Chapter 16 - Test Bank Chem 200

Package Title: Solomons Test Bank Course Title: Solomons 11e Chapter Number: 16 Question type: Multiple Choice 1) What is the correct IUPAC name for the following compound?

O

a) 2-Methyl-5-heptanone b) 7-Methyl-4-octanone c) 6-Isopropyl-4-octanone d) Isobutyl propyl ketone e) 1,1-Dimethyl-4-heptanone Answer: B Topic: Nomenclature Section: 16.2 Difficulty Level: Easy 2) What is the correct structure for 7-methyl-4-octanone? O

I

O

II

O

III O

O

V

IV

a) I b) II c) III d) IV e) V Answer: D Topic: Nomenclature 1

Section: 16.2 Difficulty Level: Easy 3) What is the correct IUPAC name for the following compound? O

a) 5,5-Dimethyl-2-heptanone b) 5-Ethyl-5,5-dimethyl-Methyl-2-octanone c) 5-Ethyl-5-methyl- 2-hexanone d) 5,5-Dimethyl-2-octanone e) 3,3-Dimethyl-6-heptanone Answer: A Topic: Nomenclature Section: 16.2 Difficulty Level: Easy 4) What is the correct structure for 5,5-dimethyl-2-heptanone? O

O

I

O

II

O

III

H

O

V

IV

a) I b) II c) III d) IV e) V Answer: B Topic: Nomenclature Section: 16.2 Difficulty Level: Easy 2

5) A correct name for the following compound would be which of those below? O H

a) 2,5-Dimethyl-6-hexanal b) 2,5-Dimethylhexanal c) 2-Aldehydoisohexane d) 3,5-Dimethylheptanone e) 1-Hydro-2,5-dimethyl-1-hexanone Answer: B Topic: Nomenclature Section: 16.2 Difficulty Level: Easy 6) What is the correct structure for 2,5-dimethylhexanal? O

O

H

I

II

III

O

O

O

H

H

IV

V

a) I b) II c) III d) IV e) V Answer: D Topic: Nomenclature Section: 16.2 Difficulty Level: Easy 7) What is the correct IUPAC name for the following compound? 3

O

a) 5,5-Dimethyl-2-heptanone b) 5-Ethyl-5,5-dimethyl-Methyl-2-octanone c) 5,5-Dimethylcycloheptanone d) 4,4-Dimethylcycloheptanone e) 3,3-Dimethylcycloheptanone Answer: D Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 8) What is the correct IUPAC name for the following compound? O

a) 2,4-dimethyl-2-pentenone b) 2,5-dimethylcyclopenten-3-one c) 2,4-dimethylcyclopent-2-enone d) 3,5-dimethylcyclopent-2-enone e) 2-methyl-5-methylcyclopent-2-enone Answer: C Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 9) What is the correct IUPAC name for the following compound?

O

4

a) 1,1,2-Trimethyl-1,3-hexenone b) 1,2-Dimethyl-1,3-hexenone c) 2,3-Dimethyl-1,3-heptenone d) 2,3-Dimethyl-2-hepten-4-one e) 5,6-Dimethyl-5-hepten-4-one Answer: D Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 10) What is the correct structure for 2,3-dimethyl-2-hepten-4-one? O

I

O

II

O

III

O

IV

O

V

a) I b) II c) III d) IV e) V Answer: E Topic: Nomenclature Section: 16.2 Difficulty Level: Medium O

11) A correct name for C6H5CH2CH2CH is? a) 3-Benzylpropanone 5

b) 3-Phenylpropanal c) 3-Benzylpropanal d) Nonanone e) Nonanal Answer: B Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 12) What is the correct structure for 3-phenylpropanal? O

O H

O

II

I

III O

H O

IV

V

a) I b) II c) III d) IV e) V Answer: E Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 13) What is the correct structure for 5-hydroxy-2-phenyl-3-hexanone?

6

O

Ph

Ph

OH

II

I Ph

OH

O

III

OH OH

OH

O

O

H

IV

V

O

Ph

a) I b) II c) III d) IV e) V Answer: C Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 14) Which is the proper name for the structure shown? CHO Cl CH3

a) 2-Chloro-5-aldehydotoluene b) 6-Chloro-3-aldehydotoluene c) 2-Methyl-4-aldehydochlorobenzene d) 4-Chloro-3-methylbenzaldehyde e) 4-Methyl-5-chloro-2-benzaldehyde Answer: D Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 15) What is the correct structure for 4-chloro-3-methylbenzaldehyde? 7

Ph

O

O

H

O

H

H

Cl

II

I

III

Cl

Cl O

H H O Cl

IV

Cl

V

a) I b) II c) III d) IV e) V Answer: A Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 16) What is the correct structure for 3-methyl-5-(2,5-dinitrophenyl)pentanal?

8

NO2

O

O

H

O2N

NO2

II

I

O

NO2

NO2

O O2N H

O2N H NO2

III

IV

O2N

H

O NO2

V

a) I b) II c) III d) IV e) V Answer: B Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 17) What is the correct structure for 3-methyl-5-(4-chlorophenyl)hexanal?

9

O

O

H

Cl

Cl

I

II O

O

H

H

Cl

IV

III

Cl

Cl

O

H

V

a) I b) II c) III d) IV e) V Answer: D Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 18) What is the correct structure for 7-bromo-1-octyn-4-one? Br

Br

Br

O

O

O

II

I

III

Br Br

IV

O

V O

10

a) I b) II c) III d) IV e) V Answer: A Topic: Nomenclature Section: 16.2 Difficulty Level: Medium 19) What is the correct IUPAC name for the following compound? Br

O

a)2-Methyl-2-bromobutanone b)(S)-2-Bromo-2-methylcyclobutanone c)(R)-2-Bromo-2-methylcyclobutanone d) (S)-1-Bromo-1-methyl-2-cyclobutanone e)(R)-1-Bromo-1-methyl-2-cyclobutanone Answer: B Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 20) What is the correct IUPAC name for the following compound?

a)2-Bromobutanone b)(S)-2-Bromo-cyclobutanone c)(R)-2-Bromo-cyclobutanone d) (S)-1-Bromo-2-cyclobutanone e)(R)-1-Bromo-2-cyclobutanone Answer:C 11

Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 21) What is the correct IUPAC name for the following compound? O

Cl

H

a) (S)-3-chloro-1-hexanone b) (S)-1-chloro-3-hexanone c) (R)-3-chlorocyclohexanone d) (S)-3-chlorocyclohexanone e) (S)-1-chloro-3-cyclohexanone Answer: D Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 22) What is the correct IUPAC name for the following compound?

a) (S)-3-chloro-1-hexanone b) (S)-1-chloro-3-hexanone c) (R)-3-chlorocyclohexanone d) (S)-3-chlorocyclohexanone e) (S)-1-chloro-3-cyclohexanone Answer:C Topic: Nomenclature Section: 16.2 Difficulty Level: Hard

12

23) What is the correct IUPAC name for the following compound?

a) (1S, 4R)-bicyclo[2.2.1]hexan-2-one b) (1S, 4R)-bicyclo[2.1.2]heptan-2-one c) (1S, 4R)-bicyclo[2.2.1]heptan-2-one d) (1R, 4S)-bicyclo[2.1.1]heptan-2-one e) (1S, 4S)-bicyclo[2.1.2]heptan-2-one Answer:C Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 24) What is the correct IUPAC name for the following compound?

a) bicyclo[1.1.0]butan-2-one b) bicyclo[1.0.1]butan-2-one c) bicyclo[1.1.0]pentan-2-one d) bicyclo[0.1.1]butan-2-one e) bicyclo[1.0.1]pentan-2-one Answer:A Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 25) What is the correct IUPAC name for the following compound?

13

a) bicyclo[1.1.1]pentan-2-one b) bicyclo[1.1.0]pentan-2-one c) cyclopentanone d) methylenepentan-2-one e) bicyclo[1.0.1]pentan-2-one Answer:B Topic: Nomenclature Section: 16.2 Difficulty Level: Hard O CH3

26) What is the IUPAC name for

CH

CH2

C

OH

C6 H5

a) 4-Oxo-5-phenyl-2-hexanol b) 5-Hydroxy-2-phenyl-3-hexanone c) 2-Hydroxy-5-phenyl-4-hexanone d) 2-Hydroxypropyl-1-phenylethyl ketone e) 5-Hydroxy-3-keto-2-phenylhexane Answer: B Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 27) Which is the proper name for the structure shown? O2 N

CH

O NO2

a) 3-Methyl-5-(1,4-dinitrobenzyl)-1-pentanal b) 3-Methyl-1-(2,5-dinitrophenyl)-5-pentanal c) 3-Methyl-5-(2,5-dinitrophenyl)pentanal d) 3-Methyl-5-(2,5-dinitrophenyl)pentanaldehyde e) 3-Methyl-5-(2,5-dinitrophenyl)pentaldehyde Answer: C Topic: Nomenclature 14

CH3

?

