Kansh

Alcohols, Phenols and Ethers

General Formula R-OH CoHs-OH R-0-R!
Compound Alcohol Phenol Ether
Alcohols and Phenols:
Classification:
IClassification based on
number of hydroxyl groups:
On the basis of number of -OH groups, alcohols are classified into
trihydric alcohols. Example, monohydric,dihydric and
CH,-CH,-OH
OH ÓH ÖH OH ÔH
Monohydric alcohol Dihydric alcohol Trihydric alcohol
Ethyl alcohoi Ethylene glycol Glycerol or glycerine
QH QH OH
OH OH OH
OH

OH OH OH
HÌ»
Monohydric phenol Dihydric phenol Trihydric phenols OH
Phenol Catechol Pyrogallol Hydroxyquinol Phloroglucinol
IIClassification based on the hybridization of carbon
containing OH group:
1) Alcohols containing OH group connected to sp carbon:
(i) Alkyl alcohols: -OH is connected to alkyl carbon.
Eg., CH3-CH,-OH Ethyl alcohol
(ii) Allylicalcohols: -OH is connected to allylic carbon.
Eg.. CH;-CH-CH,-OHAllyl alcohol
(ii) Benzylic alcohols: -OH is connected to benzylic carbon.
CH,-OH
Benzyl alcohol

Alkyl, allyl and benzyl alcohols are further classified intoprimary(1"), secondary(2") and tertiary(3)
alcohols depending onwhether -OHgroup is attached to primary(1), secondary(2) and tertiary(3)
carbon atoms.
2) Alcohols containing OH group connected to sp carbon:
(i) Vinylic alcohols: -OH is connected to vinylic carbon.
CH,-CH-OH Vinyl alcohol OH
(i) Aryl alcohols or phenols: -OH is connected to benzene ring.Phenol

Nomenclature
Compound Common name IUPAC name
ÇH,-CH,-CH,-CH,-0H n-butyl alcohol Butan-1-ol

1
CH;-ÇH-CH,-0H
CH; isobutyl alcohol
2-Methylpropan-1 -ol
CH-ÇH-CH,-CH,
OH sec-butyl alcohol
ÇH3 Butan-2-ol
CH--OH
CH tert-butyl alcohol
ÇH, 2-Methylpropan-2-ol
CH,-¢-CH,
CH -OH neopentyl alcohol 2,2-1
2-DimethyIpropan-1 -ol
OH

Cyclohexylalcohol Cyclohexanol
QH
CH;
0-cresol
2-Methylphenol
QH

m-cresol

QH
CH, 3-Methylphenol

p-cresol
CH,
QH
4-Methylphenol
OH
Catechol
OH Benzene-1,2-diol
Resorcinol
OH
OH
Benzene-1,3-diol
Quinol or Hydroxyquinone
OH Benzene-14-diol
2
 Ethers:
Classification:
(i) Simple or symmetrical ethers: Ethers with two similar alkyl groups atached to oxygen
Eg., CH,-0-CH;
(i1) Mixed or unsymmetricalether: Ethers with two different alkyl groups attached to oxygen
Eg., CH;-CH,-0-CH;
Nomenclature:
Compound Common name IUPAC name
CH;0CH3 Dimethyl ether Methoxymethane
CH;CH0CH; Ethyl methyl ether Methoxyethane
CH,-ÇH-0-CH;-CH, Ethyl isopropylether 2-Ethoxypropane
CH,
(CH;))CHOCH(CH3)2 Disopropylether 2-isopropoxypropane (or)
2-(1-Methylethoxy)propane
CH, Cycohexyl methyl ether Methoxycyclohexane

