Alcohols Phenols Ethers

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

Primary, secondary, Unsymmetrical (Mixed) –

tertiary depending on the different groups attached to
type of C (sp3) which is O
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 is Common Name – word
attached to the name of the the common name and also ‘ether’ follows the name of
alkyl group, e.g. methyl accepted in IUPAC nomenclature the alkyl groups in
alcohol, ethyl alcohol, etc. alphabetical order, e.g.
Position of OH group is denoted
Ethylmethyl ether, Diethyl
IUPAC – The suffix – ‘ol’ by o (ortho), m (meta), p (para),
ether, etc.
attached to the name of or by numbering the cyclic
alkane, e.g. methanol carbons etc. IUPAC Name – Named as
(CH3OH), ethanol (C2H5OH), alkoxy or aryloxy derivative of
E.g. o-Cresol is 2-Methylphenol,
etc. hydrocarbon. The bulkier
Catechol is Benzene-1,2-diol, etc.
group is taken as the parent
 hydrocarbon, e.g.
Methoxymethane,
Methoxybenzene, 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
and O aromatic ring and O
111.7 (Methoxymethane).
Bond Angle: Bond Angle:
It is more than tetrahedral
The C-O-H bond angle is The C-O-H bond angle is 109° in due to repulsion between the
108.9°, i.e. less than Phenol two R (bulky) groups
tetrahedral (109°-28’)
Bond Length: Bond Length:
It is due to repulsion between
The C-O bond length is 136 pm The C-O bond length is 141
electron pairs of Oxygen
in Phenol. pm, almost the same as
Bond Length: alcohols
It is less compared to Methanol
The C-O bond length is 142 due to sp2 hybridization of Carbon
pm in Methanol 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
Addition of H2O according to NaOH to form sodium phenoxide, When primary alcohols are
Markonikov’s rule which is then treated with acid to treated with protic acids
form phenol (H2SO4, H3PO4) ether is
b. By hydroboration-
formed by the nucleophilic
oxidation- Reaction with C6H5Cl + NaOH → C6H5ONa +
bimolecular reaction. This
diborane to give trialkyl HCl → C6H5OH
reaction depends on
boranes, which are oxidised
conditions, at 443 K alkene is
by H2O2 and NaOH (aq)
a major product, whereas at
The end product formed is 413 K ether is a major
opposite to Markonikov’s rule product

When alcohol is 2° or 3°,

elimination reaction
 competes 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
a. By catalytic hydrogenation The first step is the sulphonation reaction of sodium alkoxide
in presence of Ni, Pd or Pt of benzene with oleum. Benzene with an alkyl halide
metal catalyst or reduction of sulphonic acid thus formed is
With 1° alkyl halide, SN2 is
aldehyde and ketones by heated with molten NaOH to form
preferred and ether is formed
LiAlH4 or NaBH4 sodium phenoxide and then it is
as a major product but with
acidified to from phenol
Aldehydes → primary 2° or 3° elimination proceeds
alcohols and alkene is the major
product formed
Ketones → secondary
alcohols Phenol can also be converted
to 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 Benzene
reagent (R-Mg-X). There is a diazonium chloride (C6H5N2Cl),
nucleophilic addition of which on hydrolysis give phenol
Grignard reagent followed by
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 compared to Less compared to alcohols
number of C atoms due to the other compounds like arenes, due to the presence of
increase in Van der Waals ethers, haloarenes, etc. due to intermolecular hydrogen
forces intermolecular hydrogen bonding bonding in alcohols

Decreases with an increase

in 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 formation Miscibility of ether is

formation of hydrogen bonds of hydrogen bonds with H2O comparable to alcohol and
with H2O more than alkane of same
Solubility decreases with an
molecular mass due to
Solubility decreases with an increase in the size of the aryl
formation of a hydrogen bond
increase in the size of the group (hydrophobic)
with water and O of ether
alkyl group (hydrophobic)
Acidity and Basicity
Strong Bronsted acids and Strong Bronsted acids and can Ethers are more acidic than
can donate electrons to a donate electrons to a strong base hydrocarbons but less acidic
strong base than ketones and aldehydes
Benzene ring attached to the OH
Acidity is due to the polarity of group acts as an electron Ethers can act as Lewis or
the O-H bond. The electron withdrawing group. Electron pairs Bronsted bases. They form
releasing alkyl groups of oxygen are in conjugation with oxonium ion after protonation
decrease the acidity so the the double bond of benzene ring by strong acids
order of acidity of alcohol is: making the oxygen of OH positive

Phenols are stronger acids than

1° > 2° > 3° water and alcohols

Water is a better proton donor This can be explained by more

or stronger acid than alcohols stable phenoxide ion and more
polar OH bond
They also act as a proton
acceptor or Bronsted bases Electron withdrawing group (-
due to unshared electron NO2) in the substituted phenols
pairs on oxygen make it more acidic and Electron
donating groups (alkyl) decrease
the acidity