Section: 16.2 Difficulty Level: Hard 28) Which is the proper name for the structure shown? O Cl

a) 3,5-Dimethyl-5-(4-chlorobenzyl)-1-pentanal b) 3-Methyl-5-(4-chlorophenyl)hexanol c) 3,5-Dimethyl-5-(4-chlorophenyl)-1-pentanaldehyde d) 3-Methyl-5-(4-chlorophenyl)-hexanaldehyde e) 3-Methyl-5-(4-chlorophenyl)hexanal Answer: E Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 29) Which is the proper name for the structure shown below? Br O

a) 7-Bromo-1,4-octynal b) 7-Bromo-1,4-octynone c) 2-Bromo-5,7-octynal d) 7-Bromo-7-methyl-1-heptyne-3-ketone e) 7-Bromo-1-octyn-4-one Answer: E Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 30) What is the correct structure for (R)-7-bromo-1-octyn-4-one?

15

Br Br

Br O O

O

II

I

III

Br Br

IV

O

V O

a) I b) II c) III d) IV e) V Answer: A Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 31) What is the correct structure for (S)-7-bromo-1-octyn-4-one? Br Br

Br O O

O

II

I

III

Br Br

IV

O

V O

a) I b) II c) III d) IV e) V Answer: C 16

Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 32) Which is the IUPAC name for the structure shown below? Br

H O

a) (R)-5-Bromo-2-heptanal b) (S)-5-Bromo-2-heptanal c) (R)-5-Bromo-2-heptanone d) (S)-5-Bromo-2-heptanone e) (R)-3-Bromopentyl methyl ketone Answer: C Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 33) Which is the IUPAC name for the structure shown below? H

Br

O

a) (R)-5-Bromo-2-heptanal b) (S)-5-Bromo-2-heptanal c) (R)-5-Bromo-2-heptanone d) (S)-5-Bromo-2-heptanone e) (R)-3-Bromopentyl methyl ketone Answer: D Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 34) What is the correct structure for (R)-5-bromo-2-heptanone?

17

Br

H

Br

Br

H

H

O

H

O

O

II

I

III

H

Br

H

H

Br

O

O

V

IV

a) I b) II c) III d) IV e) V Answer: B Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 35) What is the correct structure for (S)-5-bromo-2-heptanone? Br

H

Br

Br

H

H

H

O

O

II

I

III

H

Br

H

H

Br

O

O

V

IV

18

O

a) I b) II c) III d) IV e) V Answer: E Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 36) Which is the IUPAC name for the structure shown below? O

a) 5-Cyclohexyl-2-hexanal b) 5-Cyclohexyl-2-hexanone c) 5-Cyclohexyl-5-methyl-2-pentanone d) 5-(1-Methylcyclohexyl)-2-pentanone e) 4-(1-Methylcyclohexyl)-2-butanone Answer: E Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 37) What is the correct structure for 4-(1-methylcyclohexyl)-2-butanone?

I

O

IV

III

O

II

V

O

a) I b) II c) III d) IV 19

O

O

e) V Answer: D Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 38) What is the correct structure for (S)-4-cyclohexyl-3-methyl-2-butanone?

I

O

IV

III

O

II

V

O

O

a) I b) II c) III d) IV e) V Answer: C Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 39) What is the correct structure for (S)-4-cyclohexyl-3-methyl-2-butanone?

a) I b) II 20

O

c) III d) IV e) V Answer: E Topic: Nomenclature Section: 16.2 Difficulty Level: Hard 40) Which of the compounds listed below would you expect to have the highest boiling point? (They all have approximately the same molecular weight.) a)Pentane b)1-Butanol c)Butanal d)1-Fluorobutane e)Diethylether Answer: B Topic: Physical Properties, Relationships, Stereochemistry Section: 16.3 Difficulty Level: Easy 41) Stereoisomers can exist in the case of which of the following? a) The hydrazone of butanone b) The oxime of acetone c) The phenylhydrazone of cyclohexanone d) The cyclic acetal formed from propanal and ethane-1,2-diol e) The imine of cyclopentanone Answer: A Topic: Physical Properties, Relationships, Stereochemistry Section: 16.8 Difficulty Level: Medium 42) Stereoisomers can exist in the case of which of the following? a) The hydrazoneof benzophenone b) The oxime of 2-methylcyclopentanone 21

c) The phenylhydrazone of 4-methylcyclohexanone d) The imine of cyclopentanone e) Two of these choices. Answer: B Topic: Physical Properties, Relationships, Stereochemistry Section: 16.8 Difficulty Level: Medium 43) In which of the following reactions is the final product expected to be formed as a racemic mixture? H

a) C6H5MgBr + C6H5C

O

O

b) HCN + c)

CH3CCH3

O

H

+

HCN

H

d) CH3C

+ xs CH3OH + HCl

O O

CH3CHCH2COC2H5

e)

+ (i-Bu)2AlH

CH3

Answer: C Topic: Physical Properties, Relationships, Stereochemistry Section: 16.9 Difficulty Level: Medium 44)Acetals are unstable in the presence of an aqueous solution of which of these? a) HCl b) NaOH c) KHCO3 d) Na2CO3 e) NaCl 22

Answer: A Topic: Reagents Section: 16.7 Difficulty Level: Easy 45) LiAlH4 (LAH) cannot be used to convert carboxylic acids to the corresponding aldehydes because: a) LAH is not sufficiently reactive. b) RCOOH is converted into RCOOLi. c) RCOOH is reduced to RCH2OH. d) RCOOH is reduced to RCH3. e) RCOOH is converted into R2C=O. Answer: C Topic: Reagents Section: 16.4 Difficulty Level: Easy 46) Identify the reagent(s) that would bring about the following reaction: CH3CH2CH2COCl ⎯⎯⎯→

CH3CH2CH2CHO

a) H2/Ni b) Li/liq.NH3 c) LiAlH[OC(CH3)3]3, ether d) NaBH4, CH3OH e) LiAlH4, ether Answer: C Topic: Reagents Section: 16.4 Difficulty Level: Easy 47) Which of these will not catalyze the reaction of a weak nucleophile with the carbonyl group of an aldehyde or ketone? a) Ib) H3O+ 23

c) AlCl3 d) BF3 e) ZnCl2 Answer: A Topic: Reagents Section: 16.6 Difficulty Level: Easy 48) Which reagent(s) could be used to carry out the following transformation? O

?

a) Zn(Hg), HCl, reflux b) LiAlH4, ether c) HSCH2CH2SH, BF3; then Raney Ni (H2) d) All of these choices. e) Two of these choices. Answer: E Topic: Reagents Section: 16.7 Difficulty Level: Medium 49) The following reduction can be carried out with which reagent(s)?

? O

a) Zn(Hg), HCl b) i) HSCH2CH2SH, BF3 ; ii)Raney Ni (H2) c) H2NNH2, KOH d) None of these choices. e) All of these choices. Answer:E Topic: Reagents Section: 16.7 24

Difficulty Level: Medium 50) The following reduction can be carried out with which reagent(s)?

