• Author / Uploaded
• Theo Caldas

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Sample Multiple-choice Questions 1. Which of the following compounds are nonpolar? H2O I

CO2 II

a) II, III

NH3 III

BF3 IV

b) II, IV

CHCl3 V

c) I, III

d) III, V

2. Which of the following Lewis structures are incorrect? O

H O O

N

Cl

Cl

N

O H

H C

H H H C N H H

H I a) I, II, III

II b) I, IV, V

III c) II, III, IV

IV d) III, IV, V

V

3. Which of the following molecules have bond angles of about 109.5˚? CS2 I

AlCl4III

BF3 II

a) I, II, IV

NH2IV

b) III, IV, V

NH4+ V

c) II, III, IV

d) I, III, V

4. Which functional groups are in the following molecule? I. Acid II. Alcohol III. Aldehyde IV. Ether V. Ketone a) I, IV, V, VI, VII

O

VI. Sulfoxide VII. Amide VIII. Thiol ester IX. Sulfide

O

O

Penicillin G b) I, III, V, VI

S

NH

c) I, IV, VII, IX

CH3

N

CH3 COOH

d) I, IV, VIII, IX

5. How many total isomers (constitutional and stereo) are there for an alcohol with the molecular formula C4H10O? a) 2

b) 3

c) 4

d) 5

6. Which of the following are NOT resonance structures? I. HN

C

O

HO

II. N

C

O

N

a) I, II

b) II, IV

C

C

N

O c) I, III

III.

CH3 C

IV.

CH3 C d) III, IV 1

O CH3 O CH2

CH3 C

CH3 C

OH CH2 O CH2

7. Which of the following ions are stabilized by resonance? O CH2

C

CH

CH2

CH3

C

I CH2

CH

CH3

II

CH

CH

CH

CH2

CH2

CH2

III a) I, II

b) I, III

CH

CH2

IV d) III, IV

c) II, IV

8. What are the correct hybrid states of the carbon atoms in the following structures? CH3

CH3

I

2

II

C

O

HC

III

3

H2C

N

IV

N

OH

V

2

3

a) sp: III, IV, V; sp : I; sp : II

b) sp: III, IV; sp : I, II; sp : V

c) sp: III, IV; sp : I, V; sp : II

d) sp: III, IV; sp : II, V; sp : I

2

3

2

3

9. What is the IUPAC name for the following compound? CH2 CH3

C

CH3 CH2

CH2

CH3

CH3

a) 2,2-diethylbutane b) 222-triehtylethane c) 3-methyl-3-ethylpentane d) 3-ethyl-3-methylpentane

10. Which of the followng is a primary alcohol with the molecular formula C4H10O? a)

OH

b)

CH2OH

c)

OH

d)

OH

11. How many total isomers (constitutional and stereo) are there for dimethylcyclopentane? a) 3

b) 5

c) 7

d) 9

12. Which of the following is a conformer of isobutane?

H

CH3

H

H CH3 a)

H CH3

H H H

CH H 3 b)

H

CH3

HH

H CH3

H H c)

H H

CH H 3 d)

13. Which of the following is more stable? Cis- or trans-1,2-dimethylcyclohexane and cis- or trans-1,3-dimethylcyclohexane? a) cis, cis b) cis, trans c) trans, cis d) trans, trans 2

14. Which of the following positions is the bridgehead carbon atom? a) d) b) c) 15. Put the following compounds in order of increasing acidity (weakest acid first). CH4

NH3

I

H2O

II

a) II, I, III, IV, V

HF

HBr

IV

V

III

b) II, III, I, V IV

c) I, III, II, V, IV

d) I, II, III, IV, V

16. Which of the following solutions of 1 mole each in water would have the highest pH? a) HI

b) HCl

c) HF

d) CH3COOH

17. Which of the following carbocations are most likely to rearrange?

CH3

CH3

I

CH3

II

a) III, IV

CH2

III

b) I, II

c) II, IV

IV

d) I, III

18. Arrange the following isomers of hexadiene in order of increasing stability (least stable first).

H H3C

H C

C

C H

C

CH3 H

H3C

H C

H

C

C

H

I a) II, IV, III, I

C

H CH3

CH3CH2

H C

C

H

II

H C H

C

H

H H H3C

C

III

b) III, II, IV, I

c) I, IV, II, III

C

C H

C

H CH3

IV d) III, II, I, IV

19. In the product of the following reaction, how many D (deuterium) atoms are in axial positions in the most stable conformation? CH3 CH3

D2 Pt

a) 0

b) 1

3

c) 2

d) 3

20. Compound A has the molecular formula, C12H18, and reacts with H2 in the presence of Pt to give B, C12H24. What is the correct combination of rings and pi bonds for compound A? a)

b)

c)

d)

rings

0

3

1

4

pi bonds

4

1

3

0

21. Which of the following pairs of structures represent tautomers? NH H3C

C

NH2 CH3

H3C

C

CH2

N

OH

I

N II

OH

H

O O H3C

OH a) I, II

O

III b) III, IV

C

O NH

O

C

H3C

NH

IV c) I, III

d) II, IV

22. What is the product of the reaction of propyne with mercuric sulfate and aqueous sulfuric acid? O a) CH3CH2CH=O

b) CH3CCH3

c) CH3CHCH2OH

d) H2C=CHCH2OH

23. Cyclopentyl acetylene is treated first with NaNH2, and then with ethyl bromide and finally with lithium metal in liquid NH3 to give compound B. What is compound B? CH2

C

C

CH2CH3

CH2CH3

H

C

C

H

C

CH2CH3

CH2CH2CH2CH3

H H a) b) c) d) 24. What is the order of increasing heat of hydrogenation for the following compounds (lowest first)?

