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Sample Multiple-choice Questions

1. Which of the following compounds are nonpolar?

H2O CO2 NH3 BF3 CHCl3 I II III IV V

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

2. Which of the following Lewis structures are incorrect?

O O O N N Cl Cl H C O HH

H

I II III IV V

HH

HHNCH

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

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

CS2 BF3 AlCl4- NH2- NH4+ I II III IV V

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. AcidII. AlcoholIII. AldehydeIV. EtherV. Ketone Penicillin G

ONH

N

S CH3

CH3

COOHO

OVI. SulfoxideVII. AmideVIII. Thiol esterIX. Sulfide

a) I, IV, V, VI, VII 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 molecularformula C4H10O?

a) 2 b) 3 c) 4 d) 5

6. Which of the following are NOT resonance structures?

I. HN C O HO C N

II. N C O N C O

III. CH3 CO

CH3CH3 C

OH

CH2

IV. CH3 CO

CH2CH3 C

O

CH2

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

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

CH3 C CH CH3CH2 C CH CH2

O

CH2 CH CH CH CH2 CH2 CH2 CH CH2

I II

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

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

H2C N OHC OCH3 HC NCH3

I II III IV V

a) sp: III, IV, V; sp2: I; sp3: II b) sp: III, IV; sp2: I, II; sp3: V

c) sp: III, IV; sp2: I, V; sp3: II d) sp: III, IV; sp2: II, V; sp3: I

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

CH3 C CH2

CH2

CH2

CH3

CH3

CH3

a) 2,2-diethylbutaneb) 222-triehtylethanec) 3-methyl-3-ethylpentaned) 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

CH3H

H

HH

CH3

CH3H

H

H

HH

CH3H

CH3

HH

CH3

HH

H

CH3

H

a) b) c) 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

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14. Which of the following positions is the bridgehead carbon atom?

a)

b)

c)

d)

15. Put the following compounds in order of increasing acidity (weakest acid first). CH4 NH3 H2O HF HBr I II III IV V

a) II, I, III, IV, V 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 CH3 CH2

I II III IV

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

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

C CC C

CH3

H3C

H

H

H

H

I

C CC C

CH3

H3C

H H

H H

II

C CC CCH3CH2

H H

H H

H

III

C CC C

CH3

H3C

H

H

H H

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

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

a) 0 b) 1 c) 2 d) 3

CH3

CH3

D2

Pt

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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

pi bonds

0 3 1 4

4 1 3 0

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

CH3C

NH

CH3C

H3C

NH2

CH2 N O

H

N OH

OH

OH

O

O

O

NHH3CC

O

NHH3CC

I II

III IV

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

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

CH3CH2CH=O CH3CCH3

O

CH3CHCH2OH H2C=CHCH2OHa) b) c) d)

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?

CCH2

CH2CH3C

H

CCH2CH3

H

CH

C

CH2CH3

H CH2CH2CH2CH3

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

I II III IV

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

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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?

IVIIIIImaleic anhydride

OO O

I

CH3CH3CH3CH2

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

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

O +

O O O O

a) 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 II. cis-1,2-cyclohexanediolIII. trans-1,4-cyclohexanediol IV. trans-1,3-cyclohexanediol

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

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

O

CH2OHHO

HOOH

a) 2

b) 4

c) 8

d) 16

31. What is the relationship of the following structures?

OH

OH

HH

OHOH

H

H

a) enantiomers b) diastereomers c) constitutional isomers d) conformational isomers

32. Which of the following structures are enantiomers? CH3

OHH

H OH

H OH

CH3

CH3

OHH

HO H

H OH

CH3

CH3

OHH

H OH

HO H

CH3

CH3

HHO

H OH

H OH

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?

CH3CHCHCH3

HO OHCH3CH CHCH2CH3OHHOCH3CHCH2CH3

OH

a) b) c) d)

34. The addition of bromine to trans-2-pentene produces two stereoisomers. Their configurationsare:

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. Acan be:

a) 1-methylcyclobutene b) 3-methylcyclobutene c) trans-1,2-dimethylcylcopropane d) cyclopentene

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36. A solution of ammonia in water contains four different kinds of hydrogen bonds. Arrange them inorder of increasing strength (weakest first).

