ALCOHOLS, PHENOLS AND ETHERS
An alcohol is any organic compound in which the hydroxyl functional group (–OH) is bound to a saturated carbon
atom. For example: methyl alcohol, CH3OH; ethyl alcohol C2H5OH, etc.
Classification of alcohols:
(i) On the basis of number of carbons attached to the α-carbon, i.e., the carbon to which the OH group is attached,
alcohols are classified as:
• Primary (1o) alcohol:
This type of alcohol has only one carbon atom attached to the α-carbon atom.
For example:
• Secondary (2o) alcohol:
Here α-carbon has two other carbon atoms attached to it.
For example:
• Tertiary (3o) alcohol:
In such alcohol three other carbon atoms are attached to the α-carbon atom.
(ii) On the basis of number of hydroxyl groups (−OH) present, alcohols can be divided into the following categories:
Monohydric alcohols:
They contain only one OH group. They have a general formula CnH2n+2O.
For example: CH3OH, CH3CH2OH, CH3CH2CH2OH, etc.
Dihydric alcohols:
Such alcohol contains two OH groups.
Trihydric alcohols:
This type of alcohol contains three OH groups.
Polyhydric alcohols:
these are the alcohols that contain more than three OH groups.
Nomenclature of alcohols:
IUPAC naming system:
(i) Select the longest possible chain that contains the α-carbon
(ii) Number the carbon atoms in the chain in such a way that α-carbon gets the minimum number
(iii) Then identify the hydrocarbon group and name it as per the IUPAC naming system.
(iv) Now replace the ‘e’ in the end of the parent hydrocarbon name by ‘ol’.
Common naming system:
o The common name of alcohol is alkyl alcohol.
o Depending upon the upon the structure of the alkyl group, prefix n, iso, sec, tert or neo is added to the common
name.
‘n’ is added when α-carbon and other carbon atoms make a straight chain.
For example:
‘Iso’ is added when the ─OH group is attached to
For example:
‘sec’ is added when the α-carbon is attached to two other carbon atoms.
For example:
‘tert’ is added when the α-carbon is attached to three other carbon atoms.
For example:
‘Neo’ is used when quaternary carbon is present.
For example:
Preparation of alcohols:
General methods of preparation of alcohols are described below:
(a) From alkenes:
(i) By acid catalysed hydration of alkenes in accordance with Markownikoffs rule.
(ii) By hydroboration-oxidation of alkenes in accordance with anti-Markownikoffs rule.
(b) From carbonyl compounds:
(i) By catalytic hydrogenation of aldehydes and ketones.
Note: Aldehydes yield primary alcohols whereas ketones give secondary alcohols.
(ii) By catalytic reduction of carboxylic acids and esters.
(c) Form Grignard reagent, RMgX:
It gives R group as a nucleophile to attack at the partially positive carbon atom of carbonyl (–C=O) group.
Preparation of Phenols:
(i) From haloarenes
(ii) From benzene sulphonic acid
(iii) From diazonium salts
(iv) From cumene
Physical Properties of Alcohols:
1. Lower alcohols are colourless liquids, members from C5 – C11 are oily liquids and higher members are waxy solids.
2. The hydroxyl groups in alcohols can form H-bonds with water, so alcohols are miscible with water. The solubility
decreases with increase in molecular mass.
3. Boiling points of alkanes are higher than expected because of the presence of intermolecular hydrogen bonding in
the polar molecules.
[The boiling point decreases in the order 1° > 2° > 3° as the van der Waals’ forces of attraction decreases]
Physical Properties of Phenols:
1. These are colourless liquids or crystalline solids but become coloured due to slow oxidation with air.
2. Phenol is also called carbolic acid.
3. Because of the presence of polar -OH bond, phenols form intermolecular H-bonding with other phenol molecules
and with water.
Chemical Reactions of Alcohols and Phenols
(i) Reactions involving cleavage of O – H Bond
(a) Acidity of alcohols and phenols
• Acid strength of alcohols
Electron releasing group increases electron density on oxygen to decrease in the polarity of – OH bond.
• Alcohols are weaker acids than water due to +I group present in alcohols, which decreases the polarity of -O-
H bond.
• Phenols are stronger acids than alcohols and water.
(b) Esterification
The reaction with R’COOH and (R’ CO)2O is reversible, so conc. H2SO4 is used to remove water.
The reaction with R’ COCI is carried out in the presence of pyridine so as to neutralise HCI which is formed during the
reaction.
The introduction of acetyl (CH3CO-) group in phenols is known as acetylation.