CoH_-0-CH; Methyl phenyl ether (or) Methoxybenzene

Anisole

CoH;-O-CH,CH; Ethylphenyl ether (or) Ethoxybenzene

Phenetole

CH),CH; Octyl phenyl ether 1-Phenoxyoctane

Diphenyl ether Phenoxybenzene

Q. The ROH bond angle in alcohol is less than the tetrahedral bond angle. Why?
It is due to greater repulsion between the lone pairs of electrons on oxygen atom.
( Q. The ROR bond angle in ether is greater than the tetrahedral bond angle. Why?
It is due to greater steric repulsion between the two bulky alkyl groups.
Q. The C-Obond length in phenol is less than that of methanol (or aliphatic alcohols). Why?
Itis because (i)The C-O bond in phenol has partialdouble bond character due to resonance effect.
and (ii) The carbon connected to -OH group is sp´ hybridized hence it forms shorter bond and stronger
bond.
Q. Phenol is less polar than methanol. (or) Dipole moment of phenol is less than that of methanol.
Why?
In methanolthere is only electron releasing inductive effect but in phenolthe electron releasing
inductive effect ispartly cancelled by electron withdrawing resonance effect of benzene. Moreover the
carbon connected to -OH group is sp hybridized and it forms shorter bond.
3
 Q. Lower alcohols are soluble in water. Why?
Lower alcohols form hydrogen bond with water.
Q. Solubility of alcohois decrease with increase in
size of alkyl group or increase in
atoms. Why? number of
carbon
Alkyl group isnon-polar and hydrophobic hence as the size of the
alkyl group increases
hydrophobic nature increases and the ability to form hydrogen bonding
Q. Solubility of alcohols increases with decreases.
branching. Why?
Branching reduces the surface area of alkyl group hence reduces the
Q. Boiling points of alcohols are
much higher than that of alkanes, ethers,hydrophobic effect.
similar nmolar mass. Why? aldehydes and ketones of
There is strong intermolecular hydrogen
Q. Boiling points of alcohols and bonding in alcohols.
phenols increase with increase in number of
with increase of branching. Why? carbons but decrease
With increase in number of carbon
atoms,
increase in Van der waal's force of attraction.molar mass and surface area increases hence there is
decreases the Van der waal's forces of Whereas branching decreases the surface area
attraction. hence
Preparation of alcohols:
(1)By acid catalysed hydration of alkenes (or)
Alkenes react with Catalytic hydration of alkenes: o
water in the presence of acid toform
alcohols:
CH, = CH, + HO H,SO4 CH;-CH,-OH Ethanol
Addition of H,0 to unsymmetrical alkene follows Markovnikov's rule.
H OH
CH;-CH=CH, + H,O
Mechanism of acid catalysed hydration of alkeneCH,-CH-CH,
to form
Propan-2-ol
alcohol:
The mechanism involves three steps
Step 1: Protonation of alkeneto form carbocation y
H,0 +H ’ H;0 elecoph ack
CH;-CH, + H;0 ’CH;-CH, + H,0
Step2: Nucleophilic attack of water on
carbocation
CH,-CH; + H,0 ’ CH,-CH,-OH,
Step3: Deprotonation to form alcohol
CH-CH,-OH; + H,0 ’ CH3-CH,-OH + H¡0*
2) Hydroboration-Oxidation:
Alkenes react with diborane to give
peroxide solution give alcohols.
trialkylboranes which on oxidation with
alkaline hydrogen
CH,-CH, + BH, ’CH;-CH,BH, CH;-CH,
(CH,-CH),BH CH,-CH, (CH;-CH,);B
H,0,/0H Triethyl borane
(CH,-CH,);B >3CH;-CH,-OH +B(OH):
4
In this reaction, water is
added indirectly toalkene to give alcohol.
In case Of unsymmetrical alkenes, the addition of water is accordin9 to
Propene on hydroboration and oxidation gives anti-Markovnikov's rule. Eg
propan-1-ol
CH,-CH-CH, (BH;), H,0,/OH 3CH,-CH,-CH,-OH+ B(OH)3
(CH;-CH,-CH);B
(OR)CH3-CH-CH, )(BH)2 CH;-CH,-CH,-OH
(i) H,0,/OH
)By catalytic reduction (or) catalytic hydrogenation of carbonyl compounds:
(i) Reduction of aldehydes and ketones:
Aldehydes and ketones can be reduced by lithium aluminium hydride (LiAlH),
sodium borohydride (NaBH4), NiH,, PH, or Pd/H,
alcohols.
Aldehydes on reduction give primary alcohols and ketones on reduction give secondary
Pd
CH,CH0 + H CH;CH,0H
NaBH4 CH,CH(OH)CH;
CH;COCH
(ii) Reduction of carboxylic acids:
Carboxylic acids are reduced to primary alcohols only by strong reducing agent LiAlH,
CH;COOH LiAlH4 CH;CH,OH
are converted esters and the esters are
A LiAlH4 is an expensive reagent, hence commercially, acids
reduced to alcohols by cheaper reducing agent like Ni/H,
H
CH,CH,COOH + CH;CH,0H CH;CH,COOCH,CH, + H,0

