1. Which product would you not expect in the crossed aldol reaction between acetaldehyde and propionaldehyde?

O H3C C O

+
H H3C CH2

cat. NaOH
H

H2O

A)
OH H3C H2C C CH2 H C H O

B)
H H3C C CH C H O

CH3 OH

C)
OH H3C C CH2 H C H O

D)
OH H3C C H CH CH3 OH H3C H2C C H CH CH3 C H C H O

E)
O

Ans: B

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2. What organic molecule would you expect to be present in significant amounts under the following conditions?
O H CH3

cat. KOD excess D2O

only (S) enantiomer A)

DO OH H CH3

B)
O D CH3

C)
O

D)
O CH3 D

racemic

E)
O CD3 D

racemic Ans: D

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3. What reactants would be used to produce cinnamaldehyde?

? A)
CHO

cat. NaOH H2O

CHO

+ CH3CHO B)
CHO O H C CHO

+ C)
O CH3

+ CH2=O

D)
O

CHO

E)
CHO O H3C C CHO

+ Ans: A

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4. What would you expect to result from the following reaction?

1. (CH3)2CuLi
O

2. H2O

A)

B)

OH

C)

OH CH3

D)

E)

Ans: A
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5. Indicate to which side, if any, the following equilibrium lies:

O

H or HO

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

To the right To the left Equally to right and left Cannot be predicted Major product is an enol or enolate ion, respectively A

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6. What would be the expected product of the following reaction?

O CH3 O

HC CH2

CH3

CH3O- Na+ CH3OH heat

A)

B)
O

C)
O

D)
O

E)
O

Ans: A

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7. What major product would you expect from the following reaction?
O CH2=O Na+ -OCH3 CH3OH, heat ?

A)
HO OCH3

B)
CH2

C)
O CH3

D)
O CH2

E)
O

Ans: D 8. Which proton in the following molecule is the most acidic?

O

H H

CH2 CH2 C

5 3 4

2 A) 1 B) 2 C) 3 D) 4 E) 5 Ans: D

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9. What product is formed in the aldol condensation of propanal?

CH3CH2CHO A)
O

KOH H2O

CHO

B)
OH CHO

C)
O OH

D)
HO CHO

E)
OH CHO

Ans: B 10. To which side, if any, would the following equilibrium lie?
OH H3C C CH2 H3C O C CH3

A) B)

To the left To the right

D) E)

Reaction cannot occur at all Equilibrium favors a different product.

C) Equally to the left and right Ans: B

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11. To which side, if any, would the following equilibrium lie?

+ O - Na

H3C

CH2

H2O

H3C

CH3

NaOH

A) B)

To the left To the right

D) E)

Reaction cannot occur at all Equilibrium favors a different product.

C) Equally to the left and right Ans: B

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12. Which major product would you expect when the following diketone undergoes aldol cyclization in base, followed by acid?
O O NaOCH2CH3 H3 O +

A)
O H3C

B)
O O

C)
O CH3

CH3

D)
O CH3

E)
O CH3

Ans: A

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13. Which set of reagents would be needed for the following conversion?
CH3 O CH3 O CH2Ph

A) B) C) Ans:

NaOCH2CH3, CH3I PhCH2MgBr, then H3O+ CH3MgBr, then PhCH2Br E

D) E)

H3O+, then PhCH2Br LDA, then PhCH2Br

14. What product results when the following aldol product is treated with dilute acid?
PhCH2 HO Ph O H

H3O+

A)
PhCH2 O H Ph

B)
Ph O CH2 O

+
H

CH2 Ph

C)
Ph O H Ph

D)
PhCH2 H Ph O OH H

E) None of these Ans: A

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15. Which of the following sets of reaction conditions will result in the following transformation?
O OH

A)

1) PhMgBr / THF 2) H3O+ 3) LAH / THF B)

1) PhMgBr / THF 2) H3O+ 3) LDA / THF

C) 1) PhMgBr / THF 2) H3O+ 3) LAH / H2O D) 1) (Ph)2CuLi 2) H3O+ 3) NaBH4 / CH3OH E)

1) (Ph)2CuLi 2) H3O+ 3) MCPBA

Ans: D

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16. Predict the major organic product of the following reaction.

CHO + O NaOH / H2O Heat

A)
OH O

B)
O

C)
O

D)
OH O

E)

Ans: B

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17. Predict the major organic product of the following reaction.

