of the following dienes would you expect to be the most stable?
CH3CH2CH=CHCH2CH=CHCH3
CH3CH=CHCH=CHCH2CH3
CH2=CHCH2CH2CH2CH=CH2
CH2=CHCH=CHCH2CH2CH3
CH3CH2CH=C=CHCH2CH3
Ans: B
441
Chapter 13
Topic: Stability (Alkenes, Cations, Radicals)
7
...
Ans: A
Topic: Stability (Alkenes, Cations, Radicals)
8
...
CH3
H
H
H
H
H
I
A)
B)
C)
D)
E)
CH3
H
H
H
CH3
H
CH3
CH3
II
H
III
I
II
III
IV
V
Ans: A
442
H
H
CH3
CH3
H
H
H
CH3
IV
H
CH3
CH3
V
Chapter 13
Topic: Stability (Alkenes, Cations, Radicals)
9
...
Which diene would be least stable?
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
V
Ans: C
443
V
Chapter 13
Topic: Stability (Alkenes, Cations, Radicals)
11
...
I
II
IV
A)
B)
C)
D)
E)
III
V
V > II > I > III > IV
III > IV > II > I > V
IV > III > II > V > I
IV > III > I > II > V
I > II > IV > III > V
Ans: D
Topic: Stability (Alkenes, Cations, Radicals)
12
...
Which carbocation would be most stable?
CH2
CH3
CH3
CH3
I
A)
B)
C)
D)
E)
CH3
II
III
IV
V
I
II
III
IV
V
Ans: C
Topic: Stability (Alkenes, Cations, Radicals)
14
...
CH3
CH3
A)
B)
C)
D)
E)
CH
CH
CH
II III
Which hydrogen atom(s) of I
susceptible to abstraction by free radicals?
I
II
III
IV
V
Ans: D
IV
CH
CH
CH3
is/are most
Topic: Heat of Hydrogenation
16
...
A)
B)
C)
D)
E)
Which compound would have the shortest carbon-carbon single bond?
CH3–CH3
CH2=CH–CH3
HC≡C–C≡CH
CH2=CH–C≡CH
CH2=CH–CH=CH2
Ans: C
Topic: Bond Lengths
18
...
Which carbon-carbon bond in the following compound would you expect to be shortest?
H
A)
B)
C)
D)
E)
C
C
CH
I II
I
II
III
IV
V
Ans: A
CH
III
CH2
IV
CH3
V
447
Chapter 13
Topic: Bond Lengths
20
...
Select the structure of the conjugated diene
...
Select the structure(s) of the conjugated diene(s)
...
A)
B)
C)
D)
E)
Which of the following dienes is a cumulated diene?
CH2=CHCH2CH2CH=CH2
CH2=CHCH=CHCH2CH3
CH3CH=C=CHCH2CH3
CH3CH=CHCH=CHCH3
CH3CH=CHCH2CH=CH2
Ans: C
Topic: Alkene Classification
24
...
A)
B)
C)
D)
E)
The allyl radical has how many bonding π molecular orbitals?
1
2
3
4
5
Ans: A
Topic: Molecular Orbitals
26
...
A)
B)
C)
D)
E)
1,3-Pentadiene has how many bonding π molecular orbitals?
1
2
3
4
0
Ans: B
450
Chapter 13
Topic: Heat of Hydrogenation
28
...
Table 1
...
Which is not an example of resonance?
I
CH2=CH−CH2
...
CH2−CH=CH2
+
CH3
+
...
IV
A)
B)
C)
D)
E)
CH2−CH=CH−CH2CCl3
CH2=CH−CH−CH2CCl3
I
II
III
IV
None of these are examples of resonance
Ans: C
451
Chapter 13
Topic: Resonance
30
...
Which pair does not represent a pair of resonance structures?
H
I
H
H
H
H
and
H
H
H
H
H
II
III
IV
A)
B)
C)
D)
E)
H
H
H
H
H
and
H
CH2
CH2
H
H
H
and
and
H
CH2
CH3
I
II
III
IV
All of these represent pairs of resonance structures
...
A)
B)
C)
D)
E)
A thermodynamically-controlled reaction will yield predominantly:
the more/most stable product
...
the product that can be formed in the fewest steps
...
the product which possesses the greatest potential energy
...
A)
B)
C)
D)
E)
A reaction under kinetic (or rate) control will yield predominantly:
the most stable product
...
the product whose formation requires the smallest free energy of activation
...
the product with the least potential energy
...
The accompanying diagram, which describes the fate of the intermediate in a reversible
reaction, implies that:
E
B
A
A)
B)
C)
D)
E)
reaction coordinate
the less stable product forms more rapidly
...
product B will predominate at equilibrium
...
No conclusions can be drawn as to either reaction rate or product stability
...
The accompanying diagram implies that:
E
B
A
A)
B)
C)
D)
E)
reaction coordinate
The formation of B from A would be favored at high temperature
...
The formation of the intermediate from A is the rate-limiting step in the transformation
of A into B
The formation of B from A is not a concerted reaction
...
A)
B)
C)
D)
E)
Which is an untrue statement concerning the Diels-Alder reaction?
The reaction is a syn addition
...
Most Diels-Alder reactions are reversible
...
Depending on the nature of the dienophile, both electron-releasing and electronwithdrawing groups in the diene can favor adduct formation
...
A)
B)
C)
D)
E)
does not undergo the Diels-Alder reaction because:
ring systems cannot function as the diene component
...
it lacks electron-withdrawing groups
...
the two double bonds are further apart than in a non-cyclic conjugated system
...
A)
B)
C)
D)
E)
does not undergo the Diels-Alder reaction because:
ring systems cannot function as the diene component
...
it lacks electron-withdrawing groups
...
the two double bonds are further apart than in a non-cyclic conjugated system
...
A)
B)
C)
D)
E)
Which of these dienes is the most reactive in the Diels-Alder reaction?
1,3-Butadiene
1,4-Pentadiene
Cyclopentadiene
1,2-Butadiene
1,4-Cyclohexadiene
Ans: C
Topic: Diels-Alder Reaction
40
...
A)
B)
C)
D)
E)
Which of these dienes can undergo the Diels-Alder reaction?
1,2-Heptadiene
1,3-Heptadiene
1,4-Heptadiene
1,5-Heptadiene
1,6-Heptadiene
Ans: B
455
Chapter 13
Topic: Diels-Alder Reaction
42
...
Which diene would be least reactive toward Diels-Alder addition of maleic anhydride?
CH3
CH2
CH
CH
CH2
CH2
I
CH
C
CH2
CH2
II
IV
A)
B)
C)
D)
E)
CH3 CH3
456
C
III
V
I
II
III
IV
V
Ans: E
C
CH2
Chapter 13
Topic: Diels-Alder Reaction
44
...
How would you synthesize:
H
O
COCH3
O
O
O
I
1,3-Cyclohexadiene + CH2
CHCOCH3,
then
O
II
RCOOH
O
1,3-Cyclohexadiene + RCOOH,
then CH2
CHCOCH3,
O
COCH3
III
+
CH2
CH2
O
O
IV
1,4-Cyclohexadiene + CH2
CHCOCH3,
O
COCH3
V
+
CH2
CH2
O
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: A
458
CH2
CH2
then
O
Chapter 13
Topic: Diels-Alder Reaction
46
...
Which diene would you expect to react most rapidly with maleic anhydride?
O
CH3
CH3
CH3C
CH3
CH3
CH3C
O
I
A)
B)
C)
D)
E)
II
III
IV
V
I
II
III
IV
V
Ans: D
Topic: Diels-Alder Reaction
48
...
Which of these conjugated dienes can undergo a Diels-Alder reaction?
II
I
IV
A)
B)
C)
D)
E)
III
V
I and V
I, II and V
III
IV
III and IV
Ans: D
461
Chapter 13
Topic: Diels-Alder Reaction
50
...
Which diene and dienophile would you choose to synthesize the following compound?
H
CHO
H
CHO
CHO
CHO
I
CHO
CHO
II
III
OHC
CHO
CHO
A)
B)
C)
D)
E)
IV
I and VI
II and V
III and IV
IV and V
I and III
Ans: E
CHO
V
VI
463
Chapter 13
Topic: Diels-Alder Reaction
52
...
Which is the major product of the following reaction?
O
H
C
C
OH
?
+
C
H
C
O
OH
H
CO2H
I
A)
B)
C)
D)
E)
H
H
H
CO2H
CO2H
H
H
CO2H
CO2H
CO2H
H
CO2H
H
II
III
I
II
III
IV
None of these
Ans: D
464
CO2H
IV
Chapter 13
Topic: Diels-Alder Reaction
54
...
Which is the major product of the following reaction?
+
I
A)
B)
C)
D)
E)
H
CHO
CHO
H
CHO
H
CHO
H
H
CHO
H
CHO
II
?
CHO
OHC
III
I
II
III
IV
V
Ans: D
465
CHO
CHO
IV
CHO
CHO
V
Chapter 13
Topic: Diels-Alder Reaction
56
...
Which diene and dienophile would you choose to synthesize the following compound?
O
COCH3
O
O
COCH3
and O2
O
O
and
HC
I
C
II
O
O
and
O
CH2
CH
and
COCH3
CH2
III
A)
B)
C)
D)
E)
IV
I
II
III
IV
None of these
Ans: B
Topic: Diels-Alder Reaction
58
...
From the standpoint of reactivity, which is the poorest choice of dienophile to react with
2,3-dimethyl-1,3-butadiene in a Diels-Alder reaction?
O
O
I
O
II
H3CO
III
O
O
H3CO
O
OCH3
IV
A)
B)
C)
D)
E)
OCH3
O
V
I
II
III
IV
V
Ans: B
468
Chapter 13
Topic: Diels-Alder Reaction
60
...
Which would be the best synthesis of the following compound?
CO2CH3
CO2CH3
CO2CH3
CO2CH3
CO2CH3
+
+
+
CO2CH3
CO2CH3
I
CH3O2C
II
III
CO2CH3
+
+ 2 HCO2CH3
CO2CH3
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: B
470
Chapter 13
Topic: Diels-Alder Reaction
62
...
Which of the following pairs of compounds could be used as the basis for a Diels-Alder
synthesis of the compound shown below?
CO2CH3
CO2CH3
I
2 CH3CH
CHCH3
+
II
III
CH3CH
CH2
+
CH2
CHCO2CH3
+
CO2CH3
IV
A)
B)
C)
D)
E)
+
CH2
CHCO2CH3
I
II
III
IV
More than one of the above
Ans: D
472
Chapter 13
Topic: Multi-step Synthesis
64
...
How could the following synthesis be carried out?
A)
B)
C)
D)
E)
(1) Br2/CCl4; (2) CH3MgCl, ether; (3) CH3ONa/CH3OH
(1) HBr (1 eq); (2) (CH3)2CuLi, ether
(1) HBr (1eq); (2) Li, ether; (3) CuI; (4) CH3Br
More than one of the above
All of the above
Ans: C
Topic: Allylic Substitution
66
...
What product(s) would you expect from the following substitution reaction?
* Cl2
?
500oC
Cl
Cl
Cl
*
I
A)
B)
C)
D)
E)
*
II
Cl
*
III
*
IV
I
II
III
IV
More than one of the above
Ans: E
Topic: Synthesis of Allylic Halides
68
...
A)
B)
C)
D)
E)
Which of the following could be used to synthesize 3-bromocyclopentene?
Cyclopentene + Br2, CCl4 , 25o
Cyclopentene + NBS, CCl4 (ROOR)
3-Cyclopentenol + PBr3
Both A) and B)
Both B) and C)
Ans: E
474
Chapter 13
Topic: Synthesis of Allylic Halides
70
...
Treatment of 4-methylcyclohexene with N-bromosuccinimide in CCl4 would yield
mainly:
Br
Br
Br
Br
I
A)
B)
C)
D)
E)
II
III
I
II
III
IV
All of the above
Ans: E
475
IV
Chapter 13
Topic: Multistep Reactions
72
...
Which is the diene that yields on ozonolysis (O3, followed by Zn/HOAc) an equimolar
CHO
CH2
mixture of CH2O, CH3CHO, and CHO
CH2
CH
CH
CH
CH2
CH3
CH3
I
CH2
III
II
CH
CH2
CH
CH
CH3
CH2
IV
A)
B)
C)
D)
E)
CH
CH2
CH2
V
I
II
III
IV
V
Ans: D
476
CH
CH2
Chapter 13
Topic: Allylic Halogenation
74
...
A)
B)
C)
D)
E)
Which set of conditions does not result in allylic halogenation of an alkene?
Cl2 at 400°C
Cl2 in CCl4 at 25°C
Cl2, ROOR,hν
Br2 at low concentration in CCl4
N-Bromosuccinimide in CCl4, ROOR
Ans: B
Topic: Allylic Halogenation
CH3
76
...
Which carbon is predicted to be the major site of substitution when this alkene reacts
with NBS?
V
I
A)
B)
C)
D)
E)
III
IV
II
I
II
III
IV
V
Ans: B
Topic: Diene Synthesis
78
...
Ignoring stereochemistry, the 1:1 reaction of bromine with 1,3-cyclohexadiene at 25°C
in the dark and in the absence of peroxide forms which of these?
Br
Br
Br
Br
Br
I
A)
B)
C)
D)
E)
Br
II
III
Br
IV
I
II
III
IV
Both I and II
Ans: E
Topic: Conjugate Addition Reactions
80
...
Hot alumina can be used as an effective dehydrating agent: when 3-methyl-2,3pentanediol vapor is passed over hot alumina (Al2O3), the chief product to be expected
is which of these?
A) 2-Ethyl-1,3-butadiene
B) 3-Methyl-1,3-pentadiene
C) 3-Methyl-1,2-pentadiene
D) 3-Methyl-2,3-pentadiene
E) 3-Methyl-1,4-pentadiene
Ans: B
479
Chapter 13
Topic: Allylic Halogenation
82
...
Which of the following dienes might react with bromine in CCl4 to yield 2,5-dibromo-3hexene?
A) CH2=CHCH2CH2CH=CH2
B) CH2=CHCH=CHCH2CH3
C) CH3CH=C=CHCH2CH3
D) CH3CH=CHCH=CHCH3
E) CH3CH=CHCH2CH=CH2
Ans: D
Allylic Halogenation
84
...
A)
B)
C)
D)
E)
Treatment of 2-butene (cis or trans) with Cl2 at 400°C would yield mainly:
CH2ClCHClCH2CH3
CH3CHClCH2CH3
CH3CH=CClCH3
CH3CH=CHCH2Cl and CH3CHClCH=CH2
CH3CHClCHClCH3
Ans: D
Topic: Conjugate Addition Reactions
86
...
ClCH2CHCH2CH2CH
ClCH2CH
CH2
CHCH
CHCH2Cl
Cl
I
II
ClCH2CH
CHCH2CH
CH2
III
CH2
CHCH2CHCH
Cl
CH2
ClCH2CHCH2CH2CHCH2Cl
IV
A)
B)
C)
D)
E)
Cl
Cl
V
I and II
II and III
III and IV
IV and V
V and I
Ans: C
481
Chapter 13
Topic: 1,2 Reactions of Conjugated Dienes
87
...
A)
B)
C)
D)
E)
Which reagent would convert 1,3-octadiene into 3-octen-2-ol?
KMnO4/-OH
OsO4
H2O2, then H3O+
Cl2/H2O
H3O+
Ans: E
Topic: UV-Vis Spectroscopy
89
...
A)
B)
C)
D)
E)
Select the most energetically favorable UV transition for 1,3-butadiene
...
Which compound would have an UV absorption band at longest wavelength?
CH
CHCH
CH2
CH
I
CHCH
CH
II
CH2CH2CH
CH2
CHCH
CH2
III
CH
IV
A)
B)
C)
D)
E)
CH2
CHCH
CH2
V
I
II
III
IV
V
Ans: A
Topic: UV-Vis Spectroscopy
92
...
Which of the following compounds is not formed as a result of a chain-termination step
in the free radical chlorination of propene?
A) CH2=CHCH2Cl
B) Cl2
C) CH2=CHCH2CH2CH=CH2
D) HCl
E) All can be formed in chain-termination steps
...
Systems that have a p orbital on an atom adjacent to a double bond are called
______________ systems
...
The hydrogen atom on a saturated (sp3) carbon adjacent to a double bond is called an
______________ hydrogen
...
The hydrogen atom on a carbon that is part of a double bond is called a ___________
hydrogen
...
Allylic radicals are ___________ stable than tertiary radicals
...
Vinyl cations are _____________ stable than tertiary cations
...
There are three types of polyenes (molecules containing two or more double bonds)
...
Ans: conjugated, cumulated, isolated
Topic: General
100
...
Ans: conjugated
Topic: General
101
...
Ans: conjugation
Topic: General
102
...
Ans: thermodynamic
Topic: General
103
...
Ans: kinetic
Topic: General
104
...
Ans: diene; dienophile
Topic: General
105
...
Ans: the more/most stable product
...
A reaction under kinetic (or rate) control will yield predominantly:___________
...
485
Chapter 13
Topic: General
107
...
Ans: stereospecific; retention
Topic: General
108
...
Ans: allylic carbocations
Topic: Diels –Alder Reactions
109
...
Ans: endo
Topic: Nomenclature
110
...
Ans:
Topic: Nomenclature
111
...
Ans:
Topic: Nomenclature
112
...
CH3
Ans:
Br
486
Chapter 13
Topic: Multistep Reactions
113
...
O
heat
+
A
O
H2
Ni
B
Ans:
O
O
O
heat
+
+
O
O
O
H2, Ni
O
O
+
O
O
+
+
O
O
+
O
487
O
Chapter 13
Topic: Multistep Reactions
114
...
i) NBS
ii) (CH3)3COK, (CH3)3COH, heat
iii) trans CH3CH=CHCHO
?
Br
Ans:
(CH3)3COK,
(CH3)3COH,
heat
NBS
O
O
+
O
Topic: Multistep Reactions
115
...
i) cis-CH3CH=CHCHO
?
ii) CH3CH2MgBr
+
iii) H3O
Ans:
H
H
CHO
CH3
H
i) CH3CH2MgBr
CH3
H
ii) H3O+
O
HO
Topic: Diels Alder Reaction
116
...
O
O
O
O
Ans:
+
O
O
488
Chapter 14
MULTIPLE CHOICE QUESTIONS
Topic: Bonding and Resonance
1
...
B) All of the hydrogen atoms of benzene are equivalent
...
D) Only one o-dichlorobenzene has ever been found
...
Ans: C
Topic: Bonding and Resonance
2
...
All of the hydrogen atoms of benzene are equivalent
...
The benzene ring is a distorted hexagon
...
Ans: B
Topic: Bonding and Resonance
3
...
of equal length and are intermediate between a double bond and a single bond
...
due only to p-orbital overlap
...
Ans: B
Topic: Nomenclature, Bonding and Resonance
4
...
We now know that the two Kekule structures for benzene are related in the following
way:
A) They are each equally correct as a structure for benzene
...
C) The two structures are in a state of rapid equilibrium
...
E) None of the above
Ans: D
Topic: Nomenclature, Bonding and Resonance
6
...
A)
B)
C)
D)
E)
Which of the following statements regarding the cyclopentadienyl radical is correct?
It is aromatic
...
It obeys Huckel's rule
...
It has a closed shell of 6 pi-electrons
...
Which of the following would you expect to be aromatic?
H
H
A)
B)
C)
D)
E)
I
I
II
III
IV
V
Ans: E
II
III
IV
V
Topic: Aromaticity, Huckel Rule
9
...
Of the following C-10 compounds, which is expected to possess the greatest resonance
(delocalization) energy?
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
V
Ans: C
Topic: Aromaticity, Huckel Rule
11
...
Which compound would you NOT expect to be aromatic?
N
A)
B)
C)
D)
E)
I
I
II
III
IV
V
Ans: E
S
N
H
O
B
R
II
III
IV
V
Topic: Aromaticity, Huckel Rule
13
...
Which of the following would you expect to be aromatic?
A)
B)
C)
D)
E)
I
II
I
II
III
IV
All of these
Ans: A
III
IV
493
Chapter 14
Topic: Aromaticity, Huckel Rule
15
...
Which of the following structures would be aromatic?
K
-2
K
Br
Br
2K
A)
B)
C)
D)
E)
I
I
II
III
IV
V
Ans: B
II
III
494
IV
V
Chapter 14
Topic: Aromaticity, Huckel Rule
17
...
Which of the following would you expect to be aromatic?
H H
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
None of the above
Ans: C
495
Chapter 14
Topic: Aromaticity, Huckel Rule
19
...
On the basis of molecular orbital theory and Huckel's rule, which of these compounds
should be aromatic?
H H
A)
B)
C)
D)
E)
I
I
II
III
IV
V
Ans: E
II
III
IV
V
496
Chapter 14
Topic: Aromaticity, Huckel Rule
21
...
A) The ring system must be planar
...
C) There must be (4n + 2) π electrons
...
E) None
...
Ans: B
Topic: Aromaticity, Huckel Rule
22
...
In which case is the indicated unshared pair of electrons NOT a contributor to the π
aromatic system?
N
H
A)
B)
C)
D)
E)
O
N
I
II
I
II
III
IV
None of these
Ans: B
H
III
IV
497
Chapter 14
Topic: Chemical Tests and Reactions
24
...
Which reagent(s) would serve as the basis for a simple chemical test that would
distinguish between ethylbenzene and vinylcyclohexane?
A) H2CrO4
B) LAH
C) NaBH4, H2O
D) KMnO4, OH−, H2O
E) Two of the above
Ans: D
Topic: Chemical Tests and Reactions
26
...
Which reagent(s)/technique would serve to distinguish between azulene and
bicyclo[5
...
0]decane?
A)
B)
C)
D)
E)
Br2, CCl4
KMnO4, OH−, H2O
NMR Spectroscopy
UV Spectroscopy
Two of these
Ans: E
498
Chapter 14
Topic: Chemical Tests and Reactions
28
...
A)
B)
C)
D)
E)
Which dibromobenzene can, in theory, yield three mononitro derivatives?
o-Dibromobenzene
m-Dibromobenzene
p-Dibromobenzene
All of these
None of these
Ans: B
Topic: Nomenclature and Isomerism
30
...
2-Bromo-4-nitroaniline is:
Br
Br
NH2
NO2
Br
NO2
NH2
NO2
I
II
H2N
III
OCH3
Br
Br
H3CO
NO2
IV
A)
B)
C)
D)
E)
NO2
V
I
II
III
IV
V
Ans: C
Topic: Nomenclature and Isomerism
32
...
4-Amino-2-chlorophenol is:
Cl
OH
Cl
O
O
Cl
NH2
NO2
I
II
H2N
III
OH
OH
Cl
Cl
NH2
IV
A)
B)
C)
D)
E)
NO2
V
I
II
III
IV
V
Ans: D
Topic: Nomenclature and Isomerism
34
...
4-amino-2-chlorobenzaldehyde is:
Cl
OH
Cl
O
O
Cl
NH2
NO2
I
II
H2N
III
OH
OH
Cl
Cl
NH2
IV
A)
B)
C)
D)
E)
NO2
V
I
II
III
IV
V
Ans: C
Topic: Nomenclature and Isomerism
36
...
4-bromomethyl-2-nitroanisole is:
Br
Br
Br
OCH3
O
H3CO
NH2
NO2
I
II
H2N
III
OCH3
Br
OCH3
Br
NH2
IV
A)
B)
C)
D)
E)
NO2
V
I
II
III
IV
V
Ans: B
Topic: Nomenclature and Isomerism
38
...
The correct name for the compound shown below is:
Br
Br
NH2
A)
B)
C)
D)
E)
3,4-Dibromoaniline
2,4-Dibromoaniline
2,5-Dibromoaniline
3,6-Dibromoaniline
2,6-Dibromoaniline
Ans: C
503
Chapter 14
Topic: Nomenclature and Isomerism
40
...
A dichlorobenzene that on reaction with nitric acid and sulfuric acid might theoretically
yield three mononitro products would be:
A) o-Dichlorobenzene
B) m-Dichlorobenzene
C) p-Dichlorobenzene
D) None of these
E) All of these
Ans: B
Topic: Nomenclature and Isomerism
42
...
Butylbenzene
Isobutylbenzene
sec-Butylbenzene
tert-Butylbenzene
None of these
Ans: C
504
Chapter 14
Topic: Nomenclature and Isomerism
43
...
A)
B)
C)
D)
E)
Toluene is the name commonly assigned to:
Hydroxybenzene
Aminobenzene
Methylbenzene
Ethylbenzene
Methoxybenzene
Ans: C
Topic: Nomenclature and Isomerism
45
...
A)
B)
C)
D)
E)
Phenol is the name commonly assigned to:
Hydroxybenzene
Aminobenzene
Methylbenzene
Ethylbenzene
Methoxybenzene
Ans: A
Topic: Nomenclature and Isomerism
47
...
The complete name for the following compound is:
CH3
H
A)
B)
C)
D)
E)
sec-Hexylbenzene
2-Phenylhexane
(R)-2-Phenylhexane
(S)-2-Phenylhexane
Butylmethylphenylmethane
Ans: D
Topic: Nomenclature and Isomerism
49
...
Which of these is the single best representation for naphthalene?
II
I
IV
A)
B)
C)
D)
E)
III
V
I
II
III
IV
V
Ans: A
Topic: Molecular Orbital Theory
51
...
In the molecular orbital model of benzene, the six p-orbitals combine to form how many
molecular orbitals?
A) 6
B) 5
C) 4
D) 3
E) 2
Ans: A
507
Chapter 14
Topic: Molecular Orbital Theory
53
...
In the ground state how many
molecular orbitals are filled with electrons?
A) 1
B) 2
C) 3
D) 4
E) 5
Ans: C
Topic: Molecular Orbital Theory
54
...
In the molecular orbital model of benzene, how many pi-electrons are in bonding
molecular orbitals?
A) 6
B) 5
C) 4
D) 3
E) 2
Ans: A
Topic: Molecular Orbital Theory
56
...
In the ground state
how many molecular orbitals are filled with electrons?
A) 1
B) 2
C) 3
D) 4
E) 5
Ans: C
508
Chapter 14
Topic: Molecular Orbital Theory
57
...
In the molecular orbital model of cyclopentadienyl anion, how many pi-electrons are in
bonding molecular orbitals?
A) 6
B) 5
C) 4
D) 3
E) 2
Ans: A
Topic: Molecular Orbital Theory
59
...
In the molecular orbital model of cycloheptadienyl cation, how many pi-electrons are
delocalized about the ring?
A) 6
B) 5
C) 4
D) 3
E) 2
Ans: A
509
Chapter 14
Topic: Molecular Orbital Theory
61
...
In the molecular orbital model of which of the following substance(s) are non-bonding
orbitals found?
A) 1,3-Cyclobutadiene
B) Cyclopentadienyl anion
C) 1,3,5,7-Cyclooctatetraene
D) Two of the above
E) All of the above
Ans: D
Topic: Molecular Orbital Theory
63
...
Application of the polygon-and-circle technique reveals that single electrons occupy
each of the two nonbonding orbitals in the molecular orbital diagram of:
A) Cyclobutadiene
B) Benzene
C) Cyclopropenyl cation
D) Cyclopentadienyl anion
E) Cycloheptatrienyl cation
Ans: A
Topic: Explanations and Predictions
65
...
Hydrogen is a small molecule
...
It would gain considerable stability by becoming benzene
...
Ans: D
Topic: Explanations and Predictions
66
...
The compound rapidly decolorizes aqueous solutions of KMnO4
...
The compound is nonplanar
...
Ans: E
Topic: Explanations and Predictions
67
...
An explanation for this is the
following statement
...
B) Cyclopentadiene is aromatic
...
D) Removal of a hydrogen atom from cyclopentadiene yields a highly stable free radical
...
Ans: C
511
Chapter 14
Topic: Explanations and Predictions
68
...
3
4
5
6
2
7
1
8
10
A)
B)
C)
D)
E)
9
1, 2
1, 4
3, 4
7, 8
9, 10
Ans: E
Topic: Spectroscopy
69
...
Which of these compounds absorbs at the longest wavelength in the UV-visible region?
I
A)
B)
C)
D)
E)
II
III
IV
V
I
II
III
IV
V
Ans: B
Topic: Spectroscopy
71
...
Its 1H NMR spectrum consists of:
doublet, δ 2
...
15
multiplet, δ 7
...
Which is a possible structure for
the compound?
Br
Br
Br
II
I
III
Br
Br
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: D
513
Chapter 14
Topic: Spectroscopy
72
...
8
triplet, δ 4
...
2
Br
Br
Br
II
I
III
Br
Br
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: C
514
Chapter 14
Topic: Spectroscopy
73
...
2
quartet, δ 2
...
