Preparation of Alcohols

Alcohols are prepared by the following methods:

1. From alkenes

(i) By acid catalyzed hydration: The addition of water to alkene in the presence of strong acid (as

catalyst) leads to formation of alcohols. In case of unsymmetrical alkenes, the addition reaction takes

place in accordance with Markovnikov’s rule (20 and 30 alcohols are major product).

.
(ii) By hydroboration–oxidation:
This is the two-step hydration reaction that converts an alkene into an alcohol. In the first step, Diborane (BH3)2 or
Boron trihydride (BH3) adds to the double bond of alkene in THF, transferring one of the hydrogen atoms to the
most substituted carbon while B atom is bonded to the less substituted one (anti- Markovnikov rule is followed). This
hydroboration can be repeated two additional times, successively reacting each B-H bond so that three alkenes add
to each BH3. In the second step, the resulting trialkyl borane is oxidized to alcohol by hydrogen peroxide in presence
of aqueous NaOH.

Anti Markovnikov’s product

Hydrolysis of alkyl halides with aqueous NaOH

When alkyl halides are heated with aqueous NaOH, nucleophilic substitution of halide ion by hydroxyl ion takes place.
This results in formation of alcohols.
Alcohols from Carbonyl Compounds: Reduction
• Reduction of a carbonyl compound in general gives an alcohol
• Note that organic reduction reactions add the equivalent of H2 to a molecule
 Reduction of Aldehydes and Ketones
• Reduction of a carbonyl compound in general gives an alcohol. Aldehydes yield primary alcohols whereas ketones give

secondary alcohols. Note that organic reduction reactions add the equivalent of H2 to a molecule

• The usual catalysts are H2/Pd, H2/Pt, H2/Ni. It is also prepared by treating aldehydes and ketones with sodium

borohydride (NaBH4) or lithium aluminium hydride (LiAlH4).

,[H]
 [H]

NaBH4 /
LiAlH4
(ii) By reduction of carboxylic acids : Carboxylic acids are reduced to primary alcohols in excellent yields by lithium
aluminium hydride, a strong reducing agent.

Acidic hydrolysis of esters

 Alcohols from Carbonyl Compounds: Grignard Reagents
• Alkyl, aryl, and vinylic halides react with magnesium in ether or tetrahydrofuran to generate Grignard
reagents, RMgX
• Grignard reagents react with carbonyl compounds to yield alcohols
3. From Grignard reagents

Alcohols are produced by the reaction of Grignard reagents with aldehydes and ketones.
The first step of the reaction is the nucleophilic addition of Grignard reagent to the carbonyl group to form an
adduct.
Second step Hydrolysis of the adduct with dilute acid yields an alcohol.

H+

H+
Reactions of Grignard Reagents with Carbonyl
Compounds
Chemical reactions of alcohols
• Dehydration (loss of water – intramolecular) – make an alkene

• Dehydration (loss of water – intermolecular) – makes an ether

• Oxidation – makes a carboxylic acid

• Halogenation – makes a halogenated alkane

Dehydration of Alcohols to Yield Alkenes
Alcohols can be dehydrated to form either alkenes (higher temperature, excess acid) or ethers (lower temperature,
excess alcohol).
The dehydration reaction of alcohols to generate alkene proceeds by heating the alcohols in the presence of excess of
a strong acid (such as sulfuric acid) at high temperatures.

The elimination involved loss of the OH group and a H-atom from adjacent C-atoms.

If the reaction is not sufficiently heated, the alcohols do not dehydrate to form alkenes, but react with one
another to form ethers.
Chemical reactions of alcohols
Elimination reactions

Conc. (excess)

Conc. (excess)
 Chemical reactions of alcohols
Elimination reactions

• If there is more than one adjacent carbon atom from which loss of a H-atom can occur (secondary and tertiary alcohols),
there will be more than one possible alkene dehydration product:

Conc.

Use Zaitsev’s Rule to predict which alkene will be produced in the greater amount. More substituted alkene is more stable,
hence is the major product
 Chemical reactions of alcohols
Elimination reactions

• Zaitsev’s Rule (for alcohol dehydrations): for cases where more than one alkene product might be formed
from an elimination reaction, the hydrogen atom tends to be removed from the carbon that already
possesses the fewest hydrogens.