Why this Chapter?

John E. McMurry

To begin to study oxygen-containing functional

groups
http://www.cengage.com/chemistry/mcmurry

Chapter 8
Alcohols, Phenols, Ethers
and Their Sulfur Analogs

These groups lie at the heart of biological

chemistry

8.1 Naming Alcohols, Phenols, and Ethers

General classifications of alcohols based on
substitution on C to which OH is attached
Methyl (C has 3 Hs), Primary (1) (C has two Hs, one
R), secondary (2) (C has one H, two Rs), tertiary (3)
(C has no H, 3 Rs)

IUPAC Rules for Naming Alcohols

Select the longest carbon chain containing the
hydroxyl group,
and derive the parent name by replacing the -e
ending of the corresponding alkane with -ol
Number the chain from the end nearer the hydroxyl
group
Number substituents according to position on chain,
listing the substituents in alphabetical order

Naming Ethers
identify the two organic substituent's and adding the word ether
If other functional groups are present, the ether part is considered
an alkoxy substituent

8.7 Cyclic Ethers: Epoxides

Cyclic ethers behave like acyclic ethers, except if ring
is 3-membered
Dioxane and tetrahydrofuran are used as solvents

Thiols and Sulfides

Thiols (RSH), are sulfur analogues of alcohols
Sulfides (RSR), are sulfur analogues of ethers

O
H2C CH2

Epoxides (oxiranes)

17.2 Properties of Alcohols and Phenols

The structure around O of the alcohol or
phenol is similar to that in water, sp3
hybridized.
Alcohols and phenols have much higher boiling
points than similar alkanes and alkyl halides.

This produces a force that holds the two molecules

together
These intermolecular attractions are present in
solution but not in the gas phase, thus elevating the
boiling point of the solution.

A positively polarized OH hydrogen atom from

one molecule is attracted to a lone pair of electrons
on a negatively polarized oxygen atom of another
molecule.

Alcohols and Phenols are Weak

Brnsted Acids
Weakly basic and weakly acidic
Can transfer a proton to water to a very small extent
Produces H3O+ and an alkoxide ion, RO, or a phenoxide ion,
ArO

pKa Values for Typical OH Compounds

Alkyl
groups
make an
alcohol a
weaker
acid

8.3 Synthesis of Alcohols from Carbonyl

Compounds
Reduction of Aldehydes and Ketones

Phenol Acidity
Phenols (pKa ~10) are much more acidic than
alcohols (pKa ~ 16) because of resonance
stabilization of the phenoxide ion

Aldehydes gives primary alcohols

Ketones gives secondary alcohols

Phenols react with NaOH solutions (but alcohols do

not), forming salts that are soluble in dilute aqueous
solution

Reduction Reagent: Sodium Borohydride

NaBH4 is not
sensitive to
moisture and it
does not reduce
other common
functional groups
Nucleophile is
the hydride ion,
:H

Reduction of Carboxylic Acids and

Esters
Carboxylic acids and esters are reduced to give primary
alcohols
LiAlH4 is used because NaBH4 is not effective

Reactions of Grignard Reagents with

Carbonyl Compounds

8.4 Reactions of Alcohols

Dehydration of an alcohol, the elimination of water, yields
an alkene
The general reaction: forming an alkene from an alcohol
through loss of OH and H (hence dehydration) of the
neighboring CH to give bond
Specific reagents are needed

3 > 2 > 1

Oxidation of Alcohols

Oxidation of Alcohols
Many oxidizing agents such as CrO3 and Na2Cr2O7
oxidize primary alcohols to carboxylic acids
The intermediate aldehyde usually cannot be isolated

Can be
accomplished by
inorganic
reagents, such as
KMnO4, CrO3,
and Na2Cr2O7 or
by more selective,
expensive
reagents

Oxidation of Alcohols

Conversion into Ethers

Many oxidizing agent s such as CrO3 and Na2Cr2O7

oxidize secondary alcohols to carboxylic acids

Reaction of metal alkoxides and primary alkyl halides

(Williamson ether syntheis)

Periodinane is used for sensitive alcohols but

is more expensive

Best method for the preparation of ethers

Alkoxides prepared by reaction of an alcohol with a strong
base such as sodium hydride, NaH

8.5 Reactions of Phenols

The reactions of phenols are quite different than
those of alcohols

phenols

8.5 Reactions of Phenols

2. The hydroxyl group is a strongly activating, making
phenols substrates for
electrophilic
halogenation,
nitration,
sulfonation,
and FriedelCrafts reactions
The OH is ortho- and para-directing

1. Phenols due react via an SN2 reaction with alkyl

halides to produce ethers

8.5 Reactions of Phenols

1. Phenols do not undergo oxidation in the same manner as
alcohols
2. Reaction of a phenol with strong oxidizing agents yields a
quinone (1,4-dione)
3. Quinones are easily and reversibly reduced to hydroquinones

8.6 Reactions of Ethers

Ethers and Cyclic

Ethers

Ethers are generally unreactive

Strong acid will cleave an ether at elevated
temperatures
HI, HBr produce an alkyl halide from less hindered
component by SN2 (tertiary ethers undergo SN1)