I. H2N-H----OH2 II. H2N----HNH2 III. H2O----HOH IV. H3N----HOH

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

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 b) 3,3-dimethyl-2-butanolc) 3,3-dimethyl-1-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 b) (CH3)3CO K + CH3I c) (CH3)3COH + CH3OH d) CH3MgBr + (CH3)3COCl

NaOH

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

I II III 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 CH3O I H2O F

I II III IV Va) I, IV b) IV, Vc) I, III d) III, IV

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43. Place the following alkyl halides in order of increasing reactivity in an SN2 reaction (least first).

Br Br Cl Br

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


Br Br Cl Br

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


CH3CHCH3

Cl

CH3CH2CH2Cl (CH3)3CCl CH3ClI II III IV

a) II, IV, I, III b) I, III, IV, II 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 (CH3)3C

I II III IVa) IV, III, II, I 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 bothdoubled, what effect will this have on the rate of reaction?

(CH3)3CBr + CH3OH (CH3)3COCH3 HBr+

a) no change b) doubles c) triples 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

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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 strongbase?

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

b) CH3CH2OH

c) CH3CH2OCH3CH2OH,

d) CH3CH2ODMSO,

25˚C

80˚C

25˚C

25˚C

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

a) CH3CH2CHCH3

OH

b) CH2OH c) (CH3)3COH d) CH3CH2CH2CH2OH

53. What is the major product from the reaction of propene epoxide and sodium methoxide.

CH3CHCH2OH

OH

CH3CHCH2OCH3

OH

CH3CHCH2OH

OH

CH3OCHOCH3

OCH3

a) b) c) d)

54. What is the product of refluxing anisole with concentrated HBr?

a) phenol and methyl bromide b) bromobenzene and methyl bromidec) bromobenzene and methanol 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.

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

c)CH3

H3C OH

D

H

HCH3

H3C H

H

OH

D+

+CH3

H3C OH

D

H

HCH3

H3C OH

H

H

Dd)b)CH3

H3C OH

H

H

D

CH3

H3C OH

D

H

Ha)

H2OLiAlD4O

H CH3

HH3C

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?

VIVIVIIIIII

OOO OOOO

a) I, II, IV b) I, III, IV c) III, V, 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 II III IV Va) I, II, III b) I, III, IV c) III, IV, V d) I, III, V

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

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

OHCOOH OH

NO2

CH2OH

I II III IV

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

61. What is the product of the following reaction?

KMnO4

H2O, heat

a) O b)COOH

COOH

c)

CHO

CHO

d)

COOH

COOH62. . Identify the most likely position to be nitrated in the following substance.

CH2 CNa)

b) c) d)

63. . Identify the most likely position to be brominated in the following substance.

d)

c)b)

a)O

OC

64. Identify the most likely position to be nitrated in the following substance.

Br

a)

b) c)

d)

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

H3C C

CH3

CH3

BrMg

ether

H2C CH2

OCrO3H3O

H3O

SOCl2 CH3NH2

CH3NHCCH2CH2CCH3

CH3

CH3O

a) CH3NHCCH2CCH3

CH3

CH3O

b)

CH3NHCH2CH2CCH3

CH3

CH3

c) (CH3)2NCCH2CCH3

CH3

CH3O

d)

66. Which of the following substituents on benzene are activating in electrophilic aromaticsubstitution?

Br NO2 OCH3 COCH3

N(CH3)2 C(CH3)3 N(CH3)3 SO3H

I II III IV

V VI VII VIII

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

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

CH3H

Br

CH3

H Br

CH3H

Br

CH3

HBr

a) b) c) d)

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

NO2

NO2H

N

N

O O

O

OH

N

N

O O

O

O

H

NO2

NO2

a) b) c) d)

