21 Alcohol Phenol Ether Revision Notes Quizrr

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ALCOHOL
PHENOL
ETHER
QUIZRR 3
ALCOHOLS
1. Physical Properties :
Ć The polar nature of the O-H bond (due to the electronegativity different of the atoms) results
in the formation of hydrogen bonds with other alcohols molecules or other H-bonding systems
(e.g. water). The implications of this are :
Ć High melting and boiling points compared to analogous alkanes
Ć High solubility in aqueous media
2. Structure :
Ć The alcohol functional group consists of an O atom bonded to a C atom and a H atom via
 bonds.
Ć Both the C-O and the O-H bonds are polar due to the high electronegativity of the O atom.
Ć Alcohols are bent shaped molecules. The central ÂOÊ atom is also sp3 hybridised and the
C-O-H bond angle is 105Ĉ.
105Ĉ
R H
3. Reactivity :
Ć The alcohol O atom are a region of high electron, density due to the lone pairs.
Ć Alcohol oxygen atoms are Lewis bases.
Ć So alcohols can react as either bases or nucleophiles at the oxygen.
Ć There is low electron density on H atom of the O-H group alcohol, i.e. H+ character.
Ć So alcohols are acidic (pKa ~ 16).
Ć The -OH group is a poor leaving group and needs to be converted to a better leaving group
before substitution can occur.
4. Solubility of alcohols :
The first three members are completely miscible with water. The solubility rapidly decreases with
increase in molecular mass. The higher members are almost insoluble in water but are soluble in
organic solvents like benzene, ether etc. The solubility of lower alcohols is due to the existence of
hydrogen bonds between water and polar -OH group of alcohol molecules.Phenols too are sparingly
soluble in water. The -OH group in alcohols contains a hydrogen bonded to an electronegative
oxygen atom. Thus they form hydrogen bonds with water molecules.
ALCOHOLS, PHENOLS & ETHERS

4 QUIZRR
H H
| |
R · O - - -H · O - - -H · O - - -H · O - - -
| |
H R
The solubility of alcohols in water decreases with increase in molecular mass because greater
carbon content makes alcohol less hydrophilic. In addition, among the isomeric alcohols, the
solubility increases with branching of chain. As the surface area of the non-polar part in the
molecule decreases, the solubility increases.
5. Acidity :
Ć Due to the electronegativity of the O atoms, alcohols are slightly acidic

Ć The anion derived by the deprotonation of an alcohol is the alkoxide.
Ć Alkoxides are important bases in organic chemistry.
Ć Alcohols react with Na (or K) like water to give the alkoxide :
2 RăOăH + 2 Na  2 NaOR + H2
2 HăOăH + 2 Na  2 NaOH + H2
NOTE : Alcohols containing more than one ăOH group linked to the same carbon atom are
highly unstable and lose water to form more stable aldehydes or ketones.
OH H
ăH2 O
CH3 CH OH CH3 CH = O
Unstable Ethanal
EXCEPTION : Few exception to the above point can be noted.
H
O Cl O
H2 O
(1) Cl3C C Cl C CH
H Cl O
H

QUIZRR 5
In this compound, owing to the presence of hydrogen bonding, alcoholic content is found to
be considerably higher.
H
Oă O
O
(2) Oă HOH
O
Oă O H
minhydrin hydrate
Classification of alcohols :
(1) Monohydric alcohols  only one ăOH group is present.
For example
CH3 CH3 OH OH
Ethanol
Cyclohexanol
(2) Dihydric alcohol : two ăOH groups are present in same molecule.
OH
CH2 · CH2 OH
| |
OH OH
1, 2-Ethanediol or
Ethylene glycol
1,2-Dihydroxy benzene
or catechol
(3) Trihydric alcohols : three ăOH groups present.
OH CH · C H · CH2
| | |
OH OH OH
Glycerol
OH OH
1,3,5-Trihydroxy benzene
or phloroglucinol

6 QUIZRR
Example 1
Explain the following :

(a) When equal volumes of ethanol and water are mixed, the total volume is less than
the sum of the two individual volumes.
(b) Propanol (MW = 60) has a higher boiling point than butane (MW = 58)
Solution :
(a) The water solubility of alcohols is attributed to intermolecular H-bonding with H2O. As the
molecular weights of the alcohols increase, their solubility in water decreases, because greater
carbon content makes the alcohols less hydrophilic. Conversely, their solubility in hydrocarbon
solvents increases.
(b) Hăbonding between ethanol and water molecules.
(c) Alcohol molecules attract each other by relatively strong Hăbonds and somewhat weaker
dipole ă dipole interactions, resulting in a higher bp. In alkanes only weaker van der WaalsÊ
attractive force must be overcome to vaporize the hydrocation.
PREPARATION OF R-OH
A summary of all the methods of preparation is given below.
ă
H2O or HO
Hydrolysis of Alkyl Halides CăX C OH
+
H
Hydration of Alkenes C=C H2O H C C OH
1.BH3
Hydroboration-Oxidation of Alkenes C=C H C C OH
2. H2O2/NaOH
Oxymercuration Demercuration
of Alkenes
1.Hg(OAc)2/THE/H2O
C=C H C C OH
2. NaBH4