Order of acidity:

Nitrophenol > Phenol > Cresol >

Ethanol
Chemical Reactions
1. Reactions where alcohol 1. Reactions where phenol 1. There is no O-H bond in
reacts as a Nucleophile (O- reacts as a Nucleophile (O-H ethers
H bond cleavage): bond cleavage):

a. Reaction with metals to a. Phenol reacts with metal or aq

form the corresponding NaOH to form sodium phenoxide
alkoxides and H2
b. Esterification: Phenols react
2R-O-H + 2Na → 2R-O-Na + with carboxylic acids, acid
H2 anhydrides and acid chlorides to
form esters
b. Esterification: Alcohols
react with carboxylic acids, Salicylic acid + Acetic anhydride
acid anhydrides and acid → Aspirin (Acetylsalicylic acid)
chlorides to form esters
2. Reactions where alcohol 2. Reactions where there is C- 2. Reactions where there is
reacts as an Electrophile O bond cleavage: C-O bond cleavage:
(C-O bond cleavage):
Phenol reacts with Zn dust to Ethers are comparatively less
a. Reaction with HX to form form benzene reactive. The C-O bond
alkyl halides. This forms the cleavage occurs under
C6H5OH + Zn → C6H6 + ZnO
basis of the Lucas test to drastic conditions
differentiate between 1°, 2°
Dialkyl ethers when react
and 3° alcohols. with HX give rise two alkyl
halides
3° alcohols form halides
easily so turbidity is produced When alkyl aryl ethers react
immediately with HX, they form phenol
and alkyl halide due to more
b. Reaction with PX3 to form
stability of the aryl-oxygen
alkyl halides
bond
c. Undergo dehydration to
The reactivity order of HX is
form alkene in the presence
of protic acid, e.g. ethanol HI > HBr > HCl
forms ethylene on reacting
with H2SO4 at 443 K

2° and 3° alcohols undergo

dehydration at comparatively
milder conditions. The order
of dehydration is:

3° > 2° > 1°

d. Oxidation or
Dehydrogenation reaction to
form aldehydes and ketones

Primary alcohols form

aldehydes

Strong oxidising agents

(KMnO4), form carboxylic acid
directly

CrO3 and PCC (pyrimidine

chlorochromate) are used to
get aldehydes

Secondary alcohols form

ketones on oxidation by CrO3

Tertiary alcohols do not

undergo oxidation. On
treating with KMnO4 at a
higher temp, dissociation of
C-C bond takes place
resulting in a mixture of
carboxylic acids with fewer
carbon atoms

e. Alcohols also undergo

dehydrogenation when
heated with Cu at 573 K.

1° alcohol → Aldehyde

2° alcohol → Ketone

3° alcohol → Alkene
(Dehydration)
3. Electrophilic Substitution: 3. Electrophilic
Substitution:
In Phenol, electrophilic aromatic
substitution takes place at ortho In Aryl ethers also
(o) and para (p) position electrophilic aromatic
substitution takes place at
a. Nitration with dil. HNO3 at 298
ortho (o) and para (p)
K gives mixture of o- and p-
position
Nitrophenols
Friedel Crafts Reaction:
p-Nitrophenol is less volatile due
to intermolecular hydrogen Halogenation and Nitration
bonding. In o-Nitrophenol, takes place at o and p
intramolecular hydrogen bonding position
is present
Anisole reacts with alkyl or
Nitration with conc. acyl halide in presence of
HNO3 forms Picric acid (2,4,6- AlCl3 (anhydrous) give o and
trinitrophenol) p substituted product

b. Halogenation: monosubstituted
phenols are formed in presence
of CS2 or CHCl3
 When treated with bromine water,
white precipitate of 2,4,6-
tribromophenol is formed

Kolbe’s Reaction

Phenol reacts with NaOH to form

sodium phenoxide

Salicylic acid (2-Hydroxybenzoic

acid) is formed when sodium
phenoxide undergoes
electrophilic substitution on
reacting with CO2

Some Important Alcohols and Ethers

Name Common Chemical Preparation Properties and Usage
Name Formula
Methanol Wood spirit CH3OH Catalytic hydrogenation Highly poisonous
of CO (carbon monoxide)
Used in paints and
varnishes
Ethanol Ethyl C2H5OH Fermentation of glucose Used in industries to
alcohol and sugar by enzymes make wine and other
like zymase and alcoholic drinks
invertase
 Ethanol is also used in
sanitisers and paint
industry
Phenol C6H5OH Prepared from cumene Precursor for various
and oxidation of benzene important compounds,
and toluene plastic and other polymers

Used as an antiseptic
Methoxybenzene Anisole CH3OC6H5 Prepared by Williamson It smells like anise seed
synthesis from sodium
It is precursor to perfumes
phenoxide and methyl
and pharmaceuticals
halide