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

CH3

CH3

H

H+

C

C

COOEt

COOEt

H

H heat

CH3

CH3

COOEt

COOEt

CH3

CH3

COOEt

COOEt

CH3

CH3

COOEt

COOEt

CH3

CH3

COOEt

COOEta) b) c) d)

70. Identify the most likely position to be nitrated in the following substance.

O2N

a) b) c)

d)

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

Cl

OCH3

OCH3

Cl

OCH3H3CO

Cl

NO2

NO2

Cl

NO2O2N

a) b) c) d)

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

NBSUV light

NBS KMnO4KMnO4

KMnO4

FeBr3

Br2Br2

d)c)

b)a)

UV light

FeBr3

KMnO4

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

Br2

CH3 COOHCl

Br

Cl2FeCl3 FeBr3

KMnO4 H3O

a)

c)

Cl2FeCl3

b)

d)KMnO4

KMnO4

OH

OH

OH

H3O

KMnO4

OH

H3O

Br2

FeBr3

Cl2FeCl3

H3O

Br2

FeBr3

Cl2FeCl3

Br2

FeBr3

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

OHSO3

100˚CH2SO4

Cl2FeCl3

dil H2SO4

100˚C

OH

HO3S

OHCl OH

Cl

Cl

SO3H

Cl

Cl

a) b) c) d)

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

OO

OHHO

C

CH2

HOH

H

HOa)

b)

c) d)

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

H3C CH

O

H2C CH

OH

a)

+

H2C CH

O

+ H3C CH

O

b)H2C CH

O

+ H3C CH

OH

c) H2C CH

OH

+ H3C CH

OH

d)

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

H3C CH

O

H2C CH

OH

a)

+

H2C CH

O

+ H3C CH

O

b)H2C CH

O

+ H3C CH

OH

c) H2C CH

OH

+ H3C CH

OH

d)

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

O

OH3C

O

CH3HO

O

OCH3

OCH3

CH3

a) b) c) d)

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

O

OH3C

O

CH3HO

O

OCH3

OCH3

CH3

a) b) c) d)

80. Which of the following combinations of reactants will give cinnamaldehyde (PhCH=CHCH=O), in amixed aldol reaction?

a) benzaldehyde and acetaldehyde b) formaldehyde and phenylacetaldehydec) formaldehyde and acetophenone d) benzaldehyde and acetone

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

I CH3CH2COCl

II CH3CH2CN

III CH3CH2COOH

IV CH3CH2CH CH2

A (CH3)2CuLi

B CH3OMgBr

C CH3Li

D CH3MgBr

a) I and C, II and A 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 saturatedhydrocarbon, B, C5H10. Compound A, on treatment with ozone followed by treatment of the ozonidewith Zn/H2O, yields a dialdehyde C, C5H8O2. Dialdehyde C on treatment with hydrazine andconcentrated potassium hydroxide at elevated temperatures gives 2-methylbutane. The structure ofA is:

a) b)CH3

CH3

c)

CH3

d)

CH3

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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 preparebenzaldehyde?

I. Benzyl alcohol A. LiAlH[OC(CH3)3]3II. Benzoyl chloride B. PCC in CH2Cl2III. Styrene C. B2H6 then H2O2 and NaOHIV. Phenyl acetylene 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, A85. What is the most likely product from the base-catalyzed condensation reaction of 2,8-nonadione?

CH3

CCH3

O

CH3

CCH3

O

O

CH3

O

CH3

a) b) c) d)

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

HC(CH2)4CCH3

O ONaOEt

CCH3

OCH

O

CH3

O

O

CH3

a) b) c) d)

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

CH3C(CH2)4COEt

O ONaOEt

CCH3

O

CHCOOEt

COOEt

O

CCH3O

Oa) b) c) d)

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

O CH O

?

O CH CHNO2

a) NH2OH b) CH3NO2 + NaOH + CH3OH 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?

