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

H2O I a) II, III CO2 II NH3 III b) II, IV BF3 IV c) I, III CHCl3 V d) III, V

2. Which of the following Lewis structures are incorrect? O H O O N N Cl Cl H C H I a) I, II, III II b) I, IV, V AlCl4III III c) II, III, IV NH2IV IV d) III, IV, V NH4+ V O H H H H C N H H V

3. Which of the following molecules have bond angles of about 109.5? CS2 I BF3 II

a) I, II, IV

b) III, IV, 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 formula C4H10O? a) 2 b) 3 c) 4 d) 5 O CH3 O CH2 OH CH2 O CH2 VI. Sulfoxide VII. Amide VIII. Thiol ester IX. Sulfide O O NH O N S CH3 CH3 COOH

Penicillin G b) I, III, V, VI c) I, IV, VII, IX

d) I, IV, VIII, IX

5. How many total isomers (constitutional and stereo) are there for an alcohol with the molecular

6. Which of the following are NOT resonance structures? I. HN C O HO C N III. CH3 C CH3 C

II. N

N b) II, IV

O c) I, III

IV.

CH3 C d) III, IV 1

CH3 C

a) I, II

7. Which of the following ions are stabilized by resonance? O CH2 C CH I CH2 CH CH III a) I, II b) I, III c) II, IV CH CH2 CH2 CH2 CH3 C CH II CH2 CH CH2 CH3

IV d) III, IV

8. What are the correct hybrid states of the carbon atoms in the following structures? CH3 I
2 2

CH3 II
3 3

HC IV

H2C
2 2

N V

OH

III

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

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

9. What is the IUPAC name for the following compound? CH2 CH3 C CH2 CH3 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) b) CH2OH c) OH d) OH

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 H

CH3

H H H H

H CH3 CH H 3
b)

H H

CH3

H CH3 H H

HH CH H 3
d)

CH3
a)

H
c)

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 I a) II, I, III, IV, V NH3 II H2O III HF IV HBr V c) I, III, II, V, IV d) I, II, III, IV, V

b) II, III, I, V IV

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

CH3 III c) II, IV

CH3 IV

CH2

d) I, III

18. Arrange the following isomers of hexadiene in order of increasing stability (least stable first). H C C CH3 H H C C H CH3 H C C III c) I, IV, II, III d) III, II, I, IV H C H C H H H3C C H C H CH3

H H3C

C H I

H3C H

C H

CH3CH2 H

C H

II b) III, II, IV, I

IV

a) II, IV, III, I

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 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) rings pi bonds 0 4 b) 3 1 c) 1 3 d) 4 0

21. Which of the following pairs of structures represent tautomers? NH H3C C CH3 I OH O O H3C OH a) I, II III b) III, IV O c) I, III O a) CH3CH2CH=O b) CH3CCH3 c) CH3CHCH2OH d) H2C=CHCH2OH d) II, IV C NH IV H3C O C NH H3C NH2 C CH2 N OH II N H O

22. What is the product of the reaction of propyne with mercuric sulfate and aqueous sulfuric acid?

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 CH2CH3 C CH2CH3 C H 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

IV d) IV, II, III, I

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

Br Br a) b) Br c) d)

Br

26. Which compounds will react with maleic anhydride in a Diels-Alder reaction? O O O CH2 I c) II, III, IV II d) I, II, IV CH3 III CH3 IV CH3

maleic anhydride a) I, II b) II, IV

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

O a)

O b) c)

O d)

28. Which of the following molecules are chiral? I. trans-1.-chloro-2-methylcyclopropane III. 1-chloro-1-methylcyclopropane a) I, IV b) II, III c) I, II II. cis-1-chloro-2-methylcyclopropane IV. Cis-1,2-dichlorocyclopropane 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

30. What is the maximum number of stereoisomers possible for the following structure? HO HO OH CH2OH O a) 2 b) 4 c) 8 d) 16

31. What is the relationship of the following structures? OH H H OH a) enantiomers b) diastereomers H c) constitutional isomers d) conformational isomers H OH OH

32. Which of the following structures are enantiomers? CH3 H H H I a) I, II b) III, IV OH OH OH CH3 H HO H II c) II, III CH3 OH H OH CH3 H H HO III d) I, IV CH3 OH OH H CH3 HO H H IV CH3 H OH OH CH3

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

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 a) I, II, III, IV II. H2N----HNH2 b) III, I, IV, II III. H2O----HOH c) II, IV, I, III IV. H3N----HOH d) I, IV, II, III