QUIZRR 7
Organometallics with Aldehydes

and Ketones
O OH
R Li
or + C R C R´
work-up
R Mg X with H+
R R´ R
O OH
LiAlH4
or + C H C R´
Reduction of Aldehydes work-up
NaBH4 with H+
and Ketones R R´ R
O OH
R Li
or + C R C R´
Organometallics with Esters work-up
R Mg X with H+
R R´ R
O OH
LiAlH4 + C H C R´
Reduction of Esters work-up
with H+
R´ OR´´ H
O OH
Reduction of Carboxylic LiAlH4 + C H C R´

work-up
with H+
Acids R´ OH R
RMgX
+ O R C C OH
Opening Epoxides or work-up
RLi with H+

8 QUIZRR
1. From alkyl Halides
Alkyl halides when boiled with aqueous solution of KOH or moist silver oxide furnish alcohols.
C2H5Br + KOH (aq)  C2H5OH + KBr
Primary alkyl halides give good yield of alcohols. However, tertiary alkyl halides mainly undergo
dehydrohalogenation resulting in formation of alkenes.
CH3 CH3
CH3 C Br + KOH CH3 C CH2 + KBr + H2O
CH3
2. FROM ALKENES
2.1 Hydration of Alkenes
CH3 CH CH2 + H2O CH3 CH CH3
OH
MECHANISM :
CH3 CH3
+
H
CH3 C CH = CH2 + H2O CH3 C CH · CH3
+
H H
CH3 CH3
H3C C CH2 + CH3 H3C C CH2 CH3

+
OH
Some points :
(1) Addition is predicted by MarkonikovÊs rule
(2) Reaction proceeds via protonation to give more stable carbocation intermediate.

QUIZRR 9
2 .2 Hydroboration / oxidation of Alkenes
1.BH3
C C + H2O H C C OH
2.BH3/NaOH
Alkenes react with diborane to form trialkyl boranes, which upon treatment with alkaline H2O2
give alcohols via anti-Markowni koffÊs addition of water. Also, it is a ÂsynÊ reaction.
Mechanism :
CH3 CH CH2 CH3 CH2 CH2
BH2
H B H
H2O2
3(CH3 CH2 CH2 OH ) + B(OH)3 ă CH3 (CH2 ) B (CH2 )2 CH3
OH
(CH2 )2 CH3
Now, let us also see the mechanism of the following reaction.
B  OH 3
NaOH
R3 B 
 3ROH 
H2O2
ă
H O O H + OH H O Oă + H2O
ă
R O OH R
ă
R B R B O O H
R R
Here lone pair - lone pair

repulsion is present, hence
the bond breaks
ă
OH

10 QUIZRR
OR R
Repeat
B OR R B OR
it again
O 2 times
R
ă
OH
2ROH + B(OH)3
Some Important Points :
B2H6/THF
(1) R C CH (R HC CH2 )3B
protolysis
CH3COOH Oxidation
H2O2/NaOH
R CH CH2
R CH CH OH
tautomerism
RCH2CHO
(1) B2H6/THF
R C C R R C C R
(2) CH3CHOOH
H H
(2) Double bond can also be selectively reduced by B2H6/THF at the least hindered
position.
For example :
unhindered
CH = CH2 CH2 CH2 BH2 CH2 CH3

(1)
B2H6/THF CH3COOH
hindered
alkene
CH · CH2 CH(CH3)2 CH(CH3)2
CH3

QUIZRR 11
(i) (BH3)2
(2) (ii) H2O2,OH
CH3 H
H3C H OH
1-methyl cyclopentene 2-methyl cyclopentene
syn-addition
2 .3 By oxymercuration-dimercuration
Alkenes can be converted into alcohols by oxymercuration-demercuration reaction. In this

reaction, addition of water takes place according to MarkownikoffÊs rule.
CH3COO 2 Ag
CH2  CH  CH2  H2 O   CH3  CH  CH3
NaBH4 |
OH
Mechanism :
H
H H H
O O+
CH3 CH CH2 CH3 CH CH2

+
Hg HgOCOCH3
ăH +
OH OH
NaBH4
CH3 C CH2 CH3 C CH2
H HgOCOCH3

12 QUIZRR
Example 2
D 2O,  CH3COO  Hg
CH 3  CH 2  CH 2  2  ?
Na BD4
Solution :
OD
D2O
CH3 CH CH2 CH3 CH CH2
(CH3COO)2Hg
HgOCOCH3
NaBD4
OD
CH3 CH CH2 D
Example 3
CH3 CH3 HgOCOCH3

Hg(OAC)2
H3C C CH CH2 H3C C CH CH2
+H2O
CH3 CH3 OH
NaBH4
CH3
H3C C CH CH3
CH3 OH
3. FROM ALDEHYDES AND KETONES
3.1 By using Grignard Reagents

When a solution of an alkyl halide in dry ethyl ether, (C2H5)2O, is allowed to stand over turnings
of metallic magnesium, a vigorous reaction takes place. The resulting solution is known as Grignard
reagent. It is one of the most useful and versatile reagents known.
Dry ether
RX  Mg  R MgX
Alkyl halide Alkyl magnesium halide