I a) I, II, III, IV

II b) II, IV, I, III

III c) I, III, IV, II

4

IV d) IV, II, III, I

25. What is the principal product from the reaction of 1,3-cyclopentadiene and HBr?

Br

Br

Br

Br

a)

b)

c)

d)

26. Which compounds will react with maleic anhydride in a Diels-Alder reaction? O

O

O

CH2

maleic anhydride a) I, II

CH3

CH3

I

II

b) II, IV

c) II, III, IV

III

CH3 IV

d) I, II, IV

27. What is the major product from the following Diels-Alder reaction? O

+

O

O a)

O

O b)

c)

d)

28. Which of the following molecules are chiral? I. trans-1.-chloro-2-methylcyclopropane

II. cis-1-chloro-2-methylcyclopropane

III. 1-chloro-1-methylcyclopropane

IV. Cis-1,2-dichlorocyclopropane

a) I, IV

b) II, III

c) I, II

d) III, IV

29. Which of the following molecules are achiral? I. trans-1,2-cyclohexanediol III. trans-1,4-cyclohexanediol a) I, IV

b) II, III

c) I, II

II. cis-1,2-cyclohexanediol IV. trans-1,3-cyclohexanediol d) III, IV

5

30. What is the maximum number of stereoisomers possible for the following structure? CH2OH

HO

a) 2 b) 4

O

c) 8

HO

d) 16

OH

31. What is the relationship of the following structures? H

OH

OH OH

H H H

OH a) enantiomers

b) diastereomers

c) constitutional isomers

d) conformational isomers

32. Which of the following structures are enantiomers? CH3

CH3

H

OH

H

H

OH

HO

H

OH

H

CH3

CH3

OH

H

OH

HO

H

H

OH

H

OH

H

H

OH

OH

HO

H

CH3

CH3

CH3

CH3

I

II

III

IV

a) I, II

b) III, IV

c) II, III

d) I, IV

33. Which of the following molecules can have both diastereoisomers and enantiomers? HO OH a) CH3CHCHCH3

OH b) CH3CHCH2CH3

c) HO

OH

d) CH3CH

CHCH2CH3

34. The addition of bromine to trans-2-pentene produces two stereoisomers. Their configurations are: a) 2R, 3R and 2S, 3S b) 2S, 3S and 2R, 3S c) 2S, 3R and 2R, 3S d) 2R, 3S and 2S, 3S 35. Substance A, C5H8 is chiral. When A is treated with H2/Pt B, C5H10, is produced. B is achiral. A can be: a) 1-methylcyclobutene b) 3-methylcyclobutene c) trans-1,2-dimethylcylcopropane d) cyclopentene

6

36. A solution of ammonia in water contains four different kinds of hydrogen bonds. Arrange them in order of increasing strength (weakest first). I. H2N-H----OH2

II. H2N----HNH2

a) I, II, III, IV

III. H2O----HOH

IV. H3N----HOH

c) II, IV, I, III

d) I, IV, II, III

b) III, I, IV, II

37. What is the major product when 2,2-dimethylcyclohexanol is heated in acid? a) 3,3-dimethylcyclohexene

b) 2,3-dimethylcyclohexene

c) 2,2-dimethylcyclohexene

d) 1,2-dimethylcyclohexene

38. What is the major product from the acid-catalyzed hydration of 3,3-dimethyl-1-butene? a) 2,3-dimethyl-2-butanol c) 3,3-dimethyl-1-butanol

b) 3,3-dimethyl-2-butanol d) 2,3-dimethyl1-1butanol

39. What is a satisfactory reagent to convert trans-2-butene into meso-2,3-butanediol ? a) OsO4, then Na2SO3

b) Dilute basic KMnO4

c) O3 followed by Zn, H2O

d) ArCO3H (a peroxy acid) followed by NaOH 40. Which of the following reactions is a good way to prepare methyl tert-butyl ether? a) CH3O Na + (CH3)3CBr c) (CH3)3COH + CH3OH

b) (CH3)3CO K + CH3I

NaOH

d) CH3MgBr + (CH3)3COCl

41. What is the order of increasing reactivity for the following nucleophiles (least first)? CH3O

H2O

I

CH3NH

II

a) IV, II, I, III

III

CH3COO IV

b) II, IV, I, III

c) IV, III, I, II

d) I, II, III, IV

42. Which of the following are examples of strong nucleophiles but weak bases in protic solvents? CH3S

CH3O

I

H2O

F

I

II

III

IV

V

a) I, IV c) I, III

7

b) IV, V d) III, IV

43. Place the following alkyl halides in order of increasing reactivity in an SN2 reaction (least first). Br I a) I, III, IV, II 44.

Cl

Br II b) IV, III, II, I

Br

III c) II, IV, III, I

IV d) II, I, IV, III

Place the following alkyl halides in order of increasing reactivity in an SN1 reaction (least first). Br

I a) I, III, IV, II

Cl

Br II b) IV, III, II, I

Br

III c) II, IV, III, I

IV d) II, I, IV, III

45. Place the following alkyl halides in order of increasing reactivity in an SN1 reaction (least first). Cl CH3CHCH3

CH3CH2CH2Cl

I a) II, IV, I, III

(CH3)3CCl

II b) I, III, IV, II

III

CH3Cl

IV c) III, I, IV, II

d) IV, II, I, III

46. What is the increasing order of stability for the following carbocations (least first)? CH3CH2CH2

(CH3)2CH

I a) IV, III, II, I

(CH3)3C

II III IV b) IV, I, II, III c) I, II, III, IV

d) I, II, IV, III

47. In the following reaction, if the concentration of tert-butyl bromide and methanol are both doubled, what effect will this have on the rate of reaction? (CH3)3CBr a) no change

+

CH3OH

b) doubles

(CH3)3COCH3 c) triples

+

HBr

d) quadruples

48. Which of the following statements apply to an SN1 reaction? I. The reaction is first order in alkyl halide and first order in nucleophile. II. The order of reactivity is 1˚>2˚>3˚ III. The reaction is first order in alkyl halide and zero order in nuclepphile. IV. Rearrangements are common. a) I, II

b) III, IV

c) I, IV

d) III 8

49. Which of the following statements apply to an SN2 reaction? I. The reaction is first order in alkyl halide and first order in nucleophile. II. The order of reactivity is 1˚>2˚>3˚ III. The reaction is first order in alkyl halide and zero order in nuclepphile. IV. Rearrangements are common. a) I, II

b) III, IV

c) I, IV

d) II, IV

50. What is the major product of the E2 reaction of trans-1-bromo-2-methylcylcohexane with strong base? a) methylcyclohexene b) 2-methylcyclohexene c) 3-methylcyclohexene

d) 4-methylcyclohexene

51. Which of the following is an optimum set of conditions for an E1 reaction of t-butyl bromide? solvent, nucleophile

temperature

a)