37. What is the major product when 2,2-dimethylcyclohexanol is heated in acid? a) 3,3-dimethylcyclohexene c) 2,2-dimethylcyclohexene b) 2,3-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 NaOH b) (CH3)3CO K + CH3I d) CH3MgBr + (CH3)3COCl

41. What is the order of increasing reactivity for the following nucleophiles (least first)? CH3O I H2O II CH3NH III CH3COO IV

a) IV, II, I, III

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 I CH3O II I III H2O IV F V a) I, IV c) I, III 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. Br II b) IV, III, II, I Cl III c) II, IV, III, I IV d) II, I, IV, III Br

Place the following alkyl halides in order of increasing reactivity in an SN1 reaction (least first). Br Br II b) IV, III, II, I Cl III c) II, IV, III, I IV d) II, I, IV, III Br

I a) I, III, IV, II Cl CH3CHCH3 I a) II, IV, I, III

45. Place the following alkyl halides in order of increasing reactivity in an SN1 reaction (least first). CH3CH2CH2Cl (CH3)3CCl III CH3Cl d) IV, II, I, III

II b) I, III, IV, II

IV c) III, I, IV, II

46. What is the increasing order of stability for the following carbocations (least first)? CH3CH2CH2 I a) IV, III, II, I (CH3)2CH (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 c) triples (CH3)3COCH3 d) quadruples + HBr

b) doubles

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 a) b) c) d) CH3OH CH3CH2OH CH3CH2OH, CH3CH2O DMSO, CH3CH2O temperature 25C 80C 25C 25C

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 b) CH3CHCH2OCH3 OH 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. 118C) 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 H3C H H3C a) H D H H LiAlD4 H2O

CH3 OH H3C c) H D H OH H3C D H OH H CH3

CH3

CH3

H3C b) D H

OH

H3C d) D H

OH

H3C H D

OH

CH3

CH3

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 I a) I, II, IV II b) I, III, IV O III c) III, V, VI O O IV d) I, II, V O V O VI O

58. Which of the following are converted to an aromatic substance on loss of a hydride ion? H H I a) I, II, III H H II b) I, III, IV H H III c) III, IV, V H H IV d) I, III, V V H H

59. Which of the following substances is converted into a hydrocarbon on reaction with water? a) CH3CH2OMgBr b) CH3CH2NH2 c) CH3CH2MgBr d) CH3COOCH3

10

60. Arraange the following substances in order of increasing acidity (weakest first). COOH OH OH CH2OH

NO2 I a) IV, III, II, I II b) IV, II, I, III III c) IV, II, III, I IV d) III, II, I, IV

61. What is the product of the following reaction? KMnO4 H2O, heat COOH COOH COOH d) CHO COOH

a) CHO c)

b)

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

CH2

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) Br 11 d)

65. What is the major product of the following sequence of reactions? CH3 H3C C CH3 Br O Mg ether O a) CH3 b) CH3 CH3 c) CH3NHCH2CH2CCH3 CH3 d) O H2C CH2 H3O CrO3 H3O O CH3 CH3 CH3 CH3 SOCl2 CH3NH2

CH3NHCCH2CH2CCH3

CH3NHCCH2CCH3

(CH3)2NCCH2CCH3

66. Which of the following substituents on benzene are activating in electrophilic aromatic substitution? Br I N(CH3)2 V a) I, II, VII b) II, IV, V NO2 II C(CH3)3 VI OCH3 III COCH3 IV N(CH3)3 VII c) II, VII, VIII SO3H 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 a) H Br b) H Br CH3 c) CH3 H Br d) CH3

Br H

68. Which of the following is the most important resonance form for the intermediate formed in the nitration of nitrobenzene? NO2 a) H NO2 b) H N O 12 O O N O O N O NO2 H N O O d) NO2

c)

69. Identify the major product of the following Diels-Alder reaction. CH3 H H CH3 COOEt b) COOEt CH3 CH3 COOEt CH3 c) COOEt CH3 H + H C C COOEt COOEt heat CH3 COOEt d) COOEt COOEt

CH3 COOEt a)

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 OCH3 a) OCH3 b) H3CO OCH3 NO2 c) Cl Cl NO2 d) O 2N NO2 Cl

72. What is the best procedure for preparing para-bromobenzic acid from toluene? a) Br2 FeBr3 NBS UV light KMnO4 KMnO4 b) KMnO4 Br2 FeBr3 KMnO4 NBS UV light

c)

d)