O + O

NaOEt / EtOH

A)

B)

C)

OH

D)

E)
O

Ans: A

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18. Predict the major organic product of the following reaction sequence.
O 1) LDA / THF O 2) EtO OEt 3) LDA / THF 4) CH3CH2OTs 5) Saponification 6) H2O / H+ 7) Heat

CH3O

A)
O

CH3O

B)
O

CH3O

C)
O O O CH3O

D)
O OEt CH3O O

E)

CH3O

Ans: A

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19. Predict the major organic product of the following reaction sequence.
O 1) LDA (0.95 eq) / THF 2) CH3OTs 3) MCPBA ?

A)
O

B)

O O

C)

D)
O

E)
O H 3C O

Ans: B

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20. The addition of either the methyl Grignard reagent or methyllithium to camphor, followed by hydrolysis, produces a tertiary alcohol known as 2-methylisoborneol, an algal metabolite which imparts a musty odor to water at very low concentrations. However, the yield of alcohol does not exceed 50%, and large amounts of camphor are recovered from the reaction even when a large excess of the Grignard or lithium reagent are used. What would be the most plausible explanation? 1. CH3MgBr or CH3Li O camphor A) B) C) 2. H2O

OH CH3 ~ 50%

+ ~ 50% unreacted camphor

Ketones do not react with Grignard or lithium reagents. The Grignard or lithium reagent had obviously degraded during storage. The mechanism requires that, for each alcohol formed, one ketone molecule must remain unreacted. D) With hindered ketones, the organometallic reagent could function as a base rather than as a nucleophile. E) Alcohol formed early in the reaction could form an unreactive hemiacetal with remaining ketone. Ans: D

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21. Predict the product of the following reaction:

O

Cl2 , H

A)
Cl O

B)
HO CH3

C)
Cl OH

D)
O

Cl

E)

Ans: D

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22. One product of the following reaction would be:

O CHO

KOH/
H

A)
O O H

B)
OH H

C)

CHO

D)
O H

E) None of these are correct. Ans: C 23. Which of the following conditions will not successfully alkylate a ketone? A) 1. H2O, H+ 2. CH3CH2OH B) 1. 2. CH3CH2Br 3. H+, H2O C) 1. LDA, THF 2. BrCH2CO2C2H5 D) 1. LDA, THF 2. (CH3)2C=CHCH2Br E) All of these will alkylate a ketone. Ans: A

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24. Predict the product of the following reaction:

O
1. nBuLi 2. H, H 2O

A)
HO

B)
OH

C)
O

D)
OH

E)
O

Ans: A

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25. Predict the product of the following reaction:

O
1. (CH3CH2CH2CH2)2CuLi 2. CH3CH2I

A)
(CH2) 3CH3 CH2 CH3

B)
O (CH2) 3CH3 (CH2) 3CH3

C)
O (CH2) 3CH3 CH2 CH3

D)
O CH2 CH3 (CH2) 3CH3

E)
HO (CH2) 3CH3 CH2 CH3

Ans: D

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27. Predict the product of the following reaction:

A)

B)

C)

D)

E) both B and C Ans: E

Page 22

28. Predict the product of the following reaction:

O CH3NH2, H2O

A)

OH NHCH3

NHCH3
B)

OH
C)

NHCH3
D)

O NHCH3

NHCH3
E)
Page 23

H NCH3

Ans: C 29. Given a large excess of D2O, what product(s) would result from the following reaction at equilibrium?
D2O
O

D or -OD

A)
OD D

B)
D D D O

C)
D D D CD3 D D D O

D D3 C

D D D D O

CD3

D)

E) both B and D would be formed Ans: E

Page 24

30. The best reactants to convert cyclohexanone to 2-methylcyclohexanone cleanly would be: O

O CH3

A)

1.

N H

, H+, - H2O

2. CH3I 3. H3O+
B)

NaOH, CH3I
C)

1. LDA 2. CH3I

D)

1. CH3Li 2. H3O+

E)

1. NaH 2. CH3I 3. H3O+

Ans: A

Page 25

31. What would be the major product of the following reaction?

cat. NaOH
O A) O

H2O heat

B)
O

C) O

D)
O

OH

E)
O

OH Ans: A

Page 26

32. Which statement is true of the following reactions? CH3OH

R CHO R OH CH OCH3

CH3OH
R

OCH3 CH OCH3

reaction I A) B) C) D) E) Ans:

reaction II

Reactions I and II are only acid-catalyzed. Reaction I is catalyzed by either acid or base, but reaction II requires acid. Reactions I and II are both base-catalyzed. Reaction II is catalyzed by either acid or base, but reaction I requires acid. Both reactions I and II are catalyzed by either acid or base. B

Page 27