CH3OH

25˚C

b)

CH3CH2OH

80˚C

c)

CH3CH2OH, CH3CH2O

25˚C

d)

DMSO, CH3CH2O

25˚C

52. An achiral compound A, C4H10O, reacts with sulfuric acid and heat to form compound B. On reaction first with mercuric acetate in water, and then sodium borohydride, B gives C which is chiral. What is a reasonable structure for A? OH a)

CH3CH2CHCH3

b)

CH2OH

c)

(CH3)3COH

d) CH3CH2CH2CH2OH

53. What is the major product from the reaction of propene epoxide and sodium methoxide. OH a) CH3CHCH2OH

OH

OH

b) CH3CHCH2OCH3

c) CH3CHCH2OH

OCH3 d) CH3OCHOCH3

54. What is the product of refluxing anisole with concentrated HBr? a) phenol and methyl bromide c) bromobenzene and methanol

b) bromobenzene and methyl bromide c) benzyl bromide and methyl bromide

55. Acetic acid, CH3COOH, boils higher (b.p. 118˚C) than 1-propanol, CH3CH2CH2OH (b.p. 97˚), because a) it has a higher formula weight. b) it is more water-soluble. c) it undergoes hydrogen bonding whereas the alcohol does not. d) it forms dimers that are linked by two hydrogen bonds. 9

56. Which product(s) would be formed from the following reaction? O H

H3C H

H

H

D

H

D

H

H

H3C

OH

c)

H

CH3

H3C b)

H2O

CH3

H3C a)

LiAlD4

D

H

d)

D

CH3

H

OH

OH H

H3C

+

D

CH3

H3C

OH

OH

H

H

H3C

+

H

CH3

CH3

D

OH

CH3

57. Protonation of a carbonyl group forms a cation with significant charge on the carbon atom. C

O

+

H

C

OH

C

OH

Which of the following carbonyl compounds form an aromatic cation on protonation? O

O

I

O

II

a) I, II, IV

O

III

b) I, III, IV

O

O

IV

c) III, V, VI

V

O VI

d) I, II, V

58. Which of the following are converted to an aromatic substance on loss of a hydride ion? H

H

H

H

H

H

H

H

H

H

I a) I, II, III

II b) I, III, IV

III c) III, IV, V

IV d) I, III, V

V

59. Which of the following substances is converted into a hydrocarbon on reaction with water? a) CH3CH2OMgBr

b) CH3CH2NH2

c) CH3CH2MgBr

10

d) CH3COOCH3

60. Arraange the following substances in order of increasing acidity (weakest first). COOH

OH

OH

CH2OH

NO2 I

II

a) IV, III, II, I

III

b) IV, II, I, III

IV

c) IV, II, III, I

d) III, II, I, IV

61. What is the product of the following reaction? KMnO4 H2O, heat

a)

O

COOH

b)

COOH COOH

CHO d)

c)

COOH

CHO

62. . Identify the most likely position to be nitrated in the following substance. c)

b) a)

d)

CH2

CN

63. . Identify the most likely position to be brominated in the following substance. c) b) O a)

C

O

d)

64. Identify the most likely position to be nitrated in the following substance. b) c) a)

d) Br 11

65. What is the major product of the following sequence of reactions? O

CH3 H3C

C

H2C

Mg

Br

H3O

CH2

CrO3

ether

CH3

CH3

O

CH3NHCCH2CH2CCH3

b)

CH3

CH3NHCCH2CCH3

CH3

CH3

CH3 c)

CH3NH2

H3O O

a)

SOCl2

O

CH3NHCH2CH2CCH3

d)

CH3

CH3

(CH3)2NCCH2CCH3 CH3

66. Which of the following substituents on benzene are activating in electrophilic aromatic substitution? Br

NO2

OCH3

COCH3

I

II

III

IV

N(CH3)2

C(CH3)3

V a) I, II, VII

N(CH3)3

VI b) II, IV, V

SO3H

VII

VIII

c) II, VII, VIII

d) III, V, VI

67. Which of the following is the most important resonance form for the intermediate formed in the electrophilic bromination of toluene? CH3

CH3

H Br

a)

CH3

b)

Br

c) H

CH3

H d)

Br H

Br

68. Which of the following is the most important resonance form for the intermediate formed in the nitration of nitrobenzene? O

NO2 a)

N

O

O

c)

b) H

NO2

N

H

N

O

NO2 d)

H N

O

O

O 12

O

NO2

69. Identify the major product of the following Diels-Alder reaction. CH3 H

H

+

H

CH3

CH3

CH3 COOEt

a)

H

COOEt

C C

COOEt

CH3

CH3

COOEt

COOEt

b)

c)

COOEt

COOEt d)

COOEt

CH3

heat

COOEt

CH3

COOEt

CH3

CH3

70. Identify the most likely position to be nitrated in the following substance. c) a) b) O 2N

d)

71. Which of the compounds undergoes nucleophilic aromatic substitution most readily? Cl

Cl

Cl

Cl

OCH3 a)

NO2 b) H3CO

c)

d)

OCH3

O 2N

OCH3

NO2

72. What is the best procedure for preparing para-bromobenzic acid from toluene? a)

c)

Br2

KMnO4

FeBr3 NBS UV light

KMnO4

b)

d)

KMnO4

Br2 FeBr3

KMnO4

NBS UV light

13

NO2

73. What is the best procedure for the following synthesis? CH3

Cl

COOH Br

a)

b) c) d)

Cl2

Br2

FeCl3

FeBr3

Cl2

KMnO4

FeCl3

OH

KMnO4

H3O

KMnO4 OH

Br2

H3O

FeBr3

Br2

OH KMnO4

H3O

H3O

Cl2

FeBr3

FeCl3

Cl2

Br2

FeCl3

OH

FeBr3

74. What is the major product from the following series of reactions? OH

SO3

Cl2

dil H2SO4

H2SO4 100˚C

FeCl3

100˚C

HO3S

Cl

Cl OH

a)

b)