13

73. What is the best procedure for the following synthesis? CH3 Cl Br Cl2 FeCl3 Cl2 FeCl3 KMnO4 OH KMnO4 OH SO3 H2SO4 100C H3O Br2 FeBr3 KMnO4 OH H3O Br2 FeBr3 Cl2 FeCl3 Cl2 FeCl3 KMnO4 OH H3O Br2 FeBr3 Cl2 FeCl3 Br2 FeBr3 dil H2SO4 100C Cl OH b) Cl OH c) Cl OH d) Cl Cl SO3H H3O COOH

a)

b) c) d)

74. What is the major product from the following series of reactions? OH HO3S a)

75. Identify the most acidic proton in the structure of ascorbic acid (vitamin C) below. a) HO CH2 O O OH d)

b)

C H HO H c) HO

76. Which of the following pair of reactants are involved in the base-catalyzed aldol reaction? O a) H2C CH OH c) H2C CH + H3C + H3C OH CH OH CH d) H2C b) H2C O CH OH CH 14 + H3C + H3C O CH O CH

77. Which of the following pair of reactants are involved in the acid-catalyzed aldol reaction? O a) H2C CH OH c) H2C CH O H3C a) O b) + H3C HO + H3C OH CH OH CH d) H2C b) H2C O CH OH CH + H3C + H3C O CH O CH

78. Which of the following is an acetal of an aldehyde? CH3 O c) OCH3 O CH3 d) OCH3

79. Which of the following is an acetal of an ketone? O H3C a) O b) HO CH3 O c) OCH3 O CH3 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 II CH3CH2COCl CH3CH2CN A B C D (CH3)2CuLi CH3OMgBr CH3Li CH3MgBr c) II and B, III and D d) I and A, II and D

III CH3CH2COOH IV CH3CH2CH CH2

a) I and C, II and A

b) III and D, IV and A

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) 15 d) CH3

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 II. Benzoyl chloride III. Styrene IV. Phenyl acetylene A. LiAlH[OC(CH3)3]3 B. PCC in CH2Cl2 C. B2H6 then H2O2 and NaOH D. HgSO4 in aqueous H2SO4

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 C a) CH3 b) O C CH3 O c) CH3 86. What is the major product of the following reaction? O O HC(CH2)4CCH3 O a) CCH3 b) CH3 O O a) CCH3 b) CHCOOEt c) O O CH c) O d) CH3 NaOEt O d) CH3 O

CH3

CH3

87. What is the most likely product when the following keto ester reacts with sodium ethoxide? CH3C(CH2)4COEt NaOEt O d) O CCH3

O COOEt

16

88. What reagents are most likely to effect the following conversion? ? O a) NH2OH CH O O CH CHNO2 d) CH3NHOH

b) CH3NO2 + NaOH + CH3OH

c) CH3CH2NO2 + H3O/H2O

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 NO2 a) CH3NH NO2 NHCH3 NO2 b) Cl NO2 c) NHCH3 NO2 d) CH3 NO2 NH2 NO2

91. Which is the correct order of decreasing base strength (i.e., strongest base first)? NH2 NH2 CH3 I II a) II > I> III > IV > V III b) I > II > III > V > IV NH2 O 2N NH2 O2N NH2

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

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? PhCH2Br Ph Ph Ph3P CH3(CH2)3Li PhCHO heat Ph Ph Ph Ph CH2 Ph O(CH2)3CH3

a)

CHO

b)

Ph

CH

CH

Ph

c)

Ph Ph

d)

17

94. Arrange the following compounds in order of increasing acid strength (weakest first). OH CH2OH OH COOH COOH

N(CH3)3 I a) II, III, I, IV, V

CH3

CF3 V d) II, I, III, V, IV

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

95. Which of the following reactions is best for preparing phenylacetic acid (PhCH2COOH)? a) b) PhCH2Cl PhCH2OH Mg ether KMnO4 H3O CO2 H3O

c)

PhCH2CH2Br O

NaCN CH3CH2OH H3O

H3O heat

NaOH 96. Which of the following reactions will yield the same carboxylic acid? I. CH2CHO O II. C CH3 K2Cr2O7 H3O Cl2 NaOH KCN H3O CO2

d)

PhCCH3

Br2

III.