? O

a) Zn(Hg), HCl b) i) HSCH2CH2SH, BF3 ; ii)Raney Ni (H2) c) NaBH4, CH3OH d) Zn(Hg), HCl and i) HSCH2CH2SH, BF3 ; ii)Raney Ni (H2) e) Zn(Hg), HCl and NaBH4, CH3OH Answer: D Topic: Reagents Section: 16.7 Difficulty Level: Medium 51) Which reagent will not differentiate between 3-butenal and 2-butanone? a) Br2/CCl4 b) Ag2O,OHc) H2NNHC6H5 d) KMnO4,OHe) None of these choices. Answer: C Topic: Reagents Section: 16.8 Difficulty Level: Medium H

H

52) The compound C6H5C N N CC6H5 is produced by the reaction of an excess of benzaldehyde with which compound? a) Ammonia b) Hydrazine c) Nitrogen d) Phenylhydrazine e) Hydroxylamine 25

Answer: B Topic: Reagents Section: 16.8 Difficulty Level: Medium 53) The migratory aptitude for groups attached to a ketone or aldehyde carbonyl during the Baeyer-Villiger oxidation is: a) H >Ph- > 3° alkyl > 2° alkyl > 1° alkyl > methyl b) Ph- > H>3° alkyl>2° alkyl>1° alkyl>methyl c) 3° alkyl > 2° alkyl > 1° alkyl > methyl>H >Phd) 3° alkyl > 2° alkyl > 1° alkyl > methyl>Ph->H e) H > 3° alkyl > 2° alkyl > 1° alkyl > methyl>PhAnswer:A Topic: Mechanisms Section: 16.12 Difficulty Level: Medium 54) Dissolving benzaldehyde in methyl alcohol establishes an equilibrium with what compound? OH

a) C6H5CHOCH3 O

b) C6H5COCH3 c) C6H5C(OCH3)3 OH

O

d) C6H5CHOCH3 and C6H5COCH3 O

e) C6H5COCH3 andC6H5C(OCH3)3 Answer: A Topic: Reaction Products Section: 16.7 Difficulty Level: Easy 55) Select the structure of the major product in the following reaction. 26

i) BH3 ii) H2O2,OH-, H2O

?

a) Ethylbenzene b) 1-Phenylethanol c) Acetophenone d) 2-Phenylethanal e) Vinylbenzene Answer: D Topic: Reaction Products Section: 16.4 Difficulty Level: Medium 56) Select the structure of the major product in the following reaction.

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

27

Answer:D Topic: Reaction Products Section: 16.12 Difficulty Level: Medium 57) Select the structure of the major product in the following reaction. O

CH3COOOH

a) I b) II c) III d) IV e) V Answer:C Topic: Reaction Products Section: 16.12 Difficulty Level: Medium 58) Select the structure of the major product in the following reaction.

28

a) I b) II c) III d) IV e) V Answer:A Topic: Reaction Products Section: 16.12 Difficulty Level: Medium 59) Select the structure of the major product in the following reaction.

29

a) I b) II c) III d) IV e) V Answer:B Topic: Reaction Products Section: 16.12 Difficulty Level: Medium 60) Select the structure of the major product in the following reaction.

30

a) I b) II c) III d) IV e) V Answer:C Topic: Reaction Products Section: 16.12 Difficulty Level: Medium 61) Select the structure of the major product in the following reaction.

31

a) I b) II c) III d) IV e) V Answer:C Topic: Reaction Products Section: 16.12 Difficulty Level: Medium 62) Select the structure of the major product in the following reaction.

32

a) I b) II c) III d) IV e) V Answer:C Topic: Reaction Products Section: 16.12 Difficulty Level: Medium 63) Select the structure of the major product in the following reaction.

i) BH3 ii) H2O2,OH-, H2O

?

33

OH

O

OH

II

I

III

H

O

IV

V

a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 16.4 Difficulty Level: Medium 64) What is the final product, Z, of the following synthesis?

1. KMnO4,

CH3

OH-,

heat

2. H3O+

X

SOCl2

Y

1. LiAlH(O-t-Bu)3 ether, -78 oC 2. H2O

O

O

O

O

O

COAl(t-Bu)2

COCH3

CH

COLi

COH

I

II

III

a) I b) II c) III d) IV e) V 34

IV

V

Z

Answer: C Topic: Reaction Products Section: 16.4 Difficulty Level: Medium 65) Select the structure of the major product in the following reaction. H2SO4 ? HgSO4, H2O a) Ethylbenzene b) 1-Phenylethanol c) Acetophenone d) 2-Phenylethanal e) Vinylbenzene Answer: C Topic: Reaction Products Section: 16.5 Difficulty Level: Medium 66) Select the structure of the major product in the following reaction.

H2SO4 HgSO4, H2O

? OH

O

II

I

III

H

O

IV

V

a) I b) II 35

c) III d) IV e) V Answer: C Topic: Reaction Products Section: 16.5 Difficulty Level: Medium 67) Select the structure of the major product in the following reaction. i.) KMnO4, OH-, hot ?

ii) H3O+

OH

OH

II

I

III

OH

IV

O

V

a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 16.5 Difficulty Level: Medium 68) Select the structure of the major product in the following reaction. i.) KMnO4, OH-, hot ?

ii) H3O+

a) cyclopentanol 36

b) 1-cyclopentylcyclopentane c) cyclopentanone d) cyclopentene e) 1-(1-hydroxycyclopentyl)-1-hydroxycyclopentane Answer: C Topic: Reaction Products Section: 16.5 Difficulty Level: Medium 69) What would be the product of the following reaction sequence? O

1. DIBAL-H, -78oC.

?

O

2. H2O

O OH

O

O H

II

I O

O

III OH

O

H

IV

OH

V

a) I b) II c) III d) IV e) V Answer:C Topic: Reaction Products Section: 16.4 Difficulty Level: Medium

37

70) The product, K, of the following sequence of reactions CH3 CH3CHCOCl

Benzene

AlCl3 OH

I

CH3CH2MgBr ether

J

H3O+

K would be:

OH

HO

O

O

I

II

III

IV

a) I b) II c) III d) IV e) V Answer: B Topic: Reaction Products Section: 16.5 and 16.6 Difficulty Level: Medium 71) The product, K, of the following sequence of reactions would be:

38

V

MgBr

AlCl3

I

H3O+

J

K

heat

ether Cl

(-H2O)

O O HO

I

III

II

OH

V

IV

a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 16.5 and 16.6 Difficulty Level: Medium 72)The product, J, of the following sequence of reactions would be:

39

a) I b) II c) III d) IV e) None of these choices. Answer:B Topic: Reaction Products Section: 16.5 and 16.6 Difficulty Level: Medium 73) The product, E, of the following sequence of reactions

would be:

40

O

OH

III

II

I O

Cl

V

IV

a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 16.5 and 16.7 Difficulty Level: Medium 74) The product, E, of the following sequence of reactions

would be:

41

a) I b) II c) III d) IV e) None of these choices. Answer:B Topic: Reaction Products Section: 16.5 and 16.12 Difficulty Level: Medium 75) The product, E, of the following sequence of reactions OH

SH

PCl5 A

AlCl3

HS

D

B BF3

O

+ C (discard)

would be:

42

Raney Ni H2

E

O

III

II

I O

Cl

V

IV

a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 16.5 and 16.7 Difficulty Level: Medium 76) The product, C, of the following reaction sequence, O

+

CH3CCH3

CN

HCN

C4H7NO

CH3

a) CH2 CCOOH b) CH3CH2COOCH3 CH3CHCH3 CN c) d) CH3CH=CHCOOH e) None of these choices.

Answer: A Topic: Reaction Products 43

H2O H2SO4 heat

C

would be:

Section: 16.9 Difficulty Level: Medium 77) The product, D, of the following reaction sequence, O -

CN

HCN

HCl C4H7NO

H2 O heat

CH3

a) CH2 CCOOH b) CH3CH2COOCH3 CH3CHCH3 CN c) d) CH3CH=CHCOOH

HO

D

COOH

e) Answer: E Topic: Reaction Products Section: 16.9 Difficulty Level: Medium 78) What is the major product of the following reaction sequence?

44

would be:

HCN

H3O+

LiAlH4

?

O

OH

OH CN

NH2

CN

I

OH

III

II

OH

COOH

V

a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 16.9 Difficulty Level: Medium 79) What is the major product of the following reaction sequence?

45

IV

HCN

HCl

O

H2O heat

OH

OH

OH CN

NH2

CN

OH

III

II

I

IV

OH

COOH

V

a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 16.9 Difficulty Level: Medium 80) What is the major product of the following reaction sequence? O

HCN

H2SO4 H2O heat CN

NOSO3H

OSO3H

CN

COH

H CNH2

O

I

II

III

IV

a) I b) II c) III d) IV e) V 46

V

Answer: B Topic: Reaction Products Section: 16.9 Difficulty Level: Medium 81) The product, H, of the following reaction sequence, O

C6H5CH2Br + (C6H5)3P

F

C6H5Li

G

ether

would be: CH3 C6H5CH2CC6H5

a)

OH O

b) C6H5CH2CC6H5 C6H5CH

CHCC6H5

O c) d) C6H5CH2CH=CHC6H5 C6H5CH

e)

CCH3 C6H5

Answer: E Topic: Reaction Products Section: 16.10 Difficulty Level: Medium 82) What would be the final product? O

(C6H5)3P

CH3I

C6H5CCH3

ether

C6H5C

a)

C6H5Li

CH2

CH3

47

?