QUIZRR 13
The carbon-magnesium bond is covalent but highly polar, with carbon pulling away electrons
 
from electropositive magnesium but the magnesium-halogen bond is essentially ionic, R M gX
The Grignard reagent belongs to a class of compounds called organometallic compounds, in which
carbon is bonded to a metal like lithium, potassium, sodium, zinc, mercury etc. Each kind of
organometallic compound has its own set of properties
But whatever the metal, it is electro negative than carbon and the carbon metal bond is always
highly polar. Although the organic group is not a full fledged carbanion but has considerable
carbanionic character. The, organometallic compounds can serve as a source of carbon bearing
negative charge.
So, when Grignard reagent is added to carbonyl compounds, the organic group attaches to carbon
and magnesium to oxygen.
+ ă ă +
C = O + R M gX C OMgX
H2O
C OH + Mg(OH)X
HX
Mg (OH) X 
 MgX 2  H2 O
Products formed by Grignard synthesis :

(a) Formaldehyde yields primary alcohol
(b) Any other aldehyde yields secondary alcohol.
(c) Ketones yield tertiary alcohols.
NOTE :
(1) Sterically hindered t-alcohols cannot be prepared by grignard reagent, but can be
prepared using lithium alkyls. This is because lithium compounds are usually more
reactive and yield a better product.

14 QUIZRR
O
tBuMgBr
tBu C tBu X
tBu
tBuLi
tBu C OH
tBu
(2) For compounds like CH2 CH2 , the reaction is :
OH Cl
Mg
CH2 CH2 CH2 CH2 MgCl
ether
OH Cl OH
CH2 CH2
OH Cl
CH2 CH3 CH2 CH2 OMgCl

+
OH Cl
(3) Reaction of RMgX with epoxide ring
O OMgX
+ ă
R (MgX)
H3C C CH2 CH3 C CH2R
SN2
CH3 CH3
H3O+
CH3
CH3 C CH2R
OH

QUIZRR 15
O
OMgX
(4) RMgX
CH2 CH CH CH2 CH2 CH CH CH2
{1Ĉ alcohol will be formed because of the allylic nature of 2Ĉ carbon}
3 .2 By reduction
The chemical reducing agents like Lithium aluminium hydride (LiAlH4), H2/Ni, B2H6/THF etc. are
used to produce alcohols.
(i) LiAlH4
LiAlH
(a) R · CHO 
4 · R · CH2 OH
LiAlH
(b) C  O 
4 CH · OH
LiAlH
(c) R · COOH 
4 R · CH2OH
LiAlH
(d) R´ · COOR 
4 R´ · CH2 · OH ·  ROH
LiAlH
(e) R · COCl 
4 R · CH2 · OH
(f)  RCO 2 O 4LiAlH

 R CH2 · OH
O LiAlH4
(g)
OH
CH2 CH2
LiAlH4
(h) R CH C=O R CH CH2 CH2 CH2 OH
O
OH
 Lactone

16 QUIZRR
Note : LiAlH4 does not reduce double or triple bonds however if double or triple bonds is in
conjugation with (C = O) group, then double or triple bond is also reduced.
LiAlH
CH2  CH · CH2 · CHO 
4 CH2  CH · CH2 · CH2 OH
LiAlH
Ph · CH = CH · CHO 
4 Ph · CH2 · CH2 · CH 2 OH
O OH
LiAlH4
(ii) Using NaBH4

It can reduce all the groups which are reduced by LiAlH4 but cannot reduce carboxylic acid
and ester. It can also reduce only the double bond which are in conjugation with C = O
group.
(iii) By H2/Ni
It can reduce all the groups reduced by LiAlH4 and it can also reduce double and triple
bonds in the carbonyl compounds irrespective of the position.
H / Ni
CH3 · CH  CH · CHO 
2  CH3 · CH 2 CH2 CH2 · OH
H / Ni
CH2  CH · CH2 · CHO 
2  CH3 CH2 CH2 CH2 · OH
Note : Hydrogenolysis (cleavage by hydrogen) of an ester requires more severe conditions

than simple hydrogenation of (addition of hydrogen to) a carbon-carbon double bond. High
pressure and elevated temperatures are required : the catalyst used most often is a mixture
of oxides known as copper chromite, of approximately the composition CuO. CuCr2O4. For
example
CH3  CH2 10 COOCH3   CH3  CH2 10 CH2 OH  CH3 OH
H , CuO CuCr O
2 2 4
150, 5000 lb/in2
 Methyl dodecanoate  1 Dodecanol

QUIZRR 17
Chemical reduction is carried out by use of sodium metal and alcohol, or more usually by
use of lithium aluminium hydride. For example
CH3  CH2 14 COOC2H5  CH3  CH2 14 CH2 OH

4 LiAlH
 Ethyl hexadecanoate  1Hexadecanol
We have learnt that one molecule of an ester on reaction with excess of Grignard reagent
followed by acidification produces a tertiary alcohol.
O · R´ R CH3
(i) CH3MgX(excess)
R C + RÓH
(ii) H3O+
O OH CH3
This simple reaction has a beautiful application in synthesis of cyclic tertiary alcohols, from
which alicyclic hydrocarbons can be synthesized.
For Example :
CH2 CH2 R
MgBr
+
H3O CH2 C
RCO2Et + (CH2)5
CH2 CH2 OH
MgBr
H3O+
H2/Ni
Example 4
(a) Why are ethers such as Et2O used as solvents for (i) BF3 and (ii) RMgBr ?
(b) Compare the Lewis basicities of tetrahydrofuran, diethyl ether and diăisopropyl
ether and give your reasoning.

