 The replacement of hydrogen atom(s) in an aliphatic hydrocarbon by –OH group

results in the formation of Alcohols. e.g CH3OH.

 The replacement of hydrogen atom(s) in an aromatic hydrocarbon by –OH group

results in the formation of Phenols. e.g C6H5OH

 The replacement of hydrogen atom of a hydrocarbon(aliphatic or aromatic) by an

alkoxy or aryloxy group (R-O/Ar-O)results in the formation of Ethers. e.g CH3OCH3,
CH3OC6H5

CLASSIFICATION OF ALCOHOLS AND PHENOLS

 Alcohols and phenols may be classified as mono-, di-, tri- or polyhydric compounds
depending on whether they contain one, two, three or many –OH groups respectively, in
there molecules.

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 When two or more hydroxyl groups attached to the same carbon atom the compound is
generally unstable. The compound loses a water molecule to form an aldehyde, ketone or a
carboxylic acid.

Classification of Monohydric Alcohols

Monohydric alcohols may be further classified according to the hybridization of carbon atom
to which the hydroxyl group is attached.

(1)Compounds containing Csp3- OH bond

(a)Alkyl alcohols
 In these alcohols, the –OH group is attached to a sp3 hybridised carbon atom of an
alkyl group.
 They are further classified as primary, secondary and tertiary alcohols.

(b) Allylic alcohols

 In these alcohols, the —OH group is attached to a sp3 hybridised carbon adjacent to the
carbon-carbon double bond, that is to an allylic carbon.
 They are further classified as Primary, Secondry and Tertiary alcohols. For example

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(c) Benzylic alcohols

 In these alcohols, the —OH group is attached to a sp3-hybridised carbon atom next to
an aromatic ring.
 They are further classified as Primary, Secondry and Tertiary alcohols.
 For example

Compounds containing Csp2 – OH bond

(a) Vinylic alcohol
 In these alcohols, the —OH group is attached to a carbon-carbon double bond, i.e., to a
vinylic carbon (CH2 = CH –).

(b)Aryl alcohols or Phenols

 -OH group is bonded to the sp2-hybridised carbon atom of an aromatic ring.

Classification of Ethers
Ethers are classified as:
(a) Simple or symmetrical Ethers
When both the alkyl or aryl groups attached to the oxygen atom are the same they are
designated as simple or symmetrical ethers.

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CH3―O―CH3 C6H5―O―C6H5 C6H5―O―C6H5

Dimethyl Ether Diethyl Ether Diphenyl Ether

(b) Mixed or unsymmetrical Ethers

When both the groups are different they are called mixed or unsymmetrical ethers.

CH3―O―C2H5 CH3―O―C3H7 C6H5―O―CH2C6H5

Ethyl methyl Ether Methyl propyl Ether Benzyl phenyl Ether

NOMENCLATURE OF ALCOHOLS
Common Names
 In this system, alcohols are called alkyl alcohols. For example

IUPAC system
 In this system alcohols are called Alkanols.
 Steps for writing the IUPAC name of the alcohols are as follows:
(a) Select the longest carbon chain (parent chain) containing ―OH group.
(b) The selected longest chain is numbered from the end nearest to the hydroxyl group.
(c) Replace the 'e' of alkane by adding suffix 'ol'.
(d) The positions of the ―OH group and other substituents are indicated by using the
numbers of carbon atoms to which these are attached.
(e) For naming polyhydric alcohols, the 'e' of alkane is retained and the ending or suffix 'ol' is
added.

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(f) Indicate the number of ―OH groups by adding prefix like di, tri, etc., before 'ol'. Example

Cyclic alcohols are named using the prefix cyclo and considering the –OH group
attached to C - 1.

NOMENCLATURE OF PHENOLS
 The simplest hydroxy derivative of benzene is called phenol. It is its common name as
well as an accepted IUPAC name. All substituted phenols are named as derivatives of
phenol.
 For disubstituted compounds the terms ortho (1,2- disubstituted), meta (1,3-
disubstituted) and para (1,4-disubstituted) are often used in the common names.

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NOMENCLATURE OF ETHERS

Common names

 Common names of ethers are derived from the names of alkyl/aryl groups written as
separate word in alphabetical order and adding the word ether at the end.
 When both alkyl groups are same, the prefix di is used. For e.g, C2H5OC2H5 is Diethyl
ether.
 In case of unsymmetrical ethers the two alkyl groups are named in alphabetical order. For
e.g, CH3OC2H5 is Ethyl methyl ether.

IUPAC names

 In this system ethers are named as alkoxyalkane.

 According to IUPAC system of nomenclature, ethers are regarded as hydrocarbon
derivatives in which a H-atom is replaced by an –OR or –OAr group.
 The larger (R) group is chosen as the parent hydrocarbon and smaller group is written
as alkoxy or phenoxy.

Ether Common Name IUPAC

CH3—O—CH3 Dimethyl ether Methoxy methane
CH3—O— C2H5 Ethyl methyl ether Methoxy Ethane

STRUCTURE OF FUNCTIONAL GROUPS

IN ALCOHOLS,
 The oxygen of the –OH group is attached to carbon by a sigma bond formed by the
overlap of a sp3 hybridised orbital of carbon with a sp3 hybridised orbital of oxygen.

 The bond angle in alcohols, (108° 9') is slightly less than the tetrahedral angle
(109° 28'). It is due to the repulsion between the unshared electron pairs of oxygen.

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IN PHENOLS,
 The –OH group is attached to sp2 hybridised carbon of an aromatic ring.
 The carbon-oxygen bond length (136 pm) in phenol is slightly less than that in
methanol.
 This is due to
(i) partial double bond character because of resonance and
(ii) sp2 hybridised state of carbon to which oxygen is attached.

Since the oxygen atom is more electronegative than both carbon and hydrogen, the
electrons of the C―O and O―H bonds are little more displaced towards the oxygen
atom. As a result, the electron density near the oxygen atom is slightly higher than
that near carbon and hydrogen atoms. In other words, an alcohol molecule is dipolar in
nature with the oxygen carrying a partial negative charge and carbon and hydrogen
each carrying a partial positive charge.

Phenol has a smaller dipole moment (1.54 D) than methanol (1.71 D). This is due to
the reason that the C―O bond in phenol is less polar due to the electron-withdrawing
effect of the benzene ring while in methanol, C―O bond is more polar due to electron-
donating effect of the CH3 group.
* Due to this dipolar nature, alcohols and phenols form intermolecular hydrogen bonds.

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IN ETHERS,
Ethers like water have a tetrahedral geometry, i.e., oxygen is sp3-hybridised. Two of the four
sp3-hybrid orbitals of the oxygen overlap with hybrid orbital of two carbon atoms to form two
sigma bonds. The remaining two sp3- orbitals of oxygen contain a lone pair of electrons each.

The C―O―C bond angle (111.7) is slightly greater than the tetrahedral angle due to
the repulsive interaction between the two bulky (‒R) group. The C―O bond length
(141 pm) is almost the same as in alcohols.

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