C6H5CCH3

H

C 6 H5 C6H5CCH3 CH3 b) c) C6H5CH=CHCH3 OH C6H5CCH3

d)

CH3

C6H5CH

CC6H5 CH3

e) Answer: A

Topic: Reaction Products Section: 16.10 Difficulty Level: Medium 83) What would be the final product? O

CH3I C6H5C

a)

P(OEt)3

+

NaH

?

CH2

CH3 C 6 H5 C6H5CCH3

CH3 b) c) C6H5CH=CHCH3 OH C6H5CCH3

d)

CH3 C6H5CH CC6H5

e)

CH3

Answer: A

48

Topic: Reaction Products Section: 16.10 Difficulty Level: Medium 84) What is the reactant W in the synthesis given below?

O

Ph3P +

C6H5Li

W

Wittig reagent

a) Cyclopentanone b) Cyclopentene c) Cyclopentanol d) Bromocyclopentane e) Triphenylphosphine oxide Answer: D Topic: Reaction Products Section: 16.10 Difficulty Level: Medium 85) Predict the major organic product of the following reaction: H

Ag(NH3)2+

O

?

H2O

O O O

HO2C

I

O O

H3C

II

H

OH O

H H 3C

H3C

III

O

IV

a) I b) II 49

O

V

c) III d) IV e) V Answer:B Topic: Reaction Products Section: 16.12 Difficulty Level: Medium 86) The product, H, of the following reaction sequence, O

Br

+

P(OEt)3

F

NaH

G

would be: CH3 C6H5CH2CC6H5

a)

OH O

b) C6H5CH2CC6H5 C6H5CH

CHCC6H5

O c) d) C6H5CH2CH=CHC6H5 C6H5CH

e)

CCH3 C6H5

Answer: E Topic: Reaction Products Section: 16.10 Difficulty Level: Hard 87) What would be the product of the following reaction sequence?

50

H

OH

i) SOCl2 ii) C6H6, AlCl3 iii) HSCH2CH2SH, BF3 iv) Raney Ni (H2)

O

O

?

OH

O OH

II

I

III

V

IV

a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 16.5 and 16.7 Difficulty Level: Hard 88) What would be the product of the following reaction sequence? OH O

i) PCl3 ii) C6H6, AlCl3 iii) HSCH2CH2SH, BF3 iv) Raney Ni (H2)

O

?

OH

II

I

III

OH

IV

V

51

a) I b) II c) III d) IV e) V Answer: B Topic: Reaction Products Section: 16.5 and 16.7 Difficulty Level: Hard 89) What would be the product of the following reaction sequence? OH i) PCl3 ? ii) C6H6, AlCl3 O iii) Zn(Hg), HCl, heat

O

O

OH OH

I

II

IV

III

V

a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.9 and 16.5 Difficulty Level: Hard 90) What would be the product of the following reaction sequence?

52

OH O

i) PCl3 ii) C6H 6, AlCl 3 iii) H 2NNH2, KOH

O

?

OH

O OH

I

II

III

IV

V

a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 16.5 and 16.8 Difficulty Level: Hard 91) What would be the product of the following reaction sequence? OH i) PCl5 ? ii) C6H6, AlCl3 O iii) Zn(Hg), HCl, heat

O

OH

O OH

II

I

IV

III

V

53

a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.9 and 16.5 Difficulty Level: Hard 92) What would be the product of the following reaction sequence?

a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 16.5 and 16.8 Difficulty Level: Hard 93) What would be the product of the following reaction sequence?

54

OH O

i) SOCl2 ii) C6H6, AlCl3 iii) Zn(Hg), HCl, heat

O

?

OH

O OH

II

I

IV

III

V

a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 15.9 and 16.5 Difficulty Level: Hard 94) What would be the product of the following reaction sequence?

55

a) I b) II c) III d) IV e) V Answer: E Topic: Reaction Products Section: 16.5 and 16.8 Difficulty Level: Hard 95) What would be the product of the following reaction sequence? OH O

i) PCl3 ii) C6H6, AlCl3 iii) NaBH4, H2O

?

O

OH

II

I

III

OH OH

IV

V

a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 16.5 Difficulty Level: Hard 96) What would be the product of the following reaction sequence?

56

OH O

i) PCl3 ii) C6H6, AlCl3 iii) LiAlH4 iv) H2O

?

O

OH

II

I

III

OH OH

V

IV

a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 16.5 Difficulty Level: Hard 97) What would be the product of the following reaction sequence? OH O

i) PCl3 ii) C6H6, AlCl3 iii) Zn(Hg), HCl, heat

?

O

OH

II

I

III

OH OH

IV

V

57

a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 15.9 and 16.5 Difficulty Level: Hard 98) What would be the product of the following reaction sequence?

a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 16.5 and 16.8 Difficulty Level: Hard

58

99) The product, E, of the following reaction sequence, PCl5 C6H6 NaBH4 CH3CH2COOH C D AlCl3 CH3OH

CH2CH2CH3

I

E

would be:

O

OH

O

COCH2CH3

CHCH2CH3

CCH2CH3

CH(CH3)2

IV

V

II

III

a) I b) II c) III d) IV e) V Answer: C Topic: Reaction Products Section: 16.5 Difficulty Level: Hard 100) The product, D, of the following sequence of reactions O

SOCl2

CH3CH2COH

A

toluene AlCl3

Zn(Hg)

B

HCl

+

D

C (discard)

would be: O CH3

CH2CH2CH3

CH3CH2CCH2

I

CH3

O CH3

II

CH2CH2CH2Cl

CH2CH2CCl

III CH3 CH CH3

CH3

IV

V

a) I b) II c) III 59

d) IV e) V Answer: A Topic: Reaction Products Section: 15.9 and 16.5 Difficulty Level: Hard 101) The product, D, of the following sequence of reactions

would be: O CH3

CH2CH2CH3

CH3CH2CCH2

I

CH3

O CH3

II

CH2CH2CH2Cl

CH2CH2CCl

III CH3 CH CH3

CH3

IV

V

a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 16.5 and 16.8 Difficulty Level: Hard 102)The product, D, of the following sequence of reactions

60

would be: O CH3

O

CH3CH2CCH2

CH2CH2CH3

I

CH3

CH2CH2CCl

II

CH3

III

CH2CH2CH2Cl

CH3 CH CH3

CH3

IV

V

a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 16.5 and 16.7 Difficulty Level: Hard 103) The product, E, of the following reaction sequence, OH

PCl5

C6H6 C

AlCl3

D

LAH

E

would

O

be: CH2CH2CH3

I

O

OH

O

COCH2CH3

CHCH2CH3

CCH2CH3

CH(CH3)2

IV

V

II

III

a) I b) II c) III d) IV 61

e) V Answer: C Topic: Reaction Products Section: 16.5 Difficulty Level: Hard 104) What is the final product of this synthetic sequence? Benzene

Br2

Mg

FeCl3

ether

1. C6H5CHO

H2Cr2O4

2. H3O+

acetone

O

a) C6H5CC6H5 b) p-BrC6H4CH2C6H5 c) C6H5CH2COOH O

d) C6H5CH2CC6H5 e) C6H5CH2C6H5 Answer: A Topic: Reaction Products Section: 16.5 Difficulty Level: Hard 105) Select the structure of the major product in the following reaction.

i) H2, Lindlar catalyst ii) O3 iii)Zn, CH3CO2H a) 4-Methylhexanal b) 4-Methyl-1-hexanol c) 3-Methylhexanal d) 4,10-Dimethyldodecane-6,7-dione e) 4,10-Dimethyldodecane-6,7-diol Answer: A 62

?

?