Acetylation of salicylic acid produces aspirin.
(ii) Reaction involving cleavage of C-O bond in alcohols:
In these reactions, the reactivity order of different alcohols:
Alkyl group due to +I effect increases the electron density on the carbon and oxygen atom of C-OH bond. As a result,
the bond cleavage becomes easy. Greater the number of alkyl groups present, more will be the reactivity of alcohol.
Thus, the relative order of reactivity of the alcohols is justified.
(a) Reaction with halogen acids Alcohols can be converted into haloalkanes by the action of halogen acids.
R – OH + HX (HCI, HBr, HI) → R-X +H2O
For a given alcohol order of reactivity of HX is: H-I > H-Br > H-Cl
For a given halogen acid order of reactivity of alcohols: Tertiary > Secondary > Primary
Lucas test:
(b) Reaction with phosphorus halides
(c) Reaction with thionyl chloride
d) Dehydration of alcohols
It requires acid catalyst and the reaction proceeds via intermediate carbonium ion. Acidic catalyst converts hydroxyl
group into a good leaving group.
Since, the rate determining step is the formation of carbocation, the ease of dehydration is
Mechanism
Step I Formation of protonated alcohol
Step II Formation of carbocation
Step III Formation of ethene by elimination of a proton
In dehydration reaction, highly substituted alkene is the major product and if the major product is capable of
showing cis-trans isomerism, trans-product is the major product. (Saytzeff’s rule).
(iii) Oxidation reactions: Oxidising reagents used for the oxidation of alcohols are neutral, acidic or alkaline
KMnO4 and acidified K2Cr2O7.
A common reagent that selectively oxidises a primary alcohol to an aldehyde (and no further) is pyridinium
chlorochromate (pCC).
(iv) Dehydrogenation
Distinction among 1°,2° and 3° Alcohols
1°, 2° and 3° alcohols are distinguished by Lucas test, oxidation and reduced copper.
Reactions of Phenols:
(i) Electrophilic substitution reactions The -OH group attached to the benzene ring activates it towards electrophilic
substitution at ortho and para positions.
(a) Halogenation
With calculated amount of Br2 in CS2 or CHCI3 it gives ortho and para product.
(b) Sulphonation
(c) Nitration
The ortho and para isomers can be separated by steam distillation. This is because o-nitrophenol is steam volatile
due to intramolecular hydrogen bonding while p nitrophenol is less volatile due to intermolecular hydrogen bonding
which causes the association of molecules.
(d) Reimer-Tiemann reaction
This reaction is an electrophilic substitution reaction and electrophile is dichlorocarbene.
Similarly with carbon tetrachloride and alkali, o- and p-hydroxybenzoic acid are obtained
(ii) Kolbe’s reaction
(iii) Reaction with zinc dust
Ethers
Ethers are the organic compounds in which two alkyl or aryl groups are attached to a divalent oxygen. known as
ethereal oxygen. These are represented by the general formula R–O-R” where R may be alkyl or aryl groups. e.g.,
These are the functional isomers of alcohols. These also exhibit chain isomerism and metamerism.
Nomenclature of Ethers
In the IUPAC system, ethers are regarded as ‘alkoxy alkanes’ in which the ethereal oxygen is taken along with smaller
alkyl group while the bigger alkyl group is regarded as a part of the alkane.
Preparation of Ethers
From alcohols:
Mechanism
(ii) Williamson’s synthesis Only primary alkyl halides when react with sodium alkoxide give ether while tertiary alkyl
halides give alkene due to steric hindrance.
Physical Properties of Ethers
Ethers are polar but insoluble inH20 and have low boiling point than alcohols of comparable molecular masses
because ethers do not form hydrogen bonds with water.
Chemical Reactions of Ether
(i) Reaction with HX
Ethers with two different alkyl groups are also cleaved in the same manner and results in the formation of a primary
halide (or smaller and less complex alkyl halide) by SN2 mechanism.
R-O-R’ + HX → RX + R’OR
The order of reactivity of hydrogen halides is as follows
HI > HBr > HCl
In ethers if one of the alkyl groups is a tertiary group, the halide formed is a tertiary halide by SN1 mechanism.
(ii) Halogenation
(v) Electrophilic substitution reactions In ethers, -OR is ortho, para directing group and activate. the aromatic ring
towards electrophilic substitution reaction.
Uses of Ethers
1. Dimethyl ether is used as refrigerant and as a solvent at low temperature.
2. Diethyl Ether is used as an anaesthesia in surgery.