NO2

NO2

CH3NH

Cl

NO2

NHCH3

Cl

NO2

NO2

NHCH3

NO2

NO2

NH2

CH3

a) b) c) d)

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

NH2 NH2 NH2

CH3

NH2

O2N

NH2O2N

I II III IV Va) II > I> III > IV > V b) I > II > III > V > IV c) I > III > II > IV > 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 CH3(CH2)3Li PhCHO heat

CPh

Ph CH2 Ph

O(CH2)3CH3

PhCH2Br

a) C CHOPh

Phb) c) d)C C

Ph

Ph

Ph

PhPh CH CH Ph

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

OH CH2OHCOOH

CH3

OH

N(CH3)3

I II III IV

COOH

CF3

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

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

a)

b)

c)

d)

PhCH2Cl

PhCH2OH

PhCH2CH2Br

PhCCH3

O

Mgether

CO2 H3O

KMnO4 H3O

NaCNCH3CH2OH

H3Oheat

Br2

NaOHH3O

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

H3OCO2

etherMg

heatH3OKCN

NaOH

Cl2

H3O

K2Cr2O7

CH2CH2Br

CH2Cl

C CH3

O

CH2CHO

IV.

III.

II.

I.

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

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97. What is the major product from heating HOOCCH2CH2COOH?

a) b) c) d)

O

OO

O

O O

OO

O

O

O

H2C CH COOH

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

HZ+C

O

OOH+C

O

Z

d)c) O C CH3

O

ClO CH3b)Oa)

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

+ CH3CCl

OAlCl3

NaOH

Cl2 H3O SOCl2 CH3OH

a)

c)

b)

d)

COCH3 COOCH3

OCOCH3 C CH3

OCH3

OCH3

100. What are the best conditions for the following transformation?

COOH CCH2CH3

O

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

a) 1) SOCl2, 2) (CH3CH2)2CuLi b) 1) SOCl2, 2) CH3CH2MgBr

d) CH3OH, H3O 2) LiAlH4

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

b) 1) SOCl2, 2) LiAlH4 3) H3O 4) NH2NH2, KOH

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

c) 1) NH2NH2, KOH 2) SOCL2, 3) Mg in ether 4) H2O

CH3COOH

d) CH3Li, 2) H3O

20


NH

OH

NH

O

NHCH2OH

CH2NH2

d)c)b)a)

LiAlH4heatCOOH

CH2NH2

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

CH2COOCH2CH3

NaOCH2CH3 H3O

O

COCH3

O

COOCH2CH3 O

O

OCOOCH2CH3

a) b) c) d)


CH3C(CH2)3COCH2CH3

O O

d)c)b)a)

H3ONaOCH2CH3

O

COCH2CH3

OO O

O

COCH3

O

O

COCH3

O

105. Toluene is treated with a mixture of HNO3 and H2SO4. The major product is reduced withSnCl2 in HCl to give A. When A is treated with NaNO2 in HCL at 0˚C, followed by reaction with CuCNto give B. B is reduced with LiAlH4 to give C. What is the most probable structure of C?

H3C NHCH3

d)

H3C NH2

c)

H3C CH2NH2

b)

H3C CH2OH

a)

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?

d)

NH2

Br

Br

Br

c)

CH2BrBr

b)

COOH

Br

Br

Bra)

COOHBr

Br

21

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

OCH3 N CH3

COCH3

COCH3 OCOCH3

a) b) c) d)

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

CCH3

O

CH2COOHA

COOH

CH2CONH2

CCH3

O

CH2NH2

NH

NHO NH

O

a) b) c) d)


COOEt + CH2COOEtNaOEt

CH C

COOEt

C CH2

O

C CH

O

COOEt

CCH2C

O O

a) b)

c) d)

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

N

O

O

NH2

N

H

NH2

N

H

a)

O

b)

c) d)O

+ +

++

22

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

IVIIIIIIH3C C CH2Br

O

PhCH2Cl(CH3)3CBrH2C CH Bra) I, III b) II, IV

c) III, IV d) I, II112. What is the major product of the following reaction?

