Chapter 6 Test Bank

Package title: Solomons Test Bank
Course Title: Solomons 11e

Chapter Number: 6
Question type: Multiple choice
1) Select the rate law for the following reaction, e.g.,

CH3CH2CH2CHBrCH3 + OH CH3CH2CH2CHOHCH3 + Br -
( RBr )
A) Rate = k [RBr]
B) Rate = k [RBr] [OH]
C) Rate = k [RBr]2 [OH]
D) Rate = k [RBr] [OH]2
E) Rate = k [RBr]2 [OH]2
Answer: B
Topic: Reaction kinetics

Section: 6.5
Difficulty Level: Easy
2) The rate equation for a nucleophilic substitution reaction of a secondary alkyl chloride (R-Cl)
with I ion would be:
A) Rate = k [RCl]
B) Rate = k [I]
C) Rate = k [RCl][I]
D) Rate = k [RCl]2[I]
E) Rate = k [RCl][I]2
Ans: C
Topic: Reaction Kinetics

Section: 6.5
3) Consider the SN2 reaction of butyl bromide with OH- ion.
CH3CH2CH2CH2Br + OH- CH3CH2CH2CH2OH + Br-
Assuming no other changes, what effect on the rate would result from simultaneously doubling
1
the concentrations of both butyl bromide and OH- ion?
A) No effect.
B) It would double the rate.
C) It would triple the rate.
D) It would increase the rate four times.
E) It would increase the rate six times.
Ans: D

Section: 6.5
Difficulty Level: Medium
4) Consider the SN2 reaction of 2-iodopentane with CH3CO2 ion.
I O O O
NaI
ONa
the concentrations of both 2-iodopentane and sodium acetate?
A) No effect.
Ans: D

Section: 6.5
5) Consider the SN2 reaction of 1-chloro-5-methylhexane with CN ion.
Cl NaCN CN NaCl
the concentrations of both 1-chloro-5-methylhexane and NaCN?
2
A) No effect.
Ans: D

Section: 6.5
6) The reaction,
CH3Cl + OH CH3OH + Cl
H2O
has the following thermodynamic values at 27.0 C: H = -75.3 kJ mol-1;

S = 54.4 J K-1 mol-1. What is the value of G for this reaction?
A) -73.8 kJ mol-1
B) -76.8 kJ mol-1
C) -59.0 kJ mol-1
D) +91.6 kJ mol-1
E) -91.6 kJ mol-1
Ans: E
Topic: Free energy changes

Sections: 6.7
7) Select the potential energy diagram that represents an exothermic (exergonic) reaction.
3
A) I
B) II
C) III
D) IV
E) V
Ans: E
Topic: Free energy diagrams

Section: 6.7
8) Select the potential energy diagram that represents a single-step endothermic (endergonic)
reaction.
A) I
4
B) II
C) III
D) IV
E) V
Ans: A

Section: 6.7
9) Select the potential energy diagram that represents a two-step endothermic (endergonic)
reaction.
A) I
B) II
C) III
D) IV
E) V
Ans: B

Section: 6.7
10) The difference in the bond energies of reactants and the transition state of a reaction is
designated by the notation:
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A) H
B) H
C) G
D) G
E) S
Ans: B

Section: 6.7
11) An increase in the temperature at which a reaction is carried out increases
A) the collision frequency.

B) the fraction of molecules with proper orientation.
C) the fraction of molecules with energy greater than Eact.
D) More than one of these choices.
E) None of these choices.
Ans: D
Topic: Activation energy

Section: 6.7
12) Which will be true for any actual or potential nucleophilic substitution reaction?
A) H is positive.
B) H is negative.
C) G is positive.
D) G is positive.
E) G is negative.
Ans: C
Topic: Transition state theory

Section: 6.7
13) Increasing the temperature of a chemical reaction usually increases greatly the rate of the
reaction. The most important reason for this is that increasing the temperature
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A) increases the collision frequency.
B) decreases the probability factor.
C) increases the fraction of collisions with energy greater than Eact.
D) decreases the energy of activation.
E) makes the reaction more exothermic.
Ans: C
Topic: Activation Energy

Section: 6.7
14) What product(s) would you expect to obtain from the following SN2 reaction?
H H
CH3ONa
?
CH3 Br CH3OH
H H H OCH3 CH3O H
CH3 OCH3 CH3 H H Br
I II III
A) I
B) II
C) An equimolar mixture of I and II.
D) III
Ans: B
Topic: Predicting products

Section: 6.8
15) The major product of the following reaction would be:
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CH2Cl
OH
H OCH3 ?
SN2
CH3
CH2OH CH2OH
H3CO H H OCH3
CH3 CH3
I II
CH2Cl CH2Cl
HO H H OH
CH3 CH3
III IV
A) I
B) II
C) III
D) IV
E) An equimolar mixture of I and II.
Ans: B

Section: 6.8
16) A true statement about the transition state(s) of an SN2 reaction is:
A) The two transition states are of unequal energy.

B) The transition states precede and follow an unstable reaction intermediate.
C) The single transition state represents the point of maximum free energy of the reaction.
D) Existence of this transition state implies an exothermic reaction.
E) The transition state will always have a net charge of -1.
Ans: C
Topic: Generalities
Sections: 6.7 and 6.8
Difficulty Level: Hard
17) The rate equation for a nucleophilic substitution reaction of a tertiary alkyl bromide (R-Br)
with I ion would be:
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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

Section: 6.9 and 6.10
18) Consider the reaction of 2-chloro-2-methylpentane with sodium iodide.
NaI NaCl
Cl I
Assuming no other changes, how would it affect the rate if one simultaneously doubled the
concentration of 2-chloro-2-methylpentane and sodium iodide?
A) No effect.
D) It would quadruple the rate.
E) It would increase the rate five times.
Ans: B

19) If the rate of reaction of [0.1 M] sodium cyanide with [0.1 M] 2-bromo-2-methylpropane is
1.2 x 10-3 M/s, what would be the effect on the overall rate if the concentration of sodium
cyanide is increased to [0.2 M] and the concentration of the alkyl bromide is decreased to [0.05
M]?
a) the rate will increase by a factor of 2

b) the rate will decrease by a factor of 2
c) the rate will increase by a factor of 10
d) the rate will decrease by a factor of 10
e) the rate will remain unchanged
Ans: B
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20) The hybridization state of the charged carbon in a carbocation is ___.
A) sp4
B) sp3
C) sp2
D) sp
E) s
Ans: C
Topic: Carbocations
Section: 6.11
21. The p orbital of a methyl cation, CH3+, contains how many electrons?
A) 0
B) 1
C) 2
D) 3
E) 4
Ans: A
Topic: Carbocations
Section: 6.11
22) The p orbital of the charged carbon in the isopropyl cation, (CH3)2CH+, contains how many
electrons?
A) 0
B) 1
C) 2
D) 3
E) 4
Ans: A
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Topic: Carbocations
Section: 6.11
23) Which of the following reactions proceeds with inversion of configuration at the carbon
bearing the leaving group?
A) SN2
B) SN1
C) E2
D) E1
E) All of these answer choices are correct.
Ans: A
Topic: Stereochemistry of SN/E reactions