CH,CH,COOCH;CH; NiH, CH,CH,CH,OH + CH;CH;OH

amide
Sodium borohydride (NaBH4)can reduce only carbonyl group but cannot reduce acid, ester and
functional groups. Eg., NaBH,
CH;COCH,COOCH,CH; CH;ÇHCH,COOCH;CH;
ÖH
4) From Grignard reagents:
Grignard reagent reacts with carbonylcompound to form an adduct which on hydrolysis give alcohols
() With methanal or formaldehyde (HCHO), GR gives a primary alcohol.
(ii) With any other aldehyde (RCHO),GR gives secondary alcohol.
(iii) With any ketone (RCOR), GR gives tertiary alcohol.
Example;

5
(i)Methyl magnesium chloride on treatmentwith methanal (formaldehyde) followed by hydrolysis
gives ethanol (primary alcohol)
H. H,0*
CH;MgCI + ’ CH,-CH,-OMgCl CH;-CH,-OH + Mg(OH)CI

(i) Methyl magnesium chloride on treatment with ethanal (acetaldehyde) followed by hydrolysis
gives isopropyl alcohol (secondary alcohol)
CH3
CH;MgCI +
H
CC=0 > CHy- ÇH-OMgCI H;0, CH3- ÇH- OH + Mg(OH)CI
CH; CH;
(i1i) Methyl magnesium chloride on treatment with propanone (acetone) followed by hydrolysis gives
tert-butyl alcohol (tertiary alcohol)
CH; ÇH, ÇH
CH;MgCI +
CH3
CC=0 -CH- Ç-OMgCl Ho, CH;-Ç- OH + Mg(OH)CI
CH, CH;
Q. Write the mechanism for addition of Grignard reagent to carbonyl
group:
The reaction occurs in two steps. In the first step Grignard reagent adds to carbonyl group to form
an adduct. In the second step, adduct is hydrolysed to give alcohol.

RMgX
+E0 RÇ-OMgX H:0 RÇ-OH + Mg(OH)X
Laboratory preparation of phenolor carbolic acid:
(i)From haloarenes:
Chloro benzene is converted to phenol by heating in aqueous NaOH solution at 623 K and at 300 atm
pressure followed by acidificatioD.
PNa QH
(i) NaOH,623 K. 300 atm H

Chlorobenzene Sodium phenoxide Phenol

(ii) From benzene sulphonic acid:
Benzene is treated with oleum togive benzene sulphonic acid which on heating with NaOH followed
by acidification gives phenol.
^O,H OH
Oleum (i))NaOH
(ii) H
Benzene Benzene sulphonic acid Phenol

6
(iii)From diazonium salts:
Aniline is treated with amixture of NaNO, and HCI(or HNO,) togive benzene diazonium sa
on treating with warm water or dilute acids gives phenol.
OH
NH, NCI
NaNO, / HCI H,0
Heat
Phenol
Aniline Benzene diazonium chloride
from cumene (isopropyl benzene):
Industrial manufacture (or) Commercial synthesis of phenol
OX1dised by air to give cumene hydroperoxide which on hydrolysis gives phenol and
Cumene1S
acetone.

CH;-C-H
fH CH;--0-0-H
OH

H;0 + CH;COCH;

Phenol Acetone
Cumene Cumene hydroperoxide
Chemical reactions of alcohols: nucleophiles the O-H
both as nucleophiles and electrophiles. When alcohols react as
Alcohols react
electrophiles the C-0 bond is broken.
bond is broken but when they react as
Example for alcohols reacting as nucleophiles:

R-O-H R-O

elecrophiles:
Example for alcohols reacting as
R-OH, + Br R-Br + H,0
R-OH+ H ’
bond:
Reactions involving cleavage of O-H
1) Acidity of alcohols and phenols: reacted with active metals like Na, K, Aletc
Alcohols are weak acids and liberate H, gas when
2 CH,-CH,-ONa + H,
2CH;-CH,-OH + 2Na
Sodium ethoxide

2 CoHs-OH + 2 Na 2 CoH;-ONa + H
Sodium phenoxide
6(CH;);C-OH + 2 Al ’ 2lCH),C-0AI + 3 H,
Aluminium tert-butoxide
Acidity of alcohols:
Alcohols are amphoteric
The acidic nature of alcohols is due to the presence of polar 0-H bond.
Alcohols are Bronsted acids (or) Arrhenius acids because they give out H ions.
7
 The basic nature of alcohols is due to the presence of lone
pairs on oxygen. Hence they are lewis
bases.

