Alcohols Phenols Ethers

Functional Group
The hydrogen of an aliphatic The hydrogen of an aromatic The hydrogen of a hydrocarbon
hydrocarbon gets replaced hydrocarbon gets replaced gets replaced by -OR/-
by -OH (hydroxyl) group by -OH (hydroxyl) group OAr (Alkoxy or Aryloxy) group
Classification
Depending on no. of -OH Depending on no. of -OH Symmetrical (Simple) – having
group present, Monohydric, group present, Monohydric, the same groups (alkyl/aryl)
dihydric and polyhydric. dihydric and polyhydric attached to O

Primary, secondary, Unsymmetrical (Mixed) –

tertiary depending on the different groups attached to O
type of C (sp3) which is
attached to -OH

Allylic – OH group is
attached to allylic carbon
(sp3), e.g. CH2=CH-CH-OH

Benzylic – OH group
attached to C (sp3) attached
to an aromatic ring

Vinylic – OH group attached

to C (sp2) with C=C, e.g.
CH2=CH-OH
Nomenclature
Common Name – ‘alcohol’ Simplest is phenol C6H5OH. It Common Name – word ‘ether’
attached to the name of the is the common name and also follows the name of the alkyl
alkyl group, e.g. methyl accepted in IUPAC groups in alphabetical order, e.g.
alcohol, ethyl alcohol, etc. nomenclature Ethylmethyl ether, Diethyl ether,
etc.
IUPAC – The suffix – ‘ol’ Position of OH group is
attached to the name of denoted by o (ortho), m IUPAC Name – Named as
alkane, e.g. methanol (meta), p (para), or by alkoxy or aryloxy derivative of
(CH3OH), ethanol (C2H5OH), numbering the cyclic carbons hydrocarbon. The bulkier group
etc. etc. is taken as the parent
hydrocarbon, e.g.
E.g. o-Cresol is 2-
Methoxymethane,
 Methylphenol, Catechol is Methoxybenzene, etc.
Benzene-1,2-diol, etc.
Structure
There is a bonding between There is a bonding between Bond Angle:
sp3 hybridised orbitals of C sp2 hybridised orbitals of C of
The C-O-C bond angle is 111.7
and O aromatic ring and O
(Methoxymethane).
Bond Angle: Bond Angle:
It is more than tetrahedral due to
The C-O-H bond angle is The C-O-H bond angle is repulsion between the two R
108.9°, i.e. less than 109° in Phenol (bulky) groups
tetrahedral (109°-28’)
Bond Length: Bond Length:
It is due to repulsion between
The C-O bond length is 136 The C-O bond length is 141 pm,
electron pairs of Oxygen
pm in Phenol. almost the same as alcohols
Bond Length:
It is less compared to
The C-O bond length is 142 Methanol due to
pm in Methanol sp2 hybridization of Carbon
and conjugation of pi
electrons of the aromatic ring
gives partial double bond
character.
Preparation
1. From Alkenes: 1. From Haloarenes: 1. By dehydration of alcohols:

a. Acid-catalyzed hydration- Chlorobenzene is treated with When primary alcohols are

Addition of H2O according to NaOH to form sodium treated with protic acids (H2SO4,
Markonikov’s rule phenoxide, which is then H3PO4) ether is formed by the
treated with acid to form nucleophilic bimolecular reaction.
b. By hydroboration-oxidation-
phenol This reaction depends on
Reaction with diborane to
conditions, at 443 K alkene is a
give trialkyl boranes, which C6H5Cl + NaOH → C6H5ONa +
major product, whereas at 413 K
are oxidised by H2O2 and HCl → C6H5OH
ether is a major product
NaOH (aq)
When alcohol is 2° or 3°,
The end product formed is
elimination reaction competes
opposite to Markonikov’s rule
with SN1 resulting in alkene as a
major product
2. From Carbonyl 2. From Benzene sulphonic 2. Williamson Synthesis:
Compounds: Acid:
Ether is formed in the reaction of
a. By catalytic hydrogenation The first step is the sodium alkoxide with an alkyl
in presence of Ni, Pd or Pt sulphonation of benzene with halide
metal catalyst or reduction of oleum. Benzene sulphonic
With 1° alkyl halide, SN2 is
aldehyde and ketones by acid thus formed is heated
preferred and ether is formed as
LiAlH4 or NaBH4 with molten NaOH to form
a major product but with 2° or 3°
sodium phenoxide and then it
Aldehydes → primary elimination proceeds and alkene
is acidified to from phenol
alcohols is the major product formed

Ketones → secondary Phenol can also be converted to

alcohols ether by this method

b. By reduction of carboxylic
acids and esters
3. From Grignard Reagents: 3. From Diazonium Salts:

By the reaction aldehyde and Aniline (C6H5NH2) when reacts

ketones with Grignard with NaNO2 + HCl forms
reagent (R-Mg-X). There is a Benzene diazonium chloride
nucleophilic addition of (C6H5N2Cl), which on
Grignard reagent followed by hydrolysis give phenol
hydrolysis

HCHO + RMgX →
RCH2OMgX + H2O →
RCH2OH + Mg(OH)X
4. From Cumene:

Cumene (isopropylbenzene)
is oxidised to form cumene
hydroperoxide and then
treated with dil. acid to form
phenol. Acetone is a by-
product in the reaction
Physical Properties
Boiling Point: Boiling Point: Boiling Point:
Increases with increase in the Boiling point is more Less compared to alcohols due
number of C atoms due to the compared to other to the presence of intermolecular
increase in Van der Waals compounds like arenes, hydrogen bonding in alcohols
forces ethers, haloarenes, etc. due
to intermolecular hydrogen
Decreases with an increase in
bonding
branching due to the
decrease in surface area and
Van der Waals forces

Boiling point is more

compared to other
compounds like alkanes,
ethers, haloalkanes, etc. due
to intermolecular hydrogen
bonding
Solubility: Solubility: Solubility:

Solubility is due to the Solubility is due to the Miscibility of ether is comparable

formation of hydrogen bonds formation of hydrogen bonds to alcohol and more than alkane
with H2O with H2O of same molecular mass due to
formation of a hydrogen bond
Solubility decreases with an Solubility decreases with an
with water and O of ether
increase in the size of the increase in the size of the aryl
alkyl group (hydrophobic) group (hydrophobic)
Acidity and Basicity
Strong Bronsted acids and Strong Bronsted acids and Ethers are more acidic than
can donate electrons to a can donate electrons to a hydrocarbons but less acidic
strong base strong base than ketones and aldehydes

Acidity is due to the polarity of Benzene ring attached to the Ethers can act as Lewis or
the O-H bond. The electron OH group acts as an electron Bronsted bases. They form
releasing alkyl groups withdrawing group. Electron oxonium ion after protonation by
decrease the acidity so the pairs of oxygen are in strong acids
order of acidity of alcohol is: conjugation with the double
bond of benzene ring making
1° > 2° > 3°
the oxygen of OH positive
Water is a better proton donor
Phenols are stronger acids
or stronger acid than alcohols than water and alcohols

They also act as a proton This can be explained by

acceptor or Bronsted bases more stable phenoxide ion
due to unshared electron and more polar OH bond
pairs on oxygen
Electron withdrawing group (-
NO2) in the substituted
phenols make it more acidic
and Electron donating groups
(alkyl) decrease the acidity

Order of acidity:

Nitrophenol > Phenol >

Cresol > Ethanol

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