Cl

OH

c)

OH

SO3H

d) Cl

Cl

75. Identify the most acidic proton in the structure of ascorbic acid (vitamin C) below. a)

HO

b)

C H HO H c)

CH2 O

HO

O d)

OH

76. Which of the following pair of reactants are involved in the base-catalyzed aldol reaction? O a)

H2C

CH

OH +

H3C

OH c)

H2C

CH

CH

b)

H2C

H3C

CH

CH

+ H3C

OH

OH +

O

O

d) H2C

CH 14

CH O

+ H3C

CH

77. Which of the following pair of reactants are involved in the acid-catalyzed aldol reaction? O a)

H2C

OH

CH

H3C

+

OH c)

H2C

CH

CH

H2C

b)

CH

H3C

+ H3C

OH

OH +

O

O

d) H2C

CH

CH

CH O

+ H3C

CH

78. Which of the following is an acetal of an aldehyde? O

HO

H3C a)

O

O

b)

OCH3

CH3

CH3

O

c)

d)

OCH3

79. Which of the following is an acetal of an ketone? O

HO

H3C a)

O

b)

OCH3

CH3 O

CH3

O

c)

d)

OCH3

80. Which of the following combinations of reactants will give cinnamaldehyde (PhCH=CHCH=O), in a mixed aldol reaction? a) benzaldehyde and acetaldehyde c) formaldehyde and acetophenone

b) formaldehyde and phenylacetaldehyde d) benzaldehyde and acetone

81. Which of the following combinations of starting materials and organometallic reagents are best for synthesizing 2-butanone? I

CH3CH2COCl

A

(CH3)2CuLi

II

CH3CH2CN

B

CH3OMgBr

C

CH3Li

D

CH3MgBr

III CH3CH2COOH IV

CH3CH2CH

a) I and C, II and A

CH2

b) III and D, IV and A

c) II and B, III and D

d) I and A, II and D

82.. Compound A, C5H8, reacts with hydrogen in the presence of Pd to yield a saturated hydrocarbon, B, C5H10. Compound A, on treatment with ozone followed by treatment of the ozonide with Zn/H2O, yields a dialdehyde C, C5H8O2. Dialdehyde C on treatment with hydrazine and

concentrated potassium hydroxide at elevated temperatures gives 2-methylbutane. The structure of A is: a)

b)

CH3 CH3

CH3 c)

CH3 d)

15

83. Which of the following reactions can be used to prepare acetophenone? I. Benzene and aluminum chloride and propionyl chloride. II. Benzoyl chloride and diethyl lithium cuprate. III. Benzene and aluminum chloride and acetic anhydride. IV. Diphenyl lithium cuprate and acetyl chloride. a) I, and II

b) III, IV

c) I, III

d) II, IV

84. What two different combinations of starting materials and reagents can be used to prepare benzaldehyde? I. Benzyl alcohol

A. LiAlH[OC(CH3)3]3

II. Benzoyl chloride

B. PCC in CH2Cl2

III. Styrene

C. B2H6 then H2O2 and NaOH D. HgSO4 in aqueous H2SO4

IV. Phenyl acetylene

a) I, A and II, B b) III, C and IV, D c) I, B and II, A d) IV, C and II, A 85. What is the most likely product from the base-catalyzed condensation reaction of 2,8-nonadione? O

O C a)

C

CH3

CH3

b)

O

O c)

d)

CH3

CH3

CH3

CH3 86. What is the major product of the following reaction? O

O

NaOEt

HC(CH2)4CCH3 O

O a)

O

CCH3

CH

b)

c)

O

d) CH3

CH3

87. What is the most likely product when the following keto ester reacts with sodium ethoxide? O

O

NaOEt

CH3C(CH2)4COEt O a)

CCH3

b)

CHCOOEt

c)

O COOEt

16

O d) O

CCH3

88. What reagents are most likely to effect the following conversion? ? CH

O a) NH2OH

O

CH

O

b) CH3NO2 + NaOH + CH3OH

CHNO2

c) CH3CH2NO2 + H3O/H2O

d) CH3NHOH

89. Which is the best method for transforming benzoic acid to benzonitrile? a) Treatment with SOCl2; then with NH3; then with SOCl2 again. b) Treatment with Br2 + FeBr3; then with CuCN.

c) Treatment with CH3OH + trace HCl; then with NH3; then with H2SO4 in water. d) Treatment with SOCl2; then with benzene + AlCl3; then with HCN. 90. Which is the major product of the reaction of 2,4-dinitrochlorobenzene with methylamine? Cl

Cl NO2

NO2

a)

NH2

NHCH3

NO2

NO2

b)

c)

d) CH3

CH3NH NO2

NHCH3

NO2

NO2

91. Which is the correct order of decreasing base strength (i.e., strongest base first)? NH2

NH2

NH2

NH2 O2N

CH3 I II a) II > I> III > IV > V

O 2N

III b) I > II > III > V > IV

IV c) I > III > II > IV > V

NH2

V d) I > III > II > V > IV

92. Which of the following statements is NOT true of acetaldehyde? a) It will undergo an aldol condensation reaction. b) It will undergo a Cannizzaro reaction. c) It will undergo a haloform reaction. d) Enolization is catalyzed by acid or base. 93. What is the most likely product of the following series of reactions? Ph3P

PhCH2Br

a)

Ph Ph

C

CHO

b)

Ph

CH

CH3(CH2)3Li

CH

Ph

c)

PhCHO

Ph Ph

17

C

C

heat Ph Ph

d)

Ph Ph

C

CH2 Ph O(CH2)3CH3

94. Arrange the following compounds in order of increasing acid strength (weakest first). OH

CH2OH

I a) II, III, I, IV, V

OH

COOH

COOH

N(CH3)3

CH3

CF3

II III IV b) V, IV, I, II, III c) II, I, III, IV, V

V d) II, I, III, V, IV

95. Which of the following reactions is best for preparing phenylacetic acid (PhCH2COOH)? PhCH2Cl

b)

PhCH2OH

c)

PhCH2CH2Br

H3O

ether KMnO4

O d)

CO2

Mg

a)

NaCN

H3O

CH3CH2OH

Br2

PhCCH3

H3O

heat

H3O

NaOH 96. Which of the following reactions will yield the same carboxylic acid? I.