Ka
R-OH + B B-H + R-O (alkoxide ion)
Alcohol Base Conjugate acid Conjugate base
Greater the Ka value (or lower the pKa value) greater is the acidic
Acidity of phenols:
strength.
The acidic strength of phenol is much greater than aliphatic
(i)Benzene ring withdraws electron from oxygen by alcohols. Explain.
of 0-H bond in phenols. resonance effect and thus increases the polarity
(ii) Eventhough both phenol and phenoxide are
resonance stabilised, phenoxide ion is more stable
than phenol because there is no charge separation in the
resonance structures of phenoxide. Therefore
the equilibrium moves to the right. Whereas alkoxide is less
stable than alcohol and hence the
equilibrium moves to the left.
QH

Phenol Phenoxide
R-OH R-O H
Alcohol Alkoxide
Resonance stabilisation of phenol:
AØH OH OH QH :ÖH

Resonance stabilisation of phenoxide:

0

Effect of substituent on acidic strength of phenols:

()The presence of electron withdrawing groups (-NO2, -CN, X etc) increases the acidic strength of
phenol.
Reason: By electron withdrawing resonance effect. they () increase the stability of phenoxide by
dispersalof negative charge. (i) increase the polarity of O-H bond.
(ii) The presence of electron releasing groups (-CHj, C;Us, OCH; clc) decreases the acidic strength of
phenol.
Reason: By electron releasing resonance effect. they (i) decrease the stability of phenoxide by
concentrating the negative charge on oxygen (ii) decrease the polarity of O-H bond.
O. Alcohols are less acidic than water. Why?
The alkyl group is electron releasing hence itdecreases the polarity of O-Hbond and also
decreasesthe stability of alkoxide.
Q. Alkoxide (OR ) is stronger base/stronger nucleophilethan hydroxide (OHdensity
).Wny on Oxygel.
electron
Ihe alkyl group is electron releasingeffect hence it increases the
Therefore alkoxide is a stronger base/stronger nucleophile than hydroxide
Q. Acidicnature of alcohols decrease with increase in branching at alpha carbon.
(or)
> tertiary. Why?
Acidic nature of alcohols decrease in the order: Primary > secondary also
number of alkyl groups increases at alpha carbon the electron releasing inductive effect
AS the also decreases the stability of alkoxide ion.
increases which decreases the polarity ofO-H bond and
Q. p-nitrophenol is more acidic than phenol. Why? stability of
group at para position withdraw electronby resonance hence it (i)increases the
NItro
polarity of 0-H bond.
phenoxide by dispersalof negative charge. (ii) increases the
Q. m-nitrophenol is more acidic than phenol. Why? stability
group at meta position withdraw electron by inductive effect hence it (i) increases the
Nitro
of phenoxide (ii) increases the polarity of O-H bond.
p-nitrophenol. Why?
Q. m-nitrophenol is less acidic than o-nitrophenol and
position hence nitro group at meta position can
This is because resonance is not possible at meta
effective than resonance. Whereas nitro group
withdraw electron only by inductive effect which is less
resonance effect hence it can increase the stability of
at ortho and para position withdraw electron by
phenoxide to greater extent.
Q. o-nitro phenol is less acidic than p-nitrophenol. Why? reduces the extent of ionisation.
The intramolecular hydrogen bonding in ortho nitro phenol
Why?
Q. p-cresol (4-methylphenol) is less acidic than phenol. (i) decreasing the stability of
Methyl group is electron releasing hence it decreases acidic strength by
polarity of O-H bond.
phenoxide by concentrating the negative charge on oxygen (ii) decreasing the
2) Esterification (or) Acylation:
The introduction of acyl (RCO) group in alcohols and phenols to form ester is known as acylation
reaction or esterification reaction. Carboxylicacids, acid chlorides and acid anhydrides are used as
acylating agents. Eg.,
H
R-OH + R'-COOH R-0COR' + H,0
(i) Acetylation:
The introduction of acetyl (CH,CO) group in alcohols and phenols is known as acetylation
reaction.

9
 H CH;COOC,Hs H,O
CH;CH,OH + CH;COOH
H + CH3COOH
CH;COOC,Hs
CH;CH,OH + (CH,CO),0
Acetic anhydride Ethyl acetate

Pyridine CH,CO0CçHs + HCI

CoH;OH + CH;COCI
Acetylchloride Phenyl acetate
Aspirin is produced by acetylation of salicylic acid. Aspirin is an analgesic (reduces pain), anti
inflammatory and antipyretic (reduces fever). IUPAC name of aspirin is 2-acetoxybenzoic acid.
ÇOOH ÇOOH
OH
H
ocOCH;
+ CH,COOH
+ (CH,CO,0

Salicylic acid Acetyl salicylic acid (Aspirin)