Topic: Reaction Products Section: 16.4 Difficulty Level: Hard 106) Select the structure of the major product in the following reaction. i) H2, P-2 ii) O3 iii)Zn, CH3CO2H

?

a) 4-Methylhexanal b) 4-Methyl-1-hexanol c) 3-Methylhexanal d) 4,10-Dimethyldodecane-6,7-dione e) 4,10-Dimethyldodecane-6,7-diol Answer: A Topic: Reaction Products Section: 16.4 Difficulty Level: Hard 107) Select the structure of the major product in the following reaction. i) H2, Ni2B ii) O3 iii)Zn, CH3CO2H

?

a) 4-Methylhexanal b) 4-Methyl-1-hexanol c) 3-Methylhexanal d) 4,10-Dimethyldodecane-6,7-dione e) 4,10-Dimethyldodecane-6,7-diol Answer: A Topic: Reaction Products Section: 16.4 Difficulty Level: Hard 108) Select the structure of the major product in the following reaction.

63

i) Li, NH3(l) ii) O3 iii)Zn, CH3CO2H

?

a) 3-Methylhexanal b) 4-Methyl-1-hexanol c) 4-Methylhexanal d) 4,10-Dimethyldodecane-6,7-dione e) 4,10-Dimethyldodecane-6,7-diol Answer: C Topic: Reaction Products Section: 16.4 Difficulty Level: Hard 109) What new compound will eventually be formed when HCl is added to a solution of pentanal in methanol? a) 1-Chloro-1-methoxypentane b) 1,1-Dimethoxypentane c) 1,1-Dihydroxypentane d) 1,1-Dichloropentane e) 1-Chloro-2-methoxypentane Answer: B Topic: Reaction Products Section: 16.7 Difficulty Level: Hard 110) What is the major product of the following reaction sequence?

64

H2SO4

HCN

H3O+

LiAlH4

?

O

H2 O heat

OH

OH CN

NH2

CN

OH

III

II

I

IV

OH

COOH

V

a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 16.9 Difficulty Level: Hard 111) What is the major product of the following reaction sequence? HCN

LiAlH4

HCl

H3O+

?

O

H2O heat

OH

OH

OH CN

NH2

CN

I

OH

III

II

IV

OH

COOH

V

65

a) I b) II c) III d) IV e) V Answer: D Topic: Reaction Products Section: 16.9 Difficulty Level: Hard 112) Select the structure of the major product in the following reaction.

i) H2, Lindlar catalyst ii) O3 iii)Zn, CH3CO2H O

? O

OH

H

I

H

III

II OH

O

OH

O

V

IV

a) I b) II c) III d) IV e) V Answer: A Topic: Reaction Products Section: 16.4 Difficulty Level: Hard 113) Which of the following reactions would yield benzaldehyde?

66

OH-

C6H5CH2Cl

H2O heat H3O+

a)

b) C6H5CH(OCH3)2

1. LiAlH4, ether

C6H5COOH

2. H2O c) d) Two of these choices. e) All of these choices.

Answer: B Topic: Synthesis Section: 16.7 Difficulty Level: Easy 114) Which of the following procedures would not yield 3-pentanone as a major product?

a) b)

H3O+

CH3CH2MgBr

CH3CH2CN

ether 1. O3 2. Zn/H+

c) d)

CH3CH2CN H

H3O+

CH3CH2Li ether CH3CH2MgBr

H3O+

ether

CH2Cl2

O

e)

CH3CH2CO2H

PCC

CH3CH2MgBr

H3O+

ether

Answer: E Topic: Synthesis Section: 16.4 Difficulty Level: Medium 115) A good synthesis of 67

H O

would be: H

H2O, H2SO4

I

HgSO4

1. DIBAL-H/-78oC

CN

II

2. H2O

H

1. O3

III

2. Zn/H+

OH

IV

1. KMnO4, NaOH, heat 2. H3O+

a) I b) II c) III d) IV e) All of these are equally useful. Answer: B Topic: Synthesis Section: 16.4 Difficulty Level: Medium 116) A good synthesis of

68

H O

would be: H

H2O, H2SO4

I

HgSO4

COOCH3

II

1. DIBAL-H/-78oC 2. H2O

H

1. O3

III

2. Zn/H+

OH

IV

1. KMnO4, NaOH, heat 2. H3O+

a) I b) II c) III d) IV e) All of these are equally useful. Answer: B Topic: Synthesis Section: 16.4 Difficulty Level: Medium 117) A good synthesis of

69

H O

would be: H

H2O, H2SO4

I

HgSO4 H

1. O3

II

2. Zn/H+

COCl

III

1. LiAl(OC(CH3)3)3H 2. H3O+

OH

IV

1. KMnO4, NaOH, heat 2. H3O+

a) I b) II c) III d) IV e) All of these are equally useful. Answer: C Topic: Synthesis Section: 16.4 Difficulty Level: Medium 118) A good synthesis of

70

H O

would be: H

H2O, H2SO4

I

HgSO4 H

1. O3

II

2. Zn/H+

PCC III

CH2Cl2

OH

OH

IV

1. KMnO4, NaOH, heat 2. H3O+

a) I b) II c) III d) IV e) All of these are equally useful. Answer: C Topic: Synthesis Section: 16.4 Difficulty Level: Medium 119) A good synthesis of

71

H O

would be: H

H2O, H2SO4

I

HgSO4 H

1. O3

II

2. Zn/H+

1. DMSO, (COCl)2 III

2. Et3N

OH

OH

IV

1. KMnO4, NaOH, heat 2. H3O+

a) I b) II c) III d) IV e) All of these are equally useful. Answer: C Topic: Synthesis Section: 16.4 Difficulty Level: Medium 120) A good synthesis of

72

H O

would be: H

1. BH3

I

2.H2O2, NaOH

1. DIBAL-H/-78oC

CN

II

2. H2O

COOCH3

III

1. DIBAL-H/-78oC 2. H2O

COCl

IV

1. LiAl(OC(CH3)3)3H 2. H3O+

a) I b) II c) III d) IV e) All of these are equally useful. Answer: E Topic: Synthesis Section: 16.4 Difficulty Level: Medium 121) Which synthesis or syntheses would yield propanal? CH3CH2CH2OH

a)

PCC CH2Cl2

73

O CH3CH2CCl

LiAlH[OC(CH3)3]3 ether, -78 oC

b) CH3C

CH

1. Sia2BH

2. H2O2, OHc) d) All of these choices. e) None of these choices. Answer: D Topic: Synthesis Section: 16.4 Difficulty Level: Medium 122) Which synthesis or syntheses would yield propanal?

a) O CH3CH2CCl

LiAlH[OC(CH3)3]3 ether, -78 oC

b) CH3C

CH

1. Sia2BH

2. H2O2, OHc) d) All of these choices. e) None of these choices. Answer: D Topic: Synthesis Section: 16.4 Difficulty Level: Medium 123) Which synthesis or syntheses would yield propanal? CH3CH2CH2OH

a)

PCC CH2Cl2

74

O CH3CH2CCl

LiAlH[OC(CH3)3]3

b)

ether, -78 oC

c) d) All of these choices. e) None of these choices. Answer: D Topic: Synthesis Section: 16.4 Difficulty Level: Medium 124) Which synthesis or syntheses would yield propanal? CH3CH2CH2OH

a)

PCC CH2Cl2

b)

c) d) All of these choices. e) None of these choices. Answer: D Topic: Synthesis Section: 16.4 Difficulty Level: Medium 125) Which synthesis or syntheses would yield propanal?

a)

75

b)

c) d) All of these choices. e) None of these choices. Answer: D Topic: Synthesis Section: 16.4 Difficulty Level: Medium 126) Which of the reactions listed below would serve as a synthesis of acetophenone, O C6H5CCH3

?

a) OH

PCC CH2Cl2

b) C6H6 + CH3COCl c) C6H5CN + CH3Li d) Two of these choices. e) All of these choices.

AlCl3 ether

H3O+

Answer: E Topic: Synthesis Section: 16.5 Difficulty Level: Medium 127) Which of the reactions listed below would serve as a synthesis of acetophenone, O C6H5CCH3

?

76

a)

AlCl3

b) C6H6 + CH3COCl

H3O+

ether

c) C6H5CN + CH3Li d) Two of these choices. e) All of these choices. Answer: E Topic: Synthesis Section: 16.5 Difficulty Level: Medium

128) Which of the following would yield 3-pentanone as the major product? a) CH3CH2CN + CH3CH2Li

ether

Product

H3O+

b) ether CN

+

Product

MgBr

c) PCC CH2Cl2 OH

d) Two of these choices. e) All of these choices. Answer: E Topic: Synthesis Section: 16.5 Difficulty Level: Medium 129) Which sequence of reactions would be utilized to convert

77

H3O+

O

CO2CH3

into

O

CH3 C CH3

?