CH2CHO O

II.

C

III.

CH2Cl

IV.

CH2CH2Br

a) I, II

CH3

b) II, III

K2Cr2O7 H3O Cl2 NaOH H3O

KCN

heat

Mg

CO2

H3O

ether c) III, IV

d) I, III

18

97. What is the major product from heating HOOCCH2CH2COOH? O

O

O a)

b)

O

O

O O

c)

O

H2C

d)

O O

CH

COOH

O

98. The following reaction is fastest when the group Z is? O

O

C

+

Z

OH

C

+

O

HZ O

a)

O

b)

O

CH3

c)

Cl

d)

O

C

CH3

99. What is the major product of the following reaction sequence? O +

a)

Cl2

AlCl3

CH3CCl

SOCl2

H3O

CH3OH

NaOH

COCH3

b)

COOCH3 OCH3

c)

OCOCH3

d)

C

CH3

OCH3 100. What are the best conditions for the following transformation? O COOH

CCH2CH3

a) 1) SOCl2, 2) (CH3CH2)2CuLi

b) 1) SOCl2, 2) CH3CH2MgBr

c) 1) LiAlH4 2) SOCl2 3) Mg in ether 4) CH3CHO

d) CH3OH, H3O 2) LiAlH4

101. What are the best conditions for the following transformation? COOH

CH3

a) 1) LiAlH4 2) H3O 3) SOCl2 4) Mg in ether 5) H2O b) 1) SOCl2, 2) LiAlH4 3) H3O

4) NH2NH2, KOH

c) 1) NH2NH2, KOH 2) SOCL2, 3) Mg in ether 4) H2O d) CH3Li, 2) H3O 19

102. What is the major product of the following sequence of reactions? COOH

LiAlH4

heat

O

CH2NH2

CH2OH b)

a)

NH

c)

OH d)

NH

NH

CH2NH2 103. What is the major product of the following sequence of reactions? CH2COOCH2CH3

H3O

NaOCH2CH3

CH2COOCH2CH3 COCH3 a)

O

COOCH2CH3 b)

O

O

O COOCH2CH3

c)

d) O

104. What is the major product of the following sequence of reactions?

O

O

CH3C(CH2)3COCH2CH3 O

O

O

COCH2CH3 a)

H3O

NaOCH2CH3

O

O

COCH3

COCH3

c)

b)

O

O d)

O

105. Toluene is treated with a mixture of HNO3 and H2SO4. The major product is reduced with

SnCl2 in HCl to give A. When A is treated with NaNO2 in HCL at 0˚C, followed by reaction with CuCN to give B. B is reduced with LiAlH4 to give C. What is the most probable structure of C?

H3C

CH2OH

H3C

CH2NH2

a)

H3C

NH2

b)

H3C

NHCH3

c)

d)

106. What is the final poroduct when benzoic acid is treated with thionyl chloride, then ammonia, followed by reaction with sodium hypobromite and finally with bromine? Br Br a)

COOH Br

Br b)

Br COOH

Br c)

Br 20

CH2Br

Br d)

NH2 Br

107. Which would give most meta-product upon nitration? COCH3 OCH3

N

a)

CH3

COCH3

b)

OCOCH3

c)

d)

108. Compound A is treated with thionyl chloride and then ammonia to give compound B. Compound B is then reacted with bromine and sodium hydroxide (tricky) to give compound C. Compound C is heated to give the final product, compound D. What is the most likely structure for compound D? O C

A

O COOH

C

a)

b) CH2CONH2

CH3

CH3

CH2COOH O NH c)

O NH

CH2NH2

d)

NH

109. What is the major product of the following reaction? COOEt

CH2COOEt

+

COOEt a)

CH

O

C

b)

C CH2

O c)

C

NaOEt

O CH

d)

O

CCH2C

COOEt 110. What are the reactants in the synthesis of the following enamine? O

N

a)

O +

b)

N

+ NH2

H O c)

O +

d)

N

+ NH2

H

21

111. Which of the following halides is NOT effective in the alkylation of malonic ester? O H2C

CH

Br

(CH3)3CBr

I

PhCH2Cl

II

H3C

III

C IV

CH2Br

a) I, III

b) II, IV

c) III, IV

d) I, II

112. What is the major product of the following reaction? O N

+

C

O

H3O

Cl O

O

C a)

b)

O

O

c)

d)

113. What is the major product of the following sequence of reactions? O CH3CCH2COOEt O

1) NaOEt

1) NaOEt

1) KOH

2) CH3COCl

2) CH3I

2) H3O

O

O

a) CH3CCH2CHCCH3

O

3) heat

O

O

O

c) CH3CCHCCH3

b) CH3CCH2CCH3

CH3

O

d) CH3CCHCH2CCH3

CH3

CH3

114. Diethyl malonate (malonic ester) and which halide can be used to prepare butanoic acid? a) methyl bromide

b) ethyl bromide

c) 1-bromopropane

d) 2-chloropropane

115. What is the final product of the following series of reactions? CH2(COOEt)2

1) NaOEt

H3O

1) PBr3, Br2

2) CH3CHCH2CH3

heat

2) H3O

Br

CH3

a) CH3CH2CHCHCOOH

CH3 b) H2NCCOOH

NH2

CH3

CH3

COOH b)

NH2

EtOOC O

c) HOOC(CH2)4COOH

d)

CH3

c) CH3CHCH2CHCOOH

116. What is the major product of the following reaction? 1) KOH 2 equiv. CH(COOEt)2 + BrCH2CH2Br 2) H3O 3) heat a) HOOC

NH3

COOEt O

CH3CCH2CH2CCH3 22

d) CH3CHCHCOOH NH2

117. Which of the following molecules can become effective nucleophiles in a Michael reaction? O

O

O

O O

a)

b)

c)

d)

O O 118. What is the major product from the following Michael reaction? 1) KOH NaOEt CH2(COOEt)2 + H2C CH C N 2) H3O 3) heat

a) HOOC(CH2)2COOH b) HOOC(CH2)3COOH c) HOOC(CH2)4COOH d) HOOC(CH2)5COOH 119. Which of the following is insoluble in water but is soluble in dilute HCl? NH2

OH a) CH3CH2CH2NH2

b)

c)

O d) N

CH3

H

120. What is the product of the reaction of one equivalent of imidazole with one equivalent of acid? H N

H

N a)

N

N

b)

H

H

N

N N H

c) N

H

N d)

N

H

H

121. Which of the following amines have a stereogenic center? CH(CH3)2 CH3CH2NHCH3

CH3

NH2

CH3NHCHCH2CH3

CH3CHCH2CH3

H

CH3

N

CH3

CH3 I a) I, II, III

II b) III, IV, V

III c) I, III, IV

IV d) II, III, IV

N

H

V

122. Methylethylamine cannot be resolved into enantiomers because a) it is planar.

b) it undergoes rapid inversion.

c) it has a plane of symmetry.

d) a tricovalent atom cannot be a center of chirality.