(ii) Benzoylation:
The introduction of benzoyl (CoH,C0) group in alcohols and phenols is known as benzoylation
reaction.
H
C,H,OH + CoH,COOH CoH,COOC,H; H,0
Q. Acylation with carboxylic acid and anhydride is carried out in the presence of H (or) small amount
of concentrated sulphuric acid. Why?
The reaction is reversible. The acid is used to remove the side product water and to shift the
equilibrium in forward direction.
Q. Acylation with acid chloride is cariedoutin the presence of a strong base like pyridine. Why?
The reaction is highly reversible. The base pyridine is used to neutralise the side product HCl and
thus to shift the equilibrium to the right.
Reactions involving cleavage of C-O bond:
1) Reaction with HX:
Alcohols react with HX to form alkyl halides.
R-OH + HX ’ R-X + H,O
Lucas test:
This test is used todistinguish primary, secondary andtertiary alcohols and it isbased on their
difference in reactivity.
Thealcohol is treated with Lucas reagent which isa mixture of con. HCland anhydrous ZnCl..
Alcohol is soluble in Lucas reagent whereas the product chloroalkane in insoluble and produce
turbidity.
If the turbidity appears immediately, it is tertiary alcohol. If the turbidity appears after 5-10
minutes, it is secondary alcohol. If turbidity is not produced at room temperatue but produced only on
heating, it is primary alcohol.
10
2) Dehydration:
ZnCi2 O
Alcohols on heating with concentrated H»SO, or HPO, or catalyst like anhydrous
alumina undergo dehydration to form alkene. Secordaly
of conc. HSO, to formethene.reactive.
Ethanol undergoes dehydration at 443 K in the presence they are more
and tertiary alcohols undergo dehydration under mild conditions because

CH;CH,OH H2SOy
443 K
CH,-CHa + H0
85% H,PO4 CH,-CH=CH, + H,0
CH;CH(OH)CH; 440K

20% H;PO, + H,0

CH,--OH 358 K
CH--CH:
CH: CH; decreasing
> secondary > primary. This is due to
follows the order: tertiary
The rate of dehydration carbocations.
order of stabilities of the respective
reactive to dehydration. Why?
Q.Tertiary alcohol is the most stable hence it is readily formed from tertiary
alcohol.
Tertiary carbocation is the most
at 443K toform ethene:
Mechanism of dehydration of ethanol
steps
The mechanism involves three
protonatedalcohol.
Step 1:Formation of
CH;-CH,-OH + H ’CH;-CH,-0H;
Step2: Formation of carbocation: +H,0
CH;-CH,
CH;-CH,-OH,*
form alkene
Step3: Deprotonation to
CH,-CH, ’ CH,-CH, + H
3) Oxidation of alcohols: aldehydes and then to carboxylic acids by stronger oxidising
to
(i) Primary alcohols are oxidisedpermanganate (KMnO4/H), acidified potassium dichromate
agents like acidified potassium
(KzCr;0,/H)and chromic acid (H,CrO4)
(0) CH;CHO
(0) CH;COOH
CH;CH,OH
(ii)Controlled oxidation: reagents are used.
to stop the oxidation at aldehyde, the following mildoxidising
dichloromethane as solvent. PCC is a complex of pyridine
Inorder
(1)Pyridinium chloro chromate (PCC) in affect double bond. It oxidises primary alcohols to
trioxide and HCI. PCC does not
with chromium
aldehydes and secondary alcohols to ketones.
Anhydrous CrO3. It also oxidises primary alcohols to aldehydes and secondary alcohols to
(2)
ketones. 11
 PCC. C
CH,-CH-CH-CH,-OH CH,CI?
But-2-en-l
CH;CH(OH)CH; Anltyd.Cro CH;COCH;
Propan-2-ol Propanone
(iii) Ketones are not easily oxidised. But under vigorous conditions, ketones are oxidised to a mixture
of carboxylic acids.
KMnO4/H
CH,COCH,CH,CH; High temperature
CH,COOH + CH,CH,COOH

(m) Tertiary alcohols do not undergo oxidation under normal condition but under vigorouscondition
they get Oxidised to a mixture of carboxylic acids with less number of carbon atoms.
4) Dehydrogenation:
When the vapours of primary and secondary alcohols are passed through copper tube at
S73 K, they undergo dehydrogenation.Primary alcohol gives aldehyde and secondary alcohol gives
ketone.
Cu
CH;-CH-OH CH,-CHO
573 K