CH2Cl

heat H3O d) I, III

IV. a) I, II

CH2CH2Br b) II, III

Mg ether

c) III, IV

18

97. What is the major product from heating HOOCCH2CH2COOH? O a) O b) O O O O C a) O Z + b) OH O CH3 c) Cl c) O O O O O O C d) O O + O C CH3 HZ O d) H2C CH COOH

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

99. What is the major product of the following reaction sequence? O + CH3CCl AlCl3 Cl2 NaOH b) COOCH3 OCH3 c) OCOCH3 d) C CH3 OCH3 100. What are the best conditions for the following transformation? O COOH a) 1) SOCl2, 2) (CH3CH2)2CuLi c) 1) LiAlH4 2) SOCl2 3) Mg in ether 4) CH3CHO CCH2CH3 b) 1) SOCl2, 2) CH3CH2MgBr d) CH3OH, H3O 2) LiAlH4 H3O SOCl2 CH3OH

a)

COCH3

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 CH2NH2 b) CH2NH2 103. What is the major product of the following sequence of reactions?
CH2COOCH2CH3 CH2COOCH2CH3 COCH3 a) O b) COOCH2CH3 O c) O O d) O COOCH2CH3 NaOCH2CH3 H3O

heat

LiAlH4 O OH d) NH

CH2OH a)

NH

c)

NH

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

CH3C(CH2)3COCH2CH3 O a) O COCH2CH3

NaOCH2CH3

H3O O c) O COCH3 d) O COCH3 O

O b)

105. Toluene is treated with a mixture of HNO3 and H2SO4. The major product is reduced with to give B. B is reduced with LiAlH4 to give C. What is the most probable structure of C?

SnCl2 in HCl to give A. When A is treated with NaNO2 in HCL at 0C, followed by reaction with CuCN

H3C a)

CH2OH

H3C b)

CH2NH2

H3C c)

NH2

H3C d)

NHCH3

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) Br COOH Br b) Br 20 COOH Br c) CH2Br Br d) Br Br NH2

107. Which would give most meta-product upon nitration? COCH3 OCH3 a) b) N CH3 c) COCH3 d) OCOCH3

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 CH3

O COOH a) CH2CONH2 b) C CH3

CH2COOH O NH c) NH O d) NH

CH2NH2

109. What is the major product of the following reaction? COOEt + CH2COOEt NaOEt

COOEt a) CH O c) C CH COOEt d) C b)

O C CH2 O O

CCH2C

110. What are the reactants in the synthesis of the following enamine? O a) + N H O c) + N H d) O + NH2 b) O + NH2

21

111. Which of the following halides is NOT effective in the alkylation of malonic ester? O H2C CH I Br (CH3)3CBr II PhCH2Cl III O N O C a) b) + O c) C Cl O O d) O H3C C IV CH2Br a) I, III c) III, IV b) II, IV d) I, II

112. What is the major product of the following reaction? H3O

113. What is the major product of the following sequence of reactions? O CH3CCH2COOEt O 1) NaOEt 2) CH3COCl O CH3 1) NaOEt 2) CH3I O O 1) KOH 2) H3O 3) heat

O CH3

a) CH3CCH2CHCCH3

b) CH3CCH2CCH3

c) CH3CCHCCH3 CH3

d) CH3CCHCH2CCH3

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 CH3 NH2 1) NaOEt 2) CH3CHCH2CH3 Br H3O heat CH3 b) H2NCCOOH CH3 1) PBr3, Br2 2) H3O CH3 c) CH3CHCH2CHCOOH NH2 CH3 d) CH3CHCHCOOH NH2 NH3

a) CH3CH2CHCHCOOH

116. What is the major product of the following reaction? 1) KOH 2 equiv. CH(COOEt)2 + BrCH2CH2Br 2) H3O 3) heat a) HOOC COOH b) EtOOC O c) HOOC(CH2)4COOH d) O COOEt

CH3CCH2CH2CCH3 22

117. Which of the following molecules can become effective nucleophiles in a Michael reaction? O a) 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? OH a) CH3CH2CH2NH2 b) c) CH3 H N N H H N a) N H b) N N H N c) H N H d) N N H NH2 d) N H 120. What is the product of the reaction of one equivalent of imidazole with one equivalent of acid? O b) O O c) O O d) O

121. Which of the following amines have a stereogenic center? CH(CH3)2 CH3CH2NHCH3 I a) I, II, III CH3 CH3NHCHCH2CH3 CH3 II b) III, IV, V III c) I, III, IV NH2 CH3CHCH2CH3 CH3 CH3 IV d) II, III, IV

122. Methylethylamine cannot be resolved into enantiomers because a) it is planar. b) it undergoes rapid inversion. d) a tricovalent atom cannot be a center of chirality.

c) it has a plane of symmetry.