24) Consider the substitution reaction that takes place when (R)-3-bromo-3-methylhexane is
treated with methanol. Which of the following would be true?
A) The reaction would take place only with inversion of configuration at the stereogenic center.
B) The reaction would take place only with retention of configuration at the stereogenic center.
C) The reaction would take place with racemization.
D) No reaction would take place.
E) The alkyl halide does not possess a stereogenic center.
Ans: C
Topic: Predicting mechanism, stereochemistry of SN reactions

25) Consider the substitution reaction that takes place when (R)-3-bromo-3-methylhexane is
treated with sodium methoxide. Which of the following would be true?
A) An SN2 reaction would take place with inversion of configuration at the stereogenic center.
B) An SN1 reaction would take place with retention of configuration at the stereogenic center.
C) An SN1 reaction would take place with racemization of configuration at the stereogenic
center.
D) An SN1 reaction would take place, accompanied by an E1 reaction, affording a complex
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mixture of products.
E) An E2 reaction would take place, during which the stereogenic center is lost.
Ans: E

26) Consider the substitution reaction that takes place when (R)-3-iodo-3-methylheptane is
treated with sodium acetate (CH3CO2Na). Which of the following would be true?
A) An SN2 reaction would take place with inversion of configuration at the stereogenic center.
B) An SN1 reaction would take place with retention of configuration at the stereogenic center.
C) An SN1 reaction would take place with racemization of configuration at the stereogenic
center.
D) An SN1 reaction would take place, accompanied by an E1 reaction, affording a complex
mixture of products.
E) An E2 reaction would take place, during which the stereogenic center is lost.
Ans: D

27) By analyzing the starting material and the product(s), the following reaction is an example of
what type of mechanism?
A) SN1
B) SN2
C) E1
D) E2
E) More than one of these choices.
Ans: B
Topic: Predicting mechanisms, products

Section: 6.13
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A) SN1
B) SN2
C) E1
D) E2
Ans: B

Section: 6.13
A) SN1
B) SN2
C) E1
D) E2
Ans: A

Section: 6.13
30) 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.

B) polar aprotic solvents strongly accelerate the rate of SN2 processes.
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C) bimolecular nucleophilic substitutions are 2nd order kinetically.
D) the transition state for an endergonic reaction step (one accompanied by an increase in free
energy) resembles the product of that step.
E) elimination reactions will always compete with nucleophilic substitution reactions.
Ans: D
Topic: Hammond-Leffler postulate

Section: 6.13
31) When 1,4-diiodo-2,2-dimethylbutane (0.10 mol) is treated with 0.10 mol of NaCN in
dimethyl sulfoxide at 30C, the product formed is:
I
NC
A)
CN
I
B)
CN
NC
C)
I
D)
Ans: B

Section: 6.13
32) 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.

B) Both covalent bond-breaking and bond-making are occurring.
C) Formation of the transition state is an exothermic reaction.
D) Necessarily, the transition state has zero charge overall.
Ans: A
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Topic: Hammond-Leffler postulate
Section: 6.13
33) By analyzing the starting material and the product(s), the following reaction is possibly an
example of what type of mechanism?
+
Br N3 N3
A) SN1
B) SN2
C) E1
D) E2
Ans: A

Section: 6.13
34) Which of the following alkyl bromide isomers would most readily undergo an SN2 reaction?
a) bromocyclobutane
b) 4-bromo-1-butene
c) 3-bromo-1-butene
d) 1-bromo-1-butene
e) All will react at the same rate.
Ans: B
Topic: Synthesis, reagent selection

Section: 6.13
35) You want to synthesize 3-methyl-2-pentene from 2-chloro-3-methylpentane. Which reagent

would you use?
A) HCl, heat
B) NH3(aq), 25oC
C) CH3CO2Na, CH3CO2H, heat
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D) CH3CH2ONa, CH3CH2OH, heat
E) CH3CH2OH, heat
Ans: D

Section: 6.13
36) Which alkyl chloride, though primary, is essentially unreactive in SN2 reactions?
Cl
A)
B)
Cl
C)
Cl
Cl
D)
Cl
E)
Ans: E
Topic: Steric hindrance

Sections: 6.13
37) Which alkyl halide would be most reactive in an SN1 reaction?
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Br
Br Br
I II III
Br
Br
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: D
Topic: Kinetics
Section: 6.13
38) Reaction of (R)-2-chloro-4-methylhexane with excess NaI in acetone gives racemic 2-iodo-
4-methylhexane. What is the explanation that best describes this transformation?
a) an SN2 reaction has occurred with inversion of configuration

b) racemization followed by an SN2 attack
c) an SNI reaction has taken over resulting in inversion of configuration
d) an SN1 reaction has occurred due to carbocation formation
e) an SN1 reaction followed by an SN2 backside attack
Ans: D
Topic: Kinetics and Mechanism

Section: 6.8, 6.13
39) An increase in the kinetic energy of reacting molecules results in
A) a decrease in reaction rate.

B) an increase in the probability factor.
C) a decrease in the probability factor.
D) an increase in the reaction rate.
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E) no changes.
Ans: D
Topic: Transition State theory

40) Which alkyl halide would you expect to undergo an SN2 reaction most slowly?
A) 1-bromohexane
B) 1-bromo-2-methylpentane
C) 1-bromo-3-methylpentane
D) 1-bromo-4-methylpentane
E) 1-bromo-2,2-dimethylbutane
Ans: E
Topic: Kinetics
41) Identify the nucleophile in the following reaction:
2 H2O + RX ROH + H3O+ + X
A) X-
B) H3O+
C) ROH
D) H2O
E) RX
Ans: D
Topic: Generalities, nucleophiles

42) Which of the following is not a nucleophile?
A) H2O
B) CH3O-
C) NH3
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D) NH4+
E) All are nucleophiles.
Ans: D

43) Ambident nucleophiles are ones which can react with a substrate at either of two
nucleophilic sites. Which of the following is not an ambident nucleophile?
.. .. .. 2
:CN: :OH :OCH
.. 2CH 2S:
..
..
I II III
.. .. H. . .. ..
. N:O:H
..
:O:N::O
.. .. H.
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: B
Topic: Nucleophiles
44) Identify the nucleophile in the following reaction:
2ROH + RX ROR + [ROH2]+ + X-
A) X
B) [ROH2]
C) ROR
D) ROH
E) RX
Ans: D
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45) Which is the strongest nucleophile?
A) OH-
B) CH3CH2O-
C)
D) CH3CH2OH
E) H2O
Ans: B
Topic: Nucleophiles
46) Rank the following in terms of nucleophilic strength:
a) I>II>III>IV>V
b) V>IV>III>II>I
c) I>IV>II>III>V
d) V>I>IV>II>III
e) I>II>IV>V>III
Ans: C
Topic: Nucleophiles
47) Which SN2 reaction would you expect to take place most rapidly? Assume that the
concentrations of the reactants and the temperature are the same in each instance.