18 QUIZRR
Solution :
(a) Because of their unshared eă´s, there are also Lewis bases capable of reacting with Lewis
acids such as BF3 and RMgBr to form coordinate covalent bonds.
+ ă
(i) Et2O + BF3 Et2O BF3
R
(ii) 2Et2O + RMgBr Et2O Mg OEt2
Br
Note that two molecules of ether coordinate tetrahedrally with one Mg2+.
(b) In addition to the amount of electron density on the nucleophilic site, steric affects also
influence basicities.The greater the steric hindrance encountered in the formation of the
coordinate bond, the weaker is the Lewis basicity. In tetrahydrofuan, the R groups (the sides
of the ring) are „tied back‰ leaving a very exposed O atom free to serve as a basic site. The
2Ĉ R groups in diăisopropyl ether furnish more steric hindrance than do the 1Ĉ ethyl groups
in ethyl ether. The order of decreasing Lewis basicity in thus tetrahydrofuran > ethyl ether
> iăpropyl ether.
(iv) By B 2H6/THF
2H2 BH3
O O O+
(THF)
ă
BH3
This reduces all the groups reduced by LiAlH4 except acid chloride (ăCOCl). It does reduce
the double / Triple bond but Selectively.
4. CHEMICAL PROPERTIES OF ALCOHOLS
In alcohols, ăOH group is the functional group. The oxygen atom of ăOH group polarize both the
C ă O bond and the OăH bond of any alcohol. Hence, alcohols can be classified into three types :
1. Reactions involving the cleavage of oxygen hydrogen bond.

2. Reactions involving the cleavage of carbon-oxygen bond.
3. Reactions involving both the alkyl and the hydroxyl groups.

QUIZRR 19
I. Reactions involving cleavage of oxygen-hydrogen bond.
Na
C2H5ONa + 1 H2
2
NaOH
RONa + 1 H2O
2
RMgX X
R · H + Mg
OC2H5
C2H5OH
CH3COOH/H+
CH3COOC2H5 + H2O
Esterification
CH3COCl
CH3COOC2H5 + HCl
Acylation
(CH3CO)2O
CH3COOC2H5 + CH3COOH
Acylation
(i) The first three reactions illustrate the reactions of alcohols as acids.
ă the order of acidic strength of different types of alcohol is
CH3OH > 1Ĉ > 2Ĉ > 3Ĉ
ă the order of acidity for some compounds
H2O > ROH > HC = CH > NH > RH

20 QUIZRR
(ii) Mechanism for esterification
+
O O H OH
+ + H
H (fast) slow
R C OH R C OH R C O
RÓH R´
OH
+
H (fast)
+
OH2
fast R C OR´ +
R C OR´ R C OR´ R C OR´
ăH+ + O H
O OH OH
(iii) Acylation : In this reaction, R ă OH should be 1Ĉ or 2Ĉ.

ă
Mechanism : O O
+
CH3 C O R CH3 C O R CH3COOR
Cl H Cl H
I llustration :
CH3 O CH3 O
CH3 C OH + R C CH3 C O C R + HCl
CH3 Cl CH3
So, HCl formed above again attacks the oxygen atom.

O CH3 O CH3
HCl +
R C O C CH3 R C O C CH3 R · COOH
CH3 H CH3
(iv) O O
ROH + CH3 C O C CH3
ă
O O
CH3COOR + CH3COOH CH3 C O C CH3
+O R
H
QUIZRR 21
 | 
II. Reactions involving cleavage of carbon-oxygen  R · C ·· OH  Bond
 | 
 
1. Reaction with hydrogen halide
HCl/ZnCl2
C2H5Cl + H2O
HBr
C3H5OH C2H5Br + H2O
(NaBr + Conc. H2SO4)
HI
C2H5I + H2O
(KI + H3PO4)
The order of reactivity of various halogen acids is HI > HBr > HCl
I llustration :
H
+ +
CH3 CH CH CH2 ăH2O
CH3 CH CH CH2
OH
+
CH3 CH CH CH2
Hence, product formed is a mixutre of
CH3 · C H · CH = CH2 + CH3 · CH = CH · C H2

| |
Br Br
2. Reaction with phosphorus halides
PCl5
C2H5Cl + POCl3 + HCl
PCl3
C2H5Cl + H3PO3
C3H5OH
PBr3 C2H5Br + H3PO3
(P + Br2)
PI3
C2H5I + H3PO3
(P + I2)

22 QUIZRR
3. Reactions with Thionyl Chloride
Pyridine

ROH + SOCl2 RCl + SO2 +HCl
Thionyl
chloride
The order of reactivity is 3Ĉ > 2Ĉ > 1Ĉ. The reaction in presence of pyridine shows inverted
configuration, while in absence of pyridine, it proceeds via SNi mehcanism showing
retention of configuration.
III. Reactions involving alkyl group as well as hydroxyl group
1. Acidic Dehydration
Conc. H SO
CH3 CH2 OH 
2 4
 CH2  CH2  H 2O
Al O
CH3 CH2 OH 
2 3  CH  CH  H O
2 2 2
The above reaction with conc. H2SO4 proceeds by E1 mechanism. Hence, for
+
H
+
CH3 OH CH2
Stability of Rings 6 > 7, 5 > 8, 9 > > 4 > 3

The ease of dehydration is 3Ĉ > 2Ĉ > 1Ĉ
2. Oxidation
Alcohols undergo oxidation with oxidizing agents (in neutral or acidic or alkaline medium)
such as CrO3, K2Cr2O7, KMO4 or HNO3.

