Organic Chemistry, 7th Edition L. G. Wade, Jr.

Chapter 14
Ethers, Epoxides, and Sulfides

2010, Prentice Hall

Ethers
Formula is ROR, where R and R are alkyl or aryl. Symmetrical or unsymmetrical
CH3 O CH3

O CH3

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Structure and Polarity

Oxygen is ________ hybridized. ________ molecular geometry. COC angles is _________. Polar CO bonds. Dipole moment of 1.3 D.
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Boiling Points
Similar to alkanes of comparable molecular weight.

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Hydrogen Bond Acceptor

Ethers cannot hydrogen-bond with other ether molecules. Molecules that cannot hydrogen-bond intermolecularly have a _____________ boiling point. Ether molecules can hydrogen-bond with water and alcohol molecules.
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Solvation of Ions with Ether

An ionic substance such as lithium iodide is moderately soluble in ethers because the small lithium cation is strongly solvated by the ethers lone pairs of electrons. Unlike alcohols, ether cannot serve as hydrogenbond donors, so they do not solvate small anions well.
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Ether Complexes
Grignard reagents: Complexation of an ether with a Grignard reagent stabilizes the reagent and helps keep it in solution.

Electrophiles: The ethers nonbonding electrons stabilize the borane (BH3).

Chapter 14

H _ + O B H H BH3 THF
7

Crown Ether Complexes

Crown ethers can complex metal cations inside the ring. The size of the cation will determine the size of the ring needed. Complexation by crown ethers often allows polar inorganic salts to dissolve in nonpolar organic solvents.
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Common Names of Ethers

Name the two alkyl groups attached to the oxygen and add the word ether. Name the groups in alphabetical order Symmetrical: Use dialkyl or just alkyl.
CH3

CH3CH2

O CH2CH3

CH3

O C CH3 CH3

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IUPAC Names
The more complex alkyl group is the alkane name. The small group (with the oxygen) becomes an alkoxy group.
CH3 CH3 O C CH3 CH3

O CH3

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10

Cyclic Ethers
Heterocyclic: Oxygen is part of the ring. Epoxides (oxiranes) Oxetanes Furans Pyrans
O

O H2C CH2

(Oxolanes (Oxanes
O

) )

O O

Dioxanes
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Epoxide Nomenclature
Name the starting alkene and add oxide.
peroxybenzoic acid H O H

The oxygen can be treated as a substituent (epoxy) on the compound. Use numbers to specify position.
H O H
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Epoxide Nomenclature (Continued)

The three-membered oxirane ring is the parent (oxygen is 1, the carbons are 2 and 3). Substituents are named in alphabetical order.
H CH3CH 2 O CH 3 H

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13

IR Spectroscopy of Ethers
IR: The CO stretch is in the fingerprint region around 10001200 cm-1. Many compounds have the CO stretch. If the IR spectrum has the CO stretch but does not have a CO or an OH stretch, then the compound is most likely an ether.
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MS Spectrometry of Ethers

Main fragmentation is the _______________ to form the resonance-stabilized oxonium ion. Either alkyl group can be cleaved this way.
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Loss of an Alkyl Group

The CO bond can be cleaved to produce a carbocation.

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MS Spectra of Diethyl Ether

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17

NMR Spectroscopy of Ethers

The typical chemical shift for ethers in NMR are: 13CO signal between 6590.
1HCO

signal between 3.54.