A) CH3S + CH3I CH3SCH3 + I
20
B)
H
CH3SH + CH3I S + I
H3C CH3

C) CH3O + CH3I CH3OCH3 + I
D)
H
CH3OH + CH3I O + I
H3C CH3

E) CH3S + CH3Cl CH3SCH3 + Cl
Ans: A
Topic: Nucleophilicity, leaving groups

Sections: 6.3, 6.8, 6.13
48) Which is not a polar aprotic solvent?

O
C
A) H3C CH3
B) H3C C N
O
S
C) H3C CH3
O
C CH3
H N
D) CH3
CH3
CH
E) H3C OH
Ans: E
Topic: Generalities, solvent effects
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Section: 6.13
49) Which is a polar aprotic solvent?
A) 2-methylhexane
B) CCl4
C) NH3(l)
D) CH3CH2CH2OCH2CH2CH3
E) 2-methyl-2-propanol
Ans: D

Section: 6.13
50) Consider an SN2 reaction of NaSH in a polar aprotic solvent with (CH3)2CHCH2CH2X. What
would be the relative order of reactivity for the following X substituents?
I. X = I II. X = Br III. X = Cl IV X = F
a) I > II > III > IV

b) II > I > IV > III
c) IV > III > II > I
d) III > I > II > IV
e) None of these choices.

Section: 6.13
51) Which is the weakest nucleophile in polar aprotic solvents?
A) I-
B) Br-
C) Cl-
D) F-
E) All of these choices are equally strong nucleophiles, regardless of the type of solvent used.
Ans: A
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Sections: 6.13
52) Which is the weakest nucleophile in polar protic solvents?
A) I-
B) Br-
C) Cl-
D) F-
E) All of these choices are equally strong nucleophiles, regardless of the type of solvent used.
Ans: D

Sections: 6.13
53) Which ion is the strongest nucleophile in aqueous solution?
A) F-
B) Cl-
C) Br-
D) I-
E) All of these choices are equally strong.
Ans: D

Sections: 6.13
54) Which ion is the strongest nucleophile in an aprotic solvent such as dimethylsulfoxide?
A) I-
B) Br-
C) Cl-
D) F-
E) All of these choices are equal.
Ans: D
Topic: Nucleophile, solvent effects

Sections: 6.13
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55) Which alkyl halide would you expect to react most slowly when heated in aqueous solution?
A) (CH3)3C-F
B) (CH3)3C-Cl
C) (CH3)3C-Br
D) (CH3)3C-I
E) All of these choices would react at the same rate.
Ans: A
Topic: Leaving groups

56) Considering the relative solvation of reactants and the transition states of substitution
reactions of these reactants, predict which general type of reaction would be most favored by the
use of a polar solvent.
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

Sections: 6.13
57) Which is the most reactive nucleophile in DMF (structure shown below)?
O
C CH3
H N
CH3
A) F-
B) Cl-
C) Br-
D) I-
E) All of these choices are equally reactive.
Ans: A
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Sections: 6.3, 6.13
58) Which of these species, acting in a protic solvent, exhibits greater nucleophilic activity than
expected on the basis of its basicity?
A) OH-
B) CH3O-
C) SH-
D) Cl-
E) H2O
Ans: C

Sections: 6.3, 6.13
59) Which SN2 reaction will occur most rapidly in a mixture of water and ethanol?
A) I- + CH3CH2Br CH3CH2I + Br-

B) I- + CH3CH2Cl CH3CH2I + Cl-
C) I- + CH3CH2F CH3CH2I + F-
D) Br- + CH3CH2Cl CH3CH2Br + Cl-
E) Br- + CH3CH2F CH3CH2Br + F-
Ans: A
Topic: Leaving groups, nucleophiles

Sections: 6.3, 6.13
60) Which SN2 reaction will occur most rapidly in aqueous acetone solution? Assume
concentrations and temperature are the same in each instance.
A) HO- + CH3-Cl CH3OH + Cl-

B) HO- + CH3CH2-Cl CH3CH2OH + Cl-
C) HO- + (CH3)2CH-Cl (CH3)2CHOH + Cl-
D) HO- + (CH3)3C-Cl (CH3)3COH + Cl-
E) HO- + (CH3)3CCH2-Cl (CH3)3CCH2OH + Cl-
Ans: A
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Topic: Predicting mechanism, kinetics
Sections: 6.3, 6.13
61) 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.

B) experimental measurements of sufficient accuracy are not available to make the comparisons.
C) nucleophilicity is a thermodynamic matter; basicity is a matter of kinetics.
D) basicity is a thermodynamic matter; nucleophilicity is a matter of kinetics.
E) Actually, the relative values do parallel one another.
Ans: D
Topic: Nucleophilicity
Sections: 6.3, 6.13
62) Which of the following is not true concerning the strength of a nucleophile?
a) Nucleophilicity may not parallel basicity.

b) Negatively charged nucleophiles are always more reactive than their conjugate acids.
c) The greater the strength of a nucleophile, the faster an SN2 reaction will occur.
d) Strong bases are always good nucleophiles
e) None of these answer choices are correct.
Ans: D
Topic: Nucleophilicity
Sections: 6.3, 6.13
63) Which of the following solvents will best promote a nucleophilic reaction between NaCN
and 1-bromopropane?
a) H2O/MeOH mixture
b) H2O
c) MeCN
d) HF(aq)
e) running with no solvent
26
Ans: C
Topic: Predicting mechanism, solvent effects

Sections: 6.3, 6.13
64) Which of the following nucleophiles will react the fastest with tert-butyl bromide in ethanol?
a) F-
b) Br-
c) I-
d) Cl-
e) All react at about the same rate.
Ans: E
Topic: Predicting mechanism, kinetics, solvent effectsh

Sections: 6.3, 6.13
65) Which of the following nucleophiles will react the fastest with 1-bromoptopane in ethanol?
a) SH-
b) OH-
c) H2O
d) H2S
e) All react at about the same rate.
Ans: A
Topic: Predicting mechanism, nucleophilicity, solvent effects

Sections: 6.3, 6.13
66) Which SN2 reaction would take place most rapidly?