4
Br
Br
Br
II
I
III
Br
Br
IV
A)
B)
C)
D)
E)
V
I
II
III
IV
V
Ans: A
515
Chapter 14
Topic: Spectroscopy
74
...
45
singlet, δ 2
...
35
Br
Br
Br
II
I
III
Br
Br
V
IV
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: E
Topic: Spectroscopy
75
...
Which of the following substances, C9H10O, would exhibit seven signals in its 13C NMR
spectrum?
O
O
O
I
II
III
HO
O
V
IV
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: A
Topic: Spectroscopy
77
...
In the 1H NMR spectra of which of the following substances, C9H10O, would you expect
to see two singlets in the range of δ 2
...
5 ppm?
O
O
I
O
II
III
HO
O
IV
A)
B)
C)
D)
E)
V
I and III
I, II, and III
IV
V
All of the above substances would exhibit two singlets δ 2
...
5 ppm in their 1H NMR
spectra
Ans: B
SHORT ANSWER QUESTIONS
Topic: General Concepts
79
...
Ans: aliphatic, aromatic
Topic: Nomenclature
80
...
Ans: phenyl
Topic: General Concepts
81
...
Ans: resonance energy
518
Chapter 14
Topic: General Concepts
82
...
Ans: degenerate
Topic: Huckel’s rule
83
...
Ans: 4n+2
Topic: General Concepts
84
...
Ans: annulenes
Topic: General Concepts
85
...
Ans: fullerenes
Topic: Aromaticity, Reactivity
86
...
Ans: part of the aromatic system
Topic: General Concepts
87
...
Therefore,
two amino acids, _____________ and ___________, are essential to the human diet
...
Benzene, while unusually unreactive, will react under certain conditions
...
Ans: substitution
519
Chapter 14
Topic: Nomenclature
89
...
Draw the structure corresponding to the following name:
3-bromo 5-phenylacetophenone
NH2
Ans:
Br
Topic: Nomenclature
91
...
Draw the structure corresponding to the following name: 3-nitro-4-iodoanisole
O
Ans: O2N
I
Topic: Nomenclature
93
...
Draw all significant resonance structures for pyridine, C6H5N
Ans:
N
...
520
Chapter 14
Topic: Resonance
95
...
Briefly explain why the aromatic hydrocarbon azulene, C10H8, possesses a significant
dipole moment
...
Ans: Azulene has the bicyclic structure shown below
...
However, closer scrutiny suggests that a shift in
electron density, in which the 7-membered ring is electron deficient and the 5membered ring is electron-rich would be especially stable: each ring is now
independently aromatic, an aromatic cycloheptatrienyl cation fused with an
aromatic cyclopentadienyl anion
...
non-polar
polar
Topic: Aromaticity, Molecular Orbital Theory
97
...
How is this diagram useful in
explaining the aromatic properties of this anion?
Ans: The following MO diagram can be generated using the polygon-in-circle method
...
Antibonding MO
Bonding MO
6 pi electrons
"closed bonding shell"
521
Chapter 14
Topic: Aromaticity, Reactivity
H
...
Explain briefly why cyclopentadiene readily reacts with strong bases
...
The conjugate base of cyclopentadiene, formed during reaction
with a base, is exceptionally stable, by virtue of being an aromatic anion (6 pi
electrons, planar ring), thus accounting for the readiness with which
cyclopentadiene reacts with bases
...
Although all bond lengths in benzene are identical, that is not always true for all
aromatic compounds
...
Explain, using resonance theory
...
The observed
bond lengths reflect the contribution of each structure to the overall resonance
hybrid:
The C1-C2 bond: two double bonds (I and II), and one single bond (III)
The C2-C3 bond: one double bond (III), and two single bonds (I and II)
Overall: C1-C2 bond more double-bond-like, thus shorter
...
The heats of hydrogenation for cyclohexene and benzene are given below
...
C6H12
ΔHo = -120 kJ/mol
C6H10 + H2
C6H6 + 3H2
C6H12
ΔHo = -208 kJ/mol
Ans: The resonance stabilization energy of benzene is the difference between the
theoretical and observed ΔHo values
...
Thus, the theoretical ΔHo for benzene
can be calculated as [3x (-120)] kJ/mol = -360 kJ/mol
Therefore,
Resonance stabilization energy of benzene = (-208) – (-360) kJ/mol
= 152 kJ/mol
523
Chapter 14
Topic: Aromaticity, Reactivity
101
...
However, only
pyridine reacts readily with HCl to form pyridinium chloride, while pyrrole is rather
unreactive
...
Ans:
+ HCl
N+ −
Cl
H
N
...
N H
+ HCl
H
−
N + Cl
H
X
not aromatic
pyrrole
electron pair:
part of aromatic pi sextet
Both pyridine and pyrrole are known to exhibit aromatic properties; the nitrogen
atom must therefore be sp2 hybridized in both cases
...
By contrast, the electron pair in pyrrole must be placed in the p orbital, since all
three sp2 orbitals are used in sigma bonds with neighboring atoms
...
Thus, the electron pair on nitrogen is not “available” for reacting
with HCl, because doing so would destroy the aromaticity of the ring
...
Consider the oxygen atom in the molecules of furan and tetrahydrofuran
...
...
O
...
...
Furan
Ans:
THF
p
...
...
sp
3
sp
3
3
Furan: sp hybridized
one electron pair in p orbital:
Tetrahydrofuran: sp hybridized
both electron pairs
part of aromatic pi sextet
in sp orbitals
3
Oxygen has 2 lone electron pairs in both species and, at first glance, it might
appear that the hybridization patterns are identical
...
In furan, there
are two possibilities that must be considered: i) the oxygen may be sp3 hybridized,
with both electron pairs sp3 hybrid orbitals, as in THF, or, ii) oxygen may be sp2
hybridized, with one electron pair in an sp3 hybrid orbital, the other in a p orbital
...
Since furan is
known to exhibit markedly aromatic properties, the oxygen must be sp2
hybridized
...
The major product(s), A, of the following reaction,
Cl2, hν
CH3CH2
CH3CH2
A
400 - 600 oC
Cl
CH3CH2
ClCH2CH2
CH3CH
Cl
Cl
I
II
III
IV
would be:
A) I
B) II
C) A mixture of I and II
D) III
E) IV
Ans: E
Topic: Reaction Products
2
...
The major product(s), C, of the following reaction,
Cl
Cl
Cl
SO3
H2SO4
C
Cl
Cl
SO3H
Cl
I
Cl
SO3H
HO3S
II
Cl
III
would be:
A) I
B) II
C) III
D) Equal amounts of I and II
E) Equal amounts of I and III
Ans: B
527
Chapter 15
Topic: Reaction Products
4
...
What would be the product of the following reaction sequence?
OH
i) SOCl2
?
ii) C6H6, AlCl3
O
iii) Zn(Hg), HCl, heat
O
O
OH
OH
II
I
IV
A)
B)
C)
D)
E)
Ans:
III
V
I
II
III
IV
V
E
529
Chapter 15
Topic: Reaction Products
6
...
What would be the major product of the following reaction?
Cl2
CH2CH2CH3
Cl
CH2CH2CH3
400 oC
?
CH2CH2CH3
Cl
Cl
I
II
CH2CHCH3
III
CH2CH2CH2Cl
Cl
IV
A)
B)
C)
D)
E)
Ans:
CHCH2CH3
V
I
II
III
IV
V
C
530
Chapter 15
Topic: Reaction Products
8
...
What would you expect to be the major product obtained from the following reaction?
O
HNO3
H2SO4, heat
HN
O
HN
II
HN
NO2
O
HN
O
O2N
?
III
O2N
I
O
O
HN
HN
IV
A)
B)
C)
D)
E)
Ans:
NO2
V
I
II
III
IV
V
E
531
NO2
Chapter 15
Topic: Reaction Products
10
...
What would you expect to be the major product obtained from the mononitration of mdichlorobenzene?
Cl
Cl
Cl
NO2
Cl
I
A)
B)
C)
D)
E)
Ans:
Cl
NO2
O2N
Cl
II
III
I
II
III
Equal amounts of I and II
Equal amounts of I, II and III
B
532
Chapter 15
Topic: Reaction Products
12
...
What product would result from the following series of reactions,
i) AlCl3
Cl
ii) N-Bromosuccinimide, peroxides
?
+
iii) CH3ONa, CH3OH, heat
iv) MMPP
v) CH3MgBr
vi) NH4Cl
Br
HO
HO
I
II
HO
IV
A)
B)
C)
D)
E)
Ans:
III
HO
V
I
II
III
IV
V
D
534
Chapter 15
Topic: Reaction Products
14
...
What would be the major product of the following reaction?
NBS, ROOR
?
light
Br
Br
Br
I
II
III
Br
Br
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
C
Topic: Reaction Products
16
...
Which would be the product, X, of the following reaction sequence?
O
i) SOCl2
?
OH ii) benzene, AlCl3
iii) Zn(Hg), HCl
SO2
CO2
CH2
I
II
III
O
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
C
537
Chapter 15
Topic: Reaction Products
18
...
When toluene is reacted in turn with 1) Cl2 (large excess), heat, and light and 2)
Br2,FeBr3, the chief product is:
Br
CCl3
CCl3
CCl3
Br
Br
Cl
I
A)
B)
C)
D)
E)
Ans:
Br
II
III
IV
I
II
III
IV
A mixture of III and IV
B
538
Chapter 15
Topic: Reaction Products
20
...
What might be predicted to happen when the following substance undergoes FriedelCrafts acylation?
O2N
A)
B)
C)
D)
E)
Ans:
CH2
A
B
Substitution occurs in ring B, p- to the methylene group
Substitution occurs in ring A, o- to the nitro group
Substitution occurs in ring A, o- to the methylene group
Substitution occurs in ring B, m- to the methylene group
None of the above
...
A
539
Chapter 15
Topic: Nomenclature, Reaction Products
22
...
5 mol) in the presence of trace amounts of FeBr3
...
What is the chief product of the Friedel-Crafts alkylation of benzene with 1-butene and
AlCl3?
A) butylbenzene
B) 2-phenylbutane
C) 2-methyl-1-phenylpropane
D) t-butylbenzene
E) 2,2-diphenylbutane
Ans: B
540
Chapter 15
Topic: Reaction Products
24
...
e
...
Which reagent(s) would you use to carry out the following transformation?
toluene ⎯⎯⎯→ benzoic acid
A) Br2, heat, and light
B) Cl2, FeCl3
C) KMnO4, OH-, heat (then H3O+)
D) HNO3/H2SO4
E) SO3/H2SO4
Ans: C
541
Chapter 15
Topic: Reagents
26
...
Which reagent(s) would you use to carry out the following transformation?
isopropylbenzene ⎯⎯⎯→ 2- and 4-chloro-1-isopropylbenzene
A) Cl2, light, and heat
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E) HCl, peroxides
Ans: B
Topic: Reagents
28
...
Which reagent(s) would you use to carry out the following transformation?
ethylbenzene ⎯⎯⎯⎯→ benzoic acid
A) Cl2, light, and heat
B) Cl2, FeCl3
C) KMnO4, OH-, heat (then H3O+)
D) HNO3/H2SO4
E) SO3/H2SO4
Ans: C
542
Chapter 15
Topic: Reagents
30
...
Which reagent(s) would you use to carry out the following transformation?
t-butylbenzene ⎯⎯⎯→ p-chloro substitution product
A) Cl2, light, and heat
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E) HCl, peroxide
Ans: B
Topic: Reagents
32
...
Which reagent(s) would you use to synthesize 2- and 4-bromo-1-cyclopentylbenzene
from cyclopentylbenzene?
A) N-Bromosuccinimide (NBS), CCl4, light
B) PBr3
C) Br2, FeBr3
D) CH3CH2Br, AlBr3
E) HBr, ROOR
Ans: C
543
Chapter 15
Topic: Reagents
34
...
Which reagent would you use as the basis for a simple chemical test that would
distinguish between toluene and vinylbenzene (C6H5CH=CH2)?
A) NaOH/H2O
B) Br2/CCl4
C) NaBH4
D) HCl/H2O
E) NaI in acetone
Ans: B
Topic: Nomenclature, Functional Group Tests
36
...
H2SO4
Ans: C
544
Chapter 15
Topic: Nomenclature, Synthesis
37
...
Ans: C
Topic: Synthesis
38
...
B) CH3Cl/AlCl3; then HNO3/H2SO4; then separation of isomers; then KMnO4/
OH/heat, followed by H3O+
...
D) HNO3/H2SO4; then KMnO4/-OH/heat, followed by H3O+; then CH3Cl/AlCl3
...
Ans: B
545
Chapter 15
Topic: Synthesis
39
...
Which would be a good synthesis of m-nitrobenzoic acid?
A)
HNO3/H2SO4
CH3Cl
1
...
H3O+
B)
Toluene
C)
Toluene
HNO3/H2SO4
1
...
H3O+
1
...
H3O+
D) More than one of the above
E) None of the above
Ans: C
heat
546
Chapter 15
Topic: Synthesis
41
...
Which of the following reactions would yield isopropylbenzene as the major product?
CH3CH CH2
A)
Benzene
H2SO4
CH3CHCH3
B)
Benzene
H2SO4
CH3CHCH3
C)
Benzene
D)
OH
Benzene
Cl
AlCl3
CH3CH2CH2Cl
AlCl3
E) All of these
Ans: E
Topic: Synthesis
43
...
Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane?
A) C6H5CH2CH3 + Cl2, Fe ⎯⎯→
B) C6H5CH2CH3 + Cl2, 400°C ⎯⎯→
C) C6H5CH2CH2OH + SOCl2 ⎯⎯→
D) C6H5CH=CH2 + HCl, peroxide ⎯⎯→
E) C6H6 + CH3CH2Cl, AlCl3 ⎯⎯→
Ans: C
Topic: Synthesis
45
...
How might the following synthesis be carried out:
CH2CH3
Benzene
A)
B)
C6H6
several
steps
CH3CH2Cl
C6H6
AlCl3
Cl2
FeCl3
?
Cl
Cl2
FeCl3
CH3CH2Cl
AlCl3
product
product
O
C)
C6H6
CH3CCl
Cl2
Zn(Hg)
AlCl3
FeCl3
HCl
Zn(Hg)
Cl2
product
O
D)
C6H6
CH3CCl
HCl
AlCl3
E) None of these syntheses is satisfactory
...
Which is the best sequence of reactions for the preparation of p-bromostyrene from
ethylbenzene?
A)
NBS, hν
Br2
KOH
product
ethylbenzene
Fe
CCl4
CH3CH2OH
B)
NBS, hν
Br2
KOH
product
ethylbenzene
Fe
CCl4
CH3CH2OH
C)
NBS, hν
KOH
Br2
product
ethylbenzene
Fe
CCl4
CH3CH2OH
ZnO
Br2
D)
product
ethylbenzene
Fe
630 oC
E) None of these syntheses is satisfactory
...
Which is the best sequence of reactions for the following transformation?
O
NO2
A)
B)
C)
D)
E)
Ans:
i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H3O+, heat
i) CH3MgBr, Et2O; ii) H3O+, heat; iii) HNO3, H2SO4
i) HNO3, H2SO4; ii) NaBH4, H2O; iii) H3O+, heat
i) HNO3, H2SO4; ii) NaBH4, H2O; iii) H3O+, heat
None of these syntheses is satisfactory
...
Which is the best sequence of reactions for the following transformation?
OH
O
OCH3
NO2
A)
B)
C)
D)
E)
Ans:
i) HNO3, H2SO4; ii) 2EtMgBr, Et2O; iii) NH4Cl
i) 2EtMgBr, Et2O; ii) H3O+; iii) HNO3, H2SO4
i) HNO3, H2SO4; ii) NaBH4, H2O; iii) 2EtMgBr, Et2O
i) LAH; ii) 2EtLi, Et2O; iii) HNO3, H2SO4, heat
None of these syntheses is satisfactory
...
Which is the best sequence of reactions for the following transformation?
O
OH
NO2
A)
B)
C)
D)
E)
Ans:
i) SOCl2; ii) C6H6, AlCl3; iii) Zn(Hg),HCl; iv) HNO3, H2SO4
i) SOCl2; ii) HNO3, H2SO4; iii) C6H6, AlCl3; iv) H2, Ni
i) HNO3, H2SO4; ii) SOCl2; iii) C6H6, AlCl3; iv) Zn(Hg),HCl
i) PBr3; ii) HNO3, H2SO4; iii) C6H6, AlCl3; iv) NaBH4, H2O
two of these syntheses are satisfactory
...
Which of the following compounds would be most reactive toward electrophilic
substitution?
OH
CH3
I
II
A)
B)
C)
D)
E)
Ans:
Br
CHO
IV
III
NO2
V
I
II
III
IV
V
A
Topic: Relative Reactivities
52
...
Which of the following compounds would you expect to be most reactive toward ring
nitration?
A) Benzene
B) Toluene
C) m-Xylene
D) p-Xylene
E) Benzoic acid
Ans: C
551
Chapter 15
Topic: Relative Reactivities
54
...
Which of the following compounds would be most reactive toward ring nitration?
O
O
O
I
A)
B)
C)
D)
E)
Ans:
II
CF3
552
NH
IV
III
I
II
III
IV
V
D
OH
V
Chapter 15
Topic: Relative Reactivities
56
...
Which of the following compounds would be most reactive toward ring bromination?
O
HO
O
O
NH2
OCH3
O
O
O
II
I
A)
B)
C)
D)
E)
Ans:
IV
III
I
II
III
IV
V
C
553
V
Chapter 15
Topic: Relative Reactivities
58
...
Which of the following structures contribute(s) to the resonance hybrid of the
intermediate formed when bromobenzene undergoes para-chlorination?
...
...
: Br :
: Br +
: Br :
: Br :
+
+
+
H Cl
H Cl
H Cl
H Cl
I
II
III
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
All of the above
E
554
Chapter 15
Topic: Mechanisms and Intermediates
60
...
Consider the structures given below
...
Which of the following structures does not contribute to the resonance hybrid of the
intermediate formed when nitrobenzene undergoes meta-chlorination?
...
...
...
:O : O:
: O : O:
: O : O:
N
N
+
I
A)
B)
C)
D)
E)
Ans:
H
Cl
+
N
+
H
Cl
II
H
Cl
III
I
II
III
None of these contribute
All of these contribute
...
Which of these is the rate-determining step in the nitration of benzene?
A) Protonation of nitric acid by sulfuric acid
B) Protonation of sulfuric acid by nitric acid
C) Loss of a water molecule by the protonated species to produce the nitronium ion
D) Addition of nitronium to benzene to produce the arenium ion
E) Loss of a proton by arenium ion to form nitrobenzene
Ans: D
Topic: Directing Effects
64
...
Which of the following is not a meta-directing substituent when present on the benzene
ring?
A) -NHCOCH3
B) -NO2
C) -N(CH3)3+
D) -C≡N
E) -CO2H
Ans: A
Topic: Directing Effects
66
...
In which of these cases
does the arrow not indicate the chief position of nitration
...
Which of the following compounds would yield the greatest amount of meta product
when subjected to ring nitration?
HO
O
HO
O
HO
O
I
A)
B)
C)
D)
E)
Ans:
O
O
HO
OH
II
IV
III
V
I
II
III
IV
V
A
Topic: Directing Effects
68
...
Which of these compounds gives essentially a single product on electrophilic
substitution of a third group?
A) p-chlorotoluene
B) m-ethylanisole
C) 1-bromo-2-chlorobenzene
D) m-xylene
E) 3-hydroxybenzoic acid
Ans: D
558
Chapter 15
Topic: Directing Effects
70
...
B) The atom attached to the aromatic ring possesses an unshared pair of electrons
...
D) The atom directly attached to the aromatic ring is more electronegative than
carbon
...
Ans: C
Topic: Directing Effects
71
...
(Trifluoromethyl)benzene, C6H5CF3, will
A) nitrate rapidly in the ortho-para positions
...
C) nitrate rapidly in the meta position
...
E) fail to nitrate under any conditions
...
What feature is common to all meta-directing groups?
A) The atom directly attached to the ring has a full or well-developed partial positive
charge
...
C) One or more halogen atoms are present in the group
...
E) The group is attached to the ring through a carbon atom
...
Arrange the following compounds in order of decreasing reactivity in electrophilic
substitution:
O
I
A)
B)
C)
D)
E)
Ans:
O
II
V > II > I > III > IV
II > V > III > I > IV
IV > I > III > V > II
III > II > I > IV > V
IV > V > II > I > III
B
Br
NO2
IV
III
V
Topic: Other EAS Considerations
75
...
Ans: A
Topic: Other EAS Considerations
76
...
This molecule cannot participate as a reactant in a Friedel-Crafts reaction
...
Which one of these molecules can be a reactant in a Friedel-Crafts reaction?
A) Aniline
B) Nitrobenzene
C) Chloroethene
D) Bromobenzene
E) p-Bromonitrobenzene
Ans: D
Topic: Other EAS Considerations
79
...
A) -OCH2CH3
B) -NO2
C) -F
D) -CF3
E) -NHCOCH3
Ans: C
Topic: Other EAS Considerations
80
...
B) Positively charged species
...
D) Proton
...
Ans: C
561
Chapter 15
Topic: Other EAS Considerations
81
...
B) A Lewis base
...
D) Peroxide
...
Ans: C
Topic: Non-EAS Reactions
82
...
SN1 solvolysis of C6H5CH=CHCH2Cl in water produces:
A) C6H5CH2C(OH)=CH2
B) C6H5CH=CHCH2OH
C) C6H5CHOHCH=CH2
D) A mixture of B) and C)
E) A mixture of A), B) and C)
Ans: D
562
V
Chapter 15
Topic: Non-EAS Reactions
84
...
Which alkyl halide can undergo both SN1 and SN2 reactions in nonacidic solvents?
A) CH3Br
B) CH3CH2CH2Br
CH2
CHCHCH3
C)
Br
D)
E)
C6H5CH2CH2CH2Br
CH3
C6H5CCH2Br
CH3
Ans: C
Topic: Non-EAS Relative Rates and Intermediates
86
...
Which of the following structures would not be a contributor to the resonance hybrid of
the benzyl cation?
CH3
H
H
+
I
A)
B)
C)
D)
E)
Ans:
CH3
+CH2
CH2
+
CH3
+
+
II
IV
III
IV
I
II
III
IV
V
A
Topic: Non-EAS Relative Rates and Intermediates
88
...
Which of the following carbocations would be most stable?
CH3
A)
C6H5CH2CH2CHCH2
B)
C)
CH2
C6H5CH2CH2CHCH3
CH3
C6H5CH2CH2CCH3
CH3
D)
E)
C6H5CH2CHCHCH3
CH3
C6H5CHCH2CHCH3
Ans: E
Topic: Non-EAS Relative Rates and Intermediates
90
...
Which alkyl halide would be most reactive in an SN1 reaction?
A) C6H5CH2CH2CH2Br
C6H5CH2CHCH3
B)
Br
CH3
C)
C6H5CH2CBr
CH3
Br
D)
C6H5CCH3
CH3
CH3
E)
C6H5CCH2Br
CH3
Ans: D
SHORT ANSWER QUESTIONS
Topic: General
92
...
Ans: arenes
Topic: General Reactivity
93
...
Ans: exposed π system
Topic: General Reactivity
94
...
Ans: substitution; addition
566
Chapter 15
Topic: EAS Mechanism
95
...
These
are:
a) formation of an _____________;
b) reaction with an aromatic ring to form an ___________; and
c) loss of a _________ to reform the aromatic system
...
Aryl and vinyl halides cannot be used in the Friedel-Crafts alkylation because they do
not __________
...
Substituent groups affect both _____________ and _______________ in electrophilic
aromatic substitution reactions
...
Electron-donating groups increase the electron density on the aromatic ring, causing it
to be more reactive than benzene itself towards EAS
...
Ans: activating
Topic: General EAS Reactivity
99
...
These types of groups are called
_____________ groups
...
With the exception of halogens, activating groups are ____________ directors and
deactivating groups are _________ directors
...
When two different groups are present on a benzene ring, the ____________ generally
determines the outcome of an EAS reaction
...
When toluene reacts with Cl2, the identity of the major product(s) obtained depends on
whether the reaction is carried out in the presence of catalytic amounts of FeCl3, or
without catalyst, at high temp
...
Ans: Reaction with Cl2/FeCl3 results in electrophilic aromatic substitution at the o- and
p- positions, since the methyl group in toluene is an activating, o-,p- director
...
Cl2
FeCl3
Cl
+
Cl
Cl
Cl2
heat
568
Chapter 15
Topic: General EAS Reactivity
103
...
What is this
major product and why are the minor products not formed to any significant degree?
Explain clearly
...
Ring B is more
electron-rich due to the electron-donation of both the nitrogen and methyl groups
attached versus the two electron-withdrawing carbonyl groups attached to Ring A,
which make it inherently electron-poor
...
Due to steric effects, bromination ortho to both the nitrogen and
methyl group would lead to a minor product
...
Ring
Ring
A
A
O
O
HN
O
Br
+
Ring
B
major products
HN
O
Br
Ring
B
Topic: Synthetic Strategy
104
...
NO2
NO2
Ans:
HNO3 (excess)
NaBH4
O
H2SO4
O H2O
OH
O2 N
O2 N
heat
benzaldehyde
3,5-dinitrobenzyl alcohol
Topic: Synthetic Strategy
105
...
Suggest a reasonable synthetic strategy for the synthesis of 6-methyl-3-phenyl-3heptanol from 4-methylpentanoyl chloride, (CH3)2CHCH2CH2COCl
Ans:
O
OH
O
i) C2H5MgBr
ii) NH4Cl
Cl
AlCl3
4-methylpentanoyl chloride
6-methyl-3-phenyl-3-heptanol
Topic: Mechanism, Carbocation Stability
107
...
Explain clearly
...
Although 1-phenyl-1-pentene is symmetrically substituted at the C=C, the relative
stabilities of the two possible carbocation intermediates is significantly different:
although both are secondary carbocations, one is also benzylic and thus stabilized
by resonance
...
H3O+
H2O
H
+
H
+
+
2o, benzylic:
stabilized by
resonance,formed
2o, but not benzylic:
almost exclusively
appreciable degree
less stable, not
formed to any
OH
H
chief product
570
H
+
OH
not detected
Chapter 15
Topic: Spectroscopic Analysis
108
...
In A, the signal may be expected at about 3
...
0 ppm
(attachment to O), while in B, it is likely to show up at about 2
...
571
Chapter 16
MULTIPLE CHOICE QUESTIONS
Topic: Nomenclature
1
...
What is the correct IUPAC name for the following compound?
O
A)
B)
C)
D)
E)
Ans:
5,5-Dimethyl-2-heptanone
5-Ethyl-5,5-dimethyl-Methyl-2-octanone
5-Ethyl-5-methyl- 2-hexanone
5,5-Dimethyl-2-octanone
3,3-Dimethyl-6-heptanone
A
Topic: Nomenclature
3
...
A correct name for C6H5CH2CH2CH is?
A) 3-Benzylpropanone
B) 3-Phenylpropanal
C) 3-Benzylpropanal
D) Nonanone
E) Nonanal
Ans: B
Topic: Nomenclature
5
...
CH3
CH
CH2
OH
What is the IUPAC name for
A) 4-Oxo-5-phenyl-2-hexanol
B) 5-Hydroxy-2-phenyl-3-hexanone
C) 2-Hydroxy-5-phenyl-4-hexanone
D) 2-Hydroxypropyl-1-phenylethyl ketone
E) 5-Hydroxy-3-keto-2-phenylhexane
Ans: B
573
C
CH
C 6H 5
CH3
?
Chapter 16
Topic: Nomenclature
7
...
Which is the proper name for the structure shown?
O2 N
O
NO2
A)
B)
C)
D)
E)
Ans:
3-Methyl-5-(1,4-dinitrobenzyl)-1-pentanal
3-Methyl-1-(2,5-dinitrophenyl)-5-pentanal
3-Methyl-5-(2,5-dinitrophenyl)pentanal
3-Methyl-5-(2,5-dinitrophenyl)pentanaldehyde
3-Methyl-5-(2,5-dinitrophenyl)pentaldehyde
C
Topic: Nomenclature
9
...
Which is the proper name for the structure shown below?
Br
O
A)
B)
C)
D)
E)
Ans:
7-Bromo-1,4-octynal
7-Bromo-1,4-octynone
2-Bromo-5,7-octynal
7-Bromo-7-methyl-1-heptyne-3-ketone
7-Bromo-1-octyn-4-one
E
Topic: Nomenclature
11
...
Which is the IUPAC name for the structure shown below?
O
A)
B)
C)
D)
E)
Ans:
5-Cyclohexyl-2-hexanal
5-Cyclohexyl-2-hexanone
5-Cyclohexyl-5-methyl-2-pentanone
5-(1-Methylcyclohexyl)-2-pentanone
4-(1-Methylcyclohexyl)-2-butanone
E
575
Chapter 16
Topic: New Functional Groups
13
...