N CO

Cl

H3O+

C

O OO O O

a) b) c) d)


d)c)b) CH3CCHCH2CCH3

O O

CH3

CH3CCHCCH3

O O

CH3

CH3CCH2CCH3

O O

CH3CCH2CHCCH3

O O

CH3

a)

1) NaOEt

2) H3O3) heat

1) KOH

2) CH3I2) CH3COCl

1) NaOEtCH3CCH2COOEt

O

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?

d)c)b)a) CH3CHCHCOOH

CH3

NH2

CH3CHCH2CHCOOH

CH3

NH2

H2NCCOOH

CH3

CH3

CH3CH2CHCHCOOH

CH3

NH2

NH3

H3O2)

1) PBr3, Br2

heat

H3O

CH3CHCH2CH3

Br

2) 1) NaOEt

CH2(COOEt)2


d)c)

b)a)

CH3CCH2CH2CCH3

O O

HOOC(CH2)4COOH

EtOOC COOEtHOOC COOH

3) heat2)

1) KOH+ BrCH2CH2Br2 equiv. CH(COOEt)2

H3O

23

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

O

O

O

O

O O

a) b) c) d)

118. What is the major product from the following Michael reaction?

CH2(COOEt)2 + H2C CH C NNaOEt 1) KOH

2) H3O3) 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?

CH3CH2CH2NH2

OH NH2

CH3

N

O

H

a) b) c) d)

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

N

N

H

H

N

N

H

d)N

N

H

c)N

N

H H

b)N

N

H

H

a)

121. Which of the following amines have a stereogenic center?

CH3CHCH2CH3

NH2 NCH3

CH3

H N HCH3CH2NHCH3

CH(CH3)2

CH3NHCHCH2CH3

CH3

CH3

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

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.

24

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

CH3CH2NHCH3 CH3CH2CHNHCH3

CH3

NCH3

CH3

H3CNHCH3

H3C

CH3

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

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

N

O

H

N O

H

N

O

HN

O

Ha) b) c) d)

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

N CH3 N N CH3 N

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

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

CH2ClMg

ether1) CO2

2) H3O

SOCl2 NH3 1) LiAlH4

2) H2O

NH2 CH2NH2 CH2CH2NH2 CH2CH2CH2NH2a) b) c) d)


PhCH2ClNaCN LiAlH4 (CH3CO)2O

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

25

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

I. CH3CH2CH2CNH2

ONaOHBr2

II. CH3CH2CH2CH2BrNaN3 LiAlH4

III. CH3CH2CH2CH2BrNaCN LiAlH4

IV.CH3CH2CH2CH2Br NH2NH2N

O

O

K

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

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

d)

b)

c)

a)

H2C CH CH2CH2 N(CH3)2N CH3

H2C CH CH2 CH CH2H2C CH CH CH2

heatH2OAg2OCH3I

heatOHNCH3

CH2CH3

130. What is the product of the following Hofmann elimination reaction?

d)c)b)a) CH2CH3CH3CH3

N(CH3)2

heatOH

CH3

N(CH3)3

26

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

IVIIIIII

CHO

CH2OH

OHH

OHH

OHH

CHO

CH2OH

OHH

OHH

HHO

CHO

CH2OH

OHH

HHO

OHH

CHO

CH2OH

OHH

HHO

HHO

a) The aldopentose is I or IV b) The aldopentose is III.

c) The aldopentose is II or IV. d) The aldopentose is I or III.

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

What is the structure of D-Hexose A?

HNO3

Wohl degradation

HNO3

CHO

OHH

HO H

H OH

H OH

CH2OH

CHO

HHO

H OH

H OH

H OH

CH2OH

CHO

HHO

HO H

HO H

H OH

CH2OH

CHO

OHH

HO H

HO 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) lactose134. What is the relationship between the following two structures?