H2O
OH + CH3Cl o CH3OH + Cl
A) 25 C
O O
H2O
+ CH3Cl + Cl
B) H3C O 25oC H3CO CH3
H2O
H2O + CH3Cl CH3OH2 + Cl
C) 25oC
27
H
CH3OH
CH3OH + CH3Cl O + Cl
D) 25oC H3C CH3
H2O
SH + CH3Cl CH3SH + Cl
E) 25oC
Ans: E
Topic: Kinetics, nucleophilicity

Sections: 6.3, 6.8, 6.13
67) Which of the following is a feasible substitution reaction?
A) CH3CH2Cl + NaBr CH3CH2Br + NaCl

B) CH3CH3 + NaCN CH3CH2CN + NaH
C) CH3CH2Cl + NaOH CH2=CH2 + H2O + NaCl
D) More than one of these choices.
Ans: A
Topic: Leaving group

Sections: 6.2, 6.4, 6.13
68) Identify the leaving group in the following reaction.
SNa S
I Na + I
A) C6H5S-
B) Na+
C) CH3CH2I
D) C6H5SCH2CH3
E) I-
Ans: E
Topic: Generalities, leaving group

28
69) Identify the leaving group in the following reaction.
CH3OH + CH3OH2 CH3OCH3 + H2O
H
A) CH3OH
B) CH3OH2+
C) CH3OCH3
D) H2O
Ans: D

70) Which nucleophilic substitution reaction would be unlikely to occur?
A) HO + CH3CH2I CH3CH2OH + I
B) I + CH3CH2H CH3CH2I + H
C) CH3S + CH3Br CH3SCH3 + Br
D) All of these choices would be unlikely to occur.
E) None of these choices would be unlikely to occur.
Ans: B

71) Which of the following would be most reactive in an SN2 reaction?

Br
A)
B) Br
C) Br
Br
D)
29
E) Br
Ans: D

72) Which of the following is the poorest leaving group?
A) H
B) CH3O
C) H2O
D) OH
E) NH2
Ans: E
Topic: Generalities, leaving group

73) Which of the following is not a good leaving group?
A) C2H5O
B) Cl
C) I
D) CH3CO2
E) All of these choices are good leaving groups.
Ans: A

74) Which nucleophilic substitution reaction is not likely to occur?
A) I + CH3CH2Cl CH3CH2I + Cl
B) I + CH3CH2Br CH3CH2I + Br
C) I + CH3CH2OH CH3CH2I + OH
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D) CH3O + CH3CH2Br CH3CH2OCH3 + Br
E) OH + CH3CH2Cl CH3CH2OH + Cl
Ans: C

Sections: 6.3, 6.4, 6.13
75) By analyzing the starting material and the product, the following reaction is possibly an
example of what type of mechanism(s)?
+
Cl
A) SN1
B) SN2
C) E1
D) E2
E) More than one of the above
Ans: E

Section: 6.18
76) Which mechanism best describes the chemical process shown below?
a) SN2
b) E1
c) E2
d) SN1
e) None of these choices.
Ans: B

Section: 6.18
31
Br
A) SN1
B) SN2
C) E1
D) E2
Ans: D

Section: 6.18
78) By analyzing the starting material and the product(s), the following reaction is possibly an
example of what type of mechanism?
HO O
A) SN1
B) SN2
C) E1
D) E2
Ans: E

79. Which alkyl halide, when treated with sodium ethoxide in ethanol, would afford a product
mixture consisting of more than one elimination product?
A) 1-bromo-3,3-dimethylpentane
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B) 1-bromo-2,3-dimethylpentane
C) 2-bromo-3,4-dimethylpentane
D) 2-bromo-3,3-dimethylpentane
E) None of these choices would yield more than one elimination product.
Ans: C

Section: 6.18
80) Elimination reactions are favored over nucleophilic substitution reactions
A) at high temperatures.
B) when tert-butoxide ion is used.
C) when 3 alkyl halides are used as substrates.
D) when nucleophiles are used which are strong bases and the substrate is a 2 alkyl halide.
E) in all of these cases.
Ans: E
Topic: Generalities
Section: 6.18
81) What would you expect to be the chief organic product(s) when tert-butyl bromide reacts
with sodium acetylide, i.e.,
Br
HC C: Na ?
I II III
HC CH
IV
A) I
B) II
C) III
D) IV
33
Ans: D

82) What would you expect to be the chief organic product(s) when 2-bromo-2-methylpentane
react(s) with sodium propynide, i.e.,
Br
C: Na ?
I II III
HC CH HC CH
IV V
A) I
B) II
C) III
D) IV
E) V
Ans: D

83) Suggest a reagent to perform the following transformation:
34
a) NaOH, H2O
b) NaH, THF
c) NaOMe, MeOH
d) t-butoxide, t-butanol
e) Ethanol
Ans: D
Topic: Predicting reagents for mechisms

Section 6.15 and 6.18
Difficulty: Medium
84) What major product(s) are likely to be obtained from the following reaction?
H
CH3CH2ONa
?
Cl
CH3CH2OH, 65oC
H
H O O H
H O H H H Cl
I II III
A) I, by predominantly SN2
B) II, by predominantly SN2
C) an equimolar mixture of I and II, by predominantly SN1
D) III, by substitution of the alkyl group, rather than substitution of the chloro group.
E) Actually, none of these products are likely to be obtained as major products, because
elimination will probably predominate, leading to the formation of an alkene.
Ans: E

Section: 6.18
85) The major product(s) of the following reaction is(are):
35
H H
NaI, CH3CH2OH
25oC
CH3 Cl
H H H I H H
CH3 I CH3 H CH3 CH3 OCH2CH3
I II III IV
A) I
B) II
C) III
D) IV
E) Equal amounts of I and II.
Ans: B

86) What would be the major product of the following reaction?