Which is the general formula for a thioacetal?
H
A)
B)
RC S
RCHSR'
C)
OH
RCHSR'
D)
SH
RCHSR'
E)
SR'
RCHOR'
SR'
Ans: D
Topic: New Functional Groups
15
...
The product, C, of the following reaction sequence,
O
CH3CCH3
+
A)
HCN
H2O
CH3
CH2
B)
C)
CN
C4H7NO
H2SO4
heat
C
would be:
CCOOH
CH3CH2COOCH3
CH3CHCH3
CN
D) CH3CH=CHCOOH
E) None of these
Ans: A
Topic: Reaction Products
17
...
What would be the product of the following reaction sequence?
OH
i) PCl3
?
ii) C6H6, AlCl3
O
iii) Zn(Hg), HCl, heat
O
O
OH
OH
I
II
IV
A)
B)
C)
D)
E)
Ans:
III
V
I
II
III
IV
V
E
Topic: Reaction Products
19
...
What would be the product of the following reaction sequence?
OH
O
i) PCl3
ii) C6H6, AlCl3
iii) NaBH4, H2O
?
O
OH
II
I
III
OH
OH
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
D
579
Chapter 16
Topic: Reaction Products
21
...
Dissolving benzaldehyde in methyl alcohol establishes an equilibrium with what
compound?
OH
A)
B)
C6H5CHOCH3
O
C6H5COCH3
C)
D)
E)
Ans:
C6H5C(OCH3)3
Answers A) and B)
Answers B) and C)
A
580
Chapter 16
Topic: Reaction Products
23
...
The product, E, of the following reaction sequence,
PCl5
C6H6
CH3CH2COOH
C
D
AlCl3
NaBH4
CH3OH
E
would be:
O
CH2CH2CH3
I
A)
B)
C)
D)
E)
Ans:
OH
O
COCH2CH3
CHCH2CH3
CCH2CH3
CH(CH3)2
IV
V
II
III
I
II
III
IV
V
C
581
Chapter 16
Topic: Reaction Products
25
...
i) BH3
?
ii) H2O2,OH-, H2O
A)
B)
C)
D)
E)
Ans:
Ethylbenzene
1-Phenylethanol
Acetophenone
2-Phenylethanal
Vinylbenzene
D
Topic: Reaction Products
26
...
H2SO4
HgSO4, H2O
A)
B)
C)
D)
E)
Ans:
?
Ethylbenzene
1-Phenylethanol
Acetophenone
2-Phenylethanal
Vinylbenzene
C
Topic: Reaction Products
27
...
i) H2, Lindlar catalyst
ii) O3
iii)Zn, CH3CO2H
A)
B)
C)
D)
E)
Ans:
4-methylhexanal
4-methyl-1-hexanol
3-methylhexanal
4,10-dimethyldodecane-6,7-dione
4,10-dimethyldodecane-6,7-diol
A
582
?
Chapter 16
Topic: Reaction Products
28
...
What is the major product of the following reaction sequence?
O
HCN
H2SO4
H2O
heat
CN
NOSO3H
CN
COH
H
OSO3H
CNH2
O
I
A)
B)
C)
D)
E)
Ans:
II
III
I
II
III
IV
V
B
584
IV
V
Chapter 16
Topic: Reaction Products
30
...
What new compound will be formed when gaseous HCl is added to a solution of
propanal in methanol?
O
A)
B)
CH3CH2COCH3
O
CH3CH2COH
C)
D)
CH3CH2CH(OCH3)2
CH3CH2CHOCH3
OH
E) None of the above
Ans: C
585
Chapter 16
Topic: Reaction Products
32
...
What would be the final product?
O
(C6H5)3P
CH3I
A)
C6H5Li
C6H5CCH3
ether
C6H5C
CH2
CH3
C6H5
B)
C6H5CCH3
CH3
C)
D)
C6H5CH=CHCH3
OH
C6H5CCH3
E)
CH3
C6H5CH
CC6H5
CH3
Ans: A
586
?
Chapter 16
Topic: Reaction Products
34
...
An aldehyde results from the reaction of which of these compounds with aqueous base?
A) CH3CH2CH2Cl
B) CH3CHClCH2Cl
C) CH3CH=CCl2
D) CH3CH2CHCl2
E) CH3CCl2CH3
Ans: D
587
Chapter 16
Topic: Reaction Products
36
...
What is compound V in the following synthesis?
1
...
H3O+
C6H5Li
ether
Wittig
reagent
CH3CH2COCl
CH3CH2MgBr
CH3COCl
(CH3)2CuLi
(CH3CH2)2CuLi
E
588
Chapter 16
Topic: Reaction Products
38
...
ether
O
O
+ V
Cl
2
...
What is the final product, Z, of the following synthesis?
1
...
H3O+
SOCl2
Y
1
...
H2O
O
O
O
O
O
COAl(t-Bu)2
COCH3
CH
COLi
COH
I
A)
B)
C)
D)
E)
Ans:
II
III
I
II
III
IV
V
C
589
IV
V
Z
Chapter 16
Topic: Reaction Products
40
...
C6H5CHO
H2Cr2O4
2
...
The reaction of tert-butyl methyl ketone with a peroxy acid produces which of these as
the principal product(s)?
O
A)
B)
(CH3)3COCCH3
O
C)
(CH3)3CCOCH3
CH3
(CH3)2C
COCH3
O
D)
E)
(CH3)3COH + HO2CCH3
O
(CH3)3COCOCH3
Ans: A
590
Chapter 16
Topic: Synthesis
42
...
LiAlH4, ether
C6H5COOH
2
...
Which of the reactions listed below would serve as a synthesis of acetophenone,
O
?
C6H5CCH3
A)
O
+ (CH3)2CuLi
AlCl3
B)
C6H6 + CH3COCl
ether
C)
C6H5CN + CH3Li
D) Answers A) and B) only
E) Answers A), B), and C)
Ans: E
C6H5CCl
H 3O +
Topic: Synthesis
44
...
Which of the following procedures would not yield (CH3)2CHCH as a product?
PCC
I
OH
CH2Cl2
SOCl2
II
CO2H
Zn
HOAc
KMnO4
IV
V
ether, -78 oC
O3
III
LiAlH(O-t-Bu)3
OH
O
H3O+
NaOH
H3O+
O
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
D
592
Chapter 16
Topic: Synthesis
46
...
How could the following synthetic conversion be accomplished?
O
CH3CH2CCH3
CH3CH2CH2CHO
A) HgSO4/H2SO4; then PCl5/0°C; then NaNH2, liq
...
NH3; then Sia2BH; then H2O2
C) PCl5/0°C; then NaNH2, liq
...
NH3; then PCl5/0°C; then HgSO4, H2SO4/H2O
E) H2O2; then PCl5/0°C; then NaNH2, liq
...
Which sequence of reactions would be utilized to convert
O
CO2CH3
into
CH3
C CH3
O
?
OH
A)
B)
C)
D)
E)
Ans:
2CH3MgBr, then NH4+
HOCH2CH2OH, H3O+; LiAlH4, ether; 2CH3MgBr, then NH4+
HOCH2CH2OH, H3O+; 2CH3MgBr, then NH4+
HOCH2CH2OH, H3O+; H2, Pt; CH3OH, NH4+
None of the above
C
Topic: Synthesis
49
...
ether
I
O
+
2
...
ether
O
II
H2
+ 2 CH3MgBr
(C6H5)3P
H2
2
...
C
594
Chapter 16
Topic: Synthesis
50
...
E
P(C6H5)3
III
595
CH3CH2CH=P(C6H5)3
IV
Chapter 16
Topic: Synthesis
51
...
Sia2BH
II
2
...
O3
III
2
...
KMnO4, NaOH, heat
2
...
B
596
Chapter 16
Topic: Synthesis
52
...
O3
2
...
ether
D)
(C6H5)2CO2H + 2 C6H5Li
2
...
Ans: E
Topic: Synthesis
53
...
CH3CH2MgBr
H2Cr2O4
CH3CH2CH2CH2CH2OH
acetone
CH2Cl2
2
...
Ans: E
597
Chapter 16
Topic: Synthesis
54
...
Sia2BH
2
...
LiAlH4 (LAH) cannot be used to convert carboxylic acids to the corresponding
aldehydes because:
A) LAH is not sufficiently reactive
...
C) RCOOH is reduced to RCH2OH
...
E) RCOOH is converted into R2C=O
...
The following reduction can be carried out with which reagent(s)?
?
O
A)
B)
C)
D)
E)
Ans:
Zn(Hg), HCl
i) HSCH2CH2SH, BF3 ; ii)Raney Ni (H2)
NaBH4, CH3OH
A&B
A&C
D
598
Chapter 16
Topic: Reagents
57
...
NH3
C) LiAlH[OC(CH3)3]3, ether
D) NaBH4, CH3OH
E) LiAlH4, ether
Ans: C
Topic: Reagents
58
...
The Reformatsky reaction involves the reaction of an aldehyde or ketone with:
A) RLi
B) R2CuLi
R
C)
XZnCHCO2R'
D) RC≡CNa
E) R3P
Ans: C
Topic: Reagents
60
...
H
The compound C6H5C N N CC6H5 is produced by the reaction of an excess of
benzaldehyde with which compound?
A) Ammonia
B) Hydrazine
C) Nitrogen
D) Phenylhydrazine
E) Hydroxylamine
Ans: B
Topic: Reagents
62
...
Which reagent(s) could be used to carry out the following transformation?
O
?
A)
B)
C)
D)
E)
Ans:
Zn(Hg), HCl, reflux
LiAlH4, ether
HSCH2CH2SH, BF3; then Raney Ni (H2)
All of the above
Two of the above
E
600
Chapter 16
Topic: Physical Properties, Relationships, Stereochemistry
64
...
)
A) pentane
B) 1-butanol
C) Butanal
D) 1-fluorobutane
E) diethylether
Ans: B
Topic: Physical Properties, Relationships, Stereochemistry
65
...
What, in general, is the order of decreasing reactivity of these carbonyl compounds
towards nucleophilic reagents?
O
CH3CCH3
H
CH3C
O
O
I
II
A) I > III > V > II > IV
B) IV > II > I > III > V
C) V > III > I > II > IV
D) II > I > V > III > IV
E) III > V > IV > II > I
Ans: B
(CH3)3CCCH3
III
601
H
HC
IV
O
O
(CH3)3CCC(CH3)3
V
Chapter 16
Topic: Physical Properties, Relationships, Stereochemistry
67
...
The relationship of 3-methyl-2-heptanone and 3-methyl-2-hepten-2-ol is designated by
the term:
A) Tautomers
B) Conformational isomers
C) Diastereomers
D) Resonance structures
E) Stereoisomers
Ans: A
602
Chapter 16
Topic: Physical Properties, Relationships, Stereochemistry
...
In which of the following reactions is the final product expected to be formed as a
racemic mixture?
H
A)
C6H5MgBr + C6H5C
O
O
B)
HCN +
C)
D)
O
H
CH3CH2C
H
CH3CCH3
CH3C
O
+
BrZnCH2COC2H5
+ xs CH3OH + HCl
O
O
E)
CH3CHCH2COC2H5
+ (i-Bu)2AlH
CH3
Ans: C
Topic: Physical Properties, Relationships, Stereochemistry
70
...
Stereoisomers can exist in the case of which of the following?
A) The hydrazone of acetophenone
B) The oxime of 2-methylcyclopentanone
C) The phenylhydrazone of 4-methylcyclohexanone
D) The imine of cyclopentanone
E) Two of the above
Ans: B
603
Chapter 16
Topic: Reactions of Aldehydes and Ketones
72
...
Which of the following is formed when 3-methylcyclopentanone reacts with
semicarbazide?
N-NH-C6H5
N-NH2
I
N-OH
II
III
NO2
O
N
N
H
NH2
N
N
H
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
D
604
NO2
Chapter 16
Topic: Reactions of Aldehydes and Ketones
74
...
Which of the following is formed when 2,2,3-trimethylcyclohexanone reacts with
hydroxylamine?
N-NH-C6H5
N-NH2
I
N-OH
III
II
NO2
O
N
N
H
NH2
N
N
H
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
C
605
NO2
Chapter 16
Topic: Reactions of Aldehydes and Ketones
76
...
Which of the following is formed when 2,2,3-trimethylcyclohexanone reacts with
hydrazine?
N-NH-C6H5
N-NH2
I
N-OH
III
II
NO2
O
N
N
H
NH2
N
N
H
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
B
606
NO2
Chapter 16
Topic: NMR
78
...
Which of these structures is a possible one for this compound?
O
A)
B)
CH3CH2CCH2CH3
O
C)
(CH3)2CHCCH3
H
(CH3)3CC
D)
O
H
CH3CH2CHC
O
CH3
H
E)
(CH3)2CHCH2C
O
Ans: C
Topic: NMR
79
...
Which
of these structures is a possible one for this compound?
A) 2-heptanone
B) 3-heptanone
C) 2,4-dimethyl-3-pentanone
D) 2,2-dimethyl-3-pentanone
E) two of the above
Ans: E
607
Chapter 16
Topic: NMR
80
...
Which of these structures is a possible one for this compound?
A) 2-heptanone
B) 3-heptanone
C) 2,2-dimethyl-3-pentanone
D) 2,4-dimethyl-3-pentanone
E) two of the above
Ans: D
Topic: NMR
81
...
2 ppm
...
Aldehydes are more reactive than ketones towards nucleophilic substitution because of
both steric and electronic factors
...
a
...
b
...
Ans: a
...
aldehydes have only one electron-releasing group to partly neutralize/stabilize
the partial positive charge at the carbonyl carbon while ketones have two
Topic: General
83
...
Ans: hemiacetal
608
Chapter 16
Topic: General
84
...
Ans: hydrate or gem-diol
Topic: General
85
...
Ans: acetal
Topic: General
86
...
Ans: imine
Topic: General
87
...
Ans: cyanohydrin
Topic: Wittig Reaction
88
...
Ans: Wittig
Topic: Wittig Reaction
89
...
Ans: P-O bond; triphenylphosphine oxide
Topic: General
90
...
Ans: Baeyer-Villiger oxidation
609
Chapter 16
Topic: Functional Group Tests
91
...
Ans: aldehydes and ketones
Topic: Functional Group Tests
92
...
Ans: aldehydes and ketones
Topic: Functional Group Tests
93
...
Oximes are formed when aldehydes and ketones react with _______________
...
Suggest a synthetic strategy for the synthesis of 3-heptanone from 1-bromobutane
...
C2H5Li, Et2O
Ans:
NaCN
Br
CN
ii
...
Suggest a synthetic strategy for the synthesis of 4-methylpentanal from 3-methyl-1bromobutane
...
DIBAL-H
O
NaCN
CN
Br
ii
...
Suggest a synthetic strategy for the synthesis of 6-methyl-3-heptanol from 4methylpentanenitrile, (CH3)2CHCH2CH2CN
...
DIBAL-H
CN
ii
...
C2H5MgBr, Et2O
iv
...
C2H5MgBr, Et2O
CN
ii
...
NaBH4, H2O
Topic: Reaction Sequence
98
...
i
...
Mg, CH3CH2CN
iii
...
RCO3H
O
Ans:
Br2, hν
Br i
...
H3O+
RCO3H
O
O
611
Chapter 16
Topic: Reaction Sequence
99
...
i
...
EtMgBr
?
+
ii
...
H3O , heat
O
Ans:
O
i
...
H3O+, heat
i
...
Zn, CH3CO2H
HO
O
O
Topic: NMR
100
...
2-Phenylacetaldehyde
Acetophenone
and
C6H5COCH3
C6H5CH2CHO
3 signals
2 signals
approximate δ ppm
approximate δ ppm
singlet (-CH3) 2
...
5
multiplet (C6H5) 7
...
Which compound would be most acidic?
A) CH3CH2CH3
B) CH3CH=CH2
C) Cyclohexane (CH3)2C=O
D) (CH3)2C=O
E) Benzene
Ans: D
Topic: Reaction Products
2
...
The product, C, of the following sequence of reactions,
CH3
CH3CCHO
+ CH3CH2CHO
OH-
A
CH3
would be:
CH3
A)
CH3CCH=CHCH2CH2OH
CH3
CH3
B)
CH3CCH=CCH2OH
CH3 CH3
CH3
C)
CH3CCH2CH2CH2OH
CH3
CH3
D)
CH3CCH2CH2CH2CH2OH
CH3
CH3
E)
CH3CCH2CHCHO
CH3 CH3
Ans: B
614
H3O+
(-H2O)
B
NaBH4
CH3OH
C
Chapter 17
Topic: Reaction Products
4
...
What would be the major product of the following reaction?
O
OH-
?
H2O
CH3CH2CH2OH + CH3CH2COO-
CH3CH2CH
A)
B)
CH3CH2CHCH2CHO
OH
O
C)
D)
CH3CH2CH2OCCH2CH3
CH3CH2CHCHCHO
HO CH3
O
E)
CH3CH2CHCCH2CH3
HO
Ans: D
615
CHCH2CCH3
Chapter 17
Topic: Reaction Products
6
...
What would be the major product of the following reaction?
O
+
O
OHheat
O
O
HO
O
O
OH
I
III
II
HO
O
IV
A)
B)
C)
D)
E)
Ans:
?
V
I
II
III
IV
V
D
617
O
Chapter 17
Topic: Reaction Products
8
...
CH3Cu
ii H3O+
B
O
O
O
OH
I
II
III
O
OH
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
C
618
Chapter 17
Topic: Reaction Products
9
...
What would be the major product of the following reaction?
O CH3
OD?
+ D2O
room
C6H5C CHCH3
temp
...
What would be the product of the following reaction?
NaCN
?
CH3CH=CO2C2H5
C2H5OH, CH3COOH
CH3CH2CHCO2C2H5
A)
CN
B)
C)
D)
CH3CH=CHCO2CN
CH3CH=CHCN
CH3CHCH2CO2C2H5
CN
CN
E)
CH3CH=CHCOC2H5
OH
Ans: D
620
Chapter 17
Topic: Reaction Products
12
...
1
...
H2O
(CH3)3CCH2COCH3
O
A)
B)
C)
(CH3)2C=CHC(CH3)2
OH
(CH3)2CHCHCOCH3
CH3
D)
2 CH3CCH3
O
OH
E)
(CH3)2C=CHCCH3
H
Ans: A
Topic: Reaction Products
13
...
What would be the final product of the following reaction sequence?
O
O
C6H5CH
A)
B)
+
CH3CCH3
OH-, heat
O
C)
C6H5CHCH2CCH3
O
D)
C6H5CH2CH2CCH3
OH
E)
LiAlH4
ether
C6H5CH2CH2CH2CH3
OH
A
C6H5CH=CHCHCH3
OH
OH
C6H5CHCH2CHCH3
Ans: D
622
Final
Product
Chapter 17
Topic: Reaction Products
15
...
What would be the major product of the following reaction?
O
C6H5CH
O
+
CH3CCH3
OH-
?
heat
O
A)
OH
B)
C6H5CCH2CHCH3
O
O
C)
C6H5CCH2CCH3
OH
OH
D)
C6H5CHCH2CHCH3
O
O
E)
C6H5CCH2CCH3
O
C6H5CH=CHCCH3
Ans: E
Topic: Reaction Products
17
...
What would be the product, C, of the following reaction sequence?
O
O
+ CH3CH2CH
(CH3)3CCH
A)
B)
OH-
A
H3O+
heat
B
CH2
(CH3)3CCH2CH2CH2OH
OH
C)
(CH3)3CCHCH2CH=CH2
(CH3)3CCH2C=CH2
D)
CH3
(CH3)3CCH=CCH=CH2
CH3
OH
E)
(CH3)3CCHCHCH=CH2
CH3
Ans: D
Topic: Reaction Products
19
...
What would be the product, C, of the following reaction sequence?
O
O
NaBH4
H3O+, heat
OHA
B
C6H5CH + CH3CH2CH
CH3OH
(-H2O)
25 oC
O
A)
C6H5CCHCH2OH
B)
CH3
C6H5CHCHCH2OH
HO CH3
O
C)
C6H5CH2CHCH
CH3
O
D)
C6H5CH=CCH
E)
CH3
C6H5CH=CCH2OH
CH3
hi
Ans: E
626
C
Chapter 17
Topic: Reaction Products
21
...
What would be the major product of the following reaction?
O
+ CN-
C6H5CH=CHCCH3
CH3CH2OH
CH3COOH
O
A)
C6H5CH2CHCCH3
CN
O
B)
C6H5CHCH2CCH3
CN
OH
C)
C6H5CH2CH2CCH3
CN
O
D)
E)
C6H5CH2CH2CCN
OH
C6H5CHCH=CCH3
CN
Ans: B
628
?
Chapter 17
Topic: Reaction Products
23
...
Cu
ii
...
What would be the major product of the following reaction?
O
O
?
OHOH
O
O
O
O
I
O
III
II
O
O
IV
A)
B)
C)
D)
E)
Ans:
O
V
I
II
III
IV
V
E
630
Chapter 17
Topic: Reaction Products
25
...
Br2, NaOH
?
ii
...
What would be the major product of the following reaction sequence?
O
i
...
C2H5I
?
O
O
O
I
II
III
O
V
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
I
Topic: Synthetic Strategy
27
...
What would be the major product of the following reaction?
O
CCHCH3
OH-
+ Br2
?
CH3
O
O
CCHCH3
CCHCH3
Br
CH3
Br
O
CCBrCH3
CH3
I
CH3
II
III
O
O
CCHCH2Br
CCHCH2Br
CH3
CH2Br
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
C
Topic: Reaction Products
29
...
Which compound would be formed when 2,3-dimethylhexanal is treated with a solution
of NaOD in D2O?
D
A)
O
D
B)
O
D
D
C)
O
D)
O
D
E)
O
D
Ans E
Topic: Reaction Products
31
...
Which of these is a product of the reaction of C6H5MgBr with
O
C6H5CH=CHCCH3
O
A)
?
C6H5CH=CCCH3
C 6H 5
OH
B)
C6H5CH=CHCCH3
C6H5
O
C)
C6H5CH=CHCCH2C6H5
O
D)
p-C6H5
E)
C6H4 CH=CHCCH3
OC6H5
C6H5CH=CHCHCH3
Ans: B
Topic: Reaction Products
33
...
(C6H5)2CuLi
?
2
...
Which reagents would you use to synthesize this compound by an aldol condensation?
O
C6H5CH=CHCC6H5
O
O
A)
and
C6H5CH
B)
and
C6H5CH2CH
C6H5CCH3
O
C)
D)
C6H5CH2CH
O
O
C6H5CH=CHCH
O
C6H5CCH3
and
and
C6H5OH
O
C6H5CH
O
E)
(C6H5)2CuLi and CH2=CHCC6H5
Ans: D
Topic: The Aldol Reaction/Condensation (Explicitly Identified)
35
...
Which reagents would you use to synthesize this compound by an aldol condensation?
O
C6H5CH=CCH
C6H5
O
A)
O
and
C6H5CH
and
C6H5CH2CH
C6H5CCH3
O
C)
D)
C6H5CH2CH
O
O
B)
C6H5CH=CHCH
O
C6H5CCH3
E)
and
and
C6H5OH
O
C6H5CH
O
C6H5CH2Cl and C6H5CHCH
ONa
Ans: A
Topic: The Aldol Reaction/Condensation (Explicitly Identified)
37
...
Which of these is not among the reaction products when a crossed aldol addition occurs
between ethanal and butanal?
OH
H
A)
B)
CH3CHCH2C=O
OH
H
CH3CH2CH2CHCHCH2C=O
CH2CH3
H
OH
C)
CH3CHCHC=O
D)
CH2CH3
OH
E)
CH3CH2CH2CHCH2C=O
OH H
H
CH3CH2CH2CHCHC=O
CH2CH3
Ans: B
Topic: The Aldol Reaction/Condensation (Explicitly Identified)
H
39
...
If butanal is added slowly to an aqueous solution of sodium hydroxide and 2,2dimethylpropanal at 25°C, the principal product is which of these?
OH H
A)
(CH3)3CCHCHC=O
CH2CH3
OH H
B)
CH3CH2CH2CHCHC=O
CH2CH3
OH
C)
(CH3)3CCHCC(CH3)3
O
OH
D)
E)
CH3CH2CH2CHC(CH3)3
OH H
CH3CH2CH2CHCHC=O
C(CH3)3
Ans: A
639
Chapter 17
Topic: The Aldol Reaction/Condensation (Explicitly Identified)
41
...
H
The aldol cyclization of CH3CCH2CH2CH2C=O produces which of these?
O
C CH3
I
A) I
B) II
C) III
D) IV
E) V
Ans: D
H
CH3
H
O
C=O
II
O
C=O
III
640
CH3
O
IV
O
V
Chapter 17
Topic: The Aldol Reaction/Condensation (Explicitly Identified)
43
...
O
The reaction of CH3CCH2CH2CH2CCH3 with base affords which of these products?
H
CH3
C=O
H
CH3
O
O
A)
B)
C)
D)
E)
Ans:
O
C=O
CH3
I
O
II
III
I
II
III
IV
V
D
641
CH3
IV
V
Chapter 17
Topic: The Aldol Reaction/Condensation (Explicitly Identified)
45
...
Which is the only one of these compounds which cannot self-condense in the presence
of dilute aqueous alkali?
A) Phenylethanal
B) Propanal
C) 2-Methylpropanal
D) 3-Methylpentanal
E) 2,2-Dimethylpropanal
Ans: E
Topic: The Aldol Reaction/Condensation (Explicitly Identified)
47
...
Which of these compounds cannot self-condense in the presence of dilute aqueous
alkali?
A) 3-(4-Nitrophenyl)propanal
B) 2-methyl-3-pentanone
C) 2-(4-Nitrophenyl)propanal
D) 3-(4-Nitrophenyl)-2-butanone
E) All of the above compounds can self-condense
Ans: E
Topic: The Aldol Reaction/Condensation (Explicitly Identified)
49
...
Which of these compounds can react with 4-methylpentanal to afford good yields of the
crossed aldol product?
A) 3-(4-Nitrophenyl)propanal
B) 2ethyl-2-methylheptanal
C) 2-(4-Nitrophenyl)propanal
D) 3-(4-Nitrophenyl)-2-butanone
E) None of the above compounds will give good yields of the crossed aldol product
with 4-methylhexanal
Ans: B
643
Chapter 17
Topic: The Aldol Reaction/Condensation (Explicitly Identified)
O
51
...
What final product is obtained when 2,8-nonanone is treated with base, followed by
reaction with sodium borohydride?
OH
OH
O
I
III
II
OH
O
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
A
644
Chapter 17
Topic: Chemical Tests
53
...
Which reagent would best serve as the basis for a simple chemical test to distinguish
between CH3CHO and CH3COCH3?
A) NaOI (I2 in NaOH)
B) Br2/CCl4
C) C6H5NHNH2
D) NaHCO3/H2O
E) Ag(NH3)2+
Ans: E
Topic: Chemical Tests
55
...
Which of the reagents listed below would serve as the basis for a simple chemical test to
distinguish between 2-methyl-1-propanol and 2-butanol?
A) NaOI (I2 in NaOH)
B) KMnO4 in H2O
C) Br2 in CCl4
D) Cold concd H2SO4
E) CrO3 in H2SO4
Ans: A
Topic: Chemical Tests
57
...
The compound could be which of these?
H
A)
B)
CH3CH2CH2CH2C=O
H
CH3CHCH2C=O
CH3
C)
D)
CH2=CHCH2CHOHCH3
O
CH3CHCCH3
CH3
O
E)
CH3CH2CCH2CH3
Ans: D
Topic: Chemical Tests
58
...
Ans: E
646
Chapter 17
Topic: Tautomerization and Keto-Enol Equilibrium
59
...
Which of these compounds would exist in an enol form to the greatest extent?
O
A)
B)
CH3COC2H5
O
O
C)
CH3CCH2CCH3
O
D)
CH3CCH3
CH3CH
E)
O
CH3CCH2CH2CCH3
O
O
Ans: B
647
Chapter 17
Topic: Tautomerization and Keto-Enol Equilibrium
61
...
Which of the following would undergo racemization in base?
CH3
O
C
CC6H5
O
CH3CH2
C6H5CC6H5
CH3CH2CH2
I
II
H
CH3CH2
O
C
CH3
CC6H5
CH3
CH3
C
CCH2C6H5
CH3
III
A)
B)
C)
D)
E)
Ans:
O
IV
I
II
III
IV
Both III and IV
C
648
Chapter 17
Topic: Tautomerization and Keto-Enol Equilibrium
63
...
Which of the following would not undergo racemization in base?
