John McMurry, Professor Emeritus

Problem 18-1

(a)

Diisopropyl ether

(b)

Cyclopentyl propyl ether

(c)

p-Bromoanisole or 4-bromo-1-methoxybenzene

(d)

1-Methoxycyclohexene

(e)

Ethyl isobutyl ether

(f)

Allyl vinyl ether

Problem 18-2

A mixture of diethyl ether, dipropyl ether, and ethyl propyl ether is formed in a 1 : 1 : 2 ratio.

Problem 18-3

(a)

CH₃CH₂CH₂O⁻ + CH₃Br

(b)

PhO⁻ + CH₃Br

(c)

(CH₃)₂CHO⁻ + PhCH₂Br

(d)

(CH₃)₃CCH₂O⁻ + CH₃CH₂Br

Problem 18-4

The formed cyclic mercury trifluoroacetate adduct from 1-methylcyclopentene's reaction with mercury(II) trifluoroacetate is treated with sodium borohydride to produce the corresponding alcohol, replacing the mercury atom with hydrogen.

Problem 18-5

(a)

Either method

(b)

Williamson

(c)

Alkoxymercuration

(d)

Williamson

Problem 18-6

(a)

Bromoethane > 2-Bromopropane > Bromobenzene

(b)

Bromoethane > Chloroethane > 1-Iodopropene

Problem 18-7

(a)

2-bromo-2-phenylpropane reacts with methanol to form unknown product(s), depicted by a question mark.

(b)

Structures of 2-butanol and 1-bromopropane separated by a plus sign.

Problem 18-8

Protonation of the oxygen atom, followed by E1 reaction

Problem 18-9

Br⁻ and I⁻ are better nucleophiles than Cl⁻.

Problem 18-10

trans-2-Butene reacts with m C P B A to form trans-2,3-epoxybutane.

Problem 18-11

Epoxidation of cis-2-butene yields cis-2,3-epoxybutane, while epoxidation of trans-2-butene yields trans-2,3-epoxybutane.

Problem 18-12

(a)

The structure of 2-chloro-1-cyclohexyl-2-methylpropan-1-ol.

(b)

The structure of cyclohexane comprising chlorine atom and C H 2 O H group linked to the C 1 position of the ring.

Problem 18-13

(a)

1-Methylcyclohexene + OsO₄; then NaHSO₃

(b)

1-Methylcyclohexene + m-chloroperoxybenzoic acid, then H₃O⁺

Problem 18-14

(a)

A four-carbon chain with hydroxyl on C 1 and C 2 and methyl on C 2 position. The oxygen atom of hydroxyl on C 1 position has an asterisk.

(b)

A four-carbon chain with hydroxyl on C 1 and C 2 and methyl on C 2 position. The oxygen atom of hydroxyl on C 2 position has an asterisk.

(c)

Structure of 3-methyl-2-phenylpentan-3-ol.

Problem 18-15

Two crown ethers: 12-crown-4 is shown with an associated lithium cation, and 15-crown-5 is shown with an associated sodium cation.

Problem 18-16

(a)

2-Butanethiol

(b)

2,2,6-Trimethyl-4-heptanethiol

(c)

2-Cyclopentene-1-thiol

(d)

Ethyl isopropyl sulfide

(e)

o-Di(methylthio)benzene

(f)

3-(Ethylthio)cyclohexanone

Problem 18-17

(a) 1. LiAlH₄; 2. PBr₃; 3. ${({\rm H}_{2}{\rm N})_{2}{\rm C}\text{═}{\rm S}}$ ; 4. H₂O, NaOH
(b) 1. HBr; 2. ${({\rm H}_{2}{\rm N})_{2}{\rm C}\text{═}{\rm S}}$ ; 3. H₂O, NaOH

Problem 18-18

1,2-Epoxybutane

Problem 18-69

Acetyl chloride is more electrophilic than acetone.

Problem 18-70

Acetone reacts with cyanide to form an intermediate. This reacts with hydronium ion to form a product in which carbon is linked to hydroxyl, cyano, wedged, and dashed methyl groups.

Problem 18-71

(a)

Nucleophilic acyl substitution

(b)

Nucleophilic addition

(c)

Carbonyl condensation

Chapter 18