CH2Cl OH
H CH3 SN2
CH2OH CH2OH
H3C H H CH3
I II
CH2Cl CH2Cl
HO CH3 H OH
III IV
A) I
B) II
C) III
D) IV
E) An equimolar mixture of I and II.
36
Ans: B

87) What would be the major product(s) of the following reaction?
CH3CH2CO2Na
I CH3CH2CO2H
O2CCH2CH3 O2CCH2CH3 O2CCH2CH3
I II III IV
A) I
B) II
C) III
D) IV
Ans: A


O
CH3SNa
O S
O CH3SH
SCH3 SCH3
I II III IV
37
A) I
B) II
C) III
D) IV
Ans: C


Br
NaI
Acetone
I I I
I II III IV
A) I
B) II
C) III
D) IV
Ans: B

90) What would be the major product of the following reaction?
38
H3C H C
H Br 25oC
H3C H H3C CN
H CN H Br
I II
H3C CN H3C H
H H NC Br
III IV
A) I
B) II
C) III
D) IV
E) Equal amounts of I and III.
Ans: C

91) The product(s) for the following reaction would mainly be dictated by which mechanism?
NaCN
DMF
Cl
A) SN1
B) SN2
C) E1
D) E2
Ans: B

39
92) Reaction of sodium ethoxide with 1-bromopentane at 30C yields primarily:
A) CH3CH2CH2CH=CH2
B) CH3CH2CH=CHCH3
C) CH3CH2CH2CH2CH3
D) CH3CH2CH2CH2CH2OH
E) CH3CH2CH2CH2CH2OCH2CH3
Ans: E

93) Heating an alcoholic solution of sodium hydroxide and 1-bromopentane at 60C yields
primarily:
A)
B)
C)
OH
D)
O
E)
Ans: D

40
O
CF3
S
O NaN3
O
DMF
N3
N3 O
I II III IV
A) I
B) II
C) III
D) IV
Ans: E


CH3OH
Br heat
H3CO
I II III IV
A) I and II
B) I, II, and III
C) III
D) I, II, and IV
41
Ans: D

96) Predict the product(s) for the following reaction sequence.

1. NaI, acetone
O
O
S
F3C 2. NaCN, DMF
O
A)
B) CN
C) CN
D)
E) More than one of these choices
Ans: C


1. NaI, acetone
Cl 2. CH3CO2Na, CH3CO2H
A)
B) O O
42
C) O O
D)
E) A mixture of two of these choices
Ans: C

98) When 0.10 mol of ICH2CH2CH2CH2Cl reacts with 0.10 mol of NaOCH3 in CH3OH at 40C,
the major product is:
A) CH3OCH2CH2CH2CH2Cl
B) CH3OCH2CH2CH2CH2I
C) CH3OCH2CH2CH2CH2OCH3
D) CH2=CHCH2CH2Cl
E) CH2=CHCH2CH2I
Ans: A

99) If 0.10 mol of HSCH2CH2OH reacts at 25C, sequentially, with 0.20 mol of NaH, 0.10 mol
of CH3CH2Br followed by the addition of H2O, which is the major product?
A) HSCH2CH2OCH2CH3
B) CH3CH2SCH2CH2OH
C) CH3CH2SCH2CH2OCH2CH3
D) CH2=CH2
E) CH3CH3
Ans: B

43
100) What would be the major product obtained when trans-1-bromo-3-methylcyclopentane is
allowed to react with NaSH at 25oC?
H3C H H3C SH H3C SH H3C H
H SH H H H Br HS Br
I II III IV
A) I
B) II
C) III
D) IV
E) Equal amounts of I and II.
Ans: B

Br CH3SNa
EtOH
A) SN1
B) SN2
C) E1
D) E2
Ans: B


OH a. NaH, THF
b. 1-iodopropane
44
O
A)
O
B)
I
+ OH
C)
+
D)
Ans: A

103) SN2 reactions of the type, Nu- + RL Nu-R + L-, are favored
A) when tertiary substrates are used.

B) by using a high concentration of the nucleophile.
C) by using a solvent of high polarity.
D) by the use of weak nucleophiles.
E) by none of these choices.
Ans: B
Topic: Generalities
Sections: 6.8, 6.13, 6.18
104) 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. (Assume that
all other experimental conditions are unchanged.)
B) The major product would be (S)-2-butanol.
C) Doubling the concentration of (R)-2-bromobutane would double the rate of the reaction.
(Assume that all other experimental conditions are unchanged.)
D) All of these choices.
45
E) Two of these choices.
Ans: D
Topic: Generalities
Sections: 6.8, 6.13, 6.18
105) 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 + CH3CH2CH2CH2OH CH3CH2CH2CH2Cl + OH
C) CH3S + CH3CH2CH2OCH3 CH3SCH2CH2CH3 + OCH3
D) All of these choices are likely to occur.
E) None of these choices are likely to occur.
Ans: A

Sections: 6.8, 6.13, 6.18
106) The major product(s) for the following reaction would mainly be dictated by which
mechanism?
O
CF3
S
O NaN3
O
CH3CH2OH
A) SN1
B) SN2
C) E1
D) E2
Ans: B

Sections: 6.8, 6.13, 6.18
46
Li
Br THF
I II III IV
A) I
B) II
C) III
D) IV
Ans: A

Sections: 6.8, 6.14, 6.18

NaCN
I DMSO
C
CN DMSO
I II III IV
A) I
B) II
C) III
D) IV
Ans: E
47
Section: 6.8, 6.14, 6.18

a. THF, H3C Li
I
b. H2 (excess), Pd/C, EtOH
A)
B)
C)
D)
Ans: C

Sections: 6.8, 6.14, 6.18

1. 1-bromobutane
2. H2 (excess), Pd/C, EtOH

Li
A)
B) Br
C)
D)
48
Ans: E

Sections: 6.8, 6.14, 6.18

t-BuOK
Cl t-BuOH
t-BuO
I II III IV
A) I
B) II
C) III
D) IV
Ans: D


O
CH3CH2ONa
O S
O 60 oC
OCH2CH3
I II III IV
A) I and II
B) II and III
C) III and IV
49
D) I and IV
E) All of these choices.
Ans: D

113) Which of these compounds would give the largest E2/SN2 product ratio on reaction with
sodium ethoxide in ethanol at 55C?
Cl
A)
B)
Cl
C)
Cl
D) Cl
Cl
E)
Ans: D
Topic: Predicting mechanisms

Sections: 6.8, 6.16, 6.18

t-BuOK, t-BuOH
Cl
Ot-Bu
I II III IV
50
A) I
B) II
C) III
D) IV
Ans: A

Sections: 6.15, 6.16, 6.18
t-BuOK
t-BuOH
Cl
A) SN1
B) SN2
C) E1
D) E2
Ans: D

Sections: 6.15, 6.16, 6.18
116) The major product(s) for the following reaction would mainly be dictated by which
mechanism?
O
CF3
S
O CH3CH2OLi
O
CH3CH2OH
A) SN1
B) SN2
C) E1
51
D) E2
Ans: D

