Chemistry 212Name ______

Organic Chemistry IIApril 11, 1997

Please write all of your answers on the examination booklet. Each question or part of a question is worth five (5) points.

11Of the following combinations of reagents, the one that does not lead to 3-methyl-3-pentanol is:

11Methyl Grignard + 3-pentanone

21Ethyl Grignard + ethyl acetate

31s-Butyl Grignard + ethylene oxide

413-methyl-2-pentene + aqueous sulfuric acid

22A crossed aldol reaction between benzaldehyde (PhCHO) and acetone (CH3COCH3) would be expected to give:


33The product expected, after workup, from the reaction of phenyl Grignard reagent (PhMgBr) with acetaldehyde (CH3CHO) is:

13PhCH2OH

23PhCH(OH)CH3

33PhCH3CH2OH

43PhC(OH)(CH3)2

44The following proposed synthesis fails to give the desired product because:

14it is not possible to make a Grignard reagent from an alkyl chloride

24the Grignard reagent produced in the first step attacks the starting material

34formaldehyde is not sufficiently reactive to be attacked by a Grignard reagent

44transesterification occurs instead

55The -hydroxyalcohol produced in the first stage of the aldol reaction of butanal in base is:

66In the Reformatsky reaction:

16an -bromoester is produced

26a -hydroxyester is produced

36a zinc enolate anion is produced by transmetallation of a Grignard reagent

46zinc metal is used to reduce an -bromoester to the ester

77Treatment of ethyl formate (HCO2CH2CH3) with methyl Grignard (CH3MgBr) produces:

172-propanol and ethanol

27acetone and ethanol

371-propanol and ethanol

47ethanol as the only organic product

88The carbonyl group most reactive toward nucleophilic acyl substitution is found in:

18an acid chloride

28an acid anhydride

38an ester

48an amide

99Which of the following reactions does not produce the alkene shown at the right,

1010To prepare leucine [(CH3)2CHCH2CH(NH2)CO2H] by a Strecker synthesis requires which carbonyl compound as the starting material:

110(CH3)2CHCH2CHO

210(CH3)2CHCH2C(O)CH3

310(CH3)2CHCHO

410(CH3)2CHCH2CO2H

1111The major product produced upon treatment of -phenylacetamide with bromine in aqueous base is:

1212When cyclobutylmethanol is treated with HBr, a ring expansion takes place in which cyclopentyl bromide is produced. The driving force for this rearrangement is:

112formation of a tertiary carbocation instead of a primary carbocation in the rate determining step

212formation of a secondary carbocation, with relief of ring strain, instead of a primary carbocation in the rate determining step

312formation of a secondary radical, with relief of ring strain instead of a primary radical in the rate determining step

412formation of a tertiary radical instead of a primary radical in the rate determining step

1313Subjecting 3-pentanone to the conditions of a Beckman rearrangement (sequential treatment with hydroxylamine and aqueous sulfuric acid) produces:

1414Wagner-Meerwein rearrangement takes place through a:

114carbocationic intermediate

214carbanionic intermediate

314carbene intermediate

414radical anionic intermediate

1515The expected product of a Claisen rearrangement of Z-1,5-heptadiene is:

1616An isocyanate has the structure

116R-CONH2

216R-N=C=O

316R-C=N=O

416R-O-C=NH

1717Of the following, the reaction that is nota pericyclic reaction is

117condensation

217cycloreversion

317electrocyclization

417sigmatropic rearrangement

1818In the benzilic acid rearrangement shown here, the group that migrates to an adjacent carbon atom is:

118phenyl

218C=O

318benzyl

418CO2H

1919In order to prepare

in a crossed Claisen condensation with dimethylcarbonate ((CH3O)2CO), the required coreactant is

119methyl acetate (CH3CO2CH3)

219propanal (CH3CH2CHO)

319methyl propanoate (CH3CH2CO2CH3)

419acetaldehyde (CH3CHO)

2020Of the following structures, that which represents the cyanohydrin of acetophenone (PhCOCH3) is

120PhCHOHCH2CN

220PhC(OH)(CN)CH3

320PhCHCNCH2OH

420PhCH(CO2H)CH2OH