23

123. Which of the following amines can be resolved into enantiomers? CH3 CH3CH2NHCH3

H3C

CH3CH2CHNHCH3

I a) I, II

II b) III, IV

CH3

CH3

N

H3C

NHCH3

CH3 III

c) I, III

IV d) II, IV

124. Which of the following compounds is the strongest base? O O

O a)

b)

c)

N

N

H

H

d)

N

O

N

H

H

125. What is the order of increasing base strength for the following compounds (weakest first)? N

CH3

N

N

CH3

I II III a) I, II, III, IV b) IV, III, II, I

N IV c) I, III, II, IV

d) IV, II, III, I

126. What is the final product of the following series of reactions? Mg

CH2Cl

a)

NH2

ether

1) CO2

SOCl2

NH3

2) H2O

2) H3O

b)

CH2NH2

1) LiAlH4

c)

CH2CH2NH2

d)

CH2CH2CH2NH2

127. What is the major product of the following sequence of reactions? PhCH2Cl

NaCN

(CH3CO)2O

LiAlH4

a) PhCH2CH2NH2 b) PhCH2CH2CONHCH3 c) PhCH2CH2ONHCOCH3 d) PhCH2CH2NHCOCH3

24

128. The same amine is prepared by which of the following reaction sequences? O

NaOH

I.

CH3CH2CH2CNH2

II.

CH3CH2CH2CH2Br

Br2 NaN3

III. CH3CH2CH2CH2Br

LiAlH4

NaCN LiAlH4

O K

N

IV.

CH3CH2CH2CH2Br

NH2NH2

O a) I, II

b) III, IV

c) I, IV

d) II, IV

129. What is the product of the following reaction sequence?

N

CH3 CH2CH3

a) H2C c)

OH

CH N

CH

heat

Ag2O

CH3I

CH2

H2O

b)

CH3

H2C

d) H2C

heat

CH

CH2

CH

CH2

CH CH2CH2 N(CH3)2

130. What is the product of the following Hofmann elimination reaction? CH3 N(CH3)3 OH

a)

CH3

b)

heat CH3

c)

CH3

N(CH3)2

25

d)

CH2

131. Oxidation of an aldopentose of the D-series with dilute nitric acid gives an optically active diacid with molecular formula C5H8O7. What conclusion can be drawn concerning the structure of the aldopentose? CHO

CHO

CHO

H

OH

HO

H

OH

H

OH

HO

H

OH

H

OH

H

CH2OH

H

H

CH2OH

CHO

OH

HO

H

H

HO

H

OH

H

CH2OH

OH CH2OH

I II a) The aldopentose is I or IV

III b) The aldopentose is III.

IV

c) The aldopentose is II or IV.

d) The aldopentose is I or III.

132. D-hexose A shows the following characteristics: 1) A 2) A 3) B

HNO3

optically active tetrahydroxyadipic acid [HOOC(CHOH)4COOH]

Wohl degradation HNO3

B (an aldopentose)

optically inactive trihydroxyglutaric acid [HOOC(CHOH)3COOH]

What is the structure of D-Hexose A? CHO H

CHO

OH

HO

HO

CHO

CHO

H

HO

H

H

OH

H

H

OH

HO

H

HO

H

H

OH

H

OH

HO

H

HO

H

H

OH

H

OH

H

CH2OH

CH2OH

OH CH2OH

H

OH CH2OH

a) b) c) d) 133. Cellulose, starch and glycogen are polysaccharides containing which of the following sugars? a) sucrose b) glucose c) fructose d) lactose 134. What is the relationship between the following two structures? I. enantiomers CHO CHO H

OH

H

OH

H

OH

H

OH

H

OH

HO

CH2OH a) I, IV

H CH2OH

b) I, III

II. diastereomers III. epimers IV. anomers c) II, III d) II, IV 26

135. What is the relationship between the following two structures?

HOCH2

OCH3

O

HOCH2

I. enantiomers

O

II. diastereomers HO

OCH3

OH

a) I, III

b) II

III. anomers

OH

HO c) III

d) II, III

136. How many stereoisomers are possible for a D-ketopentose? a) 2

b) 4

c) 8

d) 16

137. How many stereoisomers result from the following reaction? HOCH2

O HO

NaBH4

OH

HO a) 1

CH2OH

b) 2

c) 4

d) 8

138. Which of the following compounda give the same glucaric acid as its enantiomer when oxidized with Nitric acid? CHO H

CHO

CHO

OH

HO

H

HO

H

HO

OH

H

HO

H

H

OH

HO

OH

H

OH

H

H

CH2OH a)

HO

CH2OH

CHO

H

HO

H

OH

HO

H

H

HO

H

OH

H

CH2OH

b)

c)

OH CH2OH d)

139. If D-glucose is allowed to stand for several days in aqueous Ca(OH)2 which of the following sugars will appear in the mixture? I. mannose a) I, II

II. arabinose b) II, III

III. Fructose

c) II, IV

d) I, III 27

IV. ribose

140. What is the major product of the following reaction? HOCH2 OH HO

OH

O

Br2 H2O

OH COOH

COOH H

H

OH

HO

HO

H

CH2OH

OH

H

H

CHO

OH

HO

H

H

OH

HO

H

H

OH

H

OH

H

OH

H

OH

H

OH

H

OH

H

OH

H

OH

CH2OH

COOH

CH2OH

CH2OH

a) b) c) d) 141. Which of the following is a product from the reaction of D-glucose with methanol and acid followed by exhaustive acetylation with acetic anhydride? CH3OCH2 a)