Sections: 6.15, 6.16, 6.18

EtOH, EtONa
Cl
EtO
I II III IV
A) I and III
B) I and II
C) II and III
D) IV
Ans: B

Sections: 6.15, 6.16, 6.18
52
H3C CH3 CH3O/ CH3OH
H Br 55oC
H3C CH3 H3C OCH3
H OCH3 H CH3
I II
H3C CH3 H3C
III IV
A) I
B) II
C) III and IV
D) I and II
Ans: C

Sections: 6.15, 6.16, 6.18

(CH3)2CHONa
Cl (CH3)2CHOH
60 oC
OCH(CH3)2
I II III IV
A) I
B) II, III, and IV
C) III and IV
D) II and IV
E) IV and III
53
Ans: C

Sections: 6.15, 6.16, 6.18
EtOH, EtONa
Cl
A) SN1
B) SN2
C) E1
D) E2
Ans: D

Sections: 6.15, 6.16, 6.18
121) Predict the major product(s) for the following reaction sequence.
a. NaH, THF
OH
Br
b. 60 oC
O O
A) A mixture of and
O
B)
54
C)
D)
E) A mixture of two of these choices.
Ans: E

Sections: 6.15, 6.16, 6.18

1. t-BuOK, t-BuOH
Br
2. H2, Pd/C, EtOH
A)
B)
Ot-Bu
C)
D)
Ans: A

Sections: 6.15, 6.16, 6.18
123) Treating (CH3)3C-Cl with a mixture of H2O and CH3OH at room temperature would yield:
A) CH2=C(CH3)2
B) (CH3)3COH
C) (CH3)3COCH3
55
Ans: D

Section: 6.18
124) Treating 1-bromo-1-methylcyclohexane with CH3OH at room temperature would yield:
OCH3
A)
B)
C)
Ans: D

Section: 6.18
125) Which would be formed in the following reaction?

CH3
CH3OH
H3C Br ?
o
55 C
H
OCH3 CH3
H3C CH3 H3C OCH3
H H
I II
CH3 CH3
CH3 CH2
III IV
56
A) I
B) II
C) III
D) IV
Ans: E

Section: 6.18

Br EtOH
20 oC
OEt EtO
I II III IV
A) I and II
B) II and III
C) I and III
D) IV
Ans: C

57
CH3
CH3CH2CO2H
Br CH3
CH3 room temperature
O O
O
O
I II III IV
A) I
B) II
C) III
D) IV
Ans: D


HO
Br
20 oC
(CH3)2CHCH2O
(CH3)2CHCH2O (CH3)2CHCH2O
I II III IV
A) I and II
B) I, II, and III
C) III
D) IV
Ans: A

58
129) When tert-pentyl chloride undergoes solvolysis in aqueous ethanol at room temperature,
there is/are formed:
A) OH
B) OC2H5
C)
D)
Ans: E

130) Which of the following statements is (are) true of SN1 reactions of alkyl halides in general?
A) The rate of an SN1 reaction depends on the concentration of the alkyl halide.
B) The rate of an SN1 reaction depends on the concentration of the nucleophile.
C) SN1 reactions of alkyl halides are favored by polar solvents.
D) The rate of an SN1 reaction depends on the concentration of the alkyl halide and SN1 reactions
of alkyl halides are favored by polar solvents.
E) The rate of an SN1 reaction depends on the concentration of the alkyl halide and the
concentration of the nucleophile, and SN1 reactions of alkyl halides are favored by polar
solvents.
Ans: D
Topic: Generalities
Sections: 6.12, 6.13, 6.18
131) Which of the following statements is (are) true of SN1 reactions of alkyl halides in general?
A) The rate of an SN1 reaction depends on the concentration of the alkyl halide.
B) The rate of an SN1 reaction depends on the concentration of the nucleophile.
59
C) SN1 reactions of alkyl halides occur faster in polar aprotic solvents (compared to protic
solvents).
D) The rate of an SN1 reaction depends on the concentration of the alkyl halide and SN1 reactions
of alkyl halides occur faster in polar aprotic solvents (compared to protic solvents).
E) The rate of an SN1 reaction depends on the concentration of the alkyl halide and the
concentration of the nucleophile, and SN1 reactions of alkyl halides occur faster in polar aprotic
solvents (compared to protic solvents).
Ans: A
Topic: Generalities
Sections: 6.12, 6.13, 6.18
132) SN1 reactions of the type, Nu- + RL NuR + L-, are favored
A) when tertiary substrates are used.

B) by using a high concentration of the nucleophile.
C) when L- is a strong base.
D) by use of a non-polar solvent.
E) by none of these choices.
Ans: A
Topic: Generalities
Sections: 6.12, 6.13, 6.18
133) SN1 reactions of the following type:
Nu:- + R-X R-Nu + :X-
are favored
A) by the use of tertiary substrates (as opposed to primary or secondary substrates).

B) by increasing the concentration of the nucleophile.
C) by increasing the polarity of the solvent.
D) by use of a strong base.
E) by more than one of these choices.
Ans: A
Topic: Generalities
Sections: 6.12, 6.13, 6.18
60
134) SN1 reactions of the following type:
Nu:- + R-X R-Nu + :X-
are favored
A) by the use of tertiary substrates (as opposed to primary or secondary substrates).

B) by increasing the concentration of the nucleophile.
C) by increasing the polarity of the solvent.
D) by use of a weak nucleophile.
E) by the use of tertiary substrates (as opposed to primary or secondary substrates) and by use of
a weak nucleophile.
Ans: E
Topic: Generalities
Sections: 6.12, 6.13, 6.18

CH3CH2OH
Br 25 oC
OCH2CH3 OCH2CH3
I II III IV
A) I
B) II
C) III
D) IV
Ans: E

Section: 6.12, 6.14, 6.18
61
A) SN1
B) SN2
C) E1
D) E2
Ans: A

Sections: 6.12, 6.17, 6.18

(CH3)2CHOH
Br 70 oC
OCH(CH3)2
OCH(CH3)2
I II III IV
A) I
B) II
C) III
D) IV
Ans: E

Sections: 6.14, 6.15, 6.17, 6.18
62

CH3OH
Br
OCH3
I II III IV
A) I
B) II
C) III
D) IV
Ans: E

Sections: 6.15, 6.17, 6.18
1-pentanol
80 oC
Cl
A) SN1
B) SN2
C) E1
D) E2
Ans: C

Sections: 6.15, 6.17, 6.18
63
O
CF3
S
O CH3CH2OH
O
60 oC
A) SN1
B) SN2
C) E1
D) E2
Ans: C

