Reactions of Alcohols, Ethers, Epoxides, and Thiols Many Reactions in This Chapter Are Extensions From Chapter 7

Chapter 8
Reactions of Alcohols, Ethers,

Epoxides, and Thiols
Many reactions in this chapter
are extensions from chapter 7.
Strongly Basic Leaving Groups

Cannot Be Displaced
alcohols
Acid Converts the Poor Leaving Group

into a Good Leaving Group
Alcohols have to be protonated or converted into good leaving groups

SN2 chemistry
alcohols
The Reactions of Secondary and Tertiary Alcohols

with Hydrogen Halides are SN1 Reactions
alcohols
The Reactions of Primary Alcohols

with Hydrogen Halides are SN2 Reactions
alcohols
Why is It Important to Be Able

to Convert Alcohols to Alkyl Halides?
All SN2 reactions

alcohols
Other Methods to Convert

Alcohols into Alkyl Halides
NEW REACTIONS!
phosphorus tribromide & thionyl chloride
You do not need to know the mechanism of these reactions
alcohols
Sulfonate Esters in SN2 reactions
alcohols
A Sulfonate Ester is a good leaving group
alcohols
Stereochemical Considerations
2 inversions
1 inversion
alcohols
Two SN2 Reactions or

One SN2 Reaction?
inversion
inversion
inversion
Stereochemistry is important here.
alcohols
Dehydration of an Alcohol
Dehydration of an alcohol either E1 or E2

depending on the substitution of the alcohol
alcohols
Dehydration is a Reversible Reaction
The difference between concentrated and dilute acids
alcohols
Dehydration of Secondary and Tertiary

Alcohols are E1 Reactions
alcohols
Dehydration (E1) is a Regioselective

Reaction
The major product is the more stable alkene.

alcohols
Dehydration of a Primary Alcohol

is an E2 Reaction
alcohols
Dehydration is Stereoselective
The major product is the stereoisomer with the

largest groups on opposite sides of the double bond.
alcohols
A better way to eliminate an alcohol
Non-acidic conditions
alcohols
Ethers are alkylated alcohols
ethers
Ethers react with hydrogen halides
ethers
Ethers Are Common Solvents

Because They React Only with Hydrogen Halides
Common solvents
ethers
Devise a mechanism that accounts for the

following reaction
THF is a common organic solvent that is stable under many reaction
conditions except those including HCl, HBr, and HI. Under these strongly
acidic conditions, THF undergoes the following reaction. Draw a mechanism
that accounts for the formation of product using the curved arrow notation to
show all bond making and bond breaking.
ethers
Devise a mechanism that accounts for the

following reaction
Under these strongly acidic conditions (1 equivalent of HI), What would
happen with 2 equivalents of HI?
What mechanism is shown above?
ethers
Tert-butyl ethers are often used to reversibly

protect the hydroxyl group
When isobutylene gas is reacted with a compound containing a hydroxyl
group in the presence of a non-aqueous acid, a tert-butyl ether may be
formed as shown below. Devise a mechanism that accounts for the formation
of this product.
ethers

Start by remembering electrophilic addition of the proton to the alkene to
give the tert-butyl cation. The cation is attacked by the hydroyl group to give
the ether.
ethers

This reaction is reversible depending on conditions.
H+
(TFA)
ethers
Recall synthesis of an epoxide

from a per-acid
Naming epoxides: add oxide to the end of the alkene name.

For example, cyclohexene is converted to cyclohexene oxide when
reacted with m-chloroperbenzoic acid (mCPBA) in dichloromethane.
epoxides
Synthesis of an Epoxide from a

halohydrin intramolecular SN2
chlorohydrin
epoxides
Epoxides can be easily ring opened with S N2

or SN1 type chemistry because of ring strain
When the epoxide isnt symmetric
epoxides
The Acid-Catalyzed Mechanism

SN1-like
epoxides
If the Epoxide is Not Symmetrical,

Which Carbon Does the Nucleophile Attack?
The nucleophile attacks the more substituted epoxide carbon.

epoxides
Under Acidic Conditions the Nucleophile Attacks

the More Substituted Ring Carbon
epoxides
Under Neutral or Basic Conditions the Nucleophile Attacks the Less

Substituted Carbon
SN2-like
epoxides
Using Epoxides in Synthesis
P.T.
P.T. = proton transfer

epoxides
Forming a trans-1,2-Diol
enantiomers
1,2-diols
Forming a cis-1,2-Diol
: :
: :
Sulfur containing compounds
Nomenclature of Thiols
Chemistry of thiols
Acid/base & SN2
Thiols have pKa values of about 10.

The conjugate base form (thiolates) are excellent nucleophiles and less
prone to elimination chemistry
Chemistry of thiols
Redox
Chemistry of sulfides
Redox
Polar aprotic solvents

SN2
Sulfonate esters are good leaving

groups
Secondary Alcohols can be

oxidized to ketones
Redox chemistry
Primary alcohols can be oxidized

to acids and aldehydes
aldehyde
Redox chemistry
Tertiary Alcohols Cannot Be Oxidized

to a Carbonyl Compound
Redox chemistry

Reactions of Alcohols, Ethers, Epoxides, and Thiols Many Reactions in This Chapter Are Extensions From Chapter 7

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Chapter 8

Reactions of Alcohols, Ethers,

Strongly Basic Leaving Groups

Acid Converts the Poor Leaving Group

Alcohols have to be protonated or converted into good leaving groups

The Reactions of Secondary and Tertiary Alcohols

The Reactions of Primary Alcohols

Why is It Important to Be Able

All SN2 reactions

Other Methods to Convert

Sulfonate Esters in SN2 reactions

A Sulfonate Ester is a good leaving group

Two SN2 Reactions or

Stereochemistry is important here.

Dehydration of an alcohol either E1 or E2

Dehydration is a Reversible Reaction

The difference between concentrated and dilute acids

Dehydration of Secondary and Tertiary

Dehydration (E1) is a Regioselective

The major product is the more stable alkene.

Dehydration of a Primary Alcohol

The major product is the stereoisomer with the

A better way to eliminate an alcohol

Ethers are alkylated alcohols

Ethers react with hydrogen halides

Ethers Are Common Solvents

Devise a mechanism that accounts for the

Devise a mechanism that accounts for the

What mechanism is shown above?

Tert-butyl ethers are often used to reversibly

Tert-butyl ethers are often used to reversibly

Tert-butyl ethers are often used to reversibly

Recall synthesis of an epoxide

Naming epoxides: add oxide to the end of the alkene name.

Synthesis of an Epoxide from a

Epoxides can be easily ring opened with S N2

When the epoxide isnt symmetric

The Acid-Catalyzed Mechanism

If the Epoxide is Not Symmetrical,

The nucleophile attacks the more substituted epoxide carbon.

Under Acidic Conditions the Nucleophile Attacks

Under Neutral or Basic Conditions the Nucleophile Attacks the Less

Using Epoxides in Synthesis

P.T. = proton transfer

Sulfur containing compounds

Sulfur containing compounds

Sulfur containing compounds

Thiols have pKa values of about 10.

Sulfur containing compounds

Sulfur containing compounds

Polar aprotic solvents

Sulfur containing compounds

Sulfonate esters are good leaving

Sulfur containing compounds

Secondary Alcohols can be

Primary alcohols can be oxidized

Tertiary Alcohols Cannot Be Oxidized

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