A) (R)-3-methyl-4-heptanone
B) (R)-3-methyl-2-heptanone
C) (R)-4-methyl-2-heptanone
D) (R)-2,4-dimethyl-3-heptanone
E) All of the above will undergo racemization in base
Ans: C
Topic: Tautomerization and Keto-Enol Equilibrium
65
...
Which of the following represent keto-enol tautomers?
O
OH
A)
B)
CH3CCH2CH3
OH
C)
and
CH2=CCH2CH3
O
HOCH2CCH=CH2
CH3C=CHCH3
O
and
and
D) More than one of these
E) None of these
Ans: D
CH3CCH2CH3
O
CH3CCH2CH3
Topic: Tautomerization and Keto-Enol Equilibrium
67
...
B) fewer atoms are coplanar in the keto form
...
D) the C-C π bond is weaker than the C-O π bond
...
Ans: D
650
Chapter 17
Topic: Tautomerization and Keto-Enol Equilibrium
68
...
A compound, X, C9H10O, which reacts with I2/NaOH to give a pale yellow precipitate,
gives the following 1H NMR spectrum
...
0
δ 3
...
7
Singlet,
Singlet,
Multiplet,
Which is a possible structure for X?
O
O
O
I
II
III
O
O
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
B
652
Chapter 17
Topic: Reagents, Intermediates, and Spectroscopy
70
...
The conversion of C6H5CCH3
oxidizing agent?
A) Ag(NH3)2+
B) O3
C) NaOI (I2 in NaOH)
O
D)
to
C6H5COH
is accomplished by the use of which
RCOOH
E) Cu++
Ans: C
Use the following to answer questions 72-73:
H
O
A
OH-,warm
(-H2O)
B (C11H12O)
H2/Ni
high
pressure
653
OH
Chapter 17
Topic: Reagents, Intermediates, and Spectroscopy
72
...
What is compound A?
A) Butanone
B) Butanal
C) Propanal
D) 1-Butanol
E) 2-Methylpropanal
Ans: B
Topic: Reagents, Intermediates, and Spectroscopy
73
...
Which of these would not be an intermediate or final product when C6H5CH2CN and
HCHO react in basic solution and the product is treated with acid?
CH2OH
A)
B)
C6H5CHCN
CH2
C)
C6H5CCN
C6H5CHCN
D)
C6H5CH2C=NH
C6H5CHCN
C6H5CH2C=O
E) Each of these would be either an intermediate or a final product
...
The Robinson annulation reaction which produces
CH3
O
uses which of the following as starting materials?
CH3
H
O
CH3
+
CH2=CHC=O
CH2=CHCCH3
CH2
I
+
CH2
O
II
O
III
O
O
+
+
CH3CH=CHCCH3
O
O
CH3CH=CHCCH3
IV
A)
B)
C)
D)
E)
Ans:
CH3
CH=CH2
HCHO +
V
I
II
III
IV
V
B
Topic: Reagents, Intermediates, and Spectroscopy
76
...
The α-hydrogens on carbonyl carbons are unusually acidic (pKa 19-20) because:
_____________
...
The keto and enol forms of carbonyl compounds are a special type of __________
isomer called ___________
...
The interconversion of the keto and enol forms of a carbonyl compound is called
_____________
...
Diastereomers that differ in configuration at only one stereogenic center are sometimes
called ___________, and their interconversion is called __________
...
Dissolving a halogen in aqueous sodium hydroxide provides a solution of
_____________
...
The haloform reaction is an efficient method for converting methyl ketones to
____________
...
The initial product of the aldol reaction is a β-hydroxycarbonyl compound
...
Ans: is stabilized by having conjugated double bonds
656
Chapter 17
Topic: Aldol Reaction
84
...
Ans: crossed aldol reaction
Topic: Kinetic/Thermodynamic Enolates
85
...
The enolate with the more
highly substituted double bond is called the ____________
...
The kinetic enolate (the less highly substituted double bond) is favored when
__________ is used as a base
...
When α,β-unsaturated aldehydes and ketones react with nucleophiles, they do so in one
of two ways
...
When α,β-unsaturated aldehydes and ketones react with nucleophiles, simple addition is
favored when _________ nucleophiles are used, while conjugate addition is preferred
by ___________ nucleophiles
...
The sequence of a Michael addition followed by an intramolecular aldol condensation is
known as a ___________
...
When 5-methyl-3-hepten-2-one reacts with CH3Cu, the major product expected
is___________ (structure and IUPAC name)
...
When optically active 2-methyl-1-phenyl-1-butanone undergoes reaction with Br2/H3O+,
the product is observed to exhibit no optical activity
...
Ans: An achiral enol is formed in presence of H3O+, which can then undergo reaction
with Br2 from both faces, to produce a racemic mixture of the brominated product;
hence, no observed optical activity
...
O
H CH3
H3O+
+ OH
OH
CH3
H CH3
achiral enol
Br2
O
Br CH3
(S)
658
O
+
Br
CH3
(R)
Chapter 17
Topic: Multistep Reaction Sequence:
92
...
O
O
O
i
...
H3O+, heat
iii
...
H2O
v
...
H2O
O
Ans:
O
O
O
i
...
H3O+, heat
i
...
H2O
i
...
H2O
O
O
Topic: Multistep Reaction Sequence:
93
...
CN
O
i
...
H3O , heat
Ans:
O
CN
+
-
CN
EtO , EtOH
659
H3O
heat
CO2H
Chapter 17
Topic: Multistep Reaction Sequence:
94
...
i
...
iii
...
EtO-, EtOH
ii
...
Suggest a reasonable synthetic strategy to carry out the following transformation
...
O
-
EtO , EtOH
ii
...
LAH
ii
...
What is the final product of the following reaction sequence? Give structural details of
all significant intermediates
...
EtO-, EtOH
?
ii
...
There are several possible cyclization products that might be formed when 5-methyl-6oxoheptanal undergoes intramolecular aldol condensation in presence of ethoxide
...
Comment on which of these is likely
to be the major product, clearly explaining your rationale
...
The rationale for predicting the major product is the following:
i) aldehydes are typically more reactive toward nucleophilic addition than
ketones, so I and III are more likely than II; ii) since 5-membered rings are formed
much more readily than 7-membered rings, I is more likely than III
...
What is the product of the following reaction?
O
OH-
O
O
Ans:
?
OH-
O
O
661
HO
HO
I
major product
O
II
III
Chapter 17
Topic: Reaction Products
99
...
LDA, THF
ii
...
LDA, THF
ii
...
What is the product of the following reaction sequence? Give structural details of all
significant intermediates
...
OHii
...
Which of the following is the best name for the following compound?
O
O
A)
B)
C)
Isobutyl ethanoate
Ethyl isopropanoate
3-methylbutyl ethanoate
D) Ethoxy isobutyl ketone
E) Ethyl 3-methylbutanoate
Ans: C
Topic: Nomenclature
O
2
...
Cl
What is the IUPAC name for
A)
B)
C)
D)
E)
Ans:
O
∝-Chlorovaleryl chloride
2-Chloropentanoyl chloride
1-Chloropentanoyl chloride
1,2-Dichloropentanal
1-Chloro-1-butanecarbonyl chloride
B
663
Chapter 18
Topic: Nomenclature
4
...
Which of the following structures is 3,4-dimethylpentyl chloroformate?
H
Cl
O
O
Cl
O
Cl
I
O
III
Cl
Cl
IV
O
O
II
O
A)
B)
C)
D)
E)
O
O
O
V
I
II
III
IV
V
Ans: E
664
Chapter 18
Topic: Nomenclature
6
...
In which of the following sequences are
acidity?
A) CH3COOH > H2O > CH3CH2OH
B) CH3CH2OH > CH3COOH > H2O
C) CH3COOH > CH3CH2OH > H2O
D) H2O > CH3COOH > CH3CH2OH
E) CH3CH2OH > H2O > CH3COOH
Ans: A
665
the compounds listed in order of decreasing
>
>
>
>
>
HC≡CH > NH3
HC≡CH > NH3
NH3 > HC≡CH
HC≡CH > NH3
HC≡CH > NH3
Chapter 18
Topic: Acidity
8
...
Which of the following would be the strongest acid?
Cl
CO2H
CO2H
CO2H
Cl
I
Cl
II
III
CO2H
Cl
IV
A)
B)
C)
D)
E)
Ans:
Cl
CO2H
Cl
Cl
V
I
II
III
IV
V
C
Topic: Acidity
10
...
Which compound would be most acidic?
Acetone
A) Acetic acid
B) Ethanol
C)
D)
E)
Ans:
Phenol
Acetone
Water
A
Topic: Acidity
12
...
Which of the following would be the strongest acid?
A) Benzoic acid
B) 4-Nitrobenzoic acid
C) 4-Methylbenzoic acid
D) 4-Methoxybenzoic acid
E) 4-Iodobenzoic acid
Ans: B
667
Chapter 18
Topic: Acidity
14
...
A 0
...
10 mL of 0
...
Which of these is a possible structure for the acid?
A) C6H5CO2H
B) p-CH3C6H4CO2H
C) m-ClC6H4CO2H
D) o-NO2C6H4CO2H
E) p-BrC6H4CO2H
Ans: D
Topic: Chemical Tests, Relative Reactivities, and Physical Properties
16
...
Which reagent would best serve as a basis for a simple chemical test to distinguish
between CH3CH2COOH and CH3COOCH3?
A) Concd H2SO4
B) Br2/CCl4
C) CrO3/H2SO4
D) NaHCO3/H2O
E) KMnO4/H2O
Ans: D
Topic: Chemical Tests, Relative Reactivities, and Physical Properties
18
...
H2SO4
B) Br2/CCl4
C) CrO3/H2SO4
D) NaHCO3/H2O
E) KMnO4/H2O
Ans: D
Topic: Chemical Tests, Relative Reactivities, and Physical Properties
19
...
The relative reactivity of acyl compounds toward nucleophilic substitution is:
A)
B)
C)
Amide > ester > acid anhydride > acyl chloride
Acyl chloride > ester > acid anhydride > amide
Ester > acyl chloride > acid anhydride > amide
D) Acyl chloride > acid anhydride > ester > amide
E) Acid anhydride > acyl chloride > ester > amide
Ans: D
Topic: Chemical Tests, Relative Reactivities, and Physical Properties
21
...
The presence of substituents on the aromatic ring of ethyl benzoate may be
expected to increase/decrease the rate of hydrolysis of this ester
...
Which of the following will not undergo hydrolysis, whether acid or base is present?
A) CH3COCl
B) CH3CONH2
C) (CH3CO)2O
D) CH3CO2CH2CH3
E) CH3COCH2CH2CH3
Ans: D
670
Chapter 18
Topic: Chemical Tests, Relative Reactivities, and Physical Properties
23
...
In which of these species are all the carbon-oxygen bonds of equal length?
A) Diethyl carbonate
B) Methyl butanoate
C) Lithium acetate
D) Propionic anhydride
E) Pentanoic acid
Ans: C
Topic: Reaction Products
25
...
NaCN
Cl
A + NH4+
ii
...
Predict the major organic
heat
+ KMnO4
−
H2O, OH
product
H3O+
of
?
OH
CO2H
OH
I
CHO
II
III
OH
CHO
IV
A)
B)
C)
V
I
II
III
D) IV
E) V
Ans: B
672
the
reaction
sequence
below:
Chapter 18
Topic: Reaction Products
27
...
What would be the final product, F, of the following sequence of reactions?
i
...
LAH, Et2O
F
CO2H ii
...
CO2
iii
...
The product, Z, of the following sequence of reactions is which compound?
−
i
...
H3O+
Z
iii
...
CH3CH2OH, base
O
O
O
O
Cl
Cl
I
II
III
O
O
Cl
Cl
Cl
IV
A)
B)
I
II
C)
D)
E)
V
III
IV
V
Ans: B
674
Chapter 18
Topic: Reaction Products
30
...
OH− (2eq
...
H O+
3
Cl
H2
cat
...
SOCl2
ii
...
Predict the major organic product of the reaction sequence,
O
i
...
dilute HCl, cold
O
O
OH
HO
O
NH2
HO
O
O
I
O
II
O
H
N
O
III
HN
IV
A)
B)
C)
D)
E)
Ans:
NH2
H2N
O
O
V
I
II
III
IV
V
B
Topic: Reaction Products
32
...
What is(are) the likely final product(s)?
A) (R)-3-hexanol
B) (S)-2-hexanol
C) Equal amounts of A) and B)
D) 2-Hexene (cis and trans)
E) 1-Hexen-2-ol
Ans: A
676
Chapter 18
Topic: Reaction Products
33
...
CH3MgI, Et2O
ii
...
Predict the final product likely to be obtained when (S)-2-methyl-3-pentanol is
subjected to the following sequence of reactions: i) benzoyl chloride; ii) NaOH (aq),
heat
A) (S)-2-methyl-3-pentanol
B) (R)-2-methyl-3-pentanol
C) (R,S)-2-methyl-3-pentanol
D) 2-methyl-2-pentene
E) (R,S)-2-methyl-3-pentanol and 2-methyl-2-pentene in more or less equal amounts
Ans: A
Topic: Reaction Products
35
...
The product of the following reaction is:
O
heat
OH
+
O
?
O
(1 mol)
(1 mol)
O
O
O O
O OH
O
CO2H
CO2H
II
I
O
III
O
O
O
Cl
O
Cl
O
O
H
O
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
A
Topic: Reaction Products
37
...
What would be the final organic product of the following reaction?
NaCN
C6H5
Cl
i
...
H2O
?
A)
C6H5CH2CH2CO2H
B) C6H5CH2CH2NH2 C6H5CH2CH(CH3)CN
C) C6H5CH2CH(CH3)CN
D) C6H5CH2CH=NH
E) C6H5CH2NH2
Ans: B
Topic: Reaction Products
39
...
Mg, Et2O
Br
ii
...
LAH, Et2O
ii
...
H3O+
A)
B)
C)
D)
E)
Ans:
(CH3)3CCO2H
(CH3)3CCOCH3
(CH3)3CCH2OH
(CH3)3COCH3
(CH3)3CCO2CH3
C
679
?
Chapter 18
Topic: Reaction Products
40
...
O
heat
CO2H
?
O
O
O
O
OH
I
II
CO2H
+ CO
IV
A)
B)
III
2
CO2H
V
I
II
C)
D)
E)
Ans:
III
IV
V
C
Topic: Reaction Products
41
...
PCl5
CO2H
?
ii
...
P4H10, heat
A)
B)
C)
D)
E)
Ans:
+ CO2
O
CH3CH2CH2NH2
CH3CH2CONH2
CH3CH2CONHCOCH2CH3
CH3CH2CN
CH3CH2COO-NH4+
D
680
Chapter 18
Topic: Reaction Products
42
...
Mg, Et2O
Br
i
...
excess NH3
ii
...
H3O
O
NH2
NH2
CN
O
I
O
II
III
NHCl
NH2
O
IV
A)
B)
C)
V
I
II
III
D) IV
E) V
Ans: C
681
Chapter 18
Topic: Reaction Products
43
...
What would be the final product of this reaction sequence?
CO2H i
...
NH3
iii
...
What
is
the
ultimate
O
Cl
O
O
N
H
A)
B)
C)
D)
E)
Ans:
this
sequence
O
H
N
CH3NH2
O
Cl
N
H
O
I
of
CH3CH2OH
(1 eq
...
What is the product of this reaction?
O
CH3OH
?
O
O
HO
CO2H
O
O
I
II
O
O
III
HO
O
O
O
O
O
IV
A)
B)
C)
D)
E)
Ans:
O
V
I
II
III
IV
V
B
683
Cl
O
I
II
III
IV
V
A
O
reactions?
?
IV
III
of
Chapter 18
Topic: Reaction Products
47
...
)?
O
A)
N
H
O
B)
N
O
C)
O
D)
NHMgBr
+ CH4
O
E)
H2N
OMgBr
Ans: D
Topic: Reaction Products
48
...
A compound has the molecular formula, C6H12O2
...
4
and δ 2
...
The most likely structure for this compound is:
O
O
O
O
O
O
I
II
III
O
O
IV
A)
B)
C)
D)
E)
Ans:
O
O
V
I
II
III
IV
V
D
685
H
Chapter 18
Topic: Structure Identification (Spectroscopy)
50
...
Its IR spectrum shows a strong
absorption band near 1740 cm-1
...
3
δ 2
...
2
triplet,
singlet,
quartet,
The most likely structure for the compound is:
O
O
O
O
O
O
I
O
O
O
O
O
O
II
III
O
HO2C
CO2H
O
O
O
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
A
686
Chapter 18
Topic: Structure Identification (Spectroscopy)
51
...
90
δ 1
...
95
δ 3
...
The most likely
structure for the compound is:
O
A)
O
O
B)
O
O
C)
O
D)
H
O
O
O
E)
HO
Ans: A
687
Chapter 18
Topic: Structure Identification (Spectroscopy)
52
...
7
δ 3
...
3
singlet,
singlet,
multiplet,
The IR spectrum shows a strong absorption band near 1750 cm-1
...
The IR spectrum of a compound exhibits a broad absorption band at 2500-3000 cm-1
and a sharp band at 1710 cm-1
...
Which of the following reactions would constitute a reasonable synthesis of propyl
acetate?
OH
HA
A)
+
OH
O
B)
C)
OH
+
OH
+
pyridine
Cl
O
O
O
O
D) All of these
E) None of these
Ans: D
Topic: Synthesis
55
...
Mg, Et2O
ii
...
H3O+
OH
i
...
H3O+
i
...
OH−, H2O, heat
iii
...
Which of the reactions listed below would serve as a synthesis of acetophenone,
C6H5COCH3 ?
O
A)
C6H5
+ (CH3)2CuLi
Cl
O
B)
H3C
C)
Cl
O
AlCl3
+ C6H6
+ CH3MgI
OCH3
C6H5
D) Two of these
E) All of these
Ans: D
Topic: Synthesis
57
...
Cl2/OH− (excess)
A)
ii
...
CN
B)
Br
C)
Br
+
ii
...
Mg, Et2O
ii
...
H3O+
D) Answers A) and B) only
E) Answers A) and C) only
Ans: E
690
Chapter 18
Topic: Synthesis
58
...
Which reactant is unlikely to produce the indicated product upon strong heating?
2-methylpropanoic acid
A) 2,2-dimethylpropanedioic acid
Butanoic acid
B) 2-ethylpropanedioic acid
3-Pentanone
C) 2-methyl-3-oxo-pentanoic acid
2-Methyl-3-butanone
D) 2-methyl-4-oxo-pentanoic acid
3-Methyl-2-hexanone
E) 4-methyl-3-oxo-heptanoic acid
Ans: D
Topic: Synthesis
60
...
Choose the reagent(s) that would bring about the following reaction:
CH3CH2CH2COOH ⎯⎯⎯→ CH3CH2CH2CH2OH
A) H2/Ni
B) Li/liq NH3
C) LiAlH[OC(CH3)3]3
D) NaBH4, CH3OH
E) LiAlH4, ether
Ans: E
Topic: Synthesis
62
...
Choose the reagent(s) that would bring about the following reaction:
CH3C≡CCO2CH3 ⎯⎯⎯→ (E)-CH3CH=CHCO2CH3
A) H2/Ni
B) Li/liq NH3
C) LiAlH[OC(CH3)3]3
D) NaBH4, CH3OH
E) LiAlH4, ether
Ans: B
692
Chapter 18
Topic: Synthesis
64
...
Which of the following compounds is capable of forming a δ-lactone?
A) 5-hydroxypentanoic acid
B) Pentanedioic acid
C) 4-hydroxypentanoic acid
D) 3-hydroxypentanoic acid
E) 2-hydroxypentanoic acid
Ans: A
Topic: Synthesis
66
...
Which of the following would yield (S)-2-butanol?
i
...
OH , H2O, heat
−
B)
(R)-2-Bromobutane
C)
(S)-sec-Butyl acetate
OH , H2O, heat
OH−, H2O, heat
D) All of these
E) None of these
Ans: D
Topic: Synthesis
68
...
On theoretical grounds, one would predict that the (1:1) reaction of acetic propionic
anhydride with methyl alcohol would form chiefly:
A) Methyl acetate + propionic acid
B) Acetone + propionic acid
C) Methyl propionate + acetic acid
D) Methyl acetate + acetic acid
E) Methyl ethyl ketone + acetic acid
Ans: A
694
Chapter 18
Topic: Synthesis
70
...
Which carboxylic acid would decarboxylate when heated to 100-150°C?
CO2H
HO2C
I
A)
B)
C)
D)
E)
Ans:
O
CO2H
II
CO2H
HO2C
III
I
II
III
More than one of these
None of these
D
Topic: Methods and Miscellaneous
72
...
Which of the following is not a method for preparing butanoic acid?
A) CH3CH2CH2Br + NaCN; then H3O+, reflux
B) CH3CH2CH2MgBr + CO2; then H3O+
C) CH3CH2CH2OH + CO
D) CH3CH2CH2CO2Et + OH−/H2O; then H3O+
E) CH3CH2CH2CH2OH + KMnO4/OH−/H2O/heat; then H3O+
Ans: C
Topic: Methods and Miscellaneous
74
...
Which of these combinations will not produce benzoic acid?
A) C6H5CH2OH + KMnO4/OH−/H2O, heat; then H3O+
B) C6H5CH3 + KMnO4/OH−/H2O, heat; then H3O+
C) C6H6 + CO2, high pressure
D) C6H5COCH3 + Cl2/OH−/H2O; then H3O+
E) C6H5COCl + OH−/H2O; then H3O+
Ans: C
696
Chapter 18
Topic: Methods and Miscellaneous
76
...
γ - And δ-hydroxy acids can be esterified intramolecularly to form compounds known as
which of these?
A) Anhydrides
B) Cycloalkenes
C) Lactones
D) Lactams
E) Cyclic ketones
Ans: C
697
Chapter 18
Topic: Methods and Miscellaneous
78
...
B) Nitriles can be formed from (many) alkyl halides by nucleophilic substitution by
cyanide ion
...
D) Nitriles react with Grignard reagents to form tertiary alcohols
...
Ans: D
SHORT ANSWER QUESTIONS
Topic: Nomenclature
79
...
Ans: formic acid
Topic: Nomenclature
80
...
Ans: acetic acid
Topic: Reaction Mechanisms
81
...
Ans: leaving group
Topic: Miscellaneous
82
...
Ans: lactones; lactams
698
Chapter 18
Topic: Methods and Miscellaneous
83
...
Ans: Fischer esterification
Topic: Methods and Miscellaneous
84
...
Ans: saponification
Topic: Methods and Miscellaneous
85
...
Ans: amide
Topic: Methods and Miscellaneous
86
...
Ans: red
Topic: Miscellaneous
87
...
Ans: anhydride
Topic: Miscellaneous
88
...
Ans: increase; induction
Topic: Reactions
89
...
Ans: lactone (cyclic ester)
699
Chapter 18
Topic: Reactions
90
...
Ans: lactone (cyclic ester)
Topic: Miscellaneous
91
...
Ans: amide
Topic: Nomenclature
92
...
O
O
Ans:
O
Topic: Nomenclature
93
...
Ans:
CN
Topic: Nomenclature
94
...
OH
Ans:
Br
O
O
Topic: Nomenclature
95
...
O
Ans:
O
700
Chapter 18
Topic: Reaction Sequence
96
...
O
O
i
...
) CH3I
O
Ans:
?
OLi
2 equiv CH3Li
CH3I
OCH3
O
Topic: Reaction Sequence
97
...
O
i
...
) CH3CH2CH2NHCH3
OH
Ans:
O
O
SOCl2
OH
O
CH3CH2CH2NHCH3
Cl
N
Topic: Synthetic Strategy
98
...
KMnO , OH-, H O
O
Ans:
4
2
ii
...
Complete the following reaction sequence, giving details of all significant intermediates
...
KMnO4, OH-, H2O
ii
...
NaBH4, H2O
+
iv
...
KMnO4, OH-, H2O
ii
...
When propylbenzene is subjected to the sequence of reactions outlined below, the major
product is found to exhibit the following 1H NMR spectrum:
d 1
...
2 ppm, quartet
7
...
i
...
NaOH
iii
...
RCO3H
?
Ans: Reaction with NBS would lead to benzylic bromination, followed by nucleophilic
substitution to afford the corresponding alcohol
...
Br
NBS
OH
NaOH
CrO3
2
...
5 ppm
1
...
Complete the following reaction sequence, giving details of all significant intermediates
...
COCl2 (1 equivalent)
?
ii
...
Which of the compounds listed below is more acidic than 1-butanol?
A) Ethyl acetoacetate
B) 2-butanone
C) Ethyl pentanoate
D) All of these answers
E) Answers A) and B) only
Ans: A
Topic: Relative Acidities
2
...
Which of the following hydrogens is the most acidic?
O
II
I
A)
B)
C)
D)
E)
Ans:
O
I
II
III
IV
V
C
IV
III
O
V
O
Chapter 19
v
Topic: Relative Acidities
4
...
Which of the following compounds is the strongest acid?
OH
O
CN
NO2
NO2
O
II
I
O
III
CN
CN
CO2Et
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
E
V
Chapter 19
Topic: Relative Acidities
6
...
Which of the indicated hydrogens is most likely to be removed upon treatment with nbutyllithium?
(V)
H
H
H
H
H (IV)
H
S
H3C
H3C
(I)
A)
B)
C)
D)
E)
Ans:
S
H (III)
H
(II)
I
II
III
IV
V
C
Chapter 19
Topic: Reaction Products
8
...
NaOC2H5
O
?
ii
...
What would be the product of the following sequence?
O
O
O
+
O
O
i
...
H3O+
OH O
O
O
O
O
O
II
I
III
O
O
O
O
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
A
O
V
O
Chapter 19
Topic: Reaction Products
10
...
NaOC2H5, C2H5OH
+
?
O
O
ii
...
What is the product, Z, of the following reaction sequence?
O
H
N
H3O+
+
O
O
Ph
O
Ph
I
Ph
III
II
Ph
N
O
O
Ph
O
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
B
Z
(-H2O)
O
N
H3O+
PhCOCl
V
Chapter 19
Topic: Reaction Products
12
...
NaOH
ii
...
NaOEt
ii
...
Predict the product of the following reaction sequence
...
NaOC2H5
O
O
O
ii
...
NaOH
iv
...
What is the product, W, of the following reaction sequence?
O
(2 eq)
O
O
O
...
NaOH
heat
(-CO2)
+
ii
...
Predict the product of the following reaction sequence
...
NaOEt, EtOH
O
O
O
ii
...
H3O
iv
...
The product, L, of the following reaction sequence,
O
i
...
(CH3)3COK
H2N
NH2
EtO2C
CO2Et + NaOEt
−
iii
...
The product(s) of the reaction of 2 mol of ethyl butanoate with sodium ethoxide is(are):
O
A)
OH + NaOH
O
O
B)
O
C)
O
O
O
D)
O
O
O
E)
O
O
O
Ans: C
Chapter 19
Topic: Reaction Products
18
...
The product of the following reaction is:
O
weak
O
+
CN
base
O
O
OH
CN
CN
O
O
O
CN
O
I
II
III
O
O
OMe
IV
I
II
III
IV
V
D
NH O
OMe
CN
A)
B)
C)
D)
E)
Ans:
?
V
Chapter 19
Topic: Reaction Products
20
...
Malonic ester (diethyl malonate) is treated successively with sodium ethoxide (1 eq
...
What is the final product?
A) 4-Ethyl-2-methylpentanoic acid
B) 6-Methylheptanoic acid
C) 2-Ethyl-3-methylpentanoic acid
D) 2-Ethyl-4-methylpentanoic acid
E) Ethylisobutylmalonic acid
Ans: D
Topic: Reaction Products
22
...
), 1bromopentane, potassium tert-butoxide, iodomethane, hot aqueous NaOH, HCl, and
heat
...
What is the product of the Dieckmann condensation of this diester,
O
OEt
EtO
O
O
O
OEt
I
A)
B)
C)
D)
E)
Ans:
O
O
O
OEt
O
II
OEt
III
I
II
III
I and II
I, II, and III
D
Topic: Reaction Products
24
...
The Thorpe reaction of dinitriles is analogous to the Dieckmann condensation of
diesters
...
What product(s) result from the Claisen condensation carried out with an equimolar
mixture of ethyl acetate and ethyl propanoate?
O
O
O
O
I
I
II
III
IV
All of these
E
O
O
O
A)
B)
C)
D)
E)
Ans:
O
II
O
O
O
III
O
IV
Chapter 19
Topic: Reaction Products
27
...
What product is finally formed when the initial compound formed from cyclohexanone
and pyrrolidine is mixed with allyl chloride and that product is heated and then
hydrolyzed?
O
HO
N
II
I
O
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
B
III
O
V
Cl
Chapter 19
Topic: Reaction Products
29
...