Sections: 6.15, 6.17, 6.18
HO
Br
80 oC
(CH3)2CHCH2O
I II III IV
A) I
B) II
C) III
D) IV
Ans: E
64
Sections: 6.15, 6.17, 6.18
Cl (CH3)2CHOH
70 oC
OCH(CH3)2
I II III IV
A) I
B) II and III
C) II, III, and IV
D) III and IV
Ans: D

Sections: 6.15, 6.17, 6.18

t-BuOH, heat
Cl
Ot-Bu
I II III IV
A) I
B) II
C) III
D) IV
Ans: E
65
Sections: 6.15, 6.17, 6.18
A) SN1
B) SN2
C) E1
D) E2
Ans: A

Sections: 6.15, 6.17, 6.18

1. EtOH, heat
Br
2. H2, Pd/C, EtOH
EtO
A)
EtO
B)
C)
D)
E) A mixture of two of these choices.
Ans: D
66
Sections: 6.15, 6.17, 6.18
146) Which would be the major product of the following reaction?
CH3 H
(CH3)3CO
?
(CH3)3COH
H Cl 55oC
CH3 OC(CH3)3 CH3 H

H3C H3C
H I H OC(CH3)3
I II III IV
A) I
B) II
C) III
D) IV
Ans: C

Section: 6.18
A) SN1
B) SN2
C) E1
67
D) E2
Ans: A

Br EtOH
heat
A) SN1
B) SN2
C) E1
D) E2
Ans: C

Sections: 6.15, 6.17, 6.18
149) Which would be formed in the following reaction?
68
CH3 O
Br OH
H3 C ?
o
50 C
H
O
CH3 O O
H3C O H3C CH3
H H
I II
III IV
A) I
B) II
C) III
D) IV
Ans: E

Section: 6.18
150) Predict the major product(s) for the following reaction sequence.
Br 1. NaI, acetone
2. H2O, 20 oC
OH
A)
OH
B)
C)
69
D)
E) A 1:1 mixture of two of these choices. )
Ans: E

Sections: 6.8, 6.18 then 6.12
151. Predict the product(s) for the following reaction sequence.
OH
A)
OD
B)
C)
Na
D)
Ans: B

Sections: 6.15, 6.16, 6.18
152) Heating tert-butyl chloride with 1.0 M NaOH in a mixture of water and methanol would
yield mainly
70
A) (CH3)3COH through an SN1 reaction.
B) (CH3)3COCH3 through an SN1 reaction.
C) (CH3)3COH through an SN2 reaction.
D) (CH3)3COCH3 through an SN2 reaction.
E) CH2=C(CH3)2 through an E2 reaction.
Ans: E
Topic: Predicting mechanism, products

Sections: 6.18
Question type: True/false
153) In a highly exergonic SN2 reaction we can assume the transition state is similar to the
products formed in the reaction.
Ans: False
Topic: Hammond Postulate

154) An endergonic SN2 reaction will have a have a higher energy of activation (G) than an
exergonic SN2 reaction.
Ans: True

155) Increasing the temperature of a reaction will speed up the overall rate as this will increase
the energy of activation for reaction.
Ans: False
Topic: Temperature and rate

Section: 6.7
71
156) Racemic mixtures form in SN1 reactions when leaving group departure results in a loss of
chirality followed by subsequent attack of the nucleophile.
Ans: True
Topic: SN1 stereochemistry

Section: 6.12
157) All SN1 reactions will always be accompanied by a competing E1 reaction.
Ans: False
Topic: E1 reactions
Section: 6.17
Question type: text-entry
158) 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 ___.
Ans: longer; weaker
Topic: Bond length, bond strength, leaving groups

Section: 6.4
159) 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 ___.
Ans: transition state
Topic: Transition state theory

Section: 6.6
160) In order for colliding species to react, they must ___ and ___.
Ans: have energy equal/greater than the activation energy, approach with the proper orientation.
72
Topic: Activation energy, transition state theory
Section: 6.7
161) What final product is likely to be obtained through the following series of reactions?
OH NaH Cl
A B
diethylether
O
Ans:
Topic: Multistep synthesis, acid-base reactions, SN2

Sections: 6.8
162) When 5-bromo-1-pentanol is treated with sodium hydride in diethyl ether, the product is
analyzed to be C5H10O. Propose a likely structure for this product, suggesting a reasonable
mechanistic pathway for its formation.
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.
.. NaH .. + O
Cl OH
.. Cl .. : Na
O NaCl
H2
Topic: Acid-base reactions, intramolecular SN2

Sections: 6.8
163) Draw the potential energy diagram that represents an exothermic reaction between a tertiary
alkyl halide and methanol. Briefly explain your rationale.
Ans: The reaction is likely to occur via an SN1 mechanism. The first step is the rate-determining
step, leading to the formation of a tertiary carbocation. 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.
73
Energy
time

164) A nucleophile in an SN2 reaction must approach from the ___ of the carbon atom attached
to the leaving group since the electrons in the nucleophiles HOMO begins to overlap with the
___ of the carbon atom attached to the leaving group.
Ans: backside and LUMO
Topic: SN2 mechanism

Section 6.6
165) The stabilizing effect of alkyl substituents on carbocations can be explained through ___.
Ans: hyperconjugation
Topic: Carbocation stability

Section: 6.11
166) Typically, increasing the concentration of the nucleophile of an SN1 reaction has no impact
on the rate of the reaction. The reason for this is that ___.
Ans: An SN1 reaction is a multi-step process; the overall reaction rate is determined by the rate of
formation of the carbocation intermediate. Since the nucleophile is not involved in the rate-
determining step, changes in its concentration typically have no impact on the rate of reaction.
Topic: SN1 kinetics

Section: 6.12
74
167) The substitution mechanism whose rate depends primarily on the relative stability of the
intermediate carbocation is the ___.
Ans: SN1
Topic: Carbocation stability

168) A reaction in which the nucleophile is a molecule of the solvent is referred to as a ___
reaction.
Ans: solvolysis
Topic: Solvolysis
Section: 6.12
169) A student has isolated a chiral alkyl halide (shown below) with a specific rotation of [] =
+22.1o. The student decided to store the compound in the solvent MeOH overnight. However,
reanalysis of the alkyl halide showed a new chemical formula of C11H16O with a specific rotation
of [] = 0o. Suggest a mechanism to justify these results.
Ans: In leaving the compound in MeOH a solvolysis reaction has occurred which results in
carbocation formation, following the addition of the MeOH and loss of a proton a racemic
mixture is formed which gives a [] = 0o.
75
Topic: Solvolysis
Sectioin: 6.12
170) The substitution mechanism whose rate depends primarily on the degree of steric hindrance
around the leaving group is the ___.
Ans: SN2
Topic: Steric hindrance

