Alcohols
Alcohols have a hydroxyl ( OH) group bonded to a saturated carbon
atom. The alcohol carbon atom may be part of a simple alkyl group,
as in some of the following examples, or it may be part of a more
complex molecule, such as cholesterol.
The alcohol carbon atom may also be a saturated carbon atom of
an alkenyl or alkynyl group, or the carbon atom may be a
saturated carbon atom that is attached to a benzene ring:
Physical Properties of Alcohols
• Alcohols have much higher boiling points than comparable ethers or
hydrocarbons. The boiling point of butyl alcohol (MW 74) is 117.7°C.
• Alcohol molecules can associate with each other through hydrogen
bonding.
• Methanol, ethanol, both propyl alcohols, and tert-butyl alcohol are
completely miscible with water. The solubility of alcohols in water gradually
decreases as the hydrocarbon portion of the molecule lengthens; long-
chain alcohols are more “alkane-like” and are, therefore, less like water.
Acidity of alcohols
• 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 (R―O−).
• Primary alcohols are more acidic than secondary alcohols which are more
acidic than tertiary alcohols. This is because the strength of the alcohol as an
acid is dependent on the corresponding strength of its conjugate base, the
alkoxide ion. A more stabilised alkoxide is a weaker conjugate base and hence
the alcohol will be more acidic.
• Phenols are more acidic than alcohols. The conjugate base of a phenol
is a phenoxide or phenolate ion. Resonance stabilization of the
phenoxide ion coupled with the polar effect of the benzene ring
enhances the acidity of phenols over cyclohexanol. Therefore, phenol
does not need to be deprotonated with a base as strong as sodium
hydride. Instead, it can be deprotonated by hydroxide, unlike an
alcohol.
Reaction of Alcohols
Type A : Ester Formation
• Alcohols can combine with many kinds of acids to form
esters. 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.
• The reaction is reversible, and ester may hydrolyse so we
add H2SO4 dropwise or remove water from reaction.
Reaction with Grignard’s
Reagent
Type B: Reaction of Alcohols
with PBr3 PCl5 Or SOCl2
Primary and secondary alcohols react with phosphorus
tribromide to yield alkyl bromides.
• Thionyl chloride (SOCl2)
and
Phosphopentachloride
(PCl5) converts primary
and secondary alcohols
to alkyl chlorides.
Reaction with Halogens
• R+OH- + H+X- H2O + RX
Alcohol Halogen Alkyl Halide
EXAMPLE:
Reaction with Sulfuric acid
• Alcohols can dehydrate to form alkenes.
• Dehydration to an ether usually takes place at a lower temperature
than dehydration to the alkene, and dehydration to the ether can be
aided by distilling the ether as it is formed. Diethyl ether is made
commercially by dehydration of ethanol. Diethyl ether is the
predominant when alcohol is present in excess.
Oxonium ion
Oxidation
KMnO4 oxidizes primary alcohols to carboxylic acids very
efficiently.
Ter alcohols do not react with oxidizing agent as it do not
possess active hydrogens
Reduction
Dehydrogenation
Lucas test (distinguishing test for
pri, sec and tert alcohols)
The Lucas test in alcohols is a test to differentiate between primary, secondary, and tertiary alcohols. It
is based on the difference in reactivity of the three classes of alcohols with hydrogen halides via an SN
1 reaction. The differing reactivity reflects the differing ease of formation of the corresponding
carbocations. Tertiary carbocations are far more stable than secondary carbocations, and primary
carbocations are the least stable(due to hyperconjugation).
Preparation of Alcohols
Acid-Catalyzed Hydration of Alkenes
Alkenes add water in the presence of an acid catalyst to yield alcohols.
The addition takes place with Markovnikov regioselectivity. The
reaction is reversible, and the mechanism for the acid-catalyzed
hydration of an alkene is simply the reverse of that for the dehydration
of an alcohol.
Hydroboration
Oxidation
(HBO)
• An alkene reacts with
BH3:THF (borane and
tetrahydrofuran) or
diborane to produce an
alkylborane. Oxidation
and hydrolysis of the
alkylborane with hydrogen
peroxide and base yield an
alcohol.
Hydrolysis of Alkyl Halides
Addition of Grignard’s Reagent
Hydrolysis of ester
• Hydrolysis of ester to alcohol Reaction is carried out in
presence of dilute solution of an alkali or a mineral acid,
the organic esters are hydrolysed to form the parent
carboxylic acid and alcohol.
Reduction of Carbonyl Compounds
to alcohol
• Sodium borohydride (NaBH4) can reduce only aldehyde and ketone
into primary and secondary alcohol respectively.
R-CO-H (aldehyde) → R-CH2-OH ( primary alcohol)
R-CO-R (ketone) → R-CH(OH)-R (secondary alcohol)
• Lithium Aluminum hydride ( LiAlH4) can reduce carboxylic acids into
primary alcohol.
R-CO-OH (carboxylic acid) → R-CH2-OH (primary alcohol)
Uses of Alcohols
• Ethanol is used as a solvent for drugs, tinctures, oils,
perfumes, inks, dyes, varnishes.
• Ethanol is also used as a raw material for large number
of organic compounds including ethylene, ether, acetic
acid.
• Glycerol is used as a sweetening agent in beverages
and confectionary in the preparation of soaps and
cosmetics.
• Alcohols are also used as a substitute of petrol in
internal combustion engines, disinfectant and as liquor.