QUIZRR 23
(i) PCC {Mixture of pyridine, HCl and CrO3}
ClCrOă3
Pyridinium Chloro Chromate
N+
H
This reagent is used for Âcontrolled oxidationÊ. It oxidizes 1Ĉ alcohols to aldehydes, but
cannot convert them to carboxylic acids.
P.C.C.
· CH2OH  · CHO
P.C.C.
R 2CHOH  · R 2CO
It is a mild oxidizing agent
P.C.C.
3 alcohol  No reaction
(ii) MnO2 : It can selectively oxidise 1Ĉ allylic or 1Ĉ benzylic alcohols into aldehydes.
CH2OH CHO
MnO2
MnO
CH2 = CH · CH2 OH 
2  CH
2 = CH · CHO
It does not oxidize or rearrange the double bonds.
Example :
OH
| MnO2
CH3 · CH · CH2 · CH = CH · CH2 OH  
OH
|
CH3 = CH · CH2 OH
| |
CH  CH · CH · H

24 QUIZRR
(iii) H2CrO4 (Jones Reagent)
This reagent in presence of sulphuric acid is used for oxidation of alcohols. This is more
oxidizing as compared to the above reagents, hence 2Ĉ alcohols react to form ketones.
However, it does not oxidize double or triple bonds.
OH O
| ||
· C · CH · CH3  CH3 · C ·
CH3 · C · · C · C · CH3
(iv) K2Cr2O7 or KMnO4 or HNO3 are strong oxidizing agents and directly oxidize 1Ĉ alcohols
to carboxylic acids.
O
[O]
(a) CH3 CH2 OH CH3 C H
[O]
CH3COOH
CH3
[O]
(b) CH3 CH OH CH3 C O + H2O
CH3
{under prolonged treatment with oxidizing agent, they get oxidized to acids with lesser
number of carbon atoms than the alcohol}
[O]
CH3 · C  O 
 CH3COOH + CO2 + H2O
|
CH3
(c) 3Ĉ alcohols are not oxidised with mild oxidizing agents in aqueous, alkaline or under
neutral conditions. However, when oxidation is carried out under acidic conditions,
tertiary alcohols first undergo dehydration to alkene. The alcohol formed is then
oxidized to ketone which is finally oxidized to carboxylic acid with lesser number of
carbon atoms that the starting alcohol.

QUIZRR 25
CH3 CH3
Hot conc HNO3
CH3 C OH CH3 C CH2
CH3 [O]
CH3
[O]
CH3COOH + CO2 + H2O C = O + CO2 + H2O
CH3
3. Dehydrogenation (Reduced with hot reduced copper)
(i) 1Ĉ alcohol.
H H
| |
Cu / 575 K
R · C · OH   R · C  O + H2
|
H
(ii) 2Ĉ alcohol
R R
| |
Cu / 575
R · C · OH   R · C  O + H2
|
H
(iii) 3Ĉ alcohol
CH3
|
Cu / 575 K
(CH3 )3 C · OH   CH3 · C · CH2 + H2 O
Note: The reagent can also be given a name of Âred hot copper tubeÊ in the question.
However, it is the same as we have used above.

26 QUIZRR
Example 5
Give the product of each reaction
(a) CH3CH2CH = CHCH2OH + MnO2
(b) m·O2NC6H4CH2COOH + LiAIH4
(c) Ph2C = CHCH3 + BH3, THF followed by H2O2/OHă
(d) PhCOCH2CH2Br + LiAID4, followed by H2O
(e) PhCH = CHCH(OH) CH3 + PBr3/
Solution :
(a) CH3CH2CH = CHCHO
(b) măH2NC6H 4CH2CH2OH
(c) Ph2CHCH(OH)CH3
(d) PhCD(OH)CH2CH2D
(e) PhCH = CHCHBrCH3
Example 6
OH
+7 (i) C6H5CH2 ă MgBr Zn/Hg ă conc. HCl NBs/h

Mn
(A) (B) (C) (D)
(ii) HOH 
alc.KOH CF3 ăCOOH
(E) (F) (G)
 CH3OH/HCl
Solution :
OH O O
+7 (i) C6H5CH2 ă MgBr Zn/Hg ă conc. HCl

Mn
(ii) HOH 
C6H5 C6H5
NBs/h alc.KOH CF3 ăCOOH CH3OH/HCl

C6H5 O CH3
Br 
O OH C6H5
C6H5 C6H5

QUIZRR 27
O xidative Cleavage of Diols
OH OH
C C + HIO4 C=O + O=C + HIO3 + H2O
Reaction type : Oxidation-reduction
Ć 1, 2- or vicinal diols are cleaved by periodic acid, HIO4,