Section: 6.13
171) Increasing the concentration of either of the reactants of an SN2 reaction increases the rate
of the reaction. The primary reason for this is that increasing the concentration increases ___.
Ans: the frequency of collisions between reactant species, thereby statistically increasing the
chance encounters between species having the requisite Eactivation
Topic: Activation energy, kinetics

172) The relative nucleophilicity of the halide ions in polar aprotic solvents is observed to be
markedly different from that in protic solvents. Explain briefly.
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. The situation is reversed in aprotic solvents, where the
nucleophile is essentially unsolvated; thus, the nucleophilicity parallels the basicity of the halide
ions, so that the fluoride ion is the strongest nucleophile of the halide ions.
Topic: Nucleophilicity, solvent effects

173) Typically alkyl chlorides are slow in SN2 reactions with sodium methoxide in methanol,
however the rate of the reaction can be greatly increased with a small addition of NaI. Explain.
Ans: The iodide ion will attack the alkyl chloride producing alkyl iodides which are more
reactive due to the better iodide leaving group and will allow for ether formation. The iodide ion
76
is regenerated at the end of the reaction making it a catalyst, and thus only a small quantity is
needed.
R-Cl + I- Cl- + R-I + MeO- R-OMe + I-
Topic: Nucleophilicity, solvent effects

NaNH2 Br
A B
NH3(l)
Ans:
Topic: Multistep synthesis, acid-base reactions, SN2

Sections: 6.14
NaNH2 Cl excess H2
A B C
NH3(l) Ni
Ans:
Topic: Multistep synthesis, acid-base reactions, SN2, hydrogenation

Sections: 6.14, 4.16
176) Give a detailed reaction mechanism for the reaction expected to occur when 2-bromo-2-
methylpentane is heated with methanol. Draw clear structural formulas of all relevant species
and use curved arrows to represent electron flow. Also indicate which step is likely to be rate-
determining.
Ans: The reaction is likely to occur via an E1 mechanism. The first step is the rate-determining
step, leading to the formation of a tertiary carbocation, followed by base promoted elimination to
afford 2 different alkene products.
77
..
: Br : H ..
slow HOCH
.. 3
..
[ - :Br: fast
.. ] H
Topic: Predicting reaction mechanisms

Sections: 6.15, 6.16, 6.17
177) When diastereomers I and II undergo an E2 elimination on treatment with sodium ethoxide
in ethanol, one of the isomers react 500 times faster than the other one. Also, one isomer gives
only A as a product and the other isomer gives a mixture of A and B as products. Determine the
products of each isomer and explain your reasoning.
Ans: By looking at the chair conformations of I and II with the leaving group axial we can see
that compound I can only produce B with a hydrogen in anti-perplaner conformation. In addition,
this hydrogen has significant steric hindrance caused by the isopropyl group meaning compound
Is reaction will be slow. Compound II lacks this steric hindrance and can give 2 possible
products as it has 2 hydrogens that can eliminate anti to the Br.
78
Sections: 6.15, 6.16, 6.17
178) Even though sodium ethoxide is a strong nucleophile and a strong base, only one major
product is observed in the reaction below. Explain why.
Ans: Notice that an SN2 reaction is not likely due to sterics of approaching the leaving group Cl
from the backside as well as running this reaction in a polar protic solvent. SN1/E1 reaction also
seem unlikely as a secondary alkyl halide will not form a very stable carbocation without
rearrangement. E2 is the major mechanism dominating the reaction, and to be sensitive to its
mechanistic requirements, we must have the Cl leaving group anit-periplaner to the incoming
nucleophile.
79
Sections: 6.15, 6.16, 6.17
80

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Package title: Solomons Test Bank

Course Title: Solomons 11e

Question type: Multiple choice

1) Select the rate law for the following reaction, e.g.,

Topic: Reaction kinetics

Topic: Reaction Kinetics

3) Consider the SN2 reaction of butyl bromide with OH- ion.

CH3CH2CH2CH2Br + OH- CH3CH2CH2CH2OH + Br-

Topic: Reaction kinetics

4) Consider the SN2 reaction of 2-iodopentane with CH3CO2 ion.

Topic: Reaction kinetics

5) Consider the SN2 reaction of 1-chloro-5-methylhexane with CN ion.

Topic: Reaction kinetics

has the following thermodynamic values at 27.0 C: H = -75.3 kJ mol-1;

Topic: Free energy changes

Topic: Free energy diagrams

Topic: Free energy diagrams

Topic: Free energy diagrams

Topic: Free energy diagrams

11) An increase in the temperature at which a reaction is carried out increases

A) the collision frequency.

Topic: Activation energy

Topic: Transition state theory

Topic: Activation Energy

CH3 OCH3 CH3 H H Br

Topic: Predicting products

15) The major product of the following reaction would be:

Topic: Predicting products

A) The two transition states are of unequal energy.

Topic: Reaction Kinetics

18) Consider the reaction of 2-chloro-2-methylpentane with sodium iodide.

Topic: Reaction Kinetics

a) the rate will increase by a factor of 2

20) The hybridization state of the charged carbon in a carbocation is ___.

Topic: Stereochemistry of SN/E reactions

Topic: Predicting mechanism, stereochemistry of SN reactions

Topic: Predicting mechanism, stereochemistry of SN reactions

Topic: Predicting mechanism, stereochemistry of SN reactions

Topic: Predicting mechanisms, products

Topic: Predicting mechanisms, products

Topic: Predicting mechanisms, products

A) a negatively-charged nucleophile is stronger than its conjugate acid.

Topic: Hammond-Leffler postulate

Topic: Predicting mechanisms, products

A) Structurally, it closely resembles the carbocation intermediate.

Topic: Predicting mechanisms, products

Topic: Synthesis, reagent selection

35) You want to synthesize 3-methyl-2-pentene from 2-chloro-3-methylpentane. Which reagent

Topic: Synthesis, reagent selection

Topic: Steric hindrance

37) Which alkyl halide would be most reactive in an SN1 reaction?

a) an SN2 reaction has occurred with inversion of configuration

Topic: Kinetics and Mechanism

39) An increase in the kinetic energy of reacting molecules results in

A) a decrease in reaction rate.

Topic: Transition State theory

41) Identify the nucleophile in the following reaction:

2 H2O + RX ROH + H3O+ + X

Topic: Generalities, nucleophiles

42) Which of the following is not a nucleophile?

Topic: Generalities, nucleophiles

44) Identify the nucleophile in the following reaction:

2ROH + RX ROR + [ROH2]+ + X-

45) Which is the strongest nucleophile?