Conversion of Alcohol into Alkyl Halides

Primary Alcohols
Zinc chloride, a good Lewis acid, forms a complex with
alcohol through association with an unshared pair
electron on the oxygen atom.

Alkyl Halides from the Reaction of Alcohols with

PBr3 or SOCl2

Primary and secondary alcohols react with phosphorus

tribromide to yield alkyl bromides

The reaction of an alcohol with PBr3 does not involve

the formation of carbocation and usually without
rearrangement of the carbon skeleton.

Mechanism:

Thionyl chloride (SOCl2) converts primary and

secondary alcohol to alkyl chlorides (usually without
rearrangement):

A tertiary amine is added to the mixture to promote the

reaction by reacting with HCl:

Mechanism:

A chloride ion, R3N + HCl R3NH+ + Cl-

Tosylates, Mesylates, and Triflates:

Leaving Group Derivatives of Alcohols
The hydroxyl group of an alcohol can be converted to a
good leaving group by conversion to a sulfonate ester
derivative:

A method for making an alcohol hydroxyl group into

a leaving group

Substrates for Nucleophilic Substitution

Stereochemistry

A Mechanism for the reaction

Conversion of an Alcohol into an Alkyl Methanesulfonate

Synthesis Ethers

A Mechanism for the reaction

Intermolecular Dehydration of Alcohols to Form an Ether

The Williamson Synthesis of Ethers

An important route to unsymmetrical ethers is a
nucleophilic substitution reaction known as the
Williamson synthesis.

Example

Synthesis of Ethers by
Alkoxymercuration-Demercuration

tert-Butyl Ethers by Alkylation of Alcohols:

Protecting Grouos

Silyl Ether Protecting Groups

Reactions of Ethers

Mechanism:

Epoxides
Epoxides are cyclic ethers with three-membered rings.
In IUPAC nomenclature epoxides are called oxiranes.

Synthesis of Epoxides: Epoxidation

Mechanism:

Stereochemistry of Epoxidation:
The reaction of alkenes with peroxy acids take place in
a stereospesific way

Reactions of Epoxides:
Acid-Catalyzed Ring Opening of an Epoxide:

Base-Catalyzed Ring Opening of an Epoxide:

If the epoxide is unsymetrical, in base-catalyzed

ring opening, attack by the alkoxyide ion occurs
primarily at the less substituted carbon atom.

Mechanism (SN2):

If the epoxide is unsymetrical, in acid-catalyzed

ring opening, attack by the alkoxyide ion occurs
primarily at the more substituted carbon atom.

Mechanism (SN1):

Polyethers from Epoxides

Treating ethylene oxide with sodium methoxide (in the
present of a small amount of methanol) can result in
the formation of a polyether.

Anti 1,2-Dihydroxylation of Alkenes via Epoxides

Epoxidation (1) of cyclopentene produces
1,2-epoxycyclopentane:

Mechanism: