Alcohol

REACTIONS OF ALCOHOLS

Because alcohols are easily synthesized and easily transformed into other compounds,
they serve as important intermediates in organic synthesis. A multistep synthesis may
use Grignard-like reactions to form an alcohol with the desired carbon structure,
followed by reactions to convert the hydroxyl group of the alcohol to the desired
functionality. The most common reactions of alcohols can be classified as oxidation,
dehydration, substitution, esterification, and reactions of alkoxides.

OXIDATION

Alcohols may be oxidized to give ketones, aldehydes,

and carboxylic acids. These functional groups are
useful for further reactions; for example, ketones and
aldehydes can be used in subsequent Grignard
reactions, and carboxylic acids can be used for
esterification. Oxidation of organic compounds
generally increases the number of bonds from carbon
to oxygen (or another electronegative element, such
as a halogen), and it may decrease the number of
bonds to hydrogen.
Alcoholsmaybeoxidizedtogive
aldehydes,ketones,andcarboxylicacids.
Theoxidationoforganic Secondary alcohols are easily oxidized without
breaking carbon-carbon bonds only as far as the
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ketone stage. No further oxidation is seen except
under very stringent conditions. Tertiary alcohols cannot be oxidized at all without
breaking carbon-carbon bonds, whereas primary alcohols can be oxidized to aldehydes
or further oxidized to carboxylic acids.

Chromic acid (H CrO , generated by mixing sodium dichromate, Na Cr O , with

2 4 2 2 7
sulfuric acid, H SO ) is an effective oxidizing agent for most alcohols. It is a strong
2 4
oxidant, and it oxidizes the alcohol as far as possible without breaking carbon-carbon
bonds. Chromic acid oxidizes primary alcohols to carboxylic acids, and it oxidizes
secondary alcohols to ketones. Tertiary alcohols do not react with chromic acid under
mild conditions. With a higher temperature or a more concentrated acid, carbon-carbon
bonds may be oxidized; however, yields from such strong oxidations are usually poor.
Oxidizing a primary alcohol only as far as the aldehyde stage is more difficult because of
the ease with which aldehydes are oxidized to acids. Special reagents have been
developed to convert primary alcohols to aldehydes. Pyridinium chlorochromate, often
abbreviated PCC, is a milder oxidant than chromic acid and oxidizes most primary
alcohols to aldehydes. PCC is a complex of chromium trioxide (CrO ) with pyridine
3
(C H N) and hydrogen chloride (HCl), written as pyridine CrO HCl.
5 5 3
BIOLOGICAL OXIDATION

All substances are toxic if taken in large enough quantities, and alcohols are no
exception. Although ethanol is less toxic than methanol, it is nonetheless a poisonous
substance, and many people die each year from ethanol poisoning. When someone is
suffering from mild ethanol poisoning, the person is said to be intoxicated. Because
animals often consume food that has fermented and contains ethanol, their bodies have
developed methods to remove or detoxify ethanol before it can accumulate and poison
the brain. One way the body detoxifies ethanol is to oxidize it, using an enzyme produced
by the liver, alcohol dehydrogenase, or ADH. Alcohol dehydrogenase catalyzes the
oxidation of ethanol to acetaldehyde, which is further oxidized to acetic acid (as the
acetate ion), a normal metabolite. The actual oxidizing agent is the oxidized form of
+
nicotinamide adenine dinucleotide, NAD .
The bodys response to simple alcohols is to oxidize them. This strategy works well with
ethanol, because the product is acetate, a normal metabolite. When other alcohols are
ingested, however, oxidation may lead to other toxic products. For example, oxidation of
methanol produces formaldehyde and subsequently formic acid (as the formate ion);
both of these products are more toxic than methanol itself. Ethylene glycol (automotive
antifreeze) is oxidized to oxalic acid (as the oxalate ion), the toxic compound found in
rhubarb leaves and many other plants. Ethylene glycol has a sweet taste, and many dogs
and cats are poisoned each year by drinking automotive antifreeze that has been
carelessly discarded.

One common treatment for methanol or ethylene glycol poisoning is to give the patient
intravenous infusions of diluted ethanol. The ADH enzyme is kept occupied by oxidizing
ethanol to acetic acid, giving the kidneys time to excrete most of the methanol or
ethylene glycol before it is oxidized to more toxic compounds. This is an example of
competitive inhibition of an enzyme (see poison: Nature of a toxic substance).

DEHYDRATION TO ALKENES

Converting an alcohol to an alkene requires removal of the hydroxyl group and a

hydrogen atom on the neighbouring carbon atom. Because the elements of water are
removed, this reaction is called a dehydration. Dehydrations are most commonly carried
out by warming the alcohol in the presence of a strong dehydrating acid, such as
concentrated sulfuric acid.
Most alcohol dehydrations take place by the mechanism shown below. Protonation of
the hydroxyl group allows it to leave as a water molecule. The species that remains has a
carbon atom with only three bonds and a positive charge and is called a carbocation. This
intermediate species can be stabilized by loss of a proton from a carbon atom adjacent
to the positively charged carbon ion, giving the alkene.

Because they involve carbocation intermediates, alcohol dehydrations go more quickly

and easily if they form relatively stable carbocations. More highly substituted
carbocations are more stable (3 > 2 > 1); therefore, more highly substituted alcohols
undergo dehydration more readily than less highly substituted alcohols (3 > 2 > 1).
Carbocations can undergo rearrangements in which an alkyl group, aryl group, or
hydrogen atom, along with its bonding electrons, shifts to the positively charged carbon
atom to form a more stable species. Rearrangements are thus a common nuisance in
alcohol dehydrations. If more than one alkene can be formed in a dehydration, the major
product is usually the product with the most highly substituted double bond (Saytzeffs
rule).
DEHYDRATION TO ETHERS

Under carefully controlled conditions, simple alcohols can undergo intermolecular

dehydration to give ethers. This reaction is effective only with methanol, ethanol, and
other simple primary alcohols, but it is the most economical method for making ethyl
ether (also known as diethyl ether), an important industrial solvent.

SUBSTITUTION TO FORM ALKYL HALIDES

Alkyl halides are often synthesized from alcohols, in effect substituting a halogen atom
for the hydroxyl group. Hydrochloric (HCl), hydrobromic (HBr), and hydroiodic (HI) acids
are useful reagents for this substitution, giving their best yields with tertiary alcohols.
Thionyl chloride (SOCl ), phosphorus tribromide (PBr ), and phosphorus triiodide
2 3
(generated from phosphorus, P, and molecular iodine, I ) are also useful for making alkyl
2
chlorides, bromides, and iodides, respectively.
ESTERIFICATION

Alcohols can combine with many kinds of acids to form esters. When no type of acid is
specified, the word ester is assumed to mean a carboxylic ester, the ester of an alcohol
and a carboxylic acid. The reaction, called Fischer esterification, is characterized by the
combining of an alcohol and an acid (with acid catalysis) to yield an ester plus water.

Under appropriate conditions, inorganic acids also react with alcohols to form esters. To
form these esters, a wide variety of specialized reagents and conditions can be used.
ACIDITY OF ALCOHOLS: FORMATION OF ALKOXIDES

Alcohols are weak acids. The most acidic simple alcohols (methanol and ethanol) are
about as acidic as water, and most other alcohols are somewhat less acidic.

A strong base can deprotonate an alcohol to yield an alkoxide ion (RO ). For example,
sodamide (NaNH ), a very strong base, abstracts the hydrogen atom of an alcohol.
2
Metallic sodium (Na) or potassium (K) is often used to form an alkoxide by reducing the
proton to hydrogen gas.

Alkoxides can be useful reagents. For example, the most common synthesis of ethers
involves the attack of an alkoxide ion on an alkyl halide. This method is called Williamson
ether synthesis (see ether).
Leroy G. Wade

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