OH

a) 2CH3MgBr, then NH4+ b) HOCH2CH2OH, H3O+; LiAlH4, ether; 2CH3MgBr, then NH4+ c) HOCH2CH2OH, H3O+; 2CH3MgBr, then NH4+ d) HOCH2CH2OH, H3O+; H2, Pt; CH3OH, NH4+ e) None of these choices. Answer: C Topic: Synthesis Section: 16.7 Difficulty Level: Medium O

130) Which of the following procedures would not yield (CH3)2CHCH as a product? PCC I OH CH2Cl2 SOCl2

II

CO2H

ether, -78 oC O3

III

Zn HOAc

KMnO4

IV

V

LiAlH(O-t-Bu)3

OH

O

H3 O +

NaOH H3 O +

O

a) I b) II c) III d) IV e) V Answer: D Topic: Synthesis Section: 16.4 and 16.7 78

Difficulty Level: Medium O

131) Which of the following procedures would not yield (CH3)2CHCH as a product?

a) I b) II c) III d) IV e) V Answer: D Topic: Synthesis Section: 16.4 and 16.7 Difficulty Level: Medium 132) Which reaction sequence would be used to prepare

79

?

I

O

O

II

H

III

+

MgBr

+ 2 CH3MgBr (C6H5)3P

1. ether

H2

2. H3O+

Ni

1. ether

H2

2. H3O+

Ni

C6H5Li

cyclopentanone

Ni

Cl

O

IV

H2

H 3O +

CH3MgBr ether

a) I b) II c) III d) IV e) All of these choices would yield the product. Answer: C Topic: Synthesis Section: 16.10 Difficulty Level: Medium 133) Which Wittig reagent would be used to synthesize ?

CH3CH=P(C6H5)3

CH=P(C6H5)3

I

P(C6H5)3

II

III

a) I b) II c) III d) IV e) Either I or II could be used. 80

CH3CH2CH=P(C6H5)3 IV

Answer: E Topic: Synthesis Section: 16.10 Difficulty Level: Medium 134) Which of the following is not a synthesis of benzophenone, O C6H5CC6H5

? O

a) C6H6 + C6H5CCl b) c) d)

(C6H5)2CHOH (C6H5)2CH=CH2

AlCl3

H2CrO4 acetone 1. O3 2. Zn, HOAc

PCC Ph2CHOH

CH2Cl2

e) All of these choices will give benzophenone. Answer: E Topic: Synthesis Section: 16.5 Difficulty Level: Medium 135) Which of the following is not a synthesis of benzophenone, O C6H5CC6H5

? O

a) C6H6 + C6H5CCl b)

(C6H5)2CHOH

AlCl3

H2CrO4 acetone

81

c) d)

(C6H5)2CH=CH2

1. O3 2. Zn, HOAc

e) All of these choices will give benzophenone. Answer: E Topic: Synthesis Section: 16.5 Difficulty Level: Medium 136) Which of the following is not a synthesis of benzophenone, O C6H5CC6H5

? O

AlCl3

a) C6H6 + C6H5CCl PCC

b) c) d)

Ph2CHOH

CH2Cl2

(C6H5)2CH=CH2

1. O3 2. Zn, HOAc

e) All of these choices will give benzophenone. Answer: E Topic: Synthesis Section: 16.5 Difficulty Level: Medium 137) A good synthesis of

82

H O

would be: H

H2O, H2SO4

I

HgSO4 H

1. Sia2BH

II

2. H2O2, NaOH H

1. O3

III

2. Zn, HOAc OH

IV

1. KMnO4, NaOH, heat 2. H3O+

a) I b) II c) III d) IV e) All of these are equally useful. Answer: B Topic: Synthesis Section: 16.4 Difficulty Level: Hard 138) Which of the following is a synthesis of 3-heptanone?

a) CH3CH2CN

CH3(CH2)2CH2Li

b) CH3CH2CH2CH2OH

c) d)

ether PBr3

H3O+ NaCN

ether

CH3CH2MgBr ether

83

H3O+

1. O3 2. Zn/H+

e) All of these choices are syntheses of 3-heptanone. Answer: E Topic: Synthesis Section: 16.5 Difficulty Level: Hard 139) Which of the following is a synthesis of 3-heptanone?

a) CH3CH2CN

H3 O+

CH3(CH2)2CH2Li

b) CH3CH2CH2CH2OH

ether PBr3

NaCN

CH3CH2MgBr

ether

c) d)

H3O+

ether 1. O3 2. Zn/H+

e) All of these choices are syntheses of 3-heptanone. Answer: E Topic: Synthesis Section: 16.5 Difficulty Level: Hard 140) What, in general, is the order of decreasing reactivity of these carbonyl compounds towards nucleophilic reagents? O CH3CCH3

I

H CH3C

II

H

O O

HC

(CH3)3CCCH3

III

IV

a) I > III > IV> II > V b) IV > II > I > III > V c) V > III > I > II > IV 84

O O

(CH3)3CCC(CH3)3

V

d) I>IV>II>III>V e) III > V > IV > II > I Answer: B Topic: Carbonyl Reactivity Section: 16.6 Difficulty Level: Medium 141) Which of these gem-diols is expected to be the most stable? OH CF3CCF3 OH a) b) CH3CH(OH)2 OH CH3CCH3 OH c) d) C6H5CH(OH)2 e) ClCH2CH(OH)2

Answer: A Topic: Carbonyl Reactivity Section: 16.7 Difficulty Level: Medium 142) Which of these gem-diols is expected to be the least stable? OH CF3CCF3 OH a) b) CH3CH(OH)2 OH CH3CCH3 OH c) d) C6H5CH(OH)2 e) ClCH2CH(OH)2

85

Answer: C Topic: Carbonyl Reactivity Section: 16.7 Difficulty Level: Medium 143) What, in general, is the order of increasing reactivity of these carbonyl compounds towards nucleophilic reagents? H

O CH3CCH3

I

H

O

CH3C

O

II

HC

(CH3)3CCCH3

III

IV

a) I < III < V < II < IV b) IV < II < I < III < V c) V< III < I < II < IV d) II< I < V < III < IV e) III < V < IV < II < I Answer: C Topic: Carbonyl Reactivity Section: 16.6 Difficulty Level: Medium 144) Which of the following compounds is an acetal? O

O

O

O OCH3

I

O

OH

II

O

O

O

IV

III

a) I b) II c) III d) IV e) None of these choices. Answer: C Topic: New Functional Groups Section: 16.7 Difficulty Level: Easy

86

O O

(CH3)3CCC(CH3)3

V

145) Which is the general formula for a thioacetal? H

a) RC

S RCHSR'

b) OH RCHSR'

c)

SH RCHSR'

d)

SR' RCHOR'

e)

SR'

Answer: D Topic: New Functional Groups Section: 16.7 Difficulty Level: Easy 146) Which compound is an acetal? O O O

OH

O

OCH3

II

I

OH

O

III

IV

a) I b) II c) III d) IV e) All of these choices. Answer: B Topic: New Functional Groups Section: 16.7 Difficulty Level: Easy 147) Which compound is a hemiacetal? O O O

I

OH

O

II

OCH3

OH

O

III

IV 87

a) I b) II c) III d) IV e) All of these choices. Answer: A Topic: New Functional Groups Section: 16.7 Difficulty Level: Easy 148) Which of the following is formed when 3-methylcyclopentanone reacts with hydroxylamine? N-NH-C6H5

N-NH2

I

N-OH

II

III NO2

O N

IV

N H

NH2

N

N H

NO2

V

a) I b) II c) III d) IV e) V Answer: C Topic: Reactions of Aldehydes and Ketones Section: 16.8 Difficulty Level: Medium 149) Which of the following is formed when 4-methylpentanal reacts with phenylhydrazine?