OH
into two carbonyl compounds. O O
I
Ć The reaction is selective for 1, 2-diols.
O O
Ć The reaction occurs via the formation of a cyclic periodate ester
CăC
Ć This can be used as a functional group test for 1, 2-diols.
Ć The products are determined by the substituents on the diol.
Example 7
Identify, each of the following glucose derivative
A + 5HIO4  4HCOOH + 2HCHO
B + 3HIO4  2HCOOH + 2OHC ă COOH
Solution :
A  HOCH2CH(OH)CH(OH)CH(OH)CH(OH).CH2OH
B  HOOC.CH(OH) . CH(OH) . CH(OH) . CH(OH) . COOH

28 QUIZRR
PINACOL REARRANGEMENT
The pinacol rearrangement or pinacol-pinacolone rearrangement is a method for converting a

1, 2-diol to a carbonyl compound. This rearrangement takes place under acidic conditions. The
name of the reaction comes from the rearrangement of pinacol to pinacolone.
H+ H
+
H H H H H
O O O O H3C O
+
H3C CH3 H3C CH3 CH3
H3C CH3 H3C CH3 H3C CH3
pinacol
O O
H3C H3C
+
CH3 CH3
H3C H3C
CH3 CH3
pinacolone
An overview of mechanism
Protonation of one of the ăOH groups occurs and a carbocation is formed. If both the ăOH groups
are not alike, then the one which yields a more stable carbocation participates in the reaction.
Subsequently, an alkyl group from the adjacent carbon migrates to the carbocation center. The
driving force for this rearrangement step is believed to be the relative stability of the resultant
oxonium ion, which has complete octet configuration at all centers (as opposed to the preceding
carbocation). The migration of alkyl groups in this reaction occurs in accordance with their usual
migratory aptitude, i.e. Ph- > 3-alkyl > 2-alkyl > 1-alkyl > H.
Stereochemistry of the rearrangement
In cyclic systems, the reaction presents more features of interest. In these reactions, the
stereochemistry of the diol plays a crucial role in deciding the major product.
Ć An alkyl group which is situated trans-to the leaving ăOH group alone may migrate. If
otherwise, ring expansion occurs, i.e. the ring carbon itself migrates to the carbocation
centre.
Ć If the migrating alkyl group has a chiral center as its key atom, the configuration at this
center is retained even after migration takes place.

QUIZRR 29
Exampl 8
Ph Ph
O ăH
+
Ph HO Ph
Ph
Ph
Ph
Explain the mechanism.
Solution :
HO
OH
Ph Ph Ph
Ph
O H
+
+ +
Ph O Ph + Ph3C
Ph Ph
Ph H Ph
Ph
NOTE : A number of experiments have been carried out to determine the relative
migratory aptitude of -groups in Pinacol/Pinacolone type rearrangement.
H > Ph > Me3C > MeCH2 > Me
DISTINCTION BETWEEN 1°, 2°, 3° ALCOHOLS
1. Haloform Reaction
The general reaction is represented as
ă
R · CH · CH3  X 2 + NaOH  R · C · O Na   CHX3 + NaH + H2 O
| |
CH C
The CH3 carbon is lost as CHX3 and the remaining part exists as acid salt, which can be acidified
to liberate free acid.
The structural feature essential in the compound to show haloform reaction is that any of the
following moieties should be present in the molecule attached to some electron-withdrawing group
or electron donating group by +I only.
CH3 · CH · or XCH2 · CH · or X2CH · CH · or X3C · CH ·

| | | |
CH OH OH OH

30 QUIZRR
CH3 · C · or XCH2 · C · or X 2CH · C · or X 3C · C ·

|| || | ||
O O O O
or any other grouping that can be converted to any of the above moieties.
The mechanism of the reaction can be outlined as :
The reaction has 3 important steps. Step I is the oxidation, caused by mild oxidizing agent (hypo
halite ion). The second step is base-promoted halogenation and the third step is cleavage of CăC bond.
I2 + 2OHă Iă + OIă + H2O R CH CH2 ăI
OH
OIă
ă + ă
ă  ă
OI OH I I
R CH CH3 R C CH3 R C CH2 ă R C CH2 ăI
(Oxidising ăH2O ăI
agent)
OH O O O
Carbanion I
(Resonance stabilized)
OH
ă ă + ă ă
OH I2/OH I I
R C CI3 R C CI3 R C CHI2 ă R C CH ă I
ăI
Oă O O O
Carbanion I
(more resonance stabilized
OIă OIă due to-I effect of iodine)
+
R C OH CI3 R CH CI3 R CH CHI2
O OH OH
Proton
exchange
ă

R C O + CI3
O Yellow crystalline ppt.

