John McMurry, Professor Emeritus

Problem 22-1

(a)

A structure of cyclopentene with a hydroxyl group and double bond at C 1.

(b)

An alkene in which C 1 is bonded to a hydroxyl group on top and methyl sulfide group on the right.

(c)

An alkene in which C 1 has two hydrogen atoms on it and C 2 is linked to a hydroxyl group and to an oxygen which in turn is linked to an ethyl group.

(d)

(e)

An alkene in which C 1 has two hydrogen atoms on it and C 2 is linked to two hydroxyl groups.

(f)

Two alkene structures. C 2 is bonded to hydroxyl and methyl groups but in second structure, C 2 is bonded to hydroxyl and C H 2 P h.

Problem 22-2

(a) 4 (b) 3 (c) 3 (d) 2 (e) 4 (f) 5

Problem 22-3

A cyclohexane ring with two carbonyl groups, one at C 1 and one at C 3 forms two stable enolates and two unstable enolates.

Problem 22-4

Acid-catalyzed formation of an enol is followed by deuteronation of the enol double bond and dedeuteronation of oxygen.

Problem 22-5

1. Br₂; 2. Pyridine, heat

Problem 22-6

The intermediate α-bromo acid bromide undergoes a nucleophilic acyl substitution reaction with methanol to give an α-bromo ester.

Problem 22-7

(a)

CH₃CH₂CHO

(b)

(CH₃)₃CCOCH₃

(c)

CH₃CO₂H

(d)

PhCONH₂

(e)

CH₃CH₂CH₂CN

(f)

CH₃CON(CH₃)₂

Problem 22-8

Problem 22-9

Acid is regenerated, but base is used stoichiometrically.

Problem 22-10

(a)

1. Na^{+ −}OEt; 2. PhCH₂Br; 3. H₃O⁺

(b)

1. Na^{+ −}OEt; 2. CH₃CH₂CH₂Br; 3. Na^{+ −}OEt; 4. CH₃Br; 5. H₃O⁺

(c)

1. Na^{+ −}OEt; 2. (CH₃)₂CHCH₂Br; 3. H₃O⁺

Problem 22-11

Malonic ester has only two acidic hydrogens to be replaced.

Problem 22-12

1. Na^{+ −}OEt; 2. (CH₃)₂CHCH₂Br; 3. Na^{+ −}OEt; 4. CH₃Br; 5. H₃O⁺

Problem 22-13

(a)

(CH₃)₂CHCH₂Br

(b)

PhCH₂CH₂Br

Problem 22-14

None can be prepared.

Problem 22-15

1. 2 Na^{+ −}OEt; 2. BrCH₂CH₂CH₂CH₂Br; 3. H₃O⁺

Problem 22-16

(a)

Alkylate phenylacetone with CH₃I

(b)

Alkylate pentanenitrile with CH₃CH₂I

(c)

Alkylate cyclohexanone with H₂C

\text{═}

CHCH₂Br

(d)

Alkylate cyclohexanone with excess CH₃I

(e)

Alkylate C₆H₅COCH₂CH₃ with CH₃I

(f)

Alkylate methyl 3-methylbutanoate with CH₃CH₂I

Chapter 22