AcO AcO CH3OCH2

c)

AcO AcO

O

AcOCH2

b)

CH3O AcO

OAc OAc O

AcOCH2

OAc OCH3

O

d) AcO AcO

OAc

OAc O OAcOCH 3

142. An aldohexose, A, gives an aldopentose B, on Wohl or Ruff degredation. When A is subjected to a Killiani-Fischer sysnthesis, a mixture of two aldoheptoses, C and D, are produced. The glycaric acids from nitric acid oxidation of A, B, C and D are all chiral. What is the structure of A? CHO HO

H

CHO H

CHO

CHO

OH

HO

H

H

H

HO

H

HO

H H

H

OH

HO

H

OH

H

OH

H

OH

HO

H

OH

H

OH

H

OH

H

CH2OH

CH2OH

CH2OH

OH

OH CH2OH

a) b) c) d) 143. What is the structural feature of terpenes that distinguishes them from other natural products? a) phosphate esters

b) multi-ring systems

c) isoprene units

28

d) polyunsaturated chains

144. Which of the Fischer projection formulas below correspond to the following stereostructure? HO H

O

HO

CHO

H H OH

CHO

CHO

H

OH

HO

H

H

H

OH

HO

H

HO

CH2OH

OH

HO

H

CH2OH

a)

CHO H

CH2OH

b)

H OH CH2OH

c)

d)

145. In an experiment designed to determine ring size of cyclic acetals, methyl glucoside was exhaustively methylated, and then hydrolyzed in aqueous acid. Which Fischer projection formula represents the product of these reactions?

HO

HOCH2

O

HO

OH

CHO H

H3O

Ag2O

heat

CHO

OH

CH3O

OCH3

excess CH3I

H

H

CHO

OCH3

HO

H

H

CHO

OCH3

CH3O

H

H

OCH3

CH3O

H

H

OCH3

H

OCH3

H

OH

H

OCH3

H

OCH3

H

OCH3

H

OCH3

H

OH

CH2OCH3

CH2OCH3

CH2OCH3

CH2OCH3

a)

b)

c)

d)

146. Which of the following is a non-reducing sugar? (i.e., is not oxidized by Ag(NH3)2+) HOCH2 HO

HO

O CH 2

OH

O

HOCH2

OH

O

O

HO

OH

HO

O

OH HOCH2

HO

OH

a) HOCH2 HO

HO

O

b) O

OH c)

CH2OH HO

HO

HOCH2

O

CH2OH O

O HO

CH2OH 29

CH2OH

O

OH

HO

d)

OH CH2OH

OH O

OH

147. Which of the following structures is a prostaglandin? CH3 OH

HO COOH CH3

a) HO

OH

H3C b)

H3C

H H

H3C

d)

H

H

O

OH

c)

HO

148. Which of the following structures is a terpene? CH3 OH

HO COOH CH3

a) HO

OH

H3C b)

H3C

H H

H3C

d)

H

H

O

OH

c)

HO

149. Terpenes are intermediates in the biosynthesis of which natural products? a) prostaglandins

b) steroids

c) phospholipids

d) glycerides

150. What properties are characteristic for the most abundant fatty acids found in plants and animals? I. They contain an even number of carbon atoms, in the range of 10-20. II. The E isomer predominates. III. The unsaturated fatty acids have a higher melting point than the corresponding saturated acids. IV. The most abundant fatty acids are palmitic, stearic and oleic. a) I, II

b) III, IV

c) I, III

d) I, IV

151. What is the sequence of amino acids in the peptide containing gly2, lys, val, ala, that yields the following peptide fragments on partial hydrolysis? ala-val, lys-gly, gly-ala and val-gly (1) gly - gly - lys - val - ala

(2) ala - val - gly - lys - gly

(4) val - gly - ala - lys - gly

(5) ala - val - gly - lys - gly 30

(3) lys - gly - ala - val - gly

152. Which mixture of amino acids can be separated by electrophoresis? NH2 a)

CH2CHCOOH

H2NCH2COOH

H2NCCH2CH2CHCOOH

H2N(CH2)4CHCOOH

HOOCCH2CHCOOH

H2NCH2COOH

NH2

NH2

NH2

CH2CHCOOH

CH3S(CH2)2CHCOOH

c)

NH2

HOCH2CHCOOH

NH2

CH3CHCOOH

H2NCH2COOH

d)

NH2

NH2

NH2 b)

O

(CH3)2CHCHCOOH

153. Which compound would be most rapidily converted to the corresponding phenol by reaction of NaOH? Ar

Cl

+

Cl

NaOH

Ar

Cl

Cl

OH

+

NaCl Cl HO

NO2 O 2N

OH

NO2

OCH3

NO2

a) b) c) d) 154. Rank the following compounds in terms of their relative reactivity in nitration. CH3 CH3

NO2

I

II

a) b) c) d)

Cl

CH3

III

N

IV

most reactive IV>II>III>I>V least reactive most reactive V>I>III>II>IV least reactive most reactive III>II>IV>V>I least reactive most reactive V>I>IV>II>III least reactive

31

CH3

OCH3

V

155. That reaction will proceed fastest which has the a) most negative ∆G˚

b) most positive ∆S˚

c) lowest ∆G‡

d) most negative ∆H˚

156. Esterification of a racemic alcohol (ROH) with an optically active acyl chloride (R'COCl) gives a) two diastereomeric esters. c) a single optically active ester.

b) a racemic ester. d) one optically active ester and one optically inactive ester.

157. Which is the best way to convert I into II? CH2

O ?

