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Why this Chapter?

John E. McMurry

To begin to study oxygen-containing functional


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

These groups lie at the heart of biological


Chapter 8 chemistry
Alcohols, Phenols, Ethers
and Their Sulfur Analogs

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

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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 Thiols and Sulfides


Cyclic ethers behave like acyclic ethers, except if ring Thiols (RSH), are sulfur analogues of alcohols
is 3-membered Sulfides (RSR), are sulfur analogues of ethers
Dioxane and tetrahydrofuran are used as solvents

O
H2C CH2

Epoxides (oxiranes)

17.2 Properties of Alcohols and Phenols


This produces a force that holds the two molecules
The structure around O of the alcohol or together
phenol is similar to that in water, sp3
hybridized. These intermolecular attractions are present in
solution but not in the gas phase, thus elevating the
boiling point of the solution.
Alcohols and phenols have much higher boiling
points than similar alkanes and alkyl halides.

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.

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Alcohols and Phenols are Weak pKa Values for Typical OH Compounds
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, Alkyl
ArO groups
make an
alcohol a
weaker
acid

8.3 Synthesis of Alcohols from Carbonyl


Compounds
Phenol Acidity Reduction of Aldehydes and Ketones
Phenols (pKa ~10) are much more acidic than Aldehydes gives primary alcohols
alcohols (pKa ~ 16) because of resonance
stabilization of the phenoxide ion Ketones gives secondary alcohols

Phenols react with NaOH solutions (but alcohols do


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

Reduction of Carboxylic Acids and


Reduction Reagent: Sodium Borohydride
Esters
NaBH4 is not Carboxylic acids and esters are reduced to give primary
sensitive to alcohols
moisture and it
does not reduce LiAlH4 is used because NaBH4 is not effective
other common
functional groups
Nucleophile is
the hydride ion,
:H

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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 Reaction of metal alkoxides and primary alkyl halides
oxidize secondary alcohols to carboxylic acids (Williamson ether syntheis)

Periodinane is used for sensitive alcohols but Best method for the preparation of ethers
is more expensive
Alkoxides prepared by reaction of an alcohol with a strong
base such as sodium hydride, NaH

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8.5 Reactions of Phenols
The reactions of phenols are quite different than
those of alcohols

1. Phenols due react via an SN2 reaction with alkyl


halides to produce ethers
phenols

8.5 Reactions of Phenols 8.5 Reactions of Phenols


2. The hydroxyl group is a strongly activating, making
1. Phenols do not undergo oxidation in the same manner as
phenols substrates for
alcohols
electrophilic 2. Reaction of a phenol with strong oxidizing agents yields a
halogenation, quinone (1,4-dione)
nitration, 3. Quinones are easily and reversibly reduced to hydroquinones
sulfonation,
and FriedelCrafts reactions
The OH is ortho- and para-directing

8.6 Reactions of Ethers

Ethers are generally unreactive


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

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