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18

Williamson Ether Synthesis

This method involves an SN2 attack of the alkoxide on an ________________________ halide or tosylate.
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Examples of the Williamson Synthesis

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20

Phenyl Ethers
O H + NaOH _ O Na+ + HOH

Phenoxide ions are easily produced for because the alcohol proton is acidic. Phenyl halides or tosylates cannot be used in this synthesis method.
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Alkoxymercuration Demercuration Reaction

Use mercuric acetate with an alcohol. The alcohol will react with the intermediate mercurinium ion by attacking the __________ substituted carbon.
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Industrial Ether Synthesis

Industrial method, not good lab synthesis. If temperature is too high, alkene forms.
CH3CH2 O H + H O CH2CH3 H2SO4 CH3CH2 O CH2CH3

140C

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23

Cleavage of Ethers
Ethers are __________________, which makes them ideal solvents for a lot of different reactions. They can be cleaved by heating with HBr and HI. Reactivity: HI > HBr >> HCl

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24

Mechanism for Cleavage

Ether is ____________________.
CH3 O CH3 H Br CH3 H + O CH3 + Br
_
_

Alcohol leaves as halide attacks.

_

Br

CH3

H + O CH3

Br CH3 + H O CH3

Alcohol is protonated, halide attacks, and another molecule of alkyl bromide is formed. =>

Phenyl Ether Cleavage

Phenol cannot react further to become halide because an SN2 reaction cannot occur on an sp2 carbon.
O CH2CH3 OH HBr + CH3CH2 Br

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26

Autoxidation of Ethers
In the presence of atmospheric oxygen, ethers slowly _______________ to hydroperoxides and dialkyl peroxides. Both are highly explosive. Precautions:
Do not distill to dryness. Store in full bottles with tight caps.
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Mechanism of Autoxidation

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28

Synthesis of Epoxides

Peroxyacids are used to convert alkenes to epoxides. Most commonly used peroxyacid is metachloroperoxybenzoic acid (MCPBA). The reaction is carried out in an aprotic acid to prevent the opening of the epoxide.
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Selectivity of Epoxidation

The most electron-rich double bond reacts faster, making selective epoxidation possible.

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30

Halohydrin Cyclization

If an alkoxide and a halogen are located in the same molecule, the alkoxide may displace a halide ion and form a ring. Treatment of a halohydrin with a base leads to an epoxide through this _______________ Chapter 14 31 attack.

Epoxides via Halohydrins

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32

Acid-Catalyzed Opening of Epoxides

Acid-catalyzed hydrolysis of epoxides gives glycols with _________ stereochemistry. Anti stereochemistry results from the backside attack of water on the protonated epoxide. Chapter 14

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Acid-Catalyzed Opening of Epoxides in Alcohol Solution

A molecule of alcohol acts as the nucleophile and attacks and opens the epoxide. This reaction produces an alkoxy alcohol with _________ stereochemistry.
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Base-Catalyzed Opening of Epoxides

The hydroxide ion attacks and opens the ring. The diol is obtained after protonation of the alkoxide with water.
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Ring Opening in Base

An epoxide is higher in energy than an acyclic ether by about 25 kcal/mol ring strain. Release of the ring strain makes the opening of an epoxide thermodynamically favored.
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Regioselectivity of Epoxidation

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37

Reaction of Epoxides with Grignard and Organolithiums

OH O H2C CHCH3 + 2) H3O MgBr 1) ether
+

CH2

CHCH3

Strong bases, such as Grignards and organolithiums, open the epoxide ring by attacking the _________ hindered carbon.
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Epoxy Resins
Polymer of bisphenol A and epichlorohydrin
CH3 HO C CH3 bisphenol A OH

O H2C CHCH2Cl epichlorohydrin

Sulfides (Thioethers)
RSR, analog of ether. Name sulfides like ethers, replacing sulfide for ether in common name, or alkylthio for alkoxy in IUPAC system.
S CH3 methyl phenyl sulfide or methylthiobenzene
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Thiols and Thiolates

Thiolates are easily synthesized by the Williamson ether synthesis, using dithiolate as the nucleophile.
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Sulfide Reactions
Sulfides are easily oxidized to sulfoxides and sulfones.
CH3 S CH3 H2O2 CH3COOH O CH3 S CH3 H2O2 CH3COOH O CH3 S CH3 O

Sulfides react with unhindered alkyl halides to give sulfonium salts.

CH3 S CH3 + CH3 I
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CH3

+ S CH3 CH3

_ I
42