O
ii
...
What is the structure for R?
i
...
C6H5CH2Br
H Ph
HgCl2
MeOH, H2O
S
S
R
Ph
O
Ph
Ph
CHO
CHO
I
II
III
OH
Ph
Ph
CHO
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
V
O
Chapter 19
Topic: Reaction Products
31
...
C4H9Li, Et2O
?
S S
Ph ii
...
HgCl2, CH3OH, H2O
S
S
S
S
H
Ph
Ph
Ph
S
II
I
III
Ph
O
O
Ph
IV
A)
B)
C)
D)
E)
Ans:
SH
V
I
II
III
IV
V
D
Topic: Synthesis
32
...
Which of the following might be used to synthesize the following substance?
OH
Ph
OH
O
A)
Ph
i
...
H3O+
O
iii
...
H2O
O
B)
B
...
, NaOEt, EtOH
O
+
ii
...
LAH, Et2O
iv
...
Ph
O
i
...
H3O
Br
+
iii
...
H2O
D) Answers A) and C)
E) Answers B), and C)
Ans: B
, Mg, Et2O
Chapter 19
Topic: Synthesis
34
...
Which of the following could be used to synthesize the following substance in good
yield?
O
OH
O
Cyclopentanone, ClCH2CH2COOH, AlCl3, heat
Cyclopentanone, (CH3CH2)2NH, HA, (-H2O); then BrCH2CH2COOC2H5; then
OH-, H2O, heat; then H3O+
C) 3-(2-hydroxycyclopentyl)propanal, KMnO4, OH-, heat; then H3O+
D) Answers A) and B)
E) Answers B) and C)
Ans: E
A)
B)
Topic: Synthesis
36
...
Which of the following would provide the best synthesis of 3-ethyl-6-methyl-2heptanone?
A) Ethyl acetoacetate + NaOC2H5 + CH3CH2I; then KO-t-Bu +
(CH3)3CCH2CH2Br; then NaOH; then H3O+; then heat
B) Ethyl acetoacetate + NaOC2H5 + (CH3)3CCH2Br; then KO-t-Bu + CH3CH2I;
then NaOH; then H3O+; then heat
C) Ethyl acetoacetate + NaOC2H5 + (CH3)2CHCH2CH2Br; then KO-t-Bu +
CH3CH2I; then NaOH; then H3O+; then heat
D) Ethyl acetoacetate + NaOC2H5 + (CH3)2CHCH2CH2CHBrCH2CH3; then
NaOH; then H3O+; then heat
E) Ethyl acetoacetate + NaOC2H5 + CH3CH2I; then KO-t-Bu + (CH3)2CHCH2Br;
then NaOH; then H3O+; then heat
Ans: C
Topic: Synthesis
38
...
Na
B)
O
NaOC2H5
H3O+
+
OC2H5 C2H5O OC2H5 C2H5OH
O
O
NaOC2H5
H3O+
+
OC2H5 C H OH
OC2H5 C2H5O
2 5
O
Ph
C)
Ph
OC2H5
+
O
O
D)
O
O
D
...
What product is formed during the following reaction?
O
O
i
...
HOAc
O
O
OC2H5
Ph
O
O
Ph
Ph
OC2H5
O
O
III
II
I
O
Ph
OH O
O
O
Ph
IV
A)
B)
C)
D)
E)
Ans:
OC2H5
V
I
II
III
IV
V
B
Topic: Synthesis
40
...
Which compound could be prepared using a Michael reaction?
O
O
O
HO
OC2H5
O
III
II
I
O
O
O
O
O
OC2H5
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
C
Topic: Synthesis
42
...
Which reagents would you use to prepare the following substance from ethyl
acetoacetate?
O
O
Ph
A)
i) NaH/DMSO; ii) PhCOCl; iii) OH−/H2O, heat; iv) H3O+; v) heat
B)
i) NaOEt/EtOH; ii) PhCOCH2Br; iii) OH−/H2O, heat; iv) H3O+; v) heat
C)
i) heat; ii) NaOEt/EtOH; iii) PhCOCH2Br
D)
i) NaOEt/EtOH; ii) PhCl
E)
i) NaOEt/EtOH; ii) PhCOCl; iii) OH−/H2O, heat; iv) H3O+; v) heat
Ans: A
Topic: Synthesis
44
...
B) It can condense with aldehydes and ketones
...
D) It is resonance stabilized
...
Ans: E
Chapter 19
Topic: Synthesis
45
...
What combination of reagents can be used to make the following substance via an
enamine?
O
O
O
I
+
NH
+
O
O
II
+
NH
+
O
O
III
+
Cl
+
O
NH
O
IV
A)
B)
C)
D)
E)
Ans:
+
O
+
NH2
I
II
III
IV
Both reactions II and III
C
Topic: Synthesis
47
...
Which organic reagents would you need to make 2-ethylheptanoic acid from diethyl
malonate?
A) Bromoethane, 1-bromopentane, sodium ethoxide, and potassium tert-butoxide
B) 3-Bromooctane and sodium ethoxide
C) 3-Bromoheptane and sodium ethoxide
D) 1-Bromopropane, 2-bromopentane, sodium ethoxide, and potassium tert-butoxide
E) 2-Bromoheptane and potassium tert-butoxide
Ans: A
Topic: Synthesis
49
...
NaOEt
ii
...
NaOEt
ii
...
NaOEt
ii
...
2-Heptanone can be synthesized by which reaction sequence?
−
A)
NaOEt
CH3(CH2)3Br i
...
OH heat
Ethyl acetoacetate
+
EtOH
ii
...
dil
...
H3O
−
i
...
OH heat
Ethyl acetoacetate CH3(CH2)3Br
+
ii
...
NaOEt, EtOH i
...
OH heat
Ethyl hexanoate
ii
...
H O+
Ethyl acetoacetate heat
3
Ans: A
Topic: Synthesis
51
...
NaOEt, EtOH
ii
...
Consider the synthesis above
...
Consider the synthesis below
...
The Knoevenagel condensation of p-methoxybenzaldehyde with ethyl acetoacetate in
the presence of diethylamine produces which of these?
CO2Et
O
OH
CO2Et
O
MeO
O
MeO
I
EtO2C
MeO
II
III
O
O
CO2Et
CO2Et
O
MeO
IV
A)
B)
C)
D)
E)
Ans:
O
MeO
V
I
II
III
IV
V
A
Topic: Synthesis
55
...
What alkylating agent would be used with 2-phenylethanal in the Corey-Seebach
method for the preparation of 6-methyl-1-phenyl-2-heptanone?
A) 1-bromo-4-methylpentane
B) 2-bromo-4-methylpentane
C) 1-bromo-6-methylheptane
D) 1-bromo-5-methylhexane
E) None of the above could be used
Ans: A
Chapter 19
Topic: General Information
57
...
+
N
:
It has another resonance structure :
C) It can be acylated at the ∝-carbon of the original carbonyl compound
...
E) All of the above are true
...
Which of the following statements is true of the following enamine?
N:
A)
B)
The enamine can be made from cyclopentanone + pyrrolidine
...
It can be alkylated
...
E
N
:
Topic: General Information
59
...
Which of these is not a reversible process?
A) Base-promoted ester hydrolysis
B) Acid-catalyzed ester hydrolysis
C) Aldol addition
D) Claisen condensation
E) Acetal formation
Ans: A
Topic: General Information
61
...
The Claisen condensation of which of these esters demands the use of (C6H5)3CNa as
the base (as opposed to sodium ethoxide)?
A) CH3CH2CH2CO2C2H5
B) CH3CH2CO2C2H5
C) C6H5CH2CH2CO2C2H5
D) (CH3)2CHCH2CO2C2H5
E) None of these
Ans: E
Topic: General Information
63
...
Ans: A
Chapter 19
Topic: General Information
64
...
Cyclization reactions, such as the Dieckmann condensation, are best carried out using
fairly dilute solutions of the compound to be cyclized
...
B) The reagents generally are expensive
...
D) Intermolecular condensation is minimized at low concentration
...
Ans: D
Topic: General Information
66
...
B) CH3O-Na+ is more difficult to prepare than CH3CH2O-Na+
...
D) Use of CH3O-Na+ would result in transesterification
...
Ans: D
Topic: General Information
67
...
Which structure represents an ester enolate?
O
O
O
O
O
O
I
II
A) I
B) II
C) III
D) IV
E) Both B) and C)
Ans: E
O
O
III
III
Topic: General Information
69
...
Which base is employed in the alkylation of ethyl pentanoate with methyl iodide?
A) Sodium methoxide
B) Sodium ethoxide
C) Sodium hydride
D) Potassium tert-butoxide
E) Lithium diisopropylamide
Ans: E
Topic: General Information
71
...
Compounds having two carbonyl groups separated by an intervening carbon atom are
called ____________
...
The pKa for protons on the carbon between two carbonyls is about 9-11
...
Ans: resonance delocalization of the negative charge over two carbonyls rather than
just one
Topic: Claisen condensation
74
...
Ans: Claisen
Topic: Dieckmann condensation
75
...
Ans: Dieckmann condensation
Topic: General Information
76
...
Ans: transesterification
Topic: Synthetic Strategy
77
...
Ans: acetone enolate
Topic: Malonic Ester synthesis
78
...
Ans: malonic ester synthesis
Topic: Active Hydrogen compounds
79
...
Ans: active hydrogen compounds; active methylene compounds
Topic: Synthetic Strategy
80
...
Ans: polarity reversal
Chapter 19
Topic: Knoevenagel Condensation
81
...
Ans: Knoevenagel condensation
Topic: Synthetic Strategy
82
...
This was specific for forming the kinetic enolate
in ketones
...
Topic: General Information
83
...
Ans: soporifics or sleep-inducers
Topic: Claisen Condensation
84
...
Ans: In order for Claisen condensation to occur efficiently, there must be at least 2
hydrogen atoms alpha to the ester group
...
Topic: Dieckmann Condensation
85
...
Ans: Dieckmann condensation of diethyl pentanedioate would afford a four-membered
ring
...
O
O
O
O
O
O
O
Topic: Dieckmann Condensation
86
...
Ans: A cyclization similar to Dieckmann condensation is likely to occur, giving 2propanoylcyclopentanone as the major product:
O
O
O
O
O
Chapter 19
Topic: Acylation of Active Hydrogen Compounds
87
...
NaH/aprotic solvent bypasses these issues and affords the expected
products in good yields
...
Explain how the reactivity of 1,3-dithianes is different from that of the aldehydes from
which they are typically prepared
...
By contrast, upon conversion into a dithiane and subsequent
treatment with butyllithium, this same carbon becomes negatively charged, and
reacts with electrophiles
...
Topic: Multistep Reaction Sequence:
89
...
CO2Et
i
...
Br
Br
iii
...
NaOH, heat
v
...
NaOH, heat
ii
...
What is the final product of the following reaction sequence? Give structural details of
all significant intermediates
...
O
?
O
ii
...
H2O
Ans:
O
:
NH
O
N
p-TsOH
Br
N
+
O
EtOH, reflux
O
O
H2O
O
O
O
Topic: Multistep Reaction Sequence:
91
...
NH , p-TsOH
i
...
Br
O
iii
...
What is the final product of the following reaction sequence? Give structural details of
all significant intermediates
...
Zn,
Br
O
?
ii
...
PCC
iv
...
CH3I
O
Ans:
i
...
NH4Cl
PCC
O
O
O
i
...
CH3I
O
O
O
Topic: Multistep Reaction Sequence:
93
...
EtO-, EtOH
CN
?
ii
...
EtO-, EtOH
CN
CN
ii
...
What is the final product of the following reaction sequence? Give structural details of
all significant intermediates
...
Cl2, FeCl3
ii
...
Suggest a reasonable synthetic strategy to carry out the following transformation
...
LAH
ii
...
Suggest a reasonable synthetic strategy to carry out the following transformation
...
What is the final product of the following reaction sequence? Give structural details of
all significant intermediates
...
EtO-, EtOH
O
ii
...
NaBH4, H2O
Ans:
O
O
O
O
i
...
H3O+
NaBH4
H2O
O
O
O
HO
O
O
Chapter 19
Topic: Multistep Reaction Sequence
98
...
i
...
CH3CH2COCl
O
iii
...
H3O+, heat
Ans:
O
O
O
i
...
CH3CH2COCl O
i
...
H3O+, heat
O
O
O
OH
O
O
Topic: Reaction Products
99
...
SH
S
Ans:
O HS
+
H3O
S
propanal
i
...
I
O
3-heptanone
HgCl2
CH3OH, H2O
S
S
Chapter 19
Topic: Reaction Products
100
...
O
+
O
O
O
i
...
H3O+
O
O
O
O
O
...
O
O
EtOH +
H
O
−:
O
O
O
:
O
O
:
Ans:
O
O
O
O
O
−
...
−
O
O
Chapter 20
MULTIPLE CHOICE QUESTIONS
Topic: Nomenclature
1
...
Which is a correct common name for the following substance?
N
A)
B)
C)
D)
E)
Ans:
Ethylethylisobutylamine
Diethylisobutylamine
sec-Butyldiethylamine
Ethylethyl-sec-butylamine
2-Diethylaminobutane
C
Topic: Nomenclature
3
...
What type of amine is N-methyl-2-methyl-3-hexanamine?
A) Primary
B) Secondary
C) Tertiary
D) Quaternary
E) None of these
Ans: B
747
Chapter 20
Topic: Nomenclature
5
...
Which reagent would serve as the basis for a simple chemical test that would distinguish
between the pair of compounds listed below?
H
N
NH2
and
A)
B)
C)
D)
E)
Ans:
AgNO3 in H2O
Dilute NaHCO3
Dilute NaOH
C6H5SO2Cl/OH-, then H3O+
Dilute HCl
D
Topic: Chemical Tests and Separations
7
...
Which reagent will distinguish between C6H5NH2 and (C6H5)2NH?
A) HCl (aq)
B) NaOH
C) C6H5SO2Cl/OH-, then H3O+
D) Br2/CCl4
E) KMnO4
Ans: C
748
Chapter 20
Topic: Chemical Tests and Separations, Nomenclature
9
...
Which reagent could be used to separate a mixture of aniline and toluene?
A) KMnO4 in H2O
B) Dilute NaOH
C) Dilute NaHCO3
D) Ag(NH3)2OH
E) Dilute HCl
Ans: E
749
Chapter 20
Topic: Chemical Tests and Separations
11
...
Treatment of W with
benzenesulfonyl chloride in base gives no reaction
...
The 1H NMR spectrum of W consists of:
δ 1
...
5
δ 3
...
3 (5H)
triplet,
quartet,
singlet,
multiplet,
The most likely structure for W is:
A)
N
H
B)
N
C)
N
D)
N
E)
N
Ans: B
Topic: Chemical Tests and Separations
12
...
What final product is expected from the following reaction sequence?
i
...
NaHCO3
?
iii
...
HONO, 0-5oC
v
...
What compound is likely to be obtained via the following reaction sequence?
i
...
CuCl
?
iii
...
NaOH, H2O
o
v
...
H3PO2
Br
Br
Br
Br
Br
Br
Cl
A)
B)
C)
D)
E)
Ans:
NO2
I
II
Cl
Cl
Br
Br
Br
Br
PO2H
III
I
II
III
IV
V
C
752
IV
V
Chapter 20
Topic: Reaction Products
15
...
NaCN
ii
...
What final product is expected when toluene is subjected to the following reaction
sequence?
i) KMnO4, NaOH; ii) H3O+ ( product = C7H6O2); iii) SOCl2;
iv) NH3 (product = C7H7NO); v) Br2, NaOH
A) C6H5CONH2
B) C6H5CH2NH2
C) p-CH3C6H4SO2NH2
D) p-CH3C6H4NH2
E) C6H5NH2
Ans: E
753
Chapter 20
Topic: Reaction Products
17
...
What would be the product of the following reaction sequence?
i
...
Ag2O, H2O
iii
...
Which product could not be formed during the following reaction?
NH2
HONO
0-5oC
?
OH
OH
I
II
III
HO
IV
A)
B)
C)
D)
E)
Ans:
OH
V
I
II
III
IV
V
E
755
Chapter 20
Topic: Reaction Products
20
...
Fe/HCl
iv
...
Br2/H2O
v
...
H3PO2
Cl
Br
Br
OH
II
I
A)
B)
C)
D)
E)
Ans:
Br
Br
PO2H
Br
III
Br
PO2H
NO
IV
Br
NO2
V
I
II
III
IV
V
B
Topic: Reaction Products
21
...
) NaNO2, H2SO4, dil
...
Which is the predominant product formed when m-dinitrobenzene is treated with
H2S/NH3 ?
A) m -HSC6H4NH2
B) m -C6H4(NH2)2
C) m -HOC6H4NH2
D) m -H2NC6H4NO2
E) C6H5NH2
Ans: D
756
Chapter 20
Topic: Reaction Products
23
...
HONO, 0-5oC
ii
...
What is the final product?
OH
i
...
OH
C7H9N i
...
H2O
product
i
...
H2O, Cu2O,
Cu(NO3)2
Final Product
A)
B)
C)
D)
E)
Ans:
2-Bromo-4-methylaniline
2,6-Dibromo-4-methylaniline
2,6-Dibromo-4-methylphenol
2,4-Dibromophenol
3,5-Dibromotoluene
C
757
Chapter 20
Topic: Reaction Products
25
...
What would be the product of the following reaction sequence?
i) KMnO4, NaOH, heat
Br
ii) H3O+
?
iii) PCl5
iv) NaN3
v) heat
vi) H2O
A)
B)
C)
D)
E)
Ans:
p-bromobenzamide
p-bromobenzaldehyde oxime
p-bromobenzenesulfonamide
p-bromoaniline
4-bromo-3-chlorobenzoic acid
D
758
N-Br
O
V
Chapter 20
Topic: Reaction Products
27
...
HONO, 5oC
C6H6N2O2
ii
...
When an equimolar mixture of ammonia and butyl bromide reacts, which of these
products will form?
A) Butylamine
B) Dibutylamine
C) Tributylamine
D) Tetrabutylammonium bromide
E) All of these
Ans: E
Topic: Reaction Products
29
...
Which of the following reactions would yield C6H5CH2NH2?
A)
i
...
LiAlH4, ether
iii
...
NaN3
Br
ii
...
H2O
D) All of these
E) Answers B) and C) only
Ans: E
Topic: Synthesis
31
...
HNO3, H2SO4
ii
...
NaOH, H2O
Cl
B)
i
...
Br2,OH
i
...
HONO, 0-5oC, ether
iii
...
Which of the following might be used to synthesize m-bromoaniline?
A)
i
...
Fe, HCl
iii
...
Br2, H2O
Cl
B)
i
...
HNO3, H2SO4
iii
...
Br2, FeBr3
O
ii
...
NH3
iv
...
The best synthesis of 3,5-dibromotoluene would be:
A) Toluene, Br2, Fe and heat
B) p-CH3C6H4NH2, Br2, H2O; then HONO, 0-5°C; then H3PO2
C) Toluene, fuming HNO3, H2SO4; then NH3, H2S; then HONO, 0-5°C; then CuBr
D) m-Dibromobenzene, CH3Cl, AlCl3, heat
E) m-Bromotoluene, HNO3, H2SO4; then NH3, H2S; then HONO, 0-5°C; then CuBr
Ans: B
Topic: Synthesis
34
...
The best synthesis of m-fluoronitrobenzene would be:
A) Nitrobenzene, fuming HNO3, H2SO4, heat; then NH3, H2S; then HONO, 0-5°C;
then HBF4; then heat
B) Aniline, F2, heat
C) Fluorobenzene, HNO3, H2SO4, heat
D) o-Nitroacetanilide, NH3, H2S; then Br2, OH-; then HF
E) m-C6H4(NH2)2, HONO, 0-5°C; then CuNO2; then HBF4
Ans: A
Topic: Synthesis
36
...
), hν; then hot NaOH; then HCN
Ans: A
Topic: Synthesis
37
...
(1mol) 2-bromopentane + (1mol) NH3
II
...
Phthalimide
A)
B)
C)
D)
E)
Ans:
KOH
2-bromopentane
I
II
III
I and II
II and III
E
762
LAH
Et2O
NH2NH2
C2H5OH
Chapter 20
Topic: Synthesis
NH2
38
...
Identify the best method(s) to prepare
NH2
CH3I
A)
(1 mol)
(1 mol)
(CH3)2NH
B)
O
H2, Ni
C)
O
...
Your task is to convert o-xylene into o-diaminobenzene
...
How would one carry out the following transformation: ?
?
H2N
A)
B)
C)
D)
E)
Ans:
Cl
Cl
NaNO2,HCl, 0-5°C; then HNO3
NaNO2,HCl, 0-5°C; then H3PO2
NaNO2,HCl, 0-5°C; then H2,Ni
C6H5SO2Cl, OH-; then HCl
NaH, DMSO
B
Topic: Synthesis
42
...
Consider the synthesis below
...
Consider the synthesis below
...
Consider the synthesis below
...
Consider the synthesis below
...
HCl, NaNO2
ii
...
What reagent can effect the following transformation?
CN
Br
A)
B)
C)
D)
E)
Ans:
Br
Br
?
CO2H
Br
CO2; then H3O+
H3O+, heat
Mg; then CO2; then H3O+
LiAlH4, ether
KMnO4, OH-, heat; then H3O+
B
Topic: Synthesis
48
...
What reagent can effect the following transformation?
NO2
NO2
?
NO2
A)
B)
C)
D)
E)
Ans:
NH2
-
Fe/HCl; then OH
H2S, NH3, C2H5OH
H2, Ni, high pressure
Zn(Hg)/HCl
Raney Ni
B
Topic: Synthesis
50
...
What is reagent “Z”?
NO2
NO2
o
i
...
"Z"
NH2
A)
B)
C)
D)
E)
Ans:
Cl
CuCl
CuCl2
NaCl
KCl
HCl/heat
A
Topic: Synthesis
51
...
Consider the following reaction: what is the expected product?
NH2
Br2, H2O
?
Cl
Cl
NH2
Br
Br
H2N
Br
Cl
Br
NH2
Cl
I
Br
Br
II
III
NH2
NH2
Br
Br
Br
Cl
IV
A)
B)
C)
D)
E)
Ans:
Cl
V
I
II
III
IV
V
B
Topic: Synthesis
53
...
What is reagent “Y”?
NH2
Br
Br
i
...
"Y"
Cl
A)
B)
C)
D)
E)
Ans:
Br
Br
Cl
Br2/FeBr3
CuBr
CuBr2
H3PO2
H3PO4
D
768
Chapter 20
Topic: Synthesis
54
...
What is the principal product when aniline is treated with sodium nitrite and
hydrochloric acid at 0-5°C and this mixture is added to p-ethylphenol?
OH
OH
OH
N
N
N
I
II
N
III
OH
HO
N
N
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
A
Topic: Synthesis
56
...
Which combination of reactants will not produce
O
A)
i
...
H2O
H
O
B)
H
i
...
H2O
C)
NaBH3CN
+ H2N
H
N
?
O
D)
O
E)
H
N
+
H2N
NaBH3CN
Br2, NaOH
O
Ans: E
Topic: Synthesis
58
...
Which would be a good method to synthesize m-nitroaniline?
A) 1,3-Dinitrobenzene + H2S and NH3 in EtOH
B) Aniline + HNO3/H2SO4
C) Aniline + CH3COCl; then HNO3/H2SO4
D) Nitrobenzene + NH3 and AlCl3
E) More than one of the above
Ans: A
771
Chapter 20
Topic: Basicity
60
...
Which of the following compounds would be the strongest base?
N
N
H
NH2
I
III
II
O
OH
N
IV
A)
B)
C)
D)
E)
Ans:
N
V
I
II
III
IV
V
D
Topic: Basicity
62
...
Arrange the following amines in order of decreasing basicity in aqueous solution:
NH3
I
A)
B)
C)
D)
E)
Ans:
CH3CH2CH2NH2
II
(CH3CH2CH2)2NH
III
(CH3CH2CH2)3N
IV
IV > III > II > I
III > II > IV > I
I > IV > II > III
II > III > I > IV
III > I > II > IV
B
Topic: Basicity
64
...
Which of these is the strongest acid?
NH3
NH3
NH3
O2N
II
I
III
NH3
NH3
I
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
B
773
Chapter 20
Topic: Basicity
66
...
Which of these compounds is soluble in dilute sodium hydroxide solution?
O
O
NH
I
O
S
O
H
N
N
III
II
O
N
H
IV
A)
B)
C)
D)
E)
Ans:
N
H
V
I
II
III
IV
V
A
774
Chapter 20
Topic: Reactive Intermediates and General Considerations
68
...
...
Which of these compounds is expected to possess the lowest boiling point?
A) CH3CH2CH2CH2CH2NH2
B) CH3CH2CH2NHCH2CH3
C) (CH3CH2)2NCH3
D) (CH3CH2)2CHOH
E) (CH3)3CCH2NH3+ ClAns: C
Topic: Reactive Intermediates and General Considerations
70
...
When the aromatic -NH2 group is to be converted to an -OH group via a diazonium salt,
the nitrous acid used is generated in situ by the reaction of a nitrite salt with which acid?
A) HCl
B) HBr
C) HNO3
D) H2SO4
E) CH3CO2H
Ans: D
Topic: Reactive Intermediates and General Considerations
72
...
When the process ArNH2 ⎯⎯⎯⎯→ ArY is carried out via an intermediate
diazonium salt, this salt is isolated only in the case in which Y is which of these groups?
A) -F
B) -Cl
C) -Br
D) -I
E) -CN
Ans: A
Topic: Reactive Intermediates and General Considerations
74
...
B) The racemic mixture is converted into a single isomer in the basic solvent
...
D) The diastereomeric salts have different boiling points
...
Ans: C
776
Chapter 20
Topic: Reactive Intermediates and General Considerations
75
...
If the three alkyl groups of a tertiary amine are all different, the amine will be chiral
...
Ans: nitrogen inversion
Topic: Relative Basicity
77
...
These factors are:
__________________
...
Arylamines are less basic than alkylamines because of _______________
...
Explain how an enantiomerically pure amine can be used to resolve racemic forms of
acidic compounds
...
Topic: General
80
...
Ans: Sodium azide
Topic: General, Synthesis of Amines
81
...
These methods are: __________________
...
While primary amines react with nitrous acid to generate diazonium salts, secondary
amines react with nitrous acid to produce _____________
...
Azo compounds are usually intensely colored because _________________
...
Chemicals that inhibit the growth of microbes are called ______________
...
Eliminations that follow the Hofmann Rule tend to give the ______________ alkene as
the major product
...
Draw the structure corresponding to the following name:
(4Z,3S)-2,4,7-trimethyl-3-amino-4-octene
Ans:
H2N
H
Topic: Nomenclature
87
...
Before modern spectroscopic methods were developed, structures of many complex
amines were elucidated by examining the products obtained during Hofmann
elimination of their quaternary ammonium hydroxides
...
What product(s) is (are) likely to be formed if 3,4dimethylpiperidine is subjected to the above procedure?
Ans: The reaction sequence would need to be repeated twice to obtain a nitrogen-free
product, since the starting compound is a secondary amine
...
N
H
CH3I
(excess)
N I
Ag2O
H2O
heat
N OH
N
i
...
Ag2O, H2O
iii
...
What final product is likely when cyclohexene is subjected to the following reaction
sequence? Give structural details of all significant intermediates
...
) H3O+, H2O; ii) PCC; iii) (CH3)2NH; iv) NaBH3CN
Ans:
OH
O
N
+
H3O
N
(CH3)2NH
PCC
H2O
779
OH
NaBH3CN
Chapter 20
Topic: Multistep Reaction Sequence
90
...
i
...
)CH3CH2COCl; iii
...
LiAlH4, Et2O
ii
...
What final product is likely when acetophenone is subjected to the following reaction
sequence? Give structural details of all significant intermediates
...
) NaBH3CN
Ans:
O
O
Br2
FeBr3
N
CH3CH2CH2NH2
Br
Br
NaBH3CN
NH
Br
780
Chapter 20
Topic: Gabriel Synthesis
92
...
Ans:
O
NH
O
KOH
O
Br
NK
O
N
O
O
NH2NH2
EtOH
reflux
O
NH
NH
+
NH2
O
3-amino-2-methylpentane
Topic: Synthesis, Hofmann Rearrangement
93
...
HNO3, H2SO4 ; ii) KMnO4, OH-, H2O; iii) H3O+; iv) SOCl2; v) NH3
vi) Br2, OHO
O
O
−
i
...
H3O
Br
4-bromobenzaldehyde
SOCl2
O
NH2
NH2
O
Cl
NH3
Br2, NaOH
NO2
NO2
Br
Br
4-bromo-3-nitro-aniline
781
NO2
Br
Chapter 20
Topic: Synthetic Strategy
94
...