QUIZRR 31
Some of the compounds which responds positively to iodoform test are
CH3CH 2OH (only primary alcohol)
CH3 · CH · CH3 , CH3 · CH · CH2 CH3 , Ph · CH · CH3 (secondary alcohols)

| | |
OH OH OH
CH3 · C · H (only aldehyde)

||
O
CH3 · C · CH3 , CH3 · C · CH2CH3 , Ph· C· CH3

|| || || (ketones)
O O O
X
|
CH3 · CH · CH3 , CH3 · C · CH3 ,
| |
X X
CH3 · C · CH2 · C · CH3 , CH3 · C · OEt (after heating with OHă)

|| || ||
O O O
O
||
CH3 · C · CH2 CO2H (after heating)
 
The compounds that respond negatively to iodoform test are
CH3 · C · OH, CH3 · C · Cl, CH3 · C · NH2 , CH3 · C · OR , CH3 · C · O · C · CH3

|| || || || || ||
O O O O O O
CH3 · C · CH2 · C · OH, CH3 · C · CH2 · C · OEt

|| || || ||
O O O O

32 QUIZRR
Example 9
Explain the following reactions with a proper mechanism.
OH
(a) Base 18
X O +
O O O
O
18 18
CH3
CH3

CH2
(b) H2C
CH2
H3C
OH O
+
H CH3
CH3
(c) H3C H3C
OH
Solution :
(a) HO + ă
H O
X
X
O
18 O
18
O
X
O O ă
O O
18 O
18

QUIZRR 33
(b) CH3 CH3
H2C 
H2C CH2
H3C CH2 H3C CH2
H
+
(c) H3C OH H3C O H H3C
+
H +
HO CH3 HO CH3 HO CH3
H3C H3C CH3 H3C

+
+
O CH3 H O CH3 HO CH3
2. Lucas Test
Alcohols react with concentrated hydrochloric acid in the presence of anhydrous zinc chloride to
form alkyl chlorides. The alkyl chlorides appear as cloudiness because of its insolubility in Lucas
reagent.
2 ZnCl
R · OH + HCl   R · Cl + H2O
Alkyl halide
The three types of alcohols undergo this reaction at different rates. The rates of reaction with
Luca s rea gent [conc. HCl + ZnCl2 (anhydrous)] follow the given order :
Tertiary alcohol > Secondary alcohol> Primary alcohol
An unknown alcohol (monohydric) is mixed with conc. HCl and anhydrous ZnCl2 at room
temperature. The alkyl chloride formed is insoluble in the medium, thus the solution becomes
cloudy before it separates out as a distinct layer. The following observations are made,
(a) If cloudiness (white turbidity) appears immediately, the alcohol is tertiary.

(b) If cloudiness appears within 5 minutes, the alcohol is secondary.
(c) If the solution remains clear, i.e., no cloudiness is formed the alcohol is primary.
Remember that the benzyl and allyl alcohol react as rapidly as tertiary alcohol with Lucas reagent
because their cations are resonance stabilised and as stable as 3Ĉ carbocations.

34 QUIZRR
3. Victor Mayer Test :
It follows in four stages :
(i) P + I2, (ii) AgNO2, (iii) HNO2, (iv) Base
Primary alcohol Secondary Alcohol Tertiary alcohol
H3C CH3 CH3

H3C OH
H3C CH3
OH
OH
P + I2
CH3 CH2 I P + I2
H3C CH3
AgNO2 CH3
I H3C CH3
CH3 CH2 NO2 I

AgNO2
HNO2 AgNO2
H3C CH3
H3C NO2
NO2 CH3
NO H3C CH3
HNO2
Nitrolic acid NO2
NaOH NO HNO2
H3C CH3
Red colour X (Noreaction)
NO2
Pseudo Nitrolic acid

NaOH
NaOH
Colourless
Blue colour

QUIZRR 35
4. Oxidation Test
(i) Primary alcohol on oxidation in presence of acidic chromate gives aldehyde
O
ă2
R OH + Cr2O7 R C H + Cr+3
Orange Green
Colour will charge from orange to green.
(ii) Secondary alcohols gives Ketones by chromic acid
R´ O
K2Cr2O7
R OH R C R´ + Cr+3
Or CrO3 Green
Here also colour will not change.
(iii) 3Ĉ alcohol donÊt oxidise in alkaline condition but in acidic condition, it rapidly dehydrates to
alkene. Colour doesnÊt change.
Exercise 10
Effect the following conversions.
CH2 OH CH2 OH
(a)
(b)
CH2 CH2OH
(c) CH3 OH

36 QUIZRR
Solution :
+
CH2 OH CH2
+
+
(a) H
H2O
CH2 OH O OH
HBO PPh2 = CH2 K2Cr 2O 7
(b)
HCO3H MeMgl
O OH +
H3O+
OH
H+ H+
CH3 CH2Cl
PCl3 Cl2
(c) CH3OH CH3Cl
AlCl3 h
Mg/Ether
CH2 CH2 OH CH2MgCl

HCHO
H3O+

QUIZRR 37
Exercise 11
Compound (X) (C5H8O) does no react appreciably with Lucas reagent at room temperature
but gives a precipitate with ammonical silver nitrate. With excess of MeMgBr, 0.42 g of (X)
gives 224 ml CH4 at STP. Treatment of (X) with H2 in presence of Pt. catalyst followed by
boiling with excess HI gives n-pentane. Suggest structure for (X) and write the equations
involved.
Solution :
(1) (X), (C5H8O) does not react with Lucas reagent appreciably at room temperature but gives
precipitate with ammonical AgNO3 and thus, (X) has terminal alkyne linkage as well as
primary alcoholic group.
(2) (X) on hydrogenation and then reacting with HI gives pentane and thus, (X) is straight
chain compound.
(3) Keeping in view of the above facts (X) may be
CH2 . CH2 . CH2 . CH2 . C  CH*