H OH

H OH

H OH

CH2OH

CHO

H OH

H OH

HO H

CH2OH

CHO I. enantiomers

II. diastereomers

III. epimers

IV. anomersa) I, IV b) I, III c) II, III d) II, IV

27

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

I. enantiomers

II. diastereomers

III. anomers

HOCH2O

OHHO

OCH3HOCH2

O

OHHOOCH3

a) I, III b) II 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

CH2OH

HOOH

NaBH4

a) 1 b) 2 c) 4 d) 8

138. Which of the following compounda give the same glucaric acid as its enantiomer when oxidizedwith Nitric acid?

CHO

OHH

HO H

HO H

H OH

CH2OH

CHO

HHO

HO OH

H OH

H OH

CH2OH

CHO

HHO

H OH

HO H

H OH

CH2OH

CHO

HHO

HO H

HO H

H OH

CH2OH

a) b) c) d)

139. If D-glucose is allowed to stand for several days in aqueous Ca(OH)2 which of the followingsugars will appear in the mixture?

I. mannose II. arabinose III. Fructose IV. ribose

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

28


COOH

OHH

HO H

H OH

H OH

COOH

COOH

OHH

HO H

H OH

H OH

CH2OH

CH2OH

OHH

HO H

H OH

H OH

CH2OH

CHO

OHH

HO H

H OH

H OH

CH2OH

a) b) c) d)

HOCH2

OH

HO

OH

OH

O Br2

H2O

141. Which of the following is a product from the reaction of D-glucose with methanol and acidfollowed by exhaustive acetylation with acetic anhydride?

O

OAcAcOCH3O

OAcAcOCH2

O

OCH3OAcAcO

AcO

AcOCH2

CH3OCH2

AcOAcO OAc

OAc

O

CH3OCH2

AcOAcO OAc

OCH3

O

a) b)

c) d)

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

CHO

HHO

H OH

H OH

H OH

CH2OH

CHO

OH

HO H

H OH

H OH

CH2OH

H

CHO

HHO

HO H

H OH

H OH

CH2OH

CHO

OHH

HO H

HO H

H OH

CH2OH

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

a) phosphate esters b) multi-ring systems c) isoprene units d) polyunsaturated chains

29

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

HOH

O

OH

HO

H

H

d)c)b)a)

CHO

H OH

H OH

CH2OH

CHO

HO H

HO H

CH2OH

CHO

H OH

HO H

CH2OH

CHO

HO H

H OH

CH2OH

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

HOCH2

HOHO OCH3

OH

Oexcess CH3I

Ag2O

H3O

heat

d)c)b)a)

CHO

OHH

CH3O H

H OCH3

H OCH3

CH2OCH3

CHO

OCH3H

CH3O H

H OCH3

H OH

CH2OCH3

CHO

OCH3H

HO H

H OCH3

H OCH3

CH2OCH3

CHO

OCH3H

CH3O H

H OH

H OCH3

CH2OCH3

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

OCH2

HO OH

OH

O

OH

OHOCH2

HOHO

OH

a)

O

HO

HO

CH2OH

CH2OH

HOHO

HOCH2O

OH

O

b)

c) d)

OHOHHOCH2

CH2OHOOOHOCH2

HOHO OH

OH

HO

OCH2OH

O

HOCH2

HO OH

CH2OHO

30

147. Which of the following structures is a prostaglandin?

d)

c)

b)a)

HO

H3C

H3C

H

OH

CH3

H3C

OH

O

H

H

H

COOH

CH3

OH

HO

HO

148. Which of the following structures is a terpene?

d)

c)

b)a)

HO

H3C

H3C

H

OH

CH3

H3C

OH

O

H

H

H

COOH

CH3

OH

HO

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 andanimals?

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

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

31

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

a) H2NCH2COOH CH2CHCOOH

NH2

H2NCCH2CH2CHCOOH

NH2O

b) HOOCCH2CHCOOH

NH2

H2N(CH2)4CHCOOH

NH2

H2NCH2COOH

c) CH3S(CH2)2CHCOOH

NH2

CH3CHCOOH

NH2

CH2CHCOOH

NH2

HOCH2CHCOOH

NH2

d) H2NCH2COOH (CH3)2CHCHCOOH

NH2

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

Ar Cl + NaOH Ar OH + NaCl

Cl

OCH3

Cl

NO2O2N

Cl

NO2

NO2

Cl

OHHO

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

CH3 NO2 Cl NCH3

CH3CH3 OCH3

I II III IV V

a) most reactive IV>II>III>I>V least reactive b) most reactive V>I>III>II>IV least reactive c) most reactive III>II>IV>V>I least reactive d) most reactive V>I>IV>II>III least reactive

32

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. b) a racemic ester. c) a single optically active 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 II

a) I CH3MgIether

IIH3O CH3LiTHF, heat

II

c) Ph3P CH3 I BuLi I II CH3MgIether

NaOHH2O

II

b)

d)

I

I

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

d)c)

b)a) H2CCH

CHCH2

H2CCH

CHCH2

H2CCH

CHCH2

H2CCH

CHCH2

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.