23

123. Which of the following amines can be resolved into enantiomers? CH3 CH3CH2NHCH3 CH3CH2CHNHCH3 H3C N CH3 CH3 III c) I, III d) II, IV IV CH3 H3C NHCH3

I a) I, II

II b) III, IV

124. Which of the following compounds is the strongest base? O O a) N H b) N H O c) N d) H N O H

125. What is the order of increasing base strength for the following compounds (weakest first)? N CH3 N N CH3 N IV c) I, III, II, IV

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

d) IV, II, III, I

126. What is the final product of the following series of reactions? CH2Cl Mg ether 1) CO2 2) H3O SOCl2 NH3 1) LiAlH4 2) H2O

a)

NH2

b)

CH2NH2

c)

CH2CH2NH2

d)

CH2CH2CH2NH2

127. What is the major product of the following sequence of reactions? PhCH2Cl NaCN LiAlH4 (CH3CO)2O

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

24

128. The same amine is prepared by which of the following reaction sequences? O I. CH3CH2CH2CNH2 NaOH Br2 NaN3 LiAlH4

II.

CH3CH2CH2CH2Br

III. CH3CH2CH2CH2Br O IV. N O a) I, II K

NaCN LiAlH4

CH3CH2CH2CH2Br

NH2NH2

b) III, IV

c) I, IV

d) II, IV

129. What is the product of the following reaction sequence? CH3 CH2CH3 CH N CH3I Ag2O H2O heat

OH

heat

a) H2C c)

CH

CH2

b)

H2C

CH

CH2

CH

CH2

CH3

d) H2C

CH CH2CH2 N(CH3)2

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

heat CH3 c) CH3 d) CH2

a)

CH3 N(CH3)2

b)

25

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 H H H OH OH OH CH2OH HO H H CHO H OH OH CH2OH H HO H CHO OH H OH CH2OH III b) The aldopentose is III. d) The aldopentose is I or III. HO HO H CHO H H OH CH2OH IV

I II a) The aldopentose is I or IV c) The aldopentose is II or IV.

132. D-hexose A shows the following characteristics: 1) A 2) A 3) B HNO3 optically active tetrahydroxyadipic acid [HOOC(CHOH)4COOH] B (an aldopentose)

Wohl degradation HNO3

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

What is the structure of D-Hexose A? CHO H HO H H OH H OH OH CH2OH HO H H H CHO H OH OH OH CH2OH HO HO HO H CHO H H H OH CH2OH H HO HO H CHO OH H 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 H H OH OH OH CH2OH a) I, IV H H HO OH OH 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

HOCH2

O OCH3

I. enantiomers II. diastereomers

HO

OH b) II

HO c) III

OH

III. anomers

a) I, 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 CH2OH OH

NaBH4

HO a) 1 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 HO HO H OH H H OH CH2OH a) HO HO H H CHO H OH OH OH CH2OH b) HO H HO H CHO H OH H OH CH2OH c) HO HO HO H CHO H H H 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 c) II, IV 27 III. Fructose d) I, III IV. ribose

140. What is the major product of the following reaction? HOCH2 OH HO O OH Br2 H2O OH COOH H HO H H OH H OH OH COOH H HO H H COOH OH H OH OH CH2OH H HO H H CH2OH OH H OH OH CH2OH H HO H H CHO OH H OH OH 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 b) OAc OAc O OAc OCH3 AcOCH2 CH3O AcO AcOCH2 d) AcO AcO O OAcOCH 3 O OAc OAc

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 H H H OH OH OH CH2OH H HO H H CHO OH H OH OH CH2OH HO HO H H CHO H H OH OH CH2OH H HO HO H CHO OH H H 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 d) polyunsaturated chains

28

144. Which of the Fischer projection formulas below correspond to the following stereostructure? HO H HO H OH H HO O H CHO OH H CH2OH c) HO H CHO H OH CH2OH d)

CHO H H OH OH CH2OH a) HO HO

CHO H H CH2OH b)

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? HOCH2 HO HO O OH OCH3 excess CH3I Ag2O H3O heat