Outline the steps involved in the synthesis of 3-chloro-4-fluorophenyl acetate from 4aminoacetophenone
Ans: i) Cl2, FeCl3; ii) NaNO2, H3O+, 0-5oC; iii) HBF4; iv) heat ; v) MCPBA
O
O
O
NaNO2, H3O
Cl2
FeCl3
NH2
+
o
0-5 C
Cl
Cl
NH2
N2+
4-aminoacetophenone
i
...
heat
O
O
O
MCPBA
Cl
F
3-chloro-4-fluorophenyl acetate
782
Cl
F
Chapter 20
Topic: Synthesis, Nomenclature
96
...
Explain why cyclohexylamine is a stronger base than aniline
Ans: There are two major reasons for the observed difference in basicity between the
two substances:
In aniline, the electron pair on N is delocalized over the aromatic ring
i)
through resonance: this has the effect of decreasing the electron
density at the nitrogen atom, relative to cyclohexylamine, in which no
such resonance delocalization can occur, leading to lower base strength
for aniline
...
Topic: Product Analysis by NMR
98
...
In order to determine if your reaction has worked as planned, you have
obtained the 1H NMR of your crude product
...
These
signals are characteristically somewhat broad, and should disappear (or decrease
markedly) if the spectrum is rerun with an added drop of D2O to the original
sample prepared for obtaining the 1H NMR
...
783
Chapter 21
MULTIPLE CHOICE QUESTIONS
Topic: Nomenclature
1
...
The common name for 3-methylphenol is which of these?
A) Catechol
B) m -Cresol
C) m-tolylol
D) Hydroquinone
E) p-Xylenol
Ans: B
Topic: Nomenclature
3
...
What is the systematic (IUPAC) name for
OH
OH
A)
B)
C)
D)
E)
Ans:
m-Hydroxyphenol
m-Dihydroxybenzene
Resorcinol
1,3-dihydroxybenzene
1,3-Benzenediol
E
784
Chapter 21
Topic: Nomenclature
5
...
What is the systematic (IUPAC) name for
OH
NO2
A)
B)
C)
D)
E)
Ans:
m-Hydroxy-p-nitrotoluene
3-Hydroxy-4-nitrotoluene
5-methyl-2-nitrophenol
3-methyl-2-nitrophenol
2-Hydroxy-4methylnitrobenzene
C
Topic: Nomenclature
7
...
Which of the following is 5-bromo-3-methyl-1-naphthol?
OH
OH
OH
Br
Br
Br
I
II
III
OH
HO
Br
Br
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
B
Topic: Acid/Base
9
...
Which of the following phenols would have the smallest pKa?
NO2
O
HO
O
OH
OH
I
O
II
III
O
NH2
OH
HO
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
C
Topic: Acid/Base
11
...
Which of the following compounds would you expect to be the strongest acid?
A) CH3OH
B) C6H5CH2OH
C) p-CH3C6H4OH
D) C6H5OH
E) p-NO2C6H4OH
Ans: E
Topic: Acid/Base
13
...
Which of the following would be the strongest acid?
HO
HO
CH3
OH
I
III
II
OH
OH
F3C
Br
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
D
788
Chapter 21
Topic: Acid/Base
15
...
Which would be soluble in aqueous sodium bicarbonate?
A) Benzoic acid
B) 4-Methylphenol
C) 2,4-Dinitrophenol
D) More than one of these
E) All of these
Ans: D
Topic: Acid/Base
17
...
Which reagent will distinguish between C6H5OCH3 and p-CH3C6H4OH?
A) NaOH (aq)
B) NaHCO3 (aq)
C) H2CrO4
D) A) and B)
E) None of these
Ans: A
Topic: Acid/Base
19
...
Which of these species is the strongest base?
O
O
O
H3C
I
Cl
II
III
O
O
O2N
I
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
B
Topic: Reaction Products
21
...
HO
HBr
Br
Br
HO
HO
Br
Br
HO
Br
I
A)
B)
C)
D)
E)
Ans:
II
III
I
II
III
IV
There is no net reaction
...
Refluxing anisole, CH3OC6H5, with excess concentrated HBr would yield which of
these product mixtures?
A) C6H5Br + CH3OH
B) C6H5OH + CH4
C) C6H5OH + CH3OH
D) C6H5Br + CH3Br
E) C6H5OH + CH3Br
Ans: E
Topic: Reaction Products
23
...
What product(s) would you expect from the following reaction?
Br
i
...
H3O
+
Br
HO
NaO
NO2
O2N
I
A)
B)
C)
D)
E)
Ans:
NO2
O2N
HO
NH2
III
II
I
II
III
Substantial amounts of I and II
Substantial amounts of I, II, and III
A
Topic: Reaction Products
25
...
What products would you expect from the following reaction?
i
...
H3O+
A)
B)
C)
D)
E)
Ans:
2-Methylphenol
3-Methylphenol
4-Methylphenol
A) and B)
B) and C)
E
Topic: Reaction Products
27
...
Which products would be formed in the following reaction?
OCH3
H3C
A)
B)
C)
D)
E)
Ans:
conc HBr (excess)
heat
?
Methoxybenzene + methyl bromide
2-Methylphenol + methyl bromide
2-Bromotoluene + methanol
2-Bromotoluene + methyl bromide
Bromobenzene + methyl bromide
B
794
Chapter 21
Topic: Reaction Products
29
...
NaOH
C10H14O
(para-isomer) ii
...
What products(s) would you expect from the following reaction?
Cl
H3C
NaNH2
NH3(l), -33oC
?
NH2
H3C
NH2
H3C
alone
I
A)
B)
C)
D)
E)
Ans:
alone
NH2
III
II
I
II
III
Products I and II
All of the above
D
Topic: Reaction Products
31
...
H2SO4, 100oC
phenol
?
2
...
dil
...
What is the IUPAC name of the final product obtained via the following reaction
sequence?
1
...
NaOH
3
...
What is the IUPAC name of the final product obtained via the following reaction
sequence?
2-bromophenol 1
...
Butanoyl chloride, AlCl3
3
...
conc HBr, heat
A) 1-butanoyl-3-bromo-4-methoxybenzene
B) 2-bromo-4-butylphenol
C) 3-bromo-1-butyl-4-methoxybenzene
D) 3,4-dibromo-1- butanoylbenzene
E) None of the above correctly describes the product
Ans: B
Topic: Reaction Products
34
...
H2, Ni
2-nitrophenol
?
2
...
KI
4
...
What is the final product obtained via the following reaction sequence?
1
...
Mg, Et2O
3
...
H3O+
5
...
What product should be obtained if benzyne is generated in the presence of 1,3butadiene?
I
II
III
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
A
Topic: Reaction Products
37
...
When sodium phenoxide is heated to 125°C with carbon dioxide under pressure and the
product mixture acidified, which of these is produced?
O
OH
O
O
OH O
HO
OH
I
II
O
III
OH O
OH
OH
HO
IV
A)
B)
C)
D)
E)
Ans:
OH
V
I
II
III
IV
V
B
799
Chapter 21
Topic: Reaction Products
39
...
What is the product of the reaction of 1 mol of p-benzoquinone with 1 mol of isoprene
(2-methyl-1,3-butadiene)?
O
O
O
O
I
O
III
II
O
O
O
O
IV
A)
B)
C)
D)
E)
Ans:
O
V
I
II
III
IV
V
A
801
Chapter 21
Topic: Reaction Products
41
...
What is the product of the reaction of phenol and chloroacetic acid in basic solution,
followed by acidification?
O
Cl
O
OH O
OH
Cl
O
O
I
II
OH
O
III
OH
OH
O
O
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
D
803
Chapter 21
Topic: Reaction Products
43
...
What product is likely to be obtained when 1-bromo-2-nitrobenzene is heated with
aqueous NaHCO3?
A) 2-bromophenol
B) 2-nitrophenol
C) 2-bromophenyl carbonate
D) 2-nitrophenyl carbonate
E) Sodium 2-nitrophenoxide
Ans: E
Topic: Reaction Products
45
...
What product is likely to be obtained when 1-fluoro-2,4-dinitrobenzene is treated with
sodium ethoxide?
A) 2,4-dinitrophenol
B) 1-ethoxy-2,4-dinitrobenzene
C) 2,4-diethoxy-1-fluorobenzene
D) 2,4-dinitrophenylsodium
E) None of the above: no reaction is likely to occur
Ans: E
Topic: Reaction Products
47
...
Which of the following would provide a synthesis of aspirin,
o-CH3COOC6H4COOH ?
A) C6H5COOH, CH3COOH, AlCl3, heat; then H2O
B) CH3COOC6H5, CO2, heat; then H3O+
C) CH3COOC6H5, HCOOC2H5, C2H5O-; then H3O+; then OHD) C6H5OH, CO2, H3O+; separate isomers; then CH3COOH, AlCl3
E) C6H5OH, OH-, CO2, heat, pressure; then H3O+; then (CH3CO)2O
Ans: E
Topic: Synthesis
49
...
A) Chlorobenzene + NaOH at 350°C; then H3O+
B) Benzene + O2
C) C6H5CH(CH3)2 + O2; then H3O+, heat
D) A) and B)
E) A) and C)
Ans: E
805
Chapter 21
Topic: Synthesis
50
...
Which of these is an acceptable synthesis of phenetole (ethyl phenyl ether)?
A)
CH3CH2ONa
Chlorobenzene
100oC
B)
C)
Sodium phenoxide
Sodium phenoxide
CH3CH2I
70oC
(CH3CH2O)2SO2
o
100 C
D)
Phenol
CH3CH2OH, H2SO4
70oC
E) More than one of these
Ans: E
Topic: Synthesis
52
...
Which of these is a satisfactory method for the preparation of m-nitrophenol from
benzene?
A) i) HNO3 / H2SO4; ii) Sn / HCl; iii) NaNO2, H2SO4, H2O, 0-5oC;
iv) Cu2O, Cu2+, H2O; v) HNO3
iv) H3O+
B)
i) Cl2, Fe; ii) HNO3 / H2SO4; iii) NaOH, H2O;
C)
i) HNO3/H2SO4; ii) Cl2, Fe; iii) NaOH, H2O;
D)
i) 2 HNO3 / 2 H2SO4; ii) NH3, H2S; iii) NaNO2, H2SO4, H2O, 0-5oC;
iv) Cu2O, Cu2+, H2O
E)
i) HNO3 / H2SO4; ii) NaOH / fusion; iii) H3O+
Ans: D
Topic: Synthesis
54
...
NaOH, H2O
O
O
ii
...
NaNO2, H2SO4, H2O, 0-5oC
E)
ii
...
Which of the following would be most likely to undergo a nucleophilic substitution
reaction with aqueous sodium hydroxide by an addition-elimination mechanism?
Br
Br
Br
O
O
I
II
III
Br
NO2
Br
NO2
IV
A)
B)
C)
D)
E)
Ans:
O2N
NO2
V
I
II
III
IV
V
D
Topic: Relative Reactivities and General Considerations
56
...
In nucleophilic aromatic substitution, the attacking species (the nucleophile) necessarily
is:
A) A Lewis base
B) Neutral
C) Positively charged
D) Negatively charged
E) Electron deficient
Ans: A
808
Chapter 21
Topic: Relative Reactivities and General Considerations
58
...
Which is the leaving group when the following substance reacts with sodium cyanide in
DMSO solution?
I
Br
Br
H
VH
II
III
NO2
A)
B)
C)
D)
E)
Ans:
IV
I
II
III
IV
V
A
Topic: Relative Reactivities and General Considerations
60
...
Which of these resonance structures makes the greatest contribution to the hybrid for the
intermediate in the SNAr reaction of o-chloronitrobenzene with methoxide ion?
H3CO
Cl
O
H3CO
Cl
O
H3CO
O
O
II
H3CO
Cl
O
N
O
I
III
O
H3CO
Cl
N
O
N
O
O
IV
A)
B)
C)
D)
E)
Ans:
Cl
N
N
V
I
II
III
IV
V
E
Topic: Relative Reactivities and General Considerations
62
...
Phenol is less reactive than expected in Friedel-Crafts acylations for which of these
reasons?
A) The acid chloride or anhydride hydrolyzes under the reaction conditions
...
C) Interaction of the -OH group with AlCl3 forms a species less reactive than phenol
...
E) The aromatic ring complexes with AlCl3 with a resulting decrease in phenol
reactivity
...
Thymol, isolated from thyme, has the following structure:
OH
Which of the following types of signal is NOT expected to be observed in its NMR
spectrum?
A) singlet
B) doublet
C) triplet
D) septet
E) all of the above types of signals are expected to be observed
Ans: C
Topic: Spectroscopic Analysis
65
...
Eugenol, isolated from cloves, has the following structure:
OH
O
Which of the following signals is NOT expected to be observed in its NMR spectrum?
A) Singlet at ~4 ppm (3H)
B) Doublet at ~2
...
Compound L has the molecular formula C11H16O
...
The infrared spectrum of L shows a broad absorption band in the
3200-3600 cm-1 region; its 1H NMR spectrum consists of:
triplet,
singlet,
quartet,
singlet,
multiplet,
δ 0
...
2
δ 1
...
5
δ 7
...
The most important laboratory synthesis of phenols is by _______________
...
The Claisen and Cope rearrangements are two examples of a general class of reactions
called ___________
...
The carbon-halogen bonds in aryl and vinyl halides are both __________ and
_____________ than the corresponding bonds in alkyl halides
...
Nucleophilic aromatic substitution reactions (SNAr) take place via a delocalized
carbanion intermediate called a ______________
...
Nucleophilic aromatic substitution reactions (SNAr) require three components: a good
leaving group on the aromatic ring, a strong nucleophile, and ________________
...
In general, there are two types of nucleophilic aromatic substitution mechanisms
...
Ans: addition-elimination or SNAr; elimination-addition or benzyne
Topic: Benzyne Intermediate
74
...
Ans: the two carbons involved in the extra π bond are sp hybridized, causing a severe
amount of bond angle distortion and strain
Topic: Nomenclature
75
...
Ans: phenol
Topic: Industrial Synthesis
76
...
Ans: cumene hydroperoxide method
813
Chapter 21
Topic: Industrial Synthesis
77
...
Ans: benzene; propene; acetone
Topic: Nomenclature
78
...
Draw the structure corresponding to the following IUPAC name:
(R)-2-Bromo-5-(3-methylpentyl)phenol
H CH3
Ans:
Br
OH
Topic: Nomenclature
80
...
Give the IUPAC name of the following substance:
H3C
H
O
HO
O
Ans: (R)-methyl 6-(4-hydroxyphenyl)-4-methylhexanoate
814
Chapter 21
Topic: Relative Acidity
82
...
Suggest a simple chemical test to distinguish between 4-methylphenol and 2,4,6trinitrophenol, briefly explaining your rationale
...
However,
only 2,4,6-trinitrophenol, being significantly more strongly acidic, is likely to
react with aq NaHCO3, releasing gaseous CO2 (easily observed as effervescence)
...
NO2
OH
OH
O2N
NO2
stronger acid
gives CO2 with NaHCO3(aq)
weaker acid
no reaction with NaHCO3(aq)
Topic: Reaction Product
84
...
O
Ans: O
Diels Alder
+
Reaction
O
1 mol
O
2 mol
815
Chapter 21
Topic: Reaction Product
85
...
Draw the structure of the final product obtained when 2-nitrophenol reacts with acetic
anhydride in presence of base
...
Draw the structure of the final product obtained when 1-chloro-2,4-dinitrobenzene is
heated with aqueous NaHCO3 at 100oC, followed by neutralization with H3O+
...
NaHCO3 (aq), 100oC
+
ii
...
Draw the structure of the final product obtained when 3-methylphenol is subjected to
the following reaction sequence:
i) NaOH; ii) CH3CH2CH2OSO2OCF3
Ans:
OH
O
i) NaOH
ii) CH3CH2CH2OSO2OCF3
Topic: Reaction Sequence
89
...
The insecticide Sevin is synthesized from 1-naphthol and methyl isocyanate
(CH3-N=C=O)
...
O
Ans:
OH
N
H
O
+ CH3-N=C=O
Sevin
Topic: Synthesis
91
...
Indicate the synthetic steps involved in this synthesis and
draw the structure of Orange II
...
Draw the structure of the product likely to be obtained from the reaction between
acetoacetic ester, bromobenzene and 2 molar equivalents of sodium amide (in liquid
ammonia)? Briefly explain your rationale
...
1 equivalent of sodium
amide is likely to promote elimination to form benzyne, while the 2nd equivalent
of base would generate the anion of acetoacetic ester, which can then react with
the benzyne to give the following product
...
Outline the steps involved in the synthesis of 3-bromo-4-methylphenol from 4nitrotoluene
Ans: i
...
NaNO2, H2SO4
0-5oC
ii
...
A key step in the industrial synthesis of phenol from cumene is the oxidation of cumene
to cumene hydroperoxide with oxygen
...
O2
O OH
95-135oC
cumene hydroperoxide
cumene
Ans: This is a radical chain reaction
...
The ensuing chain reaction leads to the formation of cumene
hydroperoxide
...
...
O-O
...
O
O
...
+
H
O
OH +
cumene hydroperoxide
819
...
The industrial synthesis of phenol from cumene involves the acid hydrolysis of the key
intermediate, cumene hydroperoxide (formed from cumene via oxidation)
...
Which other industrially
important substance is produced as a by-product in this reaction?
H3O+
O OH
OH
50-90oC
cumene hydroperoxide
phenol
Ans: This is a hydrolytic rearrangement reaction
...
Nucleophilic addition to the resultant carbocation ultimately leads to the
formation of phenol
...
H3O+
O OH
OH + O
50-90oC
cumene hydroperoxide
O OH
phenol
H3O+
O OH2
+
- H2O
acetone
+
cumene hydroperoxide
O
- H3O+
+ HO
acetone
O
H2O
HO
H
O
+
phenol
820
+
H2O
O
Chapter 21
Topic: Synthesis
96
...
When phenol is nitrated with dilute nitric acid, a mixture of o- and p- substituted
products is obtained
...
However, analogous products from the nitration of methoxybenzene cannot
be similarly separated by steam distillation
...
Ans: In order for efficient separation of substances (from a mixture) by steam
distillation, there must be relatively large differences in volatility
...
Differences in the volatility of the o- and p- nitrophenols may be predicted by
considering hydrogen bonding effects: o-nitrophenol can exhibit intramolecular
hydrogen bonding, while p-nitrophenol can exhibit intermolecular hydrogen
bonding
...
By contrast, since no hydrogen bonding is possible in the products obtained by
nitration of methoxybenzene, there is no predictable difference in volatility
...
O
O
N
H
O
O
O
N
O
N
H
O
O
o-nitrophenol
intramolecular hydrogen bonding
more volatile
OCH3
methoxybenzene
O
H
p-nitrophenol
intermolecular hydrogen bonding
less volatile
OCH3
+
O2N
OCH3
NO2
no hydrogen bonding in either product:
volatility differences not likely to be significant
822
Chapter 21
Topic: Synthesis
98
...
Outline the steps involved in the synthesis of 3-nitrophenol from benzoic acid
Ans: i) HNO3, H2SO4 ; ii) SOCl2; iii) NH3; iv) Br2, NaOH; v) NaNO2, H2SO4,
0-5oC; vi) Cu2O, Cu2+, H2O
or
i) HNO3, H2SO4 ; ii) SOCl2; iii) NaN3; iv) heat; v) H2O; vi) NaNO2, H2SO4,
0-5oC; vii) Cu2O, Cu2+, H2O
O2N
CO2H
OH
3-nitrophenol
benzoic acid
O
O
OH
HNO3
H2SO4
O
OH
O
Cl
SOCl2
NH2
NH3
NO2
NO2
i) NaN3
ii) heat
iii) H2O
NO2
Br2
NaOH
OH
NH2
o
i) NaNO2, H2SO4, 0-5 C
NO2
ii) Cu2O, Cu2+, H2O
3-nitrophenol
823
NO2
Chapter 21
Topic: Synthesis, Grignard Synthesis
100
...
Ans: i) NaOH ; ii) CH3I; iii) Br2, FeBr3 ; iv) Mg, Et2O; v) CO2; vi) H3O+
OH
OH
O
O
p-methoxybenzoic acid
phenol
OH
O
i) NaOH
ii) CH3I
O
O
i) Mg, Et2O
Br2
FeBr3
ii) CO2
Br
iii) H3O+
(+ o- isomer)
824
O
OH
Chapter 22
MULTIPLE CHOICE QUESTIONS
Topic: Nomenclature, Definitions and Types of Carbohydrates
1
...
Epimers are represented by:
CH2OH
O
HO
H
H
H
OH
OH
CH2OH
H
HO
H
H
I
A)
B)
C)
D)
E)
Ans:
CHO
OH
H
OH
OH
CH2OH
II
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
III
I and II
II and III
I, II, and III
III and IV
I, II, and V
B
825
H
H
HO
HO
CHO
OH
OH
H
H
CH2OH
IV
HO
HO
HO
HO
CHO
H
H
H
H
CH2OH
V
Chapter 22
Topic: Nomenclature, Definitions and Types of Carbohydrates
3
...
Which of these compounds, I, II, III, IV, is a reducing disaccharide?
H
OH
CH2OH
O
H
OH H
H
CH2OH
H H
O
OH
O
H
OH H
H
H
H
OH
OH
OH
CH2OH
O
H
OH H
H
H
OH
H
H H
O
OH
H
OH
II
CH2OH
O
H
H
OH H
OCH3
H
H
OH
OH
CH2OH
O
H
OH H
H
III
A)
B)
C)
D)
E)
Ans:
O
OH
I
CH2OH
O
H
OH H
H H
CH2OH
O
H
H
OH H
OH
OH
O
OH
826
H
OH H
H
IV
I alone
II alone
III alone
IV alone
I, II, III, and IV
B
O
H
OH
CH2OH
Chapter 22
Topic: Nomenclature, Definitions and Types of Carbohydrates
5
...
Which of the following is an L-aldotetrose?
CHO
H
OH
H
OH
CH2OH
A)
B)
C)
D)
E)
Ans:
CHO
H
OH
HO
H
CH2OH
CO2H
H
OH
HO
H
CH2OH
CH2OH
H
OH
HO
H
CO2H
II
I
CHO
HO
H
H
OH
CH2OH
III
IV
V
I
II
III
IV
V
C
827
Chapter 22
Topic: Nomenclature, Definitions and Types of Carbohydrates
7
...
An aldonic acid is represented by:
HO
HO
H
H
CO2H
H
H
OH
OH
CH2OH
I
A)
B)
C)
D)
E)
Ans:
HO
HO
H
H
CH2OH
H
H
OH
OH
CH2OH
II
HO
HO
H
H
CO2H
H
H
OH
OH
CO2H
III
I
II
III
IV
V
A
828
HO
HO
H
H
CHO
H
H
OH
OH
CO2H
IV
HO
HO
H
H
CO2H
H
H
OH
OH
CHO
V
Chapter 22
Topic: Nomenclature, Definitions and Types of Carbohydrates
9
...
Which compound is D-galactose?
CH2OH
O
OH
OH
H
H
H
H
H
CH2OH
O H
H
H
OH H
OH
OH
OH OH
H
I
OH
H
II
CH2OH
O
H
H
H
H
H
OH
OH
OH
III
CH2OH
O H
OH
H
OH OH
OH
H
OH OH
H
IV
A)
B)
C)
D)
E)
Ans:
CH2OH
O
H
OH
H
OH H
H
OH
H
V
I
II
III
IV
V
C
829
Chapter 22
Topic: Nomenclature, Definitions and Types of Carbohydrates
11
...
Which of these is a non-reducing monosaccharide?
CH2OH
O
OH
OH
CH2OH
O
CH2OH
O
OH
OH
OH
OH
OH
OH
OH
I
OH
II
CH2OH
O
OH
OCH3
III
HOH2C
O
HO
OH
OH
OH
IV
A)
B)
C)
D)
E)
Ans:
OH
V
I
II
III
IV
V
D
831
OH
CH2OH
OH
Chapter 22
Topic: Nomenclature, Definitions and Types of Carbohydrates
13
...
Which are the anomers?
CH2OH
O
OH
OH
CH2OH
O
OH
OH
OH
OH
OH
I
II
CH2OH
O
OH
OH
CH2OH
O
OH
OH
OH
OH
III
A)
B)
C)
D)
E)
Ans:
OH
OH OH
IV
I and II
I and III
II and III
II and IV
III and IV
B
833
Chapter 22
Topic: Nomenclature, Definitions and Types of Carbohydrates
15
...
Which structure represents β-D-glucopyranose?
OH
HO OH
O
HO
HO
O
HO
OH
OH
OH
OH
I
II
OH
HO OH
O
HO
HO
OH
O
OH
OH
OH
III
IV
OH
O
HO
HO
OH
OCH3
V
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
834
OH
Chapter 22
Topic: Nomenclature, Definitions and Types of Carbohydrates
16
...
Which compound is not a reducing sugar?
OH
HO OH
O
HO
HO
O
HO
OH
OH
OH
OH
I
II
OH
HO OH
O
HO
HO
O
OH
OH
OH
OH
OH
III
IV
OH
O
HO
HO
OH
OCH3
V
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
E
Topic: Nomenclature, Definitions and Types of Carbohydrates
17
...
Which is not likely to give a brick-red precipitate with Benedict’s solution?
A) Maltose
B) Cellobiose
C) Sucrose
D) Lactose
E) None of these
Ans: C
Topic: Nomenclature, Definitions and Types of Carbohydrates
19
...
Which of these is an example of a glucan?
A) Maltose
B) Sucrose
C) Lactose
D) Cellobiose
E) Amylose
Ans: E
Topic: Nomenclature, Definitions and Types of Carbohydrates
21
...
Which compound will not reduce Ag(NH3)2+ ?
OH
OH
O
HO
HO
O
HO
HO
OH
OCH3
OH
HOH2C
OH
CH2OH
OH
OH
OH OH
OH
III
O
O
HO
CH2OH
A)
B)
C)
D)
E)
Ans:
OH
OH
II
CHO
OH
O
HO
I
H
O OH
OH
IV
V
I
II
III
IV
V
A
Topic: Nomenclature, Definitions and Types of Carbohydrates
23
...
What is a correct general description of the monosaccharide shown here?
HOH2C
O
OH
CH2OH
OH OH
A)
B)
C)
D)
E)
Ans:
The ∝-anomer of the pyranose form of an aldohexose
The β-anomer of the pyranose form of an aldohexose
The ∝-anomer of the furanose form of a ketohexose
The β-anomer of the furanose form of a ketohexose
The β-anomer of the furanose form of an aldohexose
D
Topic: Nomenclature, Definitions and Types of Carbohydrates
25
...
B) The compound exists in the pyranose form
...
D) The compound has the same stereochemistry at the penultimate carbon as D-(+)glucose
...
Ans: C
Topic: Nomenclature, Definitions and Types of Carbohydrates
26
...
Reaction of the following substance with sodium borohydride (NaBH4) would yield:
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
HO
HO
H
H
CO2H
H
H
OH
OH
CH2OH
I
A)
B)
C)
D)
E)
Ans:
NaBH4
HO
HO
H
H
CO2H
H
H
OH
OH
CO2H
II
?
HO
HO
H
H
CH2OH
H
H
OH
OH
CH2OH
III
I
II
III
IV
V
C
839
HO
HO
H
H
CHO
H
H
OH
OH
CO2H
IV
HO
HO
H
H
CH3
H
H
OH
OH
CH2OH
V
Chapter 22
Topic: Reactions
28
...
If J (below) were treated with dilute aqueous hydrochloric acid and the solution allowed
to stand, what compounds (other than methanol) would be formed in the solution?
CH2OH
O H
dil HCl
H
H 2O
OH H
OCH3
HO
H OH
H
CHO
H
H
OH
OH
CH2OH
HO
HO
H
H
A)
B)
C)
D)
E)
Ans:
HO
HO
H
H
I
I and II
I and III
II and III
I, III, and IV
II, III, and IV
D
CHO
H
H
OH
OH
CH2OH
?
CH2OH
O H
H
H
OH H
HO
OH
H OH
II
CH2OH
O OH
H
OH H
H
HO
H OH
H
III
IV
Topic: Reactions
30
...
What is the structure of X?
CH2OH
CHO
CHO
CH2OH
CHOH
CHOH
CHOH
C
O
C
O
CHOH
CHOH
CHOH
C
O
C
O
CH2OH
CH2OH
CHO
CH2OH
CHO
I
A)
B)
C)
D)
E)
Ans:
II
III
IV
V
I
II
III
IV
V
A
841
CHO
Chapter 22
Topic: Reactions
31
...
The degradation product is
treated with nitric acid to yield an optically inactive aldaric acid
...