33

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

excess

NH3LiAlH4

NaOH

Br2NH2NH2

d) CH3CH2 C CH2CH3

Br

CH3

CH3CH2 C CH2CH3

CN

CH3

c)

b) CH3CH2 C CH2CH3

CONH2

CH3

CH3CH2 C CH2CH3

Br

CH3

a)

C

NH2

CH3

CH2CH3CH3CH2

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

(+ ortho isomer)

(+ ortho isomer)

COOH

NO2

COOH

NO2

COOH

NO2

COOH

NO2

H3O

KMnO4

AlCl3

CH3Cl

KMnO4

isomers

separate

isomersseparateHNO3

H2SO4

HNO3

H2SO4

H2SO4

HNO3

d)

CH3

NO2

c)

b)

CN

COOH

a)

34

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

Zn(Cu)CH2I2

COOCH3

COOCH3

CH3OOC COOCH3

HHCH3OOC C C COOCH3 ++

+

d)c)

H C C Hb)+

COOCH3

COOCH3

a)

COOCH3

COOCH3

163. What is a satisfactory reagent to convert trans-2-butene into meso-2,3-butanediol ?

a) OsO4, then Na2SO3 b) Dilute basic KMnO4 c) ArCO3H (m-ClPBA) followed by NaOH d) O3 followed by Zn, H2O164. What is the major product of the following reaction?

d)

b)

CHCH3

CH3

C OH

CH2CH2CH3

CH2CH2CH3

C

CH2CH2CH3

CH2CH2CH3

OHc)

CH2CH2CH3 CHCH3

CH3

C

O

CH2CH2CH3a)

(in excess)CH3CH2CH2MgBr

CHCH3

CH3

C O

OH3O

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

3 2

1

OCH3

Aa) C-1 b C-2 c) C-3 d) C-4

35


?AlCl3

CHCH2ClCH3

CH3

+

CH3

CH3

CH2 CHCH3

CH3b)

CH3

C CH3CH3

CH3

a)

CH3

H2CCH

CH3

CH3

d)

CH3

CH2

CHCH3 CH3

c)

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

CH2NH2 CONH2

A B

(1) dissolve in CH2Cl2 (2) extract with water (3) extract with aqueous HCl (4) extract with aqueous NaHCO3

(5) extract with aqueous NaOH (6) basify aqueous layer with NaOH (7) acidify aqueous layer with HCl (8) 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?

BA

O

CH2CH2OHCH2COOCH3

O

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+

36

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

CBA

CH3 CH3

OH

CH3

OH

CH3

OH

CH3 CH3

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 isomershown below?

Cl

CH3

H

H CH3

Cl

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-3-methoxycyclohexanecarboxylic acid (A) into its enantiomeric forms?

NO2

d)CH3

NH2H

c)COOH

OCH3F3C

b)

CH2CH2NH2

a)

A

COOH

OCH3

37

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

CH3MgBr

O

CH3

HH3O

ether

a) one chiral product b) two diastereomeric products in equal amountc) a racemic mixture 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) The exact point to which an amino acid migrates in an electric field. b) The pH at which the amino acid does not migrate in an electric field. c) The point at which a given amino acid no longer exhibits resonance. d) 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) Use of unnatural amino acids. b) Complete hydrolysis into amino acids. c) digestion d) disruption of Hydrogen bonds

documentmc

Documents

ortho isomer

important

dilute basic

terminal amino

catalyzed

hoch2 ho ho

och3 och3

ii iii iv