CHO H CH3O H H OH H OCH3 OCH3 CH2OCH3 a) OH O CH 2 HO a) HOCH2 HO HO O OH c) HO O H HO H H

CHO OCH3 H OCH3 OCH3 CH2OCH3 b) H CH3O H H

CHO OCH3 H OH OCH3 CH2OCH3 c) HOCH2 O H CH3O H H

CHO OCH3 H OCH3 OH CH2OCH3 d)

146. Which of the following is a non-reducing sugar? (i.e., is not oxidized by Ag(NH3)2+) HOCH2 HO HO O OH O OH HO O O CH2OH

OH

HO

OH HOCH2 b) OH CH2OH OH O

CH2OH HO O

HOCH2

CH2OH O HO

OH

CH2OH 29

HO

OH

d)

147. Which of the following structures is a prostaglandin?

c)

OH HO

148. Which of the following structures is a terpene?

c)

OH 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 (4) val - gly - ala - lys - gly (2) ala - val - gly - 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) H2NCH2COOH NH2 b) HOOCCH2CHCOOH NH2 c) CH3S(CH2)2CHCOOH NH2 d) H2NCH2COOH CH3CHCOOH CH2CHCOOH NH2 H2N(CH2)4CHCOOH NH2 CH2CHCOOH NH2 (CH3)2CHCHCOOH H2NCH2COOH NH2 HOCH2CHCOOH O NH2 H2NCCH2CH2CHCOOH

153. Which compound would be most rapidily converted to the corresponding phenol by reaction of NaOH? Ar Cl Cl + NaOH Cl Ar Cl NO2 O 2N OCH3 NO2 NO2 HO OH + NaCl Cl OH

a) b) c) d) 154. Rank the following compounds in terms of their relative reactivity in nitration. CH3 CH3 NO2 Cl CH3 N CH3 OCH3

I a) b) c) d)

II

III

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

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? O ? CH2

I a) I CH3MgI ether H3O II

II b) I CH3Li THF, heat II

c)

Ph3P

CH3

BuLi

II

d)

CH3MgI NaOH ether H2O

II

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

a) H2C

CH

CH

CH2

b) H2C

CH

CH

CH2

c)

H2C

CH

CH

CH2

d)

H2C

CH

CH

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 CH3 Br a) CH3CH2 C CH3 CN c) CH3CH2 C CH3 CH2CH3 LiAlH4 CH2CH3 NH2NH2 CONH2 b) CH3CH2 C CH3 Br d) CH3CH2 C CH3 CH2CH3 CH2CH3 Br2 NaOH CH2CH3

NH3 excess

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

COOH HNO3 H2SO4 CN b) HNO3 H2SO4

COOH (+ ortho isomer) NO2 separate isomers COOH CH3Cl AlCl3 KMnO4 NO2 (+ ortho isomer) NO2 COOH HNO3 H2SO4 separate isomers NO2 KMnO4 H3O

a)

COOH

c) NO2 CH3

d)

33

162. Which reaction provides the best way to prepare the compound shown below? COOCH3 COOCH3 COOCH3 a) + COOCH3 CH3OOC + H CH2I2 COOCH3 b) H C C H + COOCH3 COOCH3 H

Zn(Cu)

c)

+ CH3OOC C

C COOCH3

d)

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 164. What is the major product of the following reaction? CH3 CH3 CH O C O CH3CH2CH2MgBr (in excess) CH3 CH3 CH2CH2CH3 c) C OH d) CH2CH2CH3 CH3 CH3 CH CH O C CH2CH2CH3 H3O c) ArCO3H (m-ClPBA) followed by NaOH

a)

CH2CH2CH3

b)

CH2CH2CH3 C OH CH2CH2CH3

165. . To which carbon of A would H+ or other electrophiles add most readily? 4 3 A 1 2 OCH3 b C-2 c) C-3 d) C-4

a) C-1

34

166. What is the major product of the following reaction? CH3 + CH3 CH3 CHCH2Cl AlCl3 ?

CH3 a) CH3 C CH3 CH3 b)

CH3 CH2 CH

CH3 CH3 c)

CH3 d) CH2 CH3 CH CH3

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 (1) dissolve in CH2Cl2

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

(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

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

168. Which of the following reaction sequences is best to convert A into B? CH2COOCH3 CH2CH2OH

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

O B b) (1) CrO3, H3O+; (2) NaBH4 d) (1) Ac2O, pyridine; (2) LiAlH4; (3) H3O+ 35

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

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

CH3

CH3

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 CH3 H Cl 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 c) H NH2 CH3 d) NO2

36

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

CH3

CH3MgBr ether

H3O

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