Which of the following would yield D-glucose and D-mannose when subjected to a
Kiliani-Fischer synthesis?
HO
H
H
CHO
H
OH
OH
CH2OH
I
A)
B)
C)
D)
E)
Ans:
H
H
H
CHO
OH
OH
OH
CH2OH
II
H
H
HO
CHO
OH
OH
H
CH2OH
III
I
II
III
IV
V
A
842
H
HO
H
CHO
OH
H
OH
CH2OH
IV
HO
HO
H
CHO
H
H
OH
CH2OH
V
Chapter 22
Topic: Reactions
33
...
Which aldohexose would yield an optically active aldaric acid when treated with nitric
acid?
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
I
A)
B)
C)
D)
E)
Ans:
H
H
H
H
CHO
OH
OH
OH
OH
CH2OH
II
HO
H
H
HO
CHO
H
OH
OH
H
CH2OH
III
I
II
III
IV
V
A
843
H
HO
HO
H
CHO
OH
H
H
OH
CH2OH
IV
HO
HO
HO
HO
CHO
H
H
H
H
CH2OH
V
Chapter 22
Topic: Reactions
35
...
A D-aldohexose, Z, is subjected to a Ruff degradation
...
A possible structure for
Z is:
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
I
A)
B)
C)
D)
E)
Ans:
H
H
H
H
CHO
OH
OH
OH
OH
CH2OH
HO
H
H
HO
II
CHO
H
OH
OH
H
CH2OH
III
I
II
III
IV
More than one of the above
E
844
H
HO
HO
H
CHO
OH
H
H
OH
CH2OH
IV
Chapter 22
Topic: Reactions
37
...
Which of the following substances will afford a meso- product upon reaction with
Br2/H2O ?
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
I
A)
B)
C)
D)
E)
Ans:
H
H
H
H
CHO
OH
OH
OH
OH
CH2OH
II
HO
H
H
HO
CHO
H
OH
OH
H
CH2OH
III
I
II
III and IV
II, III and IV
None of the above
E
845
H
HO
HO
H
CHO
OH
H
H
OH
CH2OH
IV
Chapter 22
Topic: Reactions
39
...
Which monosaccharide is recovered from the hydrolysis of glycogen?
A) D-Galactose
B) D-Glucose
C) D-Gulose
D) Cellobiose
E) Maltose
Ans: B
Topic: Reactions
41
...
Sucrose reacts with which of these reagents?
A) C6H5NHNH2
B) Cu2+
C) Br2/H2O
D) H3O+
E) Ag(NH3)2+
Ans: D
Topic: Reagents
43
...
Select the reagent(s) needed to perform the following transformation
...
Which reagent will distinguish between the members of the following pair?
H
HO
H
H
CHO
OH
H
OH
OH
CH2OH
H
HO
H
H
I
CH2OH
OH
H
OH
OH
CH2OH
II
Ag(NH3)2+
AgNO3/C2H5OH
Br2/CCl4
HCl
Hot KMnO4
A
A)
B)
C)
D)
E)
Ans:
Topic: Reagents
46
...
Which reagent will distinguish between the members of the following pair?
H
HO
H
H
CHO
OH
H
OH
OH
CH2OH
H
HO
H
H
I
A)
B)
C)
D)
E)
Ans:
CHO
OCH3
H
OCH3
OCH3
CH2OH
II
Ag(NH3)2+
AgNO3/C2H5OH
Br2/CCl4
KMnO4
HIO4
E
Topic: Reagents
48
...
What is the ratio of products formed by the reaction of periodic acid with the following
compound?
H
H
H
H
CHO
OH
OH
OH
OH
CH2OH
H2C=O
I
II
III
IV
V
A)
B)
C)
D)
E)
Ans:
HCO2H
CO2
5
3
1
1
0
1
3
5
4
4
0
0
0
1
2
I
II
III
IV
V
C
850
Chapter 22
Topic: Product Ratios
50
...
Which of these is a component of the mixture formed when D-galactose is placed in
aqueous base (de Bruyn - van Ekenstein transformation)?
HO
H
H
HO
CHO
H
OH
OH
H
CH2OH
I
A)
B)
C)
D)
E)
Ans:
H
H
HO
H
CHO
OH
OH
H
OH
CH2OH
II
H
HO
H
H
CHO
OH
H
OH
OH
CH2OH
III
I
II
III
IV
V
E
851
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
IV
CH2OH
HO
HO
H
C O
H
H
OH
CH2OH
V
Chapter 22
Topic: Named Reactions and Structure Identification
52
...
The Ruff degradation is the reaction of an aldose with:
A) Br2/H2O; then HCN; then H3O+; then Na-Hg, H2O
B) HCN; then Ba(OH)2; then H3O+; then Na-Hg, H2O
C) HCN; then H3O+; then Ba(OH)2; then Na-Hg, H2O
D) Br2/H2O; then H2O2, Fe2(SO4)3
E) Br2/H2O
Ans: D
Topic: Named Reactions and Structure Identification
54
...
Both Y and Z, when oxidized with nitric acid, yield optically
active aldaric acids
...
Compound X is a reducing sugar which, on hydrolysis, affords two molar equivalents of
D-glucose
...
A polysaccharide, Y, undergoes hydrolysis on catalysis by an enzyme which catalyzes
the hydrolysis of cellobiose, but not maltose
...
Which is a plausible structure for the repeating unit of Y?
CH2OH
O OR
CH2OR
OH
CH2OH
OR
O
O
OR
OH
OR
OH
OR
OH
OH
II
I
III
CH2OH
O OR
CH2OH
OR
OH
OH
IV
A)
B)
C)
D)
E)
Ans:
O
OH
OH
OR
OH
OR
OR
V
I
II
III
IV
V
D
853
Chapter 22
Topic: Named Reactions and Structure Identification
57
...
What size ring is present in the glycoside?
A) Three-membered
B) Four-membered
C) Five-membered
D) Six-membered
E) Seven-membered
Ans: C
Topic: Named Reactions and Structure Identification
58
...
Sugars that would yield the same phenylosazone are:
CH2OH
C O
HO
H
H
OH
H
OH
CH2OH
H
HO
H
H
I
A)
B)
C)
D)
E)
Ans:
CHO
OH
H
OH
OH
CH2OH
II
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
III
H
HO
H
HO
CHO
OH
H
OH
H
CH2OH
H
H
HO
H
IV
CHO
OH
OH
H
OH
CH2OH
V
I and II
II and III
I, II, and III
III and IV
I, II, and V
C
Topic: Named Reactions and Structure Identification
60
...
Reaction of D-ribose with bromine water would yield an optically:
A) active aldonic acid
...
C) active aldaric acid
...
E) active uronic acid
...
Reaction of D-ribose with HNO3 would yield an optically:
A) active aldonic acid
...
C) active aldaric acid
...
E) inactive uronic acid
...
Which would undergo mutarotation in neutral aqueous solution?
CH2OH
CH2OH
O
HO
OH
OH
A)
B)
C)
D)
E)
Ans:
OH
OH
OH
CH2OH
O OCH3
OH
O
OH
OH
CH2OH
O OH
OH
OH
OH
OH
OH
III
II
I
I
II
III
IV
More than one of these
E
IV
Topic: Stereochemical Considerations
64
...
Which of the following structures represent epimers?
H
HO
H
H
CHO
OH
H
OH
OH
CH2OH
HO
HO
H
H
I
A)
B)
C)
D)
E)
Ans:
CHO
H
H
OH
OH
CH2OH
H
H
H
H
II
CHO
OH
OH
OH
OH
CH2OH
H
H
HO
H
III
CHO
OH
OH
H
OH
CH2OH
HO
HO
HO
HO
IV
CHO
H
H
H
H
CH2OH
V
I and II
II and III
III and IV
III and V
IV and V
A
Topic: Stereochemical Considerations
66
...
Which D-aldohexose would react with NaBH4 to
yield an optically inactive alditol?
H
HO
H
H
CHO
OH
H
OH
OH
CH2OH
I
A)
B)
C)
D)
E)
Ans:
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
II
H
H
H
H
CHO
OH
OH
OH
OH
CH2OH
III
I
II
III
IV
V
C
857
H
H
HO
H
CHO
OH
OH
H
OH
CH2OH
IV
HO
HO
HO
HO
CHO
H
H
H
H
CH2OH
V
Chapter 22
Topic: Stereochemical Considerations
67
...
Which aldohexose when subjected to Fischer's endgroup interchange would be converted to a compound identical with itself?
H
HO
H
H
CHO
OH
H
OH
OH
CH2OH
HO
HO
H
H
I
A)
B)
C)
D)
E)
Ans:
CHO
H
H
OH
OH
CH2OH
H
H
H
H
II
CHO
OH
OH
OH
OH
CH2OH
H
H
HO
H
III
CHO
OH
OH
H
OH
CH2OH
HO
HO
HO
HO
IV
CHO
H
H
H
H
CH2OH
V
I
II
III
IV
V
B
Topic: Stereochemical Considerations
68
...
Which is the only one of these classes of carbohydrates which can include optically
inactive members?
A) Uronic acids
B) Alditols
C) Ketoses
D) Glycosides
E) Aldonic acids
Ans: B
Topic: Stereochemical Considerations
70
...
Consider the structures of D-allose below:
H
H
H
H
CHO
OH
OH
OH
OH
CH2OH
D-Allose
Which of the following structures represents L-allose?
HO
H
H
HO
CHO
H
OH
OH
H
CH2OH
H
H
H
HO
I
A)
B)
C)
D)
E)
Ans:
CHO
OH
OH
OH
H
CH2OH
HO
H
HO
H
II
CHO
H
OH
H
OH
CH2OH
III
HO
HO
HO
HO
CHO
H
H
H
H
CH2OH
IV
H
H
HO
HO
CHO
OH
OH
H
H
CH2OH
V
I
II
III
IV
V
B
Topic: Stereochemistry
72
...
Consider the structures below
...
Consider the structures below
...
The same L-aldohexose, X, is subjected to a Ruff
degradation and the degradation product is oxidized with nitric acid to produce an
optically inactive aldaric acid
...
Consider the structures below
...
Consider the structures above
...
Refer to the structures below
...
Refer to the structures below
...
Refer to the structures below
...
The D-glucose unit at the branching point of amylopectin has free hydroxyl groups at
which positions?
A) C2, C3, and C6
B) C2 and C3
C) C3 and C4
D) C3, C4, and C6
E) C4 and C6
Ans: B
Topic: General Information
81
...
B) Cellulose contains only D-glucose units; chitin contains only N-acetyl-Dglucosamine units
...
D) Cellulose has a linear structure; chitin has a helical structure
...
Ans: B
Topic: General Information
82
...
B) its conformation prevents attack by digestive enzymes
...
D) it passes through the digestive tract so rapidly
...
Ans: C
864
Chapter 22
SHORT ANSWER QUESTIONS
Topic: General Information
83 Sugars that give positive tests with Benedict's or Tollens' solution are called
_______________
...
Bromine water is a reagent that converts an aldose to an ___________
...
The simplest carbohydrates (those that cannot be hydrolyzed to simpler carbohydrates)
are called ______________
...
Carbohydrates that hydrolyze to give a large number of molecules of monosaccharides
are called _____________
...
Carbohydrates are synthesized in green plants by _____________
...
A monosaccharide containing six carbon atoms and an aldehyde functionality is called
an _____________
...
Many carbohydrates exist in equilibrium with cyclic hemiacetals
...
Ans: furanoses
Topic: General Information
90
...
Ans: sucrose
Topic: General Information
91
...
Ans: lactose
865
Chapter 22
Topic: General Information
92
...
Ans: Kiliani-Fischer synthesis
Topic: General Information
93
...
Ans: chitin
Topic: Aldaric Acids
94
...
CO2H
H
HO
OH
H
H
OH
H
OH
CO2H
D-glucaric acid
Ans:
CO2H
H
HO
OH
H
O
CO2H
H
-H2O
O
H
H
OH
H
OH
H
OH
H
OH
H
C
γ−lactones
866
HO
H
H
O
OH
CO2H
O
D-glucaric acid
OH
H
and
OH
CO2H
C
Chapter 22
Topic: Aldaric Acids
95
...
Draw the structure of the product
obtained upon treatment of D-erythrose with nitric acid
...
O
H
H
OH
H
OH
CH2OH
D-erythrose
Ans: The product, 2,3-dihydroxybutanedioic acid, is expected to be optically inactive,
due to a meso- configuration: (2R,3S) or (2S,3R)
...
What products are expected from the reaction of 3-hydroxy-2,4-pentanedione with 2
molar equivalents of periodic acid?
O
O
O
O
Ans:
2 eq HIO4
2
+
OH
OH
867
H
OH
Chapter 22
Topic: Periodate Oxidations
97
...
By contrast, no reaction is
expected in an analogous treatment of 2,4-pentanediol, since the hydroxyl groups
are separated by a methylene group
...
What products are expected to be formed upon subjecting L-erythrose (shown below) to
the following reaction sequence? (Draw Fischer projection formulas)
i) HCN; ii) Ba(OH)2; iii) H3O+; iv) Na(Hg), H2O, pH 3-5
Ans: Kiliani Fischer Synthesis:
O
O
H
H
i) HCN
O
H
HO
H
HO
H
CH2OH
L-erythrose
ii) Ba(OH)2
HO
iii) H3O+
HO
H
HO
H
iv) Na(Hg), H2O,
pH 3-5
868
H
H
CH2OH
+
OH
HO
H
HO
H
CH2OH
Chapter 22
Topic: Ruff Degradation
99
...
Br2, H2O
ii
...
Draw structures for 3 different epimers of D-glucose
...
Which of the following statements regarding lipids is not true?
A) Lipids are soluble in non-polar organic solvents
...
C) Lipids include waxes, steroids, and triacylglycerols
...
E) Many lipids have biological roles
...
Which of the following statements regarding triacylglycerols is not true?
A) They undergo alkaline hydrolysis to yield soaps
...
C) They are solid if they do not have alkene bonds
...
E) They are soluble in water
...
Which of the following statements regarding triacylglycerols is true?
A) They form micelles when mixed with water
...
C) They are solid if they have alkyne bonds
...
Ans: B
Topic: General Lipid Types and Information
4
...
B) They have an odd number of carbon atoms
...
D) Those which can be hydrogenated, undergo a significant change in melting point
upon hydrogenation
...
Ans: B
870
Chapter 23
Topic: General Lipid Types and Information
5
...
B) They are solid if they do not have alkene bonds
...
D) They form micelles in water
...
Ans: E
Topic: General Lipid Types and Information
6
...
Which type of lipid gives these products on saponification:
HOCH2CHOHCH2OH
A) Fat
B) Wax
C) Lecithin
D) Cephalin
E) Plasmalogen
Ans: D
RCO2¯
R'CO2¯
871
PO43¯
HOCH2CH2NH2 ?
Chapter 23
Topic: General Lipid Types and Information
8
...
Which type of lipid gives these products on saponification:
HOCH2CHOHCH2OH
A) Fat
B) Wax
C) Lecithin
D) Cephalin
E) Plasmalogen
Ans: E
RCO2¯
RCH2CHO
PO43¯
Topic: General Lipid Types and Information
10
...
Which of these lipids yields glycerol upon hydrolysis?
A) A lecithin
B) A phosphatidylserine
C) A cephalin
D) A triacylglycerol
E) All of the above
Ans: E
872
HOCH2CH2NH2 ?
Chapter 23
Topic: General Lipid Types and Information
12
...
Choline cannot be found as a product of hydrolysis of any representative of this class of
lipids
...
Choline cannot be found as a product of hydrolysis of any representative of this class of
lipids
...
D-galactose is an example of a class of compounds that can be formed during the
hydrolysis of
A) Sphingomyelins
B) Cerebrosides
C) Plasmalogens
D) Waxes
E) Both C) and D)
Ans: B
873
Chapter 23
Topic: General Lipid Types and Information
16
...
Which of these is most likely to have properties resembling natural waxes?
O
I
O
II
O
O
III
O
O
O
IV
O
O
V
A)
B)
C)
D)
E)
Ans:
N
H
O
I
II
III
IV
V
D
874
O
Chapter 23
Topic: General Lipid Types and Information
18
...
OCH2CH2NH2 is a structural unit of which type of phosphatide?
A) Cephalins
B) Phosphatidyl serines
C) Plasmalogens
D) Lecithins
E) Both A) and C)
Ans: E
Topic: Fats and Oils
20
...
Which of the following would not be helpful in distinguishing between oleic acid,
linoleic acid and linolenic acid?
A) Examine the stoichiometry of the reaction with Br2, CCl4
B) Examine the stoichiometry of complete catalytic hydrogenation
...
Ans: C
875
Chapter 23
Topic: Fats and Oils
22
...
C) Examine products obtained after subjecting the sample to catalytic hydrogenation
D) Examine products obtained after subjecting the sample to : i) O3, CH2Cl2; ii) Zn,
CH3CO2H
E) Two of the above
Ans: E
Topic: Fats and Oils
23
...
Which fatty acid is not likely to occur commonly in natural sources?
A) Tetradecanoic acid
B) Pentadecanoic acid
C) Hexadecanoic acid
D) (9Z,12Z)-octadeca-9,12-dienoic acid
E) (Z)-hexadeca-9-enoic acid
Ans: B
876
Chapter 23
25
...
Which fatty acid is likely to occur commonly in natural sources?
OH
I
O
O
II
OH
OH
III
O
OH
IV
O
O
V
A)
B)
C)
D)
E)
Ans:
OH
II
I and IV
II and III
II, III and IV
V
E
Topic: Fats and Oils
27
...
Which of the following could be used to prepare myristic acid, CH3(CH2)12COOH?
A) CH3(CH2)11CH2Br, CN-, heat; then H3O+, heat
B) CH3(CH2)11CH2Br, Mg, (C2H5)2O; then CO2; then H3O+
C) CH3(CH2)13CHO, Ag2O, OH-; then H3O+
D) Answers A) and B)
E) Answers A), B), and C)
Ans: D
Topic: Fats and Oils
29
...
How could you synthesize stearolic acid, CH3(CH2)7C≡C(CH2)7COOH from oleic acid,
CH3(CH2)7CH=CH(CH2)7COOH?
A) Br2, CCl4; then 3 NaNH2, heat; then H3O+
B) Li, liq
...
Which of these reagents would not react with oleic acid?
A) H2, Ni
B) PBr3
C) CH3MgI
D) NH3/H2O
E) NaBH4
Ans: E
878
Chapter 23
Topic: Fats and Oils
32
...
Which of these reagents would not react with stearic acid?
A) H2, Ni
B) SOCl2
C) CH3MgI
D) NH3/H2O
E) LAH
Ans: A
Topic: Fats and Oils
34
...
SOCl2
X
CH3(CH2)12COOH
ii
...
Br2, NaOH
CH3(CH2)12CHCOOH
A)
Br
B)
CH3(CH2)11CHCONH2
Br
C)
CH3(CH2)11CH2NH2
D)
CH3(CH2)12CONH2
E)
CH3(CH2)12COBr
Ans: C
879
Chapter 23
Topic: Fats and Oils
35
...
PBr3
ii
...
NaCN, HCl
+
iv
...
What would be the product of the following reaction sequence?
i
...
SOCl2
iii
...
The product of the following reaction sequence may be described as?
i
...
SOCl2
iii
...
The product of the following reaction sequence is nervonic acid
...
Which fatty acid is responsible for the putrid odor of rancid butter?
A) Valeric acid
B) Myristic acid
C) Stearic acid
D) Oleic acid
E) Butyric acid
Ans: E
Topic: Fats and Oils
40
...
Which is an untrue statement concerning the fatty acid moieties of naturally-occurring
triacylglycerols?
A) Generally, they possess an even number of carbon atoms
...
C) The double bonds, when present, all are in the cis configuration
...
E) The fatty acid moieties in a particular triacylglycerol usually are different
...
Which is not a correct statement concerning naturally-occurring triacylglycerols?
A) The greater the degree of unsaturation, the higher the melting point
...
C) Solid examples are termed "fats
...
E) Such compounds frequently, but less correctly, are called "triglycerides
...
Of the saturated fatty acids found in fats and oils, this one normally is the most
abundant:
A) Capric acid
B) Lauric acid
C) Myristic acid
D) Palmitic acid
E) Stearic acid
Ans: D
Topic: Fats and Oils
44
...
The ozonolysis of a fatty acid produces these fragments:
O
O
OH
O
O
O
What is the identity of the fatty acid?
A) Stearic acid
B) Palmitoleic acid
C) Oleic acid
D) Linoleic acid
E) Linolenic acid
Ans: D
Topic: Fats and Oils
46
...
Consider a micelle composed of phosphatidyl choline, shown below
...
Which of these is a detergent?
A) CH3(CH2)16COO-Na+
B) [CH3(CH2)14COO-]2Ca+2
C) CH3(CH2)10CH2SO3-Na+
D) HOCH2CHOHCH2OH
E) CH3(CH2)14CH2SH
Ans: C
Topic: Terpenes
49
...
Which structure represents a terpene likely to be found in nature?
O
OH
II
I
III
A)
B)
C)
D)
E)
Ans:
IV
V
I
II
III
IV
V
C
Topic: Terpenes
51
...
How many isoprene units are in vitamin A?
OH
A)
B)
C)
D)
E)
Ans:
1
2
3
4
More than 4
D
886
Chapter 23
Topic: Terpenes
53
...
Which compound below does not obey the isoprene rule?
OH
OH
I
II
HO
OH
III
A)
B)
C)
D)
E)
Ans:
IV
V
I
II
III
IV
V
D
887
Chapter 23
Topic: Terpenes
55
...
)
OH
OH
I
II
OH
OH
III
IV
OH
V
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
D
Topic: Rubber
56
...
In the vulcanization of rubber,
A) natural rubber is heated with sulfur
...
C) cross-linking results in a hardening of the rubber
...
E) All of the above
Ans: E
Topic: Rubber
58
...
What product would be obtained by catalytic hydrogenation of 5-cholesten-3β-ol?
A) 5β-Cholestan-3β-ol
B) 5∝-Cholestan-3β-ol
C) 5∝-Cholestan-3∝-ol
D) 5β-Cholestan-3∝-ol
E) 5-Cholesten-3β,6∝-diol
Ans: B
Topic: Steroids
60
...
Which reagent might serve as the basis for a simple chemical test that would distinguish
between 5∝-cholest-1-en-3-one and 5∝-cholestan-3-one?
A) Ag(NH3)2+
B) CrO3/H2SO4
C) Br2/CCl4
D) NaOH/H2O
E) C6H5NHNH2
Ans: C
Topic: Steroids
62
...
Where is position 11?
III
IV
II
V
I
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
Topic: Steroids
63
...
Which is an untrue statement concerning cholesterol?
A) Cholesterol decolorizes a solution of Br2 in CCl4
...
C) Cholesterol is optically active
...
E) All of the above are true
...
The reaction of cholesterol with dilute aqueous KMnO4 at 0–5°C produces which of
these compounds (A and B rings only shown)?
HO
HO
OH
HO
OH
I
II
HO
HO OH
IV
A)
B)
C)
D)
E)
Ans:
HO
HO
III
O
HO
V
I
II
III
IV
V
D
891
O
OH
Chapter 23
Topic: Steroids
66
...
Which of the following is a female sex hormone?
A) Ergosterol
B) Estradiol
C) Cortisone
D) Androsterone
E) Cholic acid
Ans: B
Topic: Steroids
68
...
Shown below is the formula for the antiinflammatory drug called prednisone
...
What product would you expect when progesterone is treated with one molar equivalent
of hydrogen in the presence of a platinum catalyst?
O
O
A)
B)
C)
D)
E)
Ans:
Progesterone
5∝-Pregnane-3,20-dione
5β-Pregnane-3,20-dione
5∝-Estrane-3,20-dione
5β-Estrane-3,20-dione
5∝-Androstane-3,20-dione
A
893
Chapter 23
Topic: Steroids
71
...
Which of these is a male sex hormone?
A) Estrone
B) Testosterone
C) Cholic acid
D) Cortisone
E) Estradiol
Ans: B
Topic: Prostaglandins
73
...
Unlike carbohydrates and proteins, which are defined in terms of their structures, lipids
are defined in terms of _____________
...
Saturated fatty acids pack efficiently
...
Ans: solid; fats
Topic: Fats and Oils
76
...
Therefore the corresponding triacylglycerols are generally __________ at room
temperature and are called _______
...
The primary function of triacylglycerols (triglycerides) in animals is _____________
...
Salts of long-chain fatty acids are known as ___________
...
Terpenes are built up from two or more five-carbon units known as __________
...
When natural rubber is heated with sulfur, a reaction takes place that produces
_____________ between the polymer chains
...
Ans: cross-links; vulcanization
Topic: Steroid Hormones
81
...
female sex hormones [or ____________]
b
...
pregnancy hormones [or ______________]
Ans: a
...
androgens; c
...
Sphingolipids, proteins, and polysaccharides make up ___________, the protective
coating around nerve fibers
...
Explain how soap removes dirt from clothes
...
The outer layer is hydrophilic and makes it easy for the micelle to
wash away, carrying the dirt with it
...
Myelin, the protective coating around nerve fibers, is made up of ___________
...
The characteristic odor of rancid butter is attributed to ___________
...
Topic: Fats and Oils
86
...
Ans: conjugated
Topic: Fats and Oils
87
...
Ans: cardiovascular disease
Topic: Fats and Oils
88
...
Ans: trans-
Topic: Fats and Oils
89
...
Ans: cis- to trans-
Topic: Fats and Oils
90
...
, are ____________
...
896
Chapter 23
Topic: Fats and Oils
91
...
Why are
the lipases, responsible for facilitating normal fat hydrolysis, unable to facilitate the
hydrolysis of olestra?
Ans: In order for a lipase to catalyze hydrolysis, the fat molecule must be accepted into
the active site of the enzyme
...
Consequently, the olestra is not hydrolyzed,
hence not absorbed, so that it adds nothing to the caloric value of foods prepared
with it
...
How could you synthesize stearolic acid, CH3(CH2)7C≡C(CH2)7COOH from oleic acid,
CH3(CH2)7CH=CH(CH2)7COOH? Specify stoichiometric details, providing a brief
explanation of your rationale
...
How are soaps and phosphatides similar in their interaction with water?
Ans: Both have polar and non-polar groups, so that they appear to “dissolve” when
mixed with water
...
Topic: Fats and Oils
94
...
One of the intermediates in a prostaglandin synthesis is shown below
...
Ans: Deprotonation (with base) of the active hydrogen alpha to the –NO2 group would
afford a nucleophilic species
...
CN
NO2
NO2
O
CN
base
+
O
or
O
O
O
CN
898
O
CHO
Chapter 23
Topic: Soaps and Synthetic Detergents
96
...
Ans:
−
O Na
sodium carboxylate
+
O
O
−
sodium alkanesulfonate
S O Na
+
O
O
−
sodium alkyl sulfate
O
+
S O Na
O
Each of these
substances has a polar “head” and a non-polar “tail”
...
These micelle clusters are dispersed throughout
the aqueous phase, with the polar heads on the outside and the non-polar ends on
the inside of the spherical clusters
...
Upon rinsing, the micelles, along with
the trapped dirt, get washed away
...
What products would be obtained from the ozonolysis of zingiberine, found in the oil of
ginger?
i) O3
ii) Zn, CH3CO2H
Zingiberine
Ans:
?
O
O
O
O
+
+ O
O
899
Chapter 23
Topic: Terpenes
98
...
How are
these units linked: head to head, tail to head or tail to tail ?
α-farnesene
Ans:
head
tail
head
tail
head
tail
α-farnesene
900
Chapter 23
Topic: Analysis and Structure Elucidation
99
...
Catalytic
hydrogenation of Z affords a mixture of diasteromers, which upon separation are
identified to be cis-1-isopropyl-4-methylcyclohexane and trans-1-isopropyl-4methylcyclohexane
...
Suggest a structure for Z that is consistent with all of the above data,
clearly explaining your rationale
...
e
...
- λmax at 184 nm in its UV spectrum suggests that these pi bonds are not
conjugated
...
Hydrogenation from both faces of
the pi bond at C-4 would lead to cis- and trans- orientation of the methyl and
isopropyl groups on the cyclohexane ring
...
901
Chapter 24
MULTIPLE CHOICE QUESTIONS
Topic: Isoelectric Points and pH
1
...
Which amino acid would have its isoelectric point near pH 3?
H3CCHCOO
CH2CHCOO
NH3
NH3
I
HOOCCH2CH2CHCOO
NH3
II
III
NH2
H3NCH2CH2CH2CH2CHCOO
H2NCCH2CH2CH2CHCOO
NH2
NH2
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
C
902
Chapter 24
Topic: Isoelectric Points and pH
3
...
Which amino acid would have its isoelectric point near pH 10?
