CONCEPT Alcohols, phenols and ethers are the basic

ALCOHOLS, PHENOLS compounds of organic chemistry and they

find wide applications in industry as well as
in day-to-day life.

AND ETHERS
Chemical properties
l Cleavage of O—H bond : Ease of reaction depends on stability
Physical properties of alkoxide ion.
B.pt. µ No. of C-atoms Acidity : Phenols > Water > 1° alcohol > 2° alcohol > 3° alcohol
l Cleavage of C—OH bond : Ease of reaction depends on stability of
Solubility µ Branching carbocations.
Order of reactivity : 3° alcohol > 2° alcohol > 1° alcohol
ALCOHOLS l Reactions involving whole alcohol molecule :
443 K
(CnH2n+1OH) C C
413 K
Dehydration : R—OH + conc. H2SO4 ROR
142 pm
:O: 96 pm 383 K
RO—SO2OH
H 513 K
ROR
C 108.9° H Preparation R—OH + Al2O3 633 K
H sp3 l RX + KOH(aq.) ® ROH + KX C C
H conc. H2SO4/H2O [O] [O]
Oxidation : Alcohol Aldehyde/Ketone Carboxylic acid
(Markovnikov's addition)
Cu/273 K
l C C RCH2OH Dehydrogenation : 1° alcohol Aldehyde
Alkene (i) B2H6 in THF
Cu/273 K
(ii) H2O2, OH – 2° alcohol Ketone
(Anti-Markovnikov's addition) Cu/273 K
Dehydration : 3° alcohol C C
l HCHO H2/Pt or Pd or Ni
RCH2OH
Reduction

or 1° Alcohol
RCHO
NaBH4 or LiAlH4
or Distinction tests
or R CH R l Dichromate test (oxidation) : 1° alcohol ® Acid with same
or Na/C2H5OH
Grignard's

R number of C-atoms; 2° alcohol ® Ketone with same number of

reagent

C O OH
R
Carbonyl 2° Alcohol C-atoms; 3° alcohol ® No reaction under normal conditions.
(i) RMgX/Dry ether
compounds or l Victor Meyer’s test : 1° alcohol ® Blood red colour;
(ii) H2O/H + R3C—OH
2° alcohol ® Blue colour; 3° alcohol ® Colourless.
3° Alcohol
(i) LiAlH4 or B2H6/ether l Lucas test : 1° alcohol ® No turbidity; 2° alcohol ® Turbidity in
l RCOOH RCH2OH
PHENOLS Carboxylic acids
(ii) H3O + 5 minutes; 3° alcohol ® Turbidity appears immediately.
(C6H5OH)
109° Some important alcohols
H Methanol : Prepared by catalytic hydrogenation of carbon
: :

l
O
136 pm monoxide or water gas. It is used as a solvent, preservative,
Physical properties
sp2 substitute for petrol, etc.
l Pure phenols are colourless liquids or solids.
l Form intermolecular hydrogen bonds hence, soluble in water. l Ethanol : Prepared by the hydration of ethene or by the fermentation
of molasses. It is used as an antiseptic, power alcohol, in beverages, etc.

Preparation
NaOH NaOH dil. HCl Chemical properties
l C6H5SO3H –H2O C6H5SO3Na 573-623 K, C6H5ONa –NaCl
l Electrophilic substitution of phenols : Halogenation,
–Na2SO3, –H2O
dil. H2SO4, D
sulphonation, nitration, Friedel—Crafts alkylation, etc. occur at
– +
C6H5 N2Cl + H2O C6H5OH o- and p- positions due to activating effect of —OH group.
–N2, –HCl
Phenol
623 K, 320 atm dil. HCl
C6H5Cl + NaOH C6H5ONa –NaCl
–NaCl, –H2O
1. O2 Tests to distinguish phenols from alcohols
C6H5CH(CH3)2 FeCl3 test : Gives violet colour
2. H+, H2O l
Cumene
l Br2 – H2O test : Gives white ppt.
ETHERS l Liebermann’s nitroso test : Gives blue colour which turns red on
(CnH2n + 2O dilution
l Ammonia/Sodium hypochlorite test : Gives blue colour
where n > 1)
141 pm
:O: Classification l Azo dye test : Gives orange colour
H H l Simple or symmetrical : Same alkyl groups are attached to
H C 111.7° C H oxygen, ROR.
H sp3 H Physical properties
l Mixed or unsymmetrical : Different alkyl groups are l Dipolar due to slightly polar C—O bonds.
attached to oxygen, ROR¢.
l B.pts. are lower than isomeric alcohols due to lack of hydrogen
l Aliphatic ethers : R and R¢ both are alkyl groups.
l Aromatic ethers : Either one or both R and R¢ are aryl groups. bonding.
l Solubility in water (soluble due to formation of
H–bonds with water)
l Fairly soluble in organic solvents.
Chemical properties
l Reaction of ethereal oxygen :
l Lighter than water.
R +
ROR + HCl(conc.) O – H Cl– Preparation
R
:

conc. H2SO4, 413 K

2ROH
l Cleavage of C – O bond : or Al2O3, 523 K ROR
373 K
R – OR + HX R – OH + R – X D Ether
RX + RONa
– In case of alkyl aryl ethers, phenol and an alkyl halide are obtained. (Williamson synthesis) –NaX
dil. H2SO4 l Williamson synthesis involves SN2 mechanism in case of 1° alkyl
ROR + H2O 2R – OH halides.
D
ROR + PCl5 D 2R – Cl l In the case of 2° and 3° alkyl halides, elimination takes place.
l Reactions involving alkyl group : l Dehydration of alcohols for the formation of ethers follows the order :
– Formation of peroxides with air and light. 1° > 2° > 3°
– Substitution products obtained on halogenation.
l Electrophilic substitution reactions : Uses
Aryl alkyl ethers give o- and p-substituted products due to +R effect of Ethers are used as industrial solvents, heat transfer medium (diphenyl
alkoxy group (–OR). ether), flavouring agents and in perfumes.