I a)

I

c)

Ph3P

CH3MgI ether

CH3

I

II H3O

II

BuLi

I

II

b)

I

d)

I

CH3Li THF, heat

II

CH3MgI NaOH ether H2O

II

158. Which is the best representation of the highest occupied molecular orbital of 1,3-butadiene?

a) H2C

c)

H2C

CH

CH

CH

CH

CH2

CH2

b) H2C

d)

H2C

CH

CH

CH

CH

CH2

CH2

159. The Edman degradation is a method to a) remove and identify a C-terminal amino acid from a peptide. b) remove and identify an N-terminal amino acid from a peptide. c) cleave polysaccharides specifically at galactose units. d) cleave polypeptides at the carboxy side of lysine and asparigine units. 32

160. Select the best way to prepare the amine shown below. NH2 CH3CH2

C

CH2CH3

CH3 Br a) CH3CH2

C

CH2CH3

CONH2

NH2NH2

b)

CH3CH2

CN CH3CH2

C

CH2CH3

CH3

CH3

c)

C

CH2CH3

Br

LiAlH4

d)

CH3CH2

C

CH2CH3

CH3

CH3

Br2 NaOH

NH3 excess

161. Which reaction, or reaction sequence, provides the best way to prepare p-nitrobenzoic acid?

COOH

COOH HNO3

a)

(+ ortho isomer)

H2SO4 NO2

CN b)

HNO3

separate

H2SO4

isomers

COOH H3O

COOH CH3Cl

c)

KMnO4

(+ ortho isomer)

AlCl3 NO2

NO2

COOH

CH3

d)

NO2

HNO3

separate

H2SO4

isomers

KMnO4

NO2

33

162. Which reaction provides the best way to prepare the compound shown below? COOCH3 COOCH3 COOCH3 a)

+

CH2I2

COOCH3

Zn(Cu)

b) H

C

C

H

+

COOCH3

+ CH3OOC C

c)

COOCH3

C COOCH3

CH3OOC +

d)

H

COOCH3 H

163. What is a satisfactory reagent to convert trans-2-butene into meso-2,3-butanediol ? a) OsO4, then Na2SO3 b) Dilute basic KMnO4 d) O3 followed by Zn, H2O

c) ArCO3H (m-ClPBA) followed by NaOH

164. What is the major product of the following reaction? O

CH3 CH3

CH

C

CH3CH2CH2MgBr

O

(in excess)

CH2CH2CH3

a)

b)

CH2CH2CH3 c)

C

OH

CH

CH3

C

CH2CH2CH3

CH2CH2CH3

CH3 d)

CH2CH2CH3

O

CH3 CH3

H3O

CH

C

OH

CH2CH2CH3

165. . To which carbon of A would H+ or other electrophiles add most readily? 4

1 2 OCH3

3

a) C-1

A

b C-2

c) C-3

d) C-4

34

166. What is the major product of the following reaction? CH3 +

CH3

CH3 CH3

CH3 CH2 CH

a)

b)

CHCH2Cl

AlCl3

CH3

CH3 CH3

?

CH3 d)

c) CH2

CH3

C

CH3

CH3

CH3

CH

CH3

H2C

CH

CH3

CH3

167. Which of the steps listed below would be used to separate A from a mixture of A and B? CH2NH2

CONH2

B

A

(1) dissolve in CH2Cl2

(2) extract with water (3) extract with aqueous HCl (4) extract with aqueous NaHCO3 (5) (6) (7) (8)

extract with aqueous NaOH basify aqueous layer with NaOH acidify aqueous layer with HCl extract aqueous layer with CH2Cl2

(9) dry and evaporate CH2Cl2 extract a) 1, 2, 9

b) 1, 3, 6, 8, 9

c) 1, 4, 7, 8, 9

d) 1, 5, 7, 8, 9

168. Which of the following reaction sequences is best to convert A into B? CH2COOCH3

CH2CH2OH

O

O

A

B

a) (1) LiAlH4; (2) CrO3, H3O+

b) (1) CrO3, H3O+; (2) NaBH4

c) (1) HOCH2CH2OH, H+; (2) LiAlH4; (3) H3O+

d) (1) Ac2O, pyridine; (2) LiAlH4; (3) H3O+ 35

169. What are the relationships between the three compounds below? OH

CH3

OH

CH3

OH

CH3

CH3

CH3

CH3

A B C a) A and B are diastereomers, B and C are diastereomers, and A and C are enantiomers. b) A and B are identical, B and C are diastereomers, and A and C are diasteromers. c) A and B are enantiomers, B and C are diastereomers, and A and C are diastereomers. d) A and B are identical, B and C are enantiomers, and A and C are diastereomers. 170. Which prefix correctly designates the stereochemistry of the 2,4-dichloro-2-pentene isomer shown below? Cl

H Cl

CH3

H CH3 a) (4R)-(2Z)- b) (4S)-(2Z)-

c) (4R)-(2E)-

d) (4S)-(2E)-

171. Which of the compounds below would be a reasonable reagent to try in the resolution of cis-3methoxycyclohexanecarboxylic acid (A) into its enantiomeric forms? COOH

OCH3 A F3C CH2CH2NH2 a)

b)

OCH3 COOH

H c)

36

NH2 CH3

NO2 d)

172. The reaction of optically pure 2-methylcyclopentanone with methylmagnesium bromide would give O

H

CH3

CH3MgBr

H3O

ether a) one chiral product c) a racemic mixture

b) two diastereomeric products in equal amount d) two diastereomeric products in unequal amounts

173. Eighteen of 19 L-amino acids have the (S) configuration at the a-carbon atom. Cysteine, HSCH2CHCOOH, is the only L-amino acid with the (R) configuration. | NH2 This is because a) L-cysteine is an unnatural amino acid. b) L-cysteine actually exists as the disulfide. c) The sulfur atom is easily oxidized to the sulfuric acid (-SO3H). d) The sulfur atom changes the relative Cahn-Ingold-Prelog priorities of the HSCH2- and the COOH groups. 174. The isoelectric point of an amino acid is a) b) c) d)

The exact point to which an amino acid migrates in an electric field. The pH at which the amino acid does not migrate in an electric field. The point at which a given amino acid no longer exhibits resonance. The electrical potential required to remove all charges from an amino acid.

175. a-helix and b-pleated sheet are terms which describe protein ______________ structure. a)

primary

b) secondary

c) tertiary

d) quaternary

176. Denaturation of proteins results from a) b) c) d)

Use of unnatural amino acids. Complete hydrolysis into amino acids. digestion disruption of Hydrogen bonds 37