Homework Chapter 18Ethers and Epoxides; Thiols and Sulfides

Problems with yellow highlight are mandatory homework; the rest are optional but
recommended.
Drawing Instructions: Draw structures corresponding to each of the given names.
1.

Draw: tetrahydrofuran

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2.

Draw: 12-crown-4

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3.

Draw: 1-isopropoxycyclopentene

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4.

Draw: allyl benzyl ether

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5.

Draw: diethyl ether

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CH3CH2OCH2CH3

Ethers and Epoxides; Thiols and Sulfides

6.

Draw: 3-methyl-1-butanethiol

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7.

Draw: cyclopropyl ethyl sulfide

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IUPAC Naming Instructions: Provide proper IUPAC names.

8.

Name:

ANS:
m-chloroanisole or m-chloromethoxybenzene or (m-chlorophenyl) methyl ether
9.

Name:

ANS:
1-ethoxy-2,2-dimethylpropane or ethyl neopentyl ether
10.

Name:

ANS:
dicyclohexyl sulfide

Chapter 18

Ethers and Epoxides; Thiols and Sulfides

Exhibit 18-1
Consider the reaction below to answer the following question(s).

11.

Refer to Exhibit 18-1. Write the complete stepwise mechanism for the reaction. Show all
intermediate structures and all electron flow with arrows.

ANS:

12.
a.
b.
c.
d.

Refer to Exhibit 18-1. Mechanistically, the Williamson ether synthesis outlined above is:
an E1 process
an SN1 process
an E2 process
an SN2 process

ANS:
d
13.

Refer to Exhibit 18-1. Alternatively, cyclopentyl methyl ether may be synthesized from
cyclopentene. Outline a synthesis of cyclopentyl methyl ether from cyclopentene.

ANS:

14.

Diphenyl ether is inert to cleavage by HI or HBr. Explain.

Chapter 18

ANS:
Acidic ether cleavages are typical nucleophilic substitution reactions that take place by either an
SN1 or SN2 pathway. Diaryl ethers like diphenyl ether are inert under ordinary acidic conditions
because the generation of an aryl cation is an SN1 process that is energetically unfavorable, and
"back-side" attack at the ring carbon bound to oxygen is sterically unfavorable.
15.

Write the complete stepwise mechanism for the reaction below. Show all electron flow with
arrows and draw all intermediate structures.

ANS:

Exhibit 18-2
Consider the data below to answer the following question(s).
Acetals are a special class of ethers which have two ether linkages at a single carbon.
Tetrahydropyranyl ethers are acetals that are easily cleaved with mild aqueous acids at room
temperature to yield alcohols.

Ethers and Epoxides; Thiols and Sulfides

16.

Refer to Exhibit 18-2. Draw arrows showing the electron flow for this reaction on the
structures provided below.

ANS:

17.

Refer to Exhibit 18-2. This ether cleavage occurs so easily under such mild conditions
because the carbocation intermediate in step two is very stable. Explain why this carbocation
is stabilized.

ANS:
The carbocation generated in the first step of the SN1 process is resonance-stabilized by the
adjacent oxygen lone pairs.

Chapter 18

18.

When 1,2-epoxypropane is treated with sodium ethoxide in ethanol 1-ethoxy-2-propanol is

the major product while only a trace amount of 2-ethoxy-1-propanol is produced. Explain
these results based on the reaction mechanism.

ANS:
Basic nucleophiles like ethoxide react with epoxides in a typical SN2-type process, so attack takes
place at the less hindered epoxide carbon.

Exhibit 18-3
Consider the data below to answer the following question(s).
Epoxides are synthesized industrially in one step by silver oxide air oxidation of ethylene and on a
laboratory scale in one step by treating an alkene with m-chloroperoxybenzoic acid. An alternative
two step process converts alkenes to halohydrins, which are converted by treatment with base to
epoxides.

19.

Refer to Exhibit 18-3. Show electron flow with arrows on the structures provided below for
each step in the above transformation.

Ethers and Epoxides; Thiols and Sulfides

ANS:

20.
a.
b.
c.
d.

Refer to Exhibit 18-3. The synthesis of epoxides by base treatment of halohydrins is an

example of an intramolecular:
SN1 reaction
hydrolysis reaction
dehydration reaction
Williamson ether synthesis

ANS:
d
Exhibit 18-4
Propose structure(s) for the starting material(s), reagent(s), or major organic product(s) of the
following reactions or sequences of reactions. Show all relevant stereochemistry.

21.
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Chapter 18

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Ethers and Epoxides; Thiols and Sulfides

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Chapter 18

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Ethers and Epoxides; Thiols and Sulfides

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Chapter 18

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35.

Propose a synthesis of 1,4-dioxane, starting from 1,2-dibromoethane as the only source of

carbon.

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36.

Choose the best reagent for carrying out the following reactions from the list below. Place
the letter of the reagent(s) in the box over the reaction arrow. Use only one letter per box.

A. NaH, then CH3I

B. NaOCH3, CH3OH

C. m-ClC6H4CO3H

D. CH3MgBr in ether, then H3O+

E. warm H2SO4/H2O

F.

G. H2/Pd

H. PCC, CH2Cl2

I.

J.

Cl2, H2O

Hg(O2CCF3)2, CH3OH

LiAlH4 in ether, then H3O+

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Ethers and Epoxides; Thiols and Sulfides

ANS:

37.

14

Complete the synthetic sequence below by drawing the structures of the reaction in the
boxes provided.

Chapter 18

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38.

Show how the ether below could be prepared from toluene and any other necessary reagents.
Show all reagents and all intermediate structures.

ANS:

39.

Propose a synthesis for the following compound using benzene or toluene and any other
reagents necessary. Show all major intermediate compounds that would probably be isolated
during the course of your synthesis.

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Ethers and Epoxides; Thiols and Sulfides

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40.

Name the compound shown below. Atoms other than carbon and hydrogen are labeled.

ANS:
Ethyl hexyl ether or 1-ethyoxyhexane

41.

Name the following compound. Atoms other than carbon and hydrogen are labeled.

ANS:
o-mercaptotoluene

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Chapter 18

42.

Predict the product of the following reaction.

ANS:

43.

Draw the structure of the ether that could be used to produce the following compound

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