88

N-C6H5

N-NH-C6H5

I

N-NH2

II

III

O N

IV

N H

N=N-C6H5

NH2

V

a) I b) II c) III d) IV e) V Answer: A Topic: Reactions of Aldehydes and Ketones Section: 16.8 Difficulty Level: Medium 150) Which of the following is formed when 2,2,3-trimethylcyclohexanone reacts with hydroxylamine? N-NH-C6H5

N-NH2

I

N-OH

III

II

NO2

O N

IV

N H

NH2

N

N H

NO2

V

a) I b) II c) III d) IV e) V Answer: C Topic: Reactions of Aldehydes and Ketones 89

Section: 16.8 Difficulty Level: Medium 151) Which of the following is formed when 2,2,3-trimethylcyclohexanone reacts with hydrazine? N-NH-C6H5

N-NH2

I

N-OH

III

II

NO2

O N

N H

NH2

IV

N

N H

NO2

V

a) I b) II c) III d) IV e) V Answer: B Topic: Reactions of Aldehydes and Ketones Section: 16.8 Difficulty Level: Medium 152) A compound with formula C5H10O gives two signals only, both singlets, in the 1H NMR spectrum. Which of these structures is a possible one for this compound? O

a) CH3CH2CCH2CH3 O

b) (CH3)2CHCCH3 H

c) (CH3)3CC

O H

CH3CH2CHC

d)

O

CH3

90

H

e) (CH3)2CHCH2C

O

Answer: C Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 153) A compound with formula C5H10O gives two signals only, one a triplet and the other a quartet, in the 1H NMR spectrum. Which of these structures is a possible one for this compound? O

a) CH3CH2CCH2CH3 O

b) (CH3)2CHCCH3 H

c) (CH3)3CC

O H

CH3CH2CHC

d)

O

CH3

H

e) (CH3)2CHCH2C

O

Answer: A Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 154) The1H NMR spectrum of a compound with formula C7H14O gives three signals. Which of these structures is a possible one for this compound? a) 2-Heptanone b) 3-Heptanone c) 2,4-Dimethyl-3-pentanone d) 2,2-Dimethyl-3-pentanone e) Two of these choices. Answer: D 91

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 155) The1H NMR spectrum of a compound with formula C7H14O gives two signals. Which of these structures is a possible one for this compound? a) 2-Heptanone b) 3-Heptanone c) 2,4-Dimethyl-3-pentanone d)2,2-Dimethyl-3-pentanone e) Two of these choices. Answer: C Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 156) The13C NMR spectrum of a compound with formula C7H14O gives three signals. Which of these structures is a possible one for this compound? a) 2-Heptanone b) 3-Heptanone c) 2,2-Dimethyl-3-pentanone d) 2,4-Dimethyl-3-pentanone e) Two of these choices. Answer: D Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 157) The13C NMR spectrum of a compound with formula C7H14O gives five signals. Which of these structures is a possible one for this compound? a) 2-Heptanone b) 3-Heptanone c) 2,2-Dimethyl-3-pentanone d) 2,4-Dimethyl-3-pentanone e) Two of these choices. 92

Answer: C Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 158) The1H NMR spectrum of a compound with formula C7H14O gives a doublet at 9.2 ppm. Which of these structures is a possible one for this compound? a) 2-Methyl-3-hexanone b) 2-Methylhexanal c) 2,2 -Dimethylpentanal d) 2,2-Dimethyl-3-pentanone e) Two of these choices. Answer: B Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium Question type: Molecular Drawing 159) Suggest a synthetic strategy for the synthesis of 4-methylpentanal from 3-methyl-1bromobutane.

Answer:

Br

NaCN

CN

i. DIBAL-H ii. H2O

O

Topic: Synthetic Strategy Section: 16.4 Difficulty Level: Medium 160) Suggest a synthetic strategy for the synthesis of 3-heptanone from 1-bromobutane. Br

NaCN

Answer:

CN

i. C2H5Li, Et2O ii. H3O+

Topic: Synthetic Strategy 93

O

Section: 16.5 Difficulty Level: Medium 161) Suggest a synthetic strategy for the synthesis of 4-methylpentanal from 3-methyl-1bromobutane. Answer: HBr Br

ROOR

NaCN

CN

i. DIBAL-H ii. H2O

O

Topic: Synthetic Strategy Section: 16.5 Difficulty Level: Hard 162) Suggest a synthetic strategy for the synthesis of 6-methyl-3-heptanol from 4methylpentanenitrile, (CH3)2CHCH2CH2CN.

i. DIBAL-H

CN

ii. H2O

OH

iii. C2H5MgBr, Et2O iv. H3O+ OR i. C2H5MgBr, Et2O CN

ii. H3O+

OH

iii. NaBH4, H2O

Answer:

Topic: Synthetic Strategy Section: 16.5 Difficulty Level: Hard 163) Suggest a synthetic strategy for the synthesis of 3-heptanone from 1-butene. Answer: HBr ROOR

Br

NaCN

CN

i. C2H5Li, Et2O ii. H3O+ O

Topic: Synthetic Strategy 94

Section: 16.5 Difficulty Level: Hard 164) Cis-stilbene (cis-1,2-diphenylethene) can be prepared in high yield from its trans diastereomer. Propose a reasonable synthesis. Ph

H

H

H

H

Ph

Ph

Ph

multiple steps cis-stilbene

trans-stilbene

Answer: Ph

H

O

m-CPBA H

Ph

Ph

H

H

O

PPh3

H

H

Ph3P Ph

Ph

H

Ph

Ph

Topic: Synthetic Strategy Section: 16.10 Difficulty Level: Hard 165) Complete the following reaction sequence, giving structural details of all significant intermediates and the final product. O

H

H+

OH

Answer: O OH H

H+ O

OH

Topic: Reaction Sequence Section: 16.7 Difficulty Level: Medium

95

H

Ph

166) In the total synthesis of the Cecropia juvenile hormone, the following sequence of reactions were used. Draw the intermediate and final product formed. HO

/ H+

H

1. CH3Li

O

?

2. H+/H2O O

Answer: HO

O

O

/ H+

H

H

O

1. CH3Li 2. H+/H2O

O O

HO H

HO CH3

Topic: Reaction Sequence Section: 16.7 Difficulty Level: Hard 167) Complete the following reaction sequence, giving structural details of all significant intermediates. O H

1. OsO4 2. NaHSO3

? H+

Answer: O OH

H

1. OsO4 2. NaHSO3

H+

O

O

OH

Topic: Reaction Sequence Section: 16.7 96

Difficulty Level: Hard 168) Complete the following reaction sequence, giving structural details of all significantintermediates and the final product. O

KMnO4, OH-, heat

H+

+

HO

H+

H

?

H2 O

O

Answer: O O

+

H+ HO

KMnO4, OH-, heat

H O

O

O

H O

O

H+ O

O

HO

H2O

O

OH

Topic: Reaction Sequence Section: 16.7 Difficulty Level: Hard 169) Complete the following reaction sequence, giving structural details of all significant intermediates X, Y, and final product Z. CH3

1. KMnO4,

OH-,

heat

2. H3O+

COOH

X

X

SOCl2

COCl

Y

Y

1. LiAlH(O-t-Bu)3 ether, -78 oC 2. H2O

Z

CHO

Z

Answer: Topic: Reaction Sequence Section: 16.4 Difficulty Level: Hard 170) Complete the following reaction sequence, giving structural details of all significant intermediates.

97

i. Br2, hν ii. Mg, CH3CH2CN iii. H3O+ iv. NaBH4

?

Answer: O

NaBH4

Br i. Mg, CH CH CN 3 2

Br2, hν

HO

ii. H3O+

Topic: Reaction Sequence Section: 16.5 Difficulty Level: Hard 171) Complete the following reaction sequence, giving structural details of all significant intermediates. i. O3 i. EtMgBr ? + ii.Zn, CH3CO2H ii. H3O , heat O

O

i. EtMgBr ii. H3O+, heat

i. O3 ii.Zn, CH3CO2H

HO

O O

Answer: Topic: Reaction Sequence Section: 16.5 Difficulty Level: Hard 172) Complete the following reaction sequence, giving structural details of all significant intermediates and the final product. Br2 Mg 1. C6H5CHO H2Cr2O4 Benzene ? FeCl3 acetone ether 2. H3O+ OH Br

MgBr

Answer: Topic: Reaction Sequence Section: 16.5 Difficulty Level: Hard 98

O

173) Complete the following reaction sequence, giving structural details of all significant intermediates and the final product.