A) Glycine
B) Tryptophan
C) Serine
D) Proline
E) Lysine
Ans: E
Topic: Isoelectric Points and pH
5
...
Which amino acid would not have its isoelectric point in the pH range 5-7?
A) Glycine
B) Proline
C) Cysteine
D) Glutamine
E) All of these amino acids have isoelectric point in the pH range 5-7
Ans: E
Topic: Isoelectric Points and pH
7
...
What might be concluded upon determining that an unknown amino acid has its
isoelectric point near pH 3?
A) It must have a hydrophobic side chain
B) It must have a hydrophilic side chain
C) Its side chain must contain a basic group
D) Its side chain must contain an acidic group
E) None of the above is a valid conclusion
Ans: D
Topic: Isoelectric Points and pH
9
...
B) equivalence point
...
D) isoelectric point
...
Ans: D
904
Chapter 24
Topic: Isoelectric Points and pH
10
...
4
pKa2= 10
...
6
B) 3
...
5
D) 6
...
0
Ans: B
α-NH3+
pKa3= 4
...
2
pKa2= 9
...
3
R group
2
...
2
5
...
5
7
...
What is the pI of the following amino acid?
HO2C
(CH2)n
NH2
NH2
pKa1= 2
...
0
+
α-NH3
α-CO2H
A) 1
...
3
C) 5
...
8
E) 6
...
5
R group
Topic: Isoelectric Points and pH
13
...
4
pKa2= 9
...
6
C) 4
...
0
E) 7
...
Consider the following tripeptide:
H2N-leu-lys-phe-CO2H
NH2
What is the best estimate of the pI of this compound?
pKa
leu
lys
phe
A)
B)
C)
D)
E)
Ans:
pKa
COOH
2
...
2
1
...
2
7
...
2
10
...
3
D
pKa
NH3+
9
...
0
9
...
0
9
...
5
10
...
What would be the predominant form of lysine in water at pH 14?
H3N
CO2H
H3N
CO2
H3N
NH3
NH3
I
NH2
II
H2N
CO2
III
H2N
CO2
NH3
NH2
IV
A)
B)
C)
D)
E)
Ans:
CO2
V
I
II
III
IV
V
E
907
Chapter 24
Topic: Isoelectric Points and pH
16
...
For the accompanying fully-protonated amino acid, what is the arrangement of pKa
values in order of increasing magnitude?
HO2C
I
CO2H
NH3
III
II
A) I < II < III
B) II < I < III
C) III < I < II
D) III < II < I
E) II < III < I
Ans: C
Topic: Amino Acid Structure
18
...
Which of these natural amino acids contains an amide function?
A) Asparagine
B) Proline
C) Arginine
D) Histidine
E) None of these
Ans: A
Topic: Amino Acid Structure
20
...
Which of these natural amino acids contains an amide function?
A) Asparagine
B) Methionine
C) Cysteine
D) Glutamine
E) Two of these
Ans: E
Topic: Amino Acid Structure
22
...
Which of these natural amino acids contains a phenolic group?
A) Phenylalanine
B) Tyrosine
C) Tryptophan
D) 4-Hydroxyproline
E) Serine
Ans: B
Topic: Amino Acid Structure
24
...
Which of these natural amino acids contains an indole ring?
A) Phenylalanine
B) Tyrosine
C) Tryptophan
D) 4-Hydroxyproline
E) Asparigine
Ans: C
Topic: Amino Acid Structure
26
...
Which of these natural amino acids contains an –OH group?
A) Serine
B) Threonine
C) Tyrosine
D) Two of these
E) All of these
Ans: E
Topic: Amino Acid Structure
28
...
Which of these natural amino acids, when present in a polypeptide, is not likely to
exhibit significant hydrogen bonding through its side chain?
A) Leucine
B) Threonine
C) Tyrosine
D) Serine
E) All of these are likely to exhibit significant hydrogen bonding through the side
chain
Ans: A
911
Chapter 24
Topic: Amino Acid Structure
30
...
Which amino acid is unlikely to be found in a natural protein?
CO2
H3N
H3N
H
CO2
CO2
H
H3N
H
CH3
CH2OH
CH2C6H5
I
II
III
CO2
CO2
H
NH3
CH2SH
IV
A)
B)
C)
D)
E)
Ans:
H3N
H
H
V
I
II
III
IV
V
D
912
Chapter 24
Topic: Amino Acid Structure
32
...
Which of these amino acids is described as an “essential” amino acid?
A) Methionine
B) Phenylalanine
C) Isoleucine
D) Tryptophan
E) All of these are “essential” amino acids
Ans: E
Topic: Amino Acid Structure
34
...
Pipecolic acid logically would be substituted for which natural amino acid in the
synthesis of peptide analogs?
NH
Pipecolic acid
CO2H
A)
B)
C)
D)
E)
Ans:
Histidine
Proline
Tryptophan
Phenylalanine
Tyrosine
B
913
Chapter 24
Topic: Amino Acid Structure
36
...
Logically, the following “unnatural” amino acid would be substituted for which natural
amino acid in the synthesis of peptide analogs?
CO2H
HS
A)
B)
C)
D)
E)
Ans:
NH2
Methionine
Cysteine
Cystine
Tyrosine
It could be substituted for all of these amino acids
D
Topic: Amino Acid Structure
38
...
Logically, the following “unnatural” amino acid would be substituted for which natural
amino acid in the synthesis of peptide analogs?
CO2H
H2N
NH2
A)
B)
C)
D)
E)
Ans:
Leucine
Lysine
Arginine
Alanine
Valine
B
Topic: Synthesis and Reactions of Amino Acids
40
...
Which of the following would provide a synthesis of alanine?
A) CH2=CHCH2OH, HBr, CrO3/H2SO4/H2O; then xs NH3
B) Potassium phthalimide, ClCH2CO2C2H5; then KOH/H2O; then HCl
C) Potassium phthalimide, C6H5CH2Br; then KOH/H2O; then CO2,H3O+
D) CH3CH2COOH, (C6H5)3CNa; then NH3
E) Answers A) and B)
Ans: A
Topic: Synthesis and Reactions of Amino Acids
42
...
Which of the following would provide a synthesis of leucine?
A) (CH3)2C=CHCH2OH, HBr/peroxides, CrO3/H2SO4/H2O; then excess NH3
B) Potassium phthalimide, BrCH(CO2C2H5)2; (CH3)2CHCHClCO2C2H5; then
KOH/H2O; then HCl (85%), heat
C) Potassium phthalimide, BrCH(CO2C2H5)2; (CH3)2CHCH2Br; then KOH/H2O;
then HCl (85%), heat
D) (CH3)2CHCOOH, PCl5; then NH3
E) Answers A) and C)
Ans: C
Topic: Synthesis and Reactions of Amino Acids
44
...
What product(s) would you expect from the following reaction?
Tyrosine
+
Br2 (excess)
H2O
?
Br
CO2
HO
Br
CO2
Br
NH3
CO2
NH3
HO
NH3
Br
Br
I
II
III
Br
O
CO2
Br
NH3
HO
NH3
HO
IV
A)
B)
C)
D)
E)
Ans:
V
I
II
III
IV
V
B
Topic: Synthesis and Reactions of Amino Acids
46
...
B) HBr does not add to substituted alkenes
...
D) Initial HBr addition produces a racemic intermediate which leads to racemic
product
...
Ans: D
917
Chapter 24
Topic: Synthesis and Reactions of Amino Acids
47
...
Which is an isolable intermediate in the Strecker synthesis of an amino acid?
X
R
CO2H
I
R
R
CN
II
NH2
R
CHO
IV
A)
B)
C)
D)
E)
Ans:
NH2
NH2
OH
III
CO2
NH
CO2
R
CO2
O
V
I
II
III
IV
V
B
918
Chapter 24
Topic: Protein Structure
49
...
B) disulfide bonds
...
D) hydrogen bonding
...
The secondary structure of proteins is derived from:
A) peptide linkages
...
C) hydrogen bond formation
...
E) acid-base interactions
...
Which attractive force is responsible for maintaining the tertiary structure of a protein?
A) Disulfide linkages
B) Hydrogen bonds
C) van der Waals forces
D) Hydrophobic interactions
E) All of these
Ans: E
Topic: Protein Structure
52
...
Disulfide bonds in proteins:
A) result from an oxidation of thiols
...
C) can be broken by reduction
...
E) All of the above
Ans: E
919
Chapter 24
Topic: Protein Structure
54
...
A "conjugated protein" is one which:
A) possesses catalytic properties
...
C) exists largely as an ∝-helix
...
E) contains a nonprotein group as part of the molecule
...
A pentapeptide has the molecular formula: Asp, Glu, His, Phe, Val
...
What is the amino
acid sequence of the pentapeptide?
A) Phe·Val·Asp·Glu·His
B) His·Glu·Asp·Val·Phe
C) Asp·Glu·His·Phe·Val
D) Phe·Val·Glu·His·Asp
E) Glu·His·Phe·Val·Asp
Ans: A
Topic: Peptide Sequencing, Labeling, and Synthesis
57
...
On partial hydrolysis the unlabeled heptapeptide gives
the following:
Ala·Glu, Pro·Tyr, Ala·Val, Tyr·Ala, Val·Phe·Pro
...
When the pentapeptide below is heated first with 2,4-dinitrofluorobenzene (and base)
and then subjected to acidic hydrolysis, which amino acid will bear the dinitrophenyl
group?
Leu·Val·Gly·Phe·Ile
A) Leucine
B) Valine
C) Glycine
D) Phenylalanine
E) Isoleucine
Ans: A
Topic: Peptide Sequencing, Labeling, and Synthesis
59
...
A) C6H5NHNH2
B) C6H5NH2
C) C6H5N=C=S
D) C6H5N=C=O
E) Aminopeptidase
Ans: C
Topic: Peptide Sequencing, Labeling, and Synthesis
60
...
The purple color of the anion formed in the ninhydrin test for ∝-amino acids is due to:
A) the attraction of the anion to a metal in a pi-complex
...
C) molecular vibrations
...
E) the color of the ninhydrin
...
Which one of these amino acids does not give the usual purple color with ninhydrin?
A) Histidine
B) Proline
C) Tryptophan
D) Leucine
E) Aspartic acid
Ans: B
Topic: Peptide Sequencing, Labeling, and Synthesis
63
...
O
A)
Cl
O
B)
C6H5
Cl
O
C)
C6H5
O
O
D)
C6H5
Cl
O
O
C6H5
O
E)
O
Cl
Ans: C
Topic: Peptide Sequencing, Labeling, and Synthesis
64
...
How many different tripeptides can exist, each containing one residue of glycine, one of
L-threonine, and one of L-arginine?
A) 2
B) 3
C) 6
D) 8
E) 9
Ans: C
922
Chapter 24
Topic: Peptide Sequencing, Labeling, and Synthesis
66
...
B) DCC activates the carboxyl group of one amino acid so that this amino acid reacts
more readily with a second amino acid
...
D) DCC is the resin used in the automated synthesis of peptides
...
Ans: B
Topic: Peptide Sequencing, Labeling, and Synthesis
67
...
0
...
C) Trypsin will catalyze preferentially the hydrolysis of the arginine-leucine peptide
bond
...
E) All peptide bonds will be cleaved by refluxing with 6 M HCl for 24 hours
...
Which of these amino acids has the R configuration at the stereogenic center but,
nonetheless, is an L amino acid?
CO2
H3N
H3N
H
CO2
CO2
H
H3N
H
CH2SH
CH2OH
CH2C6H5
I
II
III
CO2
H3N
CO2
H
CH2CH2SCH3
IV
A)
B)
C)
D)
E)
Ans:
H3N
H
CH2CO2H
V
I
II
III
IV
V
A
923
Chapter 24
Topic: Stereochemistry
69
...
Which of these amino acids is a D amino acid?
H2N
CO2H
H
H
HO2C
I
CO2H
H2N
H
H
NH2
II
III
H
NH2
HO2C
OH
IV
A)
B)
C)
D)
E)
Ans:
NH2
HO2C
H
V
I
II
III
IV
V
E
924
Chapter 24
Topic: Stereochemistry
71
...
Which of the following amino acids is theoretically capable of existing in
diastereomeric forms?
CO2
CO2
NH3
NH3
Glycine
NH3
Alanine
I
II
Threonine
III
CO2
CO2
NH3
NH2
Leucine
Proline
IV
A)
B)
C)
D)
E)
Ans:
CO2
HO
V
I
II
III
IV
V
C
925
Chapter 24
Topic: Stereochemistry
73
...
The exact sequence of the different α-amino acids along the protein chain is called the
________________ of the protein
...
The Henderson-Hasselbach equation shows that the ________________ of an acid is
the ________________ at which the acid is half-neutralized
...
The folding of the polyamide chain gives rise to higher levels of complexity called the
_______________ and ______________ of the protein
...
The 22 α-amino acids can be subdivided into three different types on the basis of the
structures of their side chains
...
Ans: neutral, acidic, basic
926
Chapter 24
Topic: Isoelectric Point
78
...
Ans: isoelectric point
Topic: Strecker Synthesis
79
...
This method is known as the ___________
...
A reagent that reacts with most amino acids to give an intense purple color is called
___________
...
The most widely used method for identifying the N-terminal amino acid in a peptide
chain is called the ____________
...
C-terminal amino acids can be identified through the use of _____________
...
The hormone that regulates glucose metabolism is called ______________
...
Ans: insulin; diabetes
Topic: Peptide Synthesis
84
...
These are:
Ans: protect the N-terminus, activate the carboxylic acid, react with a different amine
to form the peptide bond, deprotect the N-terminus
Topic: Protein Structure
85
...
These are:
Ans: α-helices, β-pleated sheets, turns
Topic: Enzymes
86
...
The prevailing hypothesis for enzyme catalysis is called the
____________ hypothesis
...
One common method of analysis used to measure the approximate molecular weight of
a protein is called _____________
...
The study of all proteins that are expressed in a cell at a given time is called
___________
...
A naturally occurring protein called ___________ acts as a tumor suppressant by
coordinating a complex set of responses to changes in DNA, halting abnormal growth in
normal cells
...
Draw structures to represent what happens when valine is dissolved in a strongly acidic
solution (pH=0)
...
Draw structures to represent what happens when valine is dissolved in a strongly basic
solution (pH=14)
...
Draw structures to represent what happens when lysine is dissolved in a strongly acidic
solution (pH=0)
...
Draw structures to represent what happens when lysine is dissolved in a strongly basic
solution (pH=14)
...
What is the final product formed when potassium phthalimide is subjected to the
following reaction sequence? Give structural details of all significant intermediates,
including stereochemistry, as applicable
...
BrCH(CO2H5)2
O
ii
...
NaOH
O
iv
...
Give the structure of the aldehyde which, upon treatment with HCN and ammonia,
followed by heating with aqueous acid, would afford racemic tryptophan
...
What is the final product formed via the following reaction sequence? Give structural
details of all significant intermediates
...
CH =CHCN, NaOEt, EtOH
2
HN
?
CO2Et ii
...
Suggest a reasonable strategy for the synthesis of the dipeptide Leu-Phe, using
established protocol for peptide synthesis
...
Et3N
ii
...
Draw the structure of the following tripeptide (starting with the N-terminal residue and
ending with the C-terminal residue), showing stereochemical details:
Gly-Phe-Met
Ans:
S
H
H
O
H
N
H3N
O
H
N
H
H
O
O
Gly-Phe-Met
Topic: Peptide Structure
99
...
Draw the structure of the following tripeptide (starting with the N-terminal residue and
ending with the C-terminal residue), showing stereochemical details:
Val-Trp-Asn
O
Ans:
NH2
H
H3N
O
O
H
N
H
N
H
H
O
O
N
H
Val-Trp-Asn
934
Chapter 25
MULTIPLE CHOICE QUESTIONS
Topic: The Double Helix
1
...
Which is an incorrect statement concerning the DNA double helix?
A) The sugar-phosphate backbone is on the outside of the helix and the base pairs are
on the inside
...
C) Hydrogen bonding holds together the two strands
...
E) The sugar-phosphate backbone is completely regular
...
Which is an incorrect statement concerning the DNA double helix?
A) The sugar-phosphate backbone is on the inside of the helix and the base pairs are
on the outside
...
C) The two strands are linked by glycosidic bonds
...
E) All of the above statements are incorrect
...
Which is an incorrect statement concerning DNA structure?
A) The base and the phosphate units are linked by phosphodiester bonds
...
C) The base and the sugar units are linked by β-N-glycosidic bonds
...
E) All of the above statements are incorrect
...
Which is a correct statement concerning DNA structure?
A) The base and the phosphate units are linked by hydrogen bonds
...
C) The base and the sugar units are linked by β-N-glycosidic bonds
...
E) None of the above statements are correct
...
The analytical data for DNA samples which led to generalizations such as (%G + %A) ≈
(%C + %T) came from the research of what individual?
A) James Watson
B) Francis Crick
C) Edwin Chargaff
D) Arthur Kornberg
E) Maurice Wilkins
Ans: C
Topic: DNA Structure
7
...
In DNA, thymine can pair via hydrogen bonding to _________?
A) Cytosine
B) Uracil
C) Adenine
D) Guanine
E) Deoxyribose
Ans: C
2
Chapter 25
Topic: DNA Structure
9
...
In DNA, adenine can be linked to _________
...
In RNA, adenine can be linked to _________
...
In DNA, the lactim form of guanine will pair with which base?
A) Cytosine
B) Adenine
C) Uracil
D) Thymine
E) No pairing is possible
...
Consideration of tautomerism in guanine suggests that it can exist in lactam and lactim
forms
...
A) Lactam, cytosine, thymine
B) Lactam, cytosine, adenine
C) Lactim, cytosine, thymine
D) Lactam, uracil, cytosine
E) Lactim, cytosine, thymine
Ans: A
Topic: The Double Helix
14
...
The
product now resembles __________, and is likely to pair with __________, instead of
with ___________, leading to the possible mutations
...
Which is the predominant tautomeric form of cytosine when it is present in DNA?
NH
NH2
I
A)
B)
C)
D)
E)
Ans:
NH
N
N
N
H
O
N
II
N
O
N
O
III
I
II
III
None of these
I, II and III are present in approximately equal amounts
...
The following structure represents the less common (in DNA, at least) tautomeric form
of __________
...
Which is the predominant tautomeric form of guanine when it is present in DNA?
O
N
N
H
OH
N
NH
N
N
H
NH2
I
N
N
N
NH2
O
N
II
H
N
N
O
N
N
IV
NH2
NH
III
OH
N
A)
B)
C)
D)
E)
Ans:
H
N
N
H
N
N
H
NH2
V
I
II
III
IV
V
A
5
NH2
Chapter 25
Topic: DNA Structure
18
...
In DNA sequencing, what is used to convert DNA molecules into smaller, more
manageable fragments?
A) DNA polymerase
B) Dilute HCl
C) Trypsin
D) Chymotrypsin
E) Restriction endonucleases
Ans: E
Topic: Sequencing
20
...
If the base sequence along a segment of DNA were G—C—C—A—T, what would be
the base sequence of messenger RNA synthesized from this sequence?
A) G—C—C—A—T
B) C—G—G—T—A
C) C—G—G—U—A
D) G—C—C—A—U
E) A—T—T—G—C
Ans: C
Topic: Sequencing
22
...
If the base sequence along a segment of DNA were T—C—G—T—A, what would be
the antisense oligonucleotide synthesized from this sequence?
A) G—C—C—A—T
B) C—G—G—T—A
C) U—G—C—U—T
D) A—G—C—A—U
E) A—G—C—A—T
Ans: E
Topic: Sequencing
24
...
During translation, the segment on the mRNA that corresponds to the base sequence
C—G—A along a gene segment of DNA, would bind to the anticodon __________ on a
tRNA
...
Complete hydrolysis of adenylic acid would yield which of these?
A) Adenosine and a phosphate ion
B) Adenine, D-ribose, and a phosphate ion
C) Adenine and D-ribose
D) Adenine and 2-deoxy-D-ribose
E) A pyrimidine, a pentose, and a phosphate ion
Ans: B
Topic: Nucleotide Synthesis
27
...
HO
O
HO
base
+ ?
H3O
OH OH
O
H3C
A)
B)
C)
D)
E)
Ans:
base
O
+
(CH3)2C=O
HOCH2CH2OH
CH3CHOHCH3
CH3CCl2CH3
CH3CHClCH3
A
8
O
CH3
Chapter 25
Topic: Nucleotide Synthesis
28
...
O
HO
O
base
O
A)
B)
C)
pyridine
O
H3C
base
O
+ ?
O
P(OCH2C6H5)2
O
CH3
H3C
O
CH3
PO4-3 and C6H5CH2OH
PO4-3 and C6H5CH2Cl
O
P(OCH2C6H5)2
Cl
D) C6H5CH3 + POCl3
E) C6H5CH2OH + H3PO4
Ans: C
Topic: Assorted Reactions
29
...
The action of nitrous acid on 5-methylcytosine produces which nitrogen base?
NH2
H3C
N
N
H
O
5-methylcytosine
A) Adenine
B) Guanine
C) Cytosine
D) Thymine
E) Uracil
Ans: D
Topic: Assorted Reactions
31
...
Which are the products of hydrolysis of a RNA nucleotide?
A) D-Ribose, adenine
B) D-Ribose, guanine, phosphate
C) D-Ribose, thymine, phosphate
D) 2-Deoxy-D-ribose, cytosine, phosphate
E) 2-Deoxy-D-ribose, adenine
Ans: B
Topic: Assorted Reactions
33
...
B) The mole percentage of cytosine is approximately equal to that of guanine
...
D) All of the above
E) None of the above
Ans: D
10
Chapter 25
Topic: Codons and Anticodons
34
...
Where is the sequence of bases termed an "anticodon" found?
A) mRNA
B) tRNA
C) rRNA
D) DNA
E) Polysomes
Ans: B
Topic: Codons and Anticodons
36
...
Which is the messenger codon which calls for the initiation of protein synthesis?
A) AUG
B) GUA
C) UAG
D) AUC
E) CAC
Ans: A
Topic: Codons and Anticodons
38
...
B) There are a total of 64 different triplets
...
D) The triplet codons are incorporated in messenger RNA
...
Ans: C
11
Chapter 25
Topic: Nucleic Acid Structure
39
...
The primary function of nucleic acids is:
A) the catalysis of biochemical reactions
...
C) the preservation, transcription and translation of information
...
E) the neutralization of nucleic bases
...
A nucleotide unit is composed of:
A) a five carbon monosaccharide
...
C) a heterocyclic base
...
E) A), B) and C)
Ans: E
Topic: Nucleic Acid Structure
42
...
B) is bicyclic
...
D) is a heterocyclic base
...
In a nucleotide unit, the components are sequentially linked:
A) monosaccharide--phosphate--heterocyclic base
...
C) phosphate--monosaccharide--heterocyclic base
...
E) heterocyclic base--phosphate--monosaccharide
...
Which of the following is not a pyrimidine?
A) Cytosine
B) Thymine
C) Guanine
D) Uracil
E) All of the above are pyrimidines
...
The hydrogen bonding for the base pairs of DNA is between:
A) amide carbonyl and -NH2
...
C) alcohols and carbonyls
...
Which heterocyclic base found in RNA does not occur in DNA?
A) Guanine
B) Thymine
C) Cytosine
D) Uracil
E) Adenine
Ans: D
Topic: Assorted Definitions
47
...
Nitrous acid is a suspected mutagen because of its reaction with:
A) amine groups
...
C) phosphates
...
E) ketones
...
The synthesis of proteins according to "the central dogma of molecular genetics" would
require:
A) replication then translation
...
C) replication then transcription
...
E) Any of these
Ans: D
Topic: Protein Synthesis
50
...
Which of these has the smallest molecular weight?
A) rRNA
B) mRNA
C) tRNA
D) DNA
Ans: C
Topic: Miscellaneous
52
...
B) The linkage to phosphate is at carbon #3
...
D) The monosaccharide - nitrogen base linkage is ∝
...
Ans: C
14
Chapter 25
Topic: Miscellaneous
53
...
B) templates
...
D) endonucleases
...
Ans: A
Topic: Transcription
54
...
The codon is part of
A) mRNA
B) rRNA
C) tRNA
D) DNA
E) None of these
Ans: A
Topic: Transcription
56
...
Specific amino acids attach to the arm of a tRNA that ends in __________, via a(n)
_________ bond
...
The time required to synthesize a protein depends on the number of amino acid residues
it contains
...
A) 30
B) 50
C) 100
D) 150
E) 200
Ans: D
Topic: Polymerase Chain Reaction
59
...
Which of the following is not a valid application of the PCR (polymerase chain
reaction) ?
A) Semen analysis in forensic investigations
B) Evolutionary biology
C) Detection of cytomegalovirus
D) Prenatal diagnosis of sickle cell anemia
E) All of these are valid applications of the PCR
Ans: E
16
Chapter 25
SHORT ANSWER QUESTIONS
Topic: Protein Synthesis
61
...
The
molecules that transcribe and translate these instructions are called ______
...
The four bases that make up the DNA “ladder” are: ____________
...
The four bases found in RNA are: _________
...
Each section of DNA that codes for a particular protein is called a _______
...
Amino acids bear the same relation to proteins as __________ do to nucleic acids
...
While proteins are made up of amino acids connected by amide bonds, nucleic acids are
made up of nucleotides connected by __________
...
The secondary structure of DNA was proposed by Watson and Crick to be a
___________________
...
In the DNA double helix, two strands of nucleic acids are held together by
_____________
...
In the DNA base pairs, adenine always bonds with _________ and cytosine with
__________
...
The backbone of DNA is made up of __________
...
A chemical that causes mutations in DNA is called a _________
...
Protein synthesis requires that two major processes take place
...
The
second involves two other types of RNA: __________ and ____________
...
The anticodon is a specific sequence of ____________, found on the ___________,
which allows it to bind to the ____________, of _____________
...
The molecular weight of tRNA is _________, compared with mRNA or rRNA;
consequently, the solubility of tRNA is __________
...
The function of tRNA is ___________
...
Explain why 3 bases (triplet code) are needed in the genetic code to unambiguously
identify each amino acid
...
A set of two bases would uniquely code for (42) ,
i
...
, 16 amino acids, still not quite enough
...
18
Chapter 25
Topic: DNA Structure
77
...
H
Ans:
...
Draw structures to represent the hydrogen bonding between cytosine and guanine
...
O:
H N
N
N
:N
N H
N
N
N
guanine
:O
...
Draw structures to represent the hydrogen bonding between adenine and uracil
...
:O
N H
N
N
N:
H
N
N
N
O
uracil
adenine
Topic: DNA Structure
80
...
O
Ans:
N
HO
O
N
H
thymine
O
OH H
deoxyribose
19
Chapter 25
Topic: DNA Structure
81
...
O
Ans:
H
N
HO
uracil
N
O
O
OH OH
ribose
Topic: DNA Structure
82
...
NH2
NH2
Ans:
N
5'
O
N
P
3'
O
HO
N
O
NaOH
H2O
O
O
N
N
HO
OH
O
HO
cyclic AMP
O
N
N
N
OH
P
O
3'-adenylic acid
The reaction appears to follow an SN2 mechanism, with nucleophilic attack by
OH− at the primary 5’- position to afford 3’-adenylic acid (rather than at the
secondary 3’- position, which would yield 5’-adenylic acid)
...
Suggest a reasonable strategy for the specific phosphorylation of the 5’ –OH group of a
nucleoside
...
HO
HO
base
O
base
O
acetone
H3O+
OH OH
O
O
H3C
CH3
O
P(OCH2C6H5)2
Cl
pyridine
O
O
P(OCH2C6H5)2
O
base
O
P(OCH2C6H5)2
O
base
O
i
...
H2, Pd
OH OH
O
O
H3C
CH3
Topic: Tautomerism, Mutation
84
...
Explain the possible involvement of the lactim form in causing spontaneous
mutation during replication
...
This
mistake, if uncorrected, can then be passed on to the next strand being synthesized
from this “mutated” strand, by introducing an adenine residue, where there should
be a guanine residue
...
O:
OH
N
N
N
H
N H
N
N
N
H
N:
N
H
N
H
H
H
lactam
(likely to pair with cytosine)
lactim
(likely to pair with thymine)
21
Chapter 25
85
...
Ans: The product resembles a guanine nucleotide, thus might pair with cytosine instead
of thymine, causing the first error in the new DNA strand being synthesized
...
NH2
N
N
R
N
O
N
HNO2
N
adenine nucleotide
(pairs with thymine)
N
R
NH
N
hypoxanthine nucleotide
(likely to pair with cytosine)
22
Title: organic chemistry - I - notes and questions
Description: this file contain organic chemistry test banks SN1 and SN2 E1 E2
Description: this file contain organic chemistry test banks SN1 and SN2 E1 E2