John McMurry, Professor Emeritus

Problem 17-1

(a)

5-Methyl-2,4-hexanediol

(b)

2-Methyl-4-phenyl-2-butanol

(c)

4,4-Dimethylcyclohexanol

(d)

trans-2-Bromocyclopentanol

(e)

4-Bromo-3-methylphenol

(f)

2-Cyclopenten-1-ol

Problem 17-2

(a)

(b)

(c)

(d)

(e)

(f)

Problem 17-3

Hydrogen-bonding is more difficult in hindered alcohols.

Problem 17-4

(a)

HC

\text{≡}

CH < (CH₃)₂CHOH < CH₃OH < (CF₃)₂CHOH

(b)

p-Methylphenol < Phenol < p-(Trifluoromethyl)phenol

(c)

Benzyl alcohol < Phenol < p-Hydroxybenzoic acid

Problem 17-5

The electron-withdrawing nitro group stabilizes an alkoxide ion, but the electron-donating methoxyl group destabilizes the anion.

Problem 17-6

(a)

2-Methyl-3-pentanol

(b)

2-Methyl-4-phenyl-2-butanol

(c)

meso-5,6-Decanediol

Problem 17-7

(a)

NaBH₄

(b)

LiAlH₄

(c)

LiAlH₄

Problem 17-8

(a)

Benzaldehyde or benzoic acid (or ester)

(b)

Acetophenone

(c)

Cyclohexanone

(d)

2-Methylpropanal or 2-methylpropanoic acid (or ester)

Problem 17-9

(a)

1-Methylcyclopentanol

(b)

1,1-Diphenylethanol

(c)

3-Methyl-3-hexanol

Problem 17-10

(a)

Acetone reacts first with methylmagnesium bromide, then hydronium, to produce 2-methyl-2-propanol. C H 3 C O R reacts first with 2 equivalents methylmagnesium bromide, then hydronium, to produce same product.

(b)

Cyclohexanone reacts first with methylmagnesium bromide, then hydronium, to produce 1-methylcyclohexanol.

(c)

Three ways to make 3-methyl-3-pentanol: 2-pentanone with methylmagnesium bromide, then hydronium; 2-butanone with ethylmagnesium bromide, then hydronium; alkyl acetate with two equivalents ethylmagnesium bromide, then hydronium.

(d)

Three ways to make 2-phenyl-2-butanol: propiophenone with methylmagnesium bromide, then hydronium; acetophenone with ethylmagnesium bromide, then hydronium; 2-butanone with phenylmagnesium bromide, then hydronium.

(e)

Formaldehyde reacts first with phenylmagnesium bromide, then hydronium, to make benzyl alcohol.

(f)

Formaldehyde reacts first with isopentylmagnesium bromide, then hydronium, to make 4-methyl-1-pentanol.

Problem 17-11

Cyclohexanone + CH₃CH₂MgBr

Problem 17-12

1. p-TosCl, pyridine; 2. NaCN

Problem 17-13

(a)

2-Methyl-2-pentene

(b)

3-Methylcyclohexene

(c)

1-Methylcyclohexene

(d)

2,3-Dimethyl-2-pentene

(e)

2-Methyl-2-pentene

Problem 17-14

(a)

1-Phenylethanol

(b)

2-Methyl-1-propanol

(c)

Cyclopentanol

Problem 17-15

(a)

Hexanoic acid, hexanal

(b)

2-Hexanone

(c)

Hexanoic acid, no reaction

Problem 17-16

S_N2 reaction of F⁻ on silicon with displacement of alkoxide ion.

Problem 17-17

Protonation of 2-methylpropene gives the tert-butyl cation, which carries out an electrophilic aromatic substitution reaction.

Problem 17-18

Disappearance of –OH absorption; appearance of C

\text{=}

O

Problem 17-19

(a)

Singlet

(b)

Doublet

(c)

Triplet

(d)

Doublet

(e)

Doublet

(f)

Singlet

Chapter 17