CH,CH(OH)CH, Cu CH,COCH,
Propan-2-ol 573 K
Propanone
Tertiary alcohols do not undergo dehydrogenation due to absence of
dehydration to form alkenes. alpha hydrogen but undergo
ÇH;
Cu
CH-¢-OH 573 K CH-Ç-CH + H0
CH,
CH,
Reactions of phenol:
1) Electrophilic aromatic substitution:
OHgroup in phenol is strongly activating and ortho/para directing.
(i)Nitration:
(a) Mononitration: Phenol when treated with dilute
nitric acid gives a mixture of ortho and paranitro
phenols.
QH OH QH
NO,
Dilute HNO,

NO,
Phenol o-Nitrophenol p-Nitrophenol

12
 2,4,6-trinitrophenol also
(b) Trinitration: Phenol when treated with concentrated nitric acid gives 2
known as picric acid. OH
OH NO,
0,N
Conc. HNO; Picric acid

NO2
distillation. Why ! attraction between the
Q. Ortho and para nitro phenols can be separated by steam hence force of
In o-nitrophenol there is intramolecular hydrogen bonding
Hence it is volatile in steam. amount of
molecules is weak Van der waal's force of attraction. bonding hencelarge
hydrogen
Whereas p- nitrophenol is associated by intermolecular is non-volatile in steam. Also it has
bonds. Therefore it
energy is required to break the hydrogen
higher boiling point than o-nitrophenol.
(i)Halogenation:
(a) Monosubstitution (or) monobromination: low polarity i.e. organic solvent like CS; or CCl4
a solvent of
Phenol when treated with Br, in
phenols.
gives a nmixture of ortho and para bromo QH
OH
QH Br
Br2
CHCI;/CS,
Br
p-Bromophenol
o-Bromophenol
gives 2,4,6
Phenol
tribromination: Phenol when treated with aqueous bromine
(b) Trisubstitution (or)
tribromophenol. QH
Br
OH Br

Br/H,0
Br

by acidification gives salicylic acid.

2)Kolbe's reaction:
CO, followed
Sodium phenoxide when treated with
ONa OH
QH COOH
NaOH () CO Salicylic acid (or)
(ii) H" 2-Hydroxy benzoic acid

13
 3) Reimer-Tiemann reaction:
Phenolwhen when treated with chloroform and alkali followed by acidification gives
salicylaldehyde.
QH ONa ONa OH
CHCI; CHO CHO
CHCl, + NaOH NaOH H

Intermediate Salicylaldehyde (or)

4) Reaction with zinc dust: 2-Hydroxy benzaldehyde
Phenol when heated with zinc dust gives benzene.
OH

Zn

Oxidation of phenol:
Phenol is oxidised tobenzoquinone by
acidified potassium dichromate. chromic acid (or) acidified potassium permanganate (or)
QH

Na,Cr,07
H,SO4
Benzoquinone
Phenols are oxidised by air to give a dark
Commercially important alcolhols: coloured mixture containing quinones.
Methanol and ethanol are the two commercially
Methanol is also known as wood spirit because itimportant
was
alcohols:
() Commercial synthesis of produced by destructive distillation of wood.
methanol from water gas:
Methanol isproduced by catalytic
300atm pressure and in the hydrogenation
presence
of
of carbon monoxide at 573 673 K
and at 200 -
ZnO- CrrO; catalyst.
CO + 2H, ZnO-Crn03
573 673 K CH;OH
200 -300 atm
(ii) Commercial synthesis of
ethanol:
Ethanol is manufactured by
|-Grapes are the source of sugar forfermentation of sugar in molasses,
sugarcane or in grapes using yeast.
making wine. Fermentation is anaerobic
converts sugar to ethanol in the absence of process because yeast
Theenzyme invertase present in Oxygen.
yeast converts sugar into glucose and
fructose.

14
 C1rH2O11 + H,0 Invertas CotHi0% + CoHi20%
Glucose Fructose
Sucrose and COz.
and fructose into ethanol
Another enzyme zymase present in yeast converts glucose