Answer: Topic: Reaction Sequence Section: 16.5 and 16.12 Difficulty Level: Hard Question type: Essay 174) Aldehydes are more reactive than ketones towards nucleophilic substitution because of both steric and electronic factors. Briefly explain. a) Steric reasons: ___. b) Electronic reasons: ___. Answer: a) aldehydes have a small hydrogen substituent on one side, so less steric crowding than ketones with alkyl groups either side of the carbonyl carbon. b) aldehydes have only one electron-releasing group to partly neutralize/stabilize the partial positive charge at the carbonyl carbon while ketones have two Topic: Relative Reactivity Section: 16.6 Difficulty Level: Medium Question type: fill-in-the-blank 175) A compound with an OH and OR group attached to the same carbon is known as a(n) ___. Answer: hemiacetal Topic: Hemiacetals Section: 16.7 Difficulty Level: Easy

99

176) A compound with two OH groups attached to the same carbon is known as a(n) ___. Answer: hydrate or gem-diol Topic: Hydrates Section: 16.7 Difficulty Level: Easy 177) A compound with two OR groups attached to the same carbon is known as a(n) ___. Answer: acetal Topic: Acetals Section: 16.7 Difficulty Level: Easy 178) A compound with an OH and CN group attached to the same carbon is known as a(n) ___. Answer: cyanohydrin Topic: Cyanohydrins Section: 16.9 Difficulty Level: Easy 179) A compound containing a C=N double bond is known as a(n) ___. Answer: imine Topic: Imines Section: 16.8 Difficulty Level: Easy 180) 2,4-DNP is a reagent frequently used for functional group tests; it detects the presence of ___. Answer: aldehydes and ketones Topic: Functional Group Tests Section: 16.8 Difficulty Level: Easy

100

181) Oximes are formed when aldehydes and ketones react with ___. Answer:hydroxylamine, NH2OH Topic: Functional Group Tests Section: 16.8 Difficulty Level: Easy 182) The reaction between a phosphorus ylide and an aldehyde or ketone is called the ___ reaction. Answer: Wittig Topic: Wittig Reaction Section: 16.10 Difficulty Level: Easy 183) The driving force for the Wittig reaction is the formation of the very strong ___ bond in ___. Answer: P-O bond; triphenylphosphine oxide Topic: Wittig Reaction Section: 16.10 Difficulty Level: Easy 184) The conversion of a trans epoxide to a cis alkene using triphenylphosphine is an example of a ___ reaction. Answer: stereospecific Topic: General Section: 16.10 Difficulty Level: Hard 185) The conversion of a cis epoxide to a trans alkene using triphenylphosphine is an example of a ___ reaction. Answer: stereospecific Topic: General Section: 16.10 101

Difficulty Level: Hard Question type: Molecular Drawing 186) Draw a complete mechanism, using arrow convention to indicate electron movement, for the following transformation:

Answer: H+

O

O

H H N

H N

H HO

N ~H

H2O

+

N H -H2O

-H+

N

102

N

Topic: Mechanisms Section: 16.8 Difficulty Level: Medium 187) Draw a complete mechanism, using arrow convention to indicate electron movement,for the following transformation: O

H

H

H3C

+

PPh3

+

CH3

H

H

H3 C

Ph3P

O

CH3

Answer:

O H3C

O H

H3C

+

O

PPh3

H

H

PPh3 H3C

CH3

H

H

H

O

PPh3

H

PPh3

rotation 180o as shown

CH3 H

CH3

H

+ H3C

H3C

H3C

Ph3P

O

CH3

H

Topic: Mechanisms Section: 16.10 Difficulty Level: Hard 188) Draw a complete mechanism, using arrow convention to indicate electron movement, for the following transformation: O H

H3 C

H

H3C

+

H

PPh3

+

CH3

H

Answer:

103

CH3

Ph3P

O

O H3C

O H

H3C

H

+

H

O

PPh3

CH3

H

PPh3 H H3C

CH3

O

PPh3

H3C

PPh3

rotation 180o as shown

CH3 CH3

H

CH3

H

+ H

H

Ph3P

O

CH3

H

Topic: Mechanisms Section: 16.10 Difficulty Level: Hard Question type: fill-in-the-blank 189) The Tollens test, used in conjunction with 2,4-DNP, can distinguish between ___ and ___. Answer: aldehydes and ketones Topic: Functional Group Tests Section: 16.13 Difficulty Level: Easy Question type: Essay 190) What reagent would help you distinguish between acetophenone and 2methylbenzaldehyde? Answer: Tollen’s Reagent Topic: Functional Group Tests Section: 16.13 Difficulty Level: Easy 191) Explain clearly how you might use 1H NMR to distinguish between 2-phenylacetaldehyde and acetophenone.

104

Answer: A quick inspection of 1H NMR of the two substances would allow easy identification and distinction between them: the expected 1H NMR spectra of the two substances are described below. 2-Phenylacetaldehyde Acetophenone and C6H5COCH3 C6H5CH2CHO 3 signals 2 signals approximate δ ppm approximateδ ppm singlet (-CH3) 2.0 doublet (-CH2-) 2.5 multiplet (C6H5) 7.2 multiplet (C6H5) 7 triplet(-CHO) 9 Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 192) Propose a structure that fits the following spectroscopic data: C5H10O IR: 1720 cm−1 1

H NMR: 1.9δ (triplet, 3H), 1.7δ (sextet, 2H), 2.1δ (singlet, 3H), 2.4δ (triplet, 2H) O

Answer:

CH3CH2CH2CCH3

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 193) Propose a structure that fits the following spectroscopic data: C5H10O IR: 1720 cm−1 1

H NMR: 1.1δ (triplet, 3H), 2.4δ (quartet, 2H)

Answer:

O

Topic: Spectroscopy Section: 16.14 105

Difficulty Level: Medium 194) Propose a structure that fits the following spectroscopic data: C9H10O IR: 1680 cm−1 1

H NMR: 1.25δ (triplet, 3H), 3.0δ (quartet, 2H), 7-8δ (complexmultiplet, 5H) O

Answer: Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 195) Propose a structure that fits the following spectroscopic data: C7H6O IR: 1703 cm−1 1

H NMR: 7-8δ (complexmultiplet, 5H), 10.0δ (singlet, 1H) O

H

Answer: Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 196) Propose a structure that fits the following spectroscopic data: C3H6O IR: 1730 cm−1 106

1

H NMR: 1.1δ (triplet, 3H), 2.5δ (doubletofquartets, 2H), 9.8δ (doublet, 1H) H

Answer:

O

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 197) Propose a structure that fits the following spectroscopic data: C5H10O IR: 1716 cm−1 Broadband decoupled 13C NMR: 7.93, 35.50, 212.07δ DEPT Experiments show: signal at 7.93 δ as CH3 and signal at 35.50 δ as CH2

Answer:

O

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 198) Propose a structure that fits the following spectroscopic data: C5H10O IR: 1717 cm−1 Broadband decoupled 13C NMR: 13.70, 17.41, 29.78, 45.71, 208.93δ DEPT Experiments show: signals at 13.70, 29.78 δ as CH3 and signals at 17.41, 45.71 δ as CH2 O

Answer: CH3CH2CH2CCH3 107

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 199) Propose a structure that fits the following spectroscopic data: C4H8O IR: 1728 cm−1 Broadband decoupled 13C NMR: 13.71, 15.69, 45.82, 202.80δ DEPT Experiments show: signal at 13.71 δ as CH3 and signals at 15.69, 45.82 δ as CH2 O

Answer:

H

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 200) Propose a structure that fits the following spectroscopic data: C6H12O IR: 1708 cm−1 Broadband decoupled 13C NMR: 24.61, 26.42, 44.31, 213.81δ DEPT Experiments show: signals at 24.61, 26.42 δ as CH3

Answer:

O

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium

108

201) Propose a structure that fits the following spectroscopic data: C4H8O IR: 1737 cm−1 Broadband decoupled 13C NMR: 15.48, 41.07, 204.86δ DEPT Experiments show: signal at 41.07 δ as CH and signal at 15.48 δ as CH3

H

Answer:

O

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 202) Propose a structure that fits the following spectroscopic data: C5H10O IR: 1728 cm−1 Broadband decoupled 13C NMR: 22.59, 23.57, 52.66, 202.71 δ DEPT Experiments show: signal at 23.57 δ as CH, signal at 22.59 δ as CH3, and signal at 52.66 δ as CH2. O

Answer:

H

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium 203) Acetaldehyde is reacted with excess methanol in acid. The product was isolated and gave the following 1H NMR spectroscopic data: 1.3 δ (doublet, 3H) 3.4 δ (singlet, 6H) 109

4.6 δ (quartet, 1H) Propose a structure consistent with this information. Answer: O

O

Topic: Spectroscopy Section: 16.14 Difficulty Level: Medium

110