Organic Chemistry

Problems 779

10. Reactions of -unsaturated carboxylic acid derivativeswith nucleophiles (Section 18.14):

Nucleophiles form nucleophilic acyl substitution products with reactive carbonyl groups and conjugate addition products with less

reactive carbonyl groups.

RCH RCH

RCH

CHCCl ++NuH

O

CHCNu HCl

O

nucleophilic acyl

substitution

CHCNHR + NuH

O

Nu

O

conjugate addition

RCHCH 2 CNHR

a,b

Key Terms

acetal (p. 755)
aldehyde (p. 731)
conjugate addition (p. 769)
cyanohydrin (p. 741)
deoxygenation (p. 752)
disconnection (p. 766)
direct addition (p. 769)
enamine (p. 747)
gem-diol (p. 753)
hemiacetal (p. 755)
hemiketal (p. 756)

hydrate (p. 753)

hydrazone (p. 751)

imine (p. 747)

ketal (p. 756)

ketone (p. 731)

nucleophilic acyl substitution (p. 737)

nucleophilic addition (p. 737)

nucleophilic addition–elimination

reaction (p. 738)

oxime (p. 751)

phenylhydrazone (p. 751)

pH–rate profile (p. 749)

prochiral carbonyl carbon (p. 765)

protecting group (p. 758)

Reand Sifaces (p. 765)

reduction reaction (p. 743)

Schiff base (p. 747)

semicarbazone (p. 751)

synthetic equivalent (p. 766)

synthon (p. 766)

Wittig reaction (p. 761)

ylide (p. 761)

Problems

40. Draw the structure for each of the following compounds:

a. isobutyraldehyde f. 4-bromo-3-heptanone

b. 4-hexenal g.

c. diisopentyl ketone h. 2-ethylcyclopentanecarbaldehyde

d. 3-methylcyclohexanone i. 4-methyl-5-oxohexanal

e. 2,4-pentanedione j. benzene-1,3-dicarbaldehyde

41. Give the products of each of the following reactions:

a. e.

b. f.

c. g.

d. h. NaC N HCl

excess

+

CH 3

O

O

CH 3 CH 2 CCH 3

1. NaBH 4
   2. H 3 O+

+

O

CH 3 CH 2 CH 2 CCH 3 HOCH 2 CH 2 OH

HCl

O

CCH 2 CH 3 + NH 2 NH 2 HO

−

∆

O

CH 3 CH 2 CH 2 COCH 2 CH 3

1. LiAlH 4
   2. H 3 O+

O

CCH 2 CH 3 + NH 2 NH 2

catalytic

H+

O

CH 3 CH 2 CCH 2 CH 3 NaC N

HCl

excess

+

O

CH 3 CH 2 CH + CH 3 CH 2 OH

HCl

excess

g-bromocaproaldehyde