Zymase + 2C0; until

CoH0% 2C,H,0H
purifiedbyfractional distillation
Ethanol produced by fermentation is very dilute. It is H,SO4.
removed by using conc.
95% (v/v) of ethanol is produced. Remaining water is
rectified spirit or rectified alcohol.
95% (v/v) of ethanol in water is known as
or absolute spirit.
100% pure alcohol is known as absolute alcohol foul
and copper and
smelling and poisonous)denatured spirit
Commercial ethanol is mixed with pyridine (which is known as
Thisis
for drinking.
sulphate(which gives blue colour) to make it unfit
alcohol.
the process is known as denaturation of itis known as methylated
spirit.
is a poison),
If ethanol is mixed with methanol (which solvent in paint industry, as fuel etc
in alcoholic beverages, as
EthanoLis used
only in anaerobic condition. Why? spoils the taste of alcoholic drinks.
Q. Fermentation must be done ethanoic acid which
presence of air ethanol is oxidised to
n the
Preparation of ethers:
ether.
1) By dehydration of alcohols: presence of sulphuricacid at 413 K to give diethyl
Ethanol is dehydrated in the
H;SOs + H,0
2CH,CH,OH 413K
CH,CH,0CH,CH)
ether:
ethanolat 413 K to form diethyl
Mechanism of dehydration of
three steps
The mechanism involves
protonatedalcohol:
Step 1: Formation of CH;-CH,-OH;
CH-CH,-OH + H ’
protonated alcohol:
Step2: Nucleophilic attack on
CH;-CH-Q-CH,-CH; + H,0
CH;CH,OH + CH;-CH,-OH, ’ H
Nucleophile Electrophile
form ether:
Step3: Deprotonation to
+
CH;-CH,-0-CH,-CH; + H
CH;-CHy-Q-CH;-CH; ’
Limitations: H
cannot be used to get ethers because they dehydrate to give alkenes
(i) Secondary and tertiary alcohols
as major product. are used.
is not suitable to prepare unsymmetrical ethers because when two alcohols
(ii) This method
productswhich are difficult to be separated.
the reaction gives mixture of many
15
 appropriate for the preparation of ethyl methyl ether. Explain?
dehydration is not aredifficult to be
separated.
Q. Bimolecular mixture of many products which
The reaction gives
2) Williamson synthesis: produce ethers.
sodium alkoxide to
Alkyl halides react with
+ NaX
R-X + R- ONa ’R-0-R
CH;CH,-0-CH; + NaX
CH;CH,Br + CH;ONa ’
Limitationsof Williamson synthesis:
unsymmetrical ethers containing a secondary or tertiary alkyl group, aprimary
((i)lnorder to prepare
alkoxide.
halide must be used with a secondary or tertiary
ethyl halide must be treated with sodium
Example, in order to prepare tert-butyl ethyl ether,
tert-butoxide.

ÇH, NaBr
CH-(-ONa CH,CH,Br CH-¢-0-CH,CH;
CH:
Sodium tert-butoxidert-butyl ethyl ether
Secondary and tertiary halides cannot be used because in the presence of alkoxide which is a stronger
base, secondary and tertiary halides undergo elimination to give alkenes as major product. Exanmple,
ÇH;
CH,-C-Br CH:CHONa CH,--CH; + CH;CH,OH + NaBr
CH;
tert-butyl alcohol sodium ethoxide 2-methylpropene
(iü)In order to prepare aryl alkyl ethers, alkyl halides must be treated with sodium phenoxide. Eg.
ONa OCH,
+ CH;Br + NaBr

Sodium phenoxide Methoxy benzene (Anisole)

While preparing aryl alkylethers, aryl halides should not be used because arylhalides donot
undergo nucleophilic substitution reaction.
Reactions of ethers:
1) Cleavage of C-0 bond in ethers: Reaction with HX
(i) When ethers are treated with HX in equal mole ratio, an alkyl halide and an alcohol are produced.
R-O-R + HX ’ RX + ROH
(ii) When ethers are treated with excess of HX, to moles of alkyl halides are produced.
R-0-R + 2 HX 2RX + H,0
Product formation in case of unsymmetrical ethers:

16
 (i)Ifthere is no tertiary alkyl group, then the halogen goes with smaller alkyl group. Example,
CH-0-CH,-CH; + HI ’ CH-I + CH,-CH,-OH lesser steric
Reason: The reaction follows SN2 mechanism. Hence the halide attacksthe carbon with
hindrance.
tertiary halide.
(ii) If there is a tertiary carbon, then halogen goes to tertiary carbon producing. a
Example,
ÇH
CHy-Ç-0-CH, + HI ’ CH,-C-1 + CH3-OH
CH3 H;
nstSp
mechanism ifthere is atertiary alkylgroup. In the leadingto the
Reason: The reaction follows Sul second step
carbon inthe
tertiary carbocation is formed and halide attacks the tertiary
formation of tertiary halide. halides. Example,
combines with alkyl group forming alkyl
(iii) In alkyl aryl ethers, the halogen
OCH3 OH
CH;-I
+ HI
hence its
partial double bond character due to resonance
carbon-0xygen bond has therefore it attacks
Reason: The phenyl
halide ion is sterically hindered by benzene ring
the
cleavage is difficult. Moreover
the alkyl group. HF
of reactivity of hydrogen halides: HI >HBr>HC>
The order
enthalpy.
This is due to increase in bond
due to low bond enthalpy.
HIis the most reactive substitution:
is the major
2 Electrophilic
aromatic
activating and ortho/para directing. Para isomer
ethers is
Alkoxy group in aromatic
hindrance.
product due to lesser steric
acid
(i) Nitration: concentrated nitricacid and concentrated sulphuric
mixture of
Anisole when treated with a o-nitroanisole and p-nitroanisole. OCH;
gives a mixture of
(Nitrating mixture) OCH;
QCH; NO
Con. H,SO4
+Con. HNO,
NO,

17
(i) Halogenation: aceticacid gives mixture of o-bromoanisole and
a
bromine in
Anisole when treated with
p-bromoanisole. pCH;
QCH;
OCH; Br
CH,COOH
+ Br
Br

(ii) Sulphonation: concentrated sulphuric acid gives a mixture of o-methoxy

Anisole when treated with
OCH;
benzenesulphonic acid and p-methoxy benzenesulphonic acid.
QCH; oCH;sO;H
Con. H;SO, `O,H

(iv) Friedel - Crafts alkylation of anisole:

presence of anhydrous AlCl3 gives a mixture of
Anisole when treated with chloromethane in the
o-methoxy toluene and p-methoxy toluene.
OCH;
QCH; pCH;
CH;
Anhyd. AICI
+ CH;CI
CH;

(iv) Friedel - Crafts acylation of anisole:

anhydrous AICl; gives a mixture of
Anisole when treated with acetylchloride in the presence of
2-methoxy acetophenone and 4-methoxy acetophenone. QCH;
QCH;
QCH; COCH;
Anhyd. AICl;
+ CH;COCI
COCH;
alcohols. Why?
converted to esters and then reduced to
0. Commercially, acids are expensive reagent. But esters can be reduced
reduced by LiAIH, which is an
Carboxylic acids are converted to
agent like Ni/H), Hence to make the process economical, acids are
by cheaper reducing alcohols.
esters and then reduced to alcohols. Why?
much lower than the isomeric
Q. Boiling points of ethers are forces whereas alcohols have stronger
intermolecular
Ethers have only weak dipole-dipole
hydrogen bonds.
in water. Why?
). Lower ethers are soluble with water hence they are soluble.
can form hydrogen bonds
Lower ethers 18
 substitution. Why?
aromatic
group in phenol is ortho and para directing towards electrophilic increases the
O.-OH electrons it
is electron releasing by resonance effect and by releasing
Hydroxy group
electron density at ortho and para positions. aromaticsubstitution. Why?
activating towards electrophilic increasesthe
Q. -OH groupin phenol is strongly releasing electrons it
and by
Hydroxy group is electron releasing by resonance effect
reactivity.
overallelectron density in benzene. Hence it increases the directing towards electrophilic
and para
Q. Alkoxy group (-OR) in aromatic ethers is ortho increases the
substitution. Why? electrons it
releasing by resonance effect and by releasing
Alkoxy group is electron substitution.
electrophilic
electron density at ortho and para positions. towards
Q. AlkOxy group (-OR)in
aromatic ethers is strongly acctivating increases the
releasing electrons it
Why? resonance effect and
by
Alkoxy group is electron releasing by reactivity.
electron density in benzene. Hence it increases the FeBr3. Why?
overall
bromination even in the absence of catalyst and strongly
activating.
undergoes resonance
Q. Phenol electron releasing by
Becausethe -OH group in phenol is FeB3. Why? activating.
bromination even in the absence of catalyst resonance and strongly
Q. Anisole undergoes anisole is electron
releasing by
Because the methoxy group in
and causes brain
harmful effects of ethanol? the ability to thing
Q. What are the hence it reduces
centralnervous system consciousness and even death.
Ethanol acts on the nausea, loss of
concentration, it causes
damage. Athigher effect and unpleasant
use of diethyl ether. because of its slow
). Give one anaesthetic but
as general
used
Diethylether was widely anaesthetics.
period it is replaced by better
recovery
test to distinguish phenol from ethanol. doesn't.
Q.Give a chemical
neutral FeCl; solution whereas ethanol
with
Phenol gives violet colour

19