(x)
OH* Pent ă 4 ă yn ă 1 ă ol
(4) Its reaction with MeMgBr gives CH4. (It has two acidic or active H* atoms) and thus, 1 mole
of (X) will give two mole of CH4.
CH2 . CH2 . CH2 . C  CH + 2CH3 MgBr  2CH4

(X)
OH
 84 g (X) gives 2 ï 22.4 litre CH4
2  22.4  0.42
 0.42 g (X) will give = 224 ml CH4
84
Given fact is confirmed.
Thiols
Nomenclature :
Thiols are the sulfur analogues of alcohols.
Functional group suffix = ă thiol
Functional group prefix = mercapto

38 QUIZRR
Physical Properties :
Ć Hydrogen bonding is much weaker than that in alcohols.
Ć Lower boiling points than similar alcohols.
Structure :
Ć Generally similar to alcohols, but bonds to S are longer and weaker than those to O.
Ć The thiol functional group consists of an S atom bonded to a C atom and a H atom via 
bonds.
Ć The SăH bonds is less polar than that in alcohols since S is less electronegativity than O.
Reactivity :
Ć Thiols are much more acidic than similar alcohols, e.g., RSH (pKa = 10) versus ROH (pKa
= 16 to 19)

QUIZRR 39
PHENOLS
When hydroxyl group is directly attached to the benzene ring, the compounds are called phenols.
Some examples :
OH OH OH OH
CH3
CH3
CH3
phenol P-cresol m-cresol o-cresol
OH
OH
1-naphthol 2-naphthol
(-naphthol) (-naphthol)
Physical Properties :
Ć The polar nature of the OăH bond (due to the electronegativity difference of the atoms)
results in the formation of hydrogen bonds with other phenol molecules or other H-bonding
systems (e.g. water). The implications of this are :
* high melting and boiling points compared to analogous arenes

* high solubility in aqueous media
Ć The presence of intramolecular hydrogen bonding is believed responsible for the significantly
lower boiling points of certain ortho-substituted phenols vs the meta-and para-analogs.
Structure :
Ć The alcohol functional group consists of an O atom bonded to an sp2ăhybridised aromatic

C atom and a H atom via  bonds.
Ć Both ther CăO and the OăH bonds are polar due to the high electronegativity of the O atom.
Ć Conjugation exists between an unshared electron pair on the oxygen and the aromatic ring.

40 QUIZRR
Ć This results in, compared to simple alcohols :
Ć a shorter carbon-oxygen bond distance
Ć a more basic hydroxyl oxygen
Ć a more acidic hydroxyl proton (ăOH)
OH + OH + OH + OH
H H H H H H H H
ă
ă
ă
H H H H H H H H
H H H H
A cidity
Ć Phenols are more acidic (pKa  10) than alcohols (pKa  16 ă 20), but less acidic than
carboxylic acids (pKa  5)
Ć The negative charge of the phenolate ion is stabilised by resonance due to electron
delocalisation onto the ring as shown below :
ă
O O O O
H H H H H H H H
ă
ă
ă
H H H H H H H H
H H H H
Ć The acidity difference means that it is possible to separate phenols from alcohols and/or
carboxylic acids.
* Mixing an ether solution, of either phenol and alcohol or phenol and carboxylic acid,
with dilute base (sodium hydroxide and sodium bicarbonate, respectively), results in
the stronger acid being converted to its alkali salt, which is then extracted to the
aqueous phase and can be separated from the organic phase.
Ć Nucleophilic substitution reactions of phenols are generally carried out under basic conditions
as the phenolate ion is a better nucleophile.

QUIZRR 41
Substituent Effects on Acidity
Substituents, particularly those located ortho or para to the ăOH group, can dramatically influence
the acidity of the phenol due to resonance and / or inductive effects. Electron withdrawing groups
enhance the acidity, electron donating substituents decrease the acidity. The resonance stabilisation
of o-nitrophenol is shown below :
ă ă
O O O O
N N
+ +
O O
ă
Acidity of Phenol can be explained by :
(a) electron ă attracting and

(b) electron ă releasing substituents on the acid strength of phenols are as follows.
Electron ă attracting substituents disperse negative charges and therefore stabilize ArOă and
increase acidity of ArOH. Electron ă releasing substituents concentrate the negative charge on O
destabilizes ArOă and decreases acidity of ArOH.
Electron ă Attracting Electron ă Releasing

(· NO2, · CN, · CHO, · COOH, · NR3, · X)
OH Oă OH Oă
+ B BH + + B BH +
A A R R
More acidic Charge dispersed lon Less acidic Charge concentrated

stabilized lon destabilized
I. In terms of resonance and inductive effects we can account for the following relative acidities.
(a) păO2NC6H4OH > măO2C6H4OH > C6H5OH
(b) măClC6H4OH > p-ClC6OH > C6H5OH

42 QUIZRR
(a) The ă NO2 is electron ă withdrawing and acid ă strengthening. Its resonance effect,
which occurs only from para and ortho positions, predominates over its inductive
effect, which occurs also from the meta position. Other substituents in this category
are
C = 0 ă CN ăCOOR ăSO2R
(b) Cl is electron ă withdrawing by induction. This effect diminishes with increasing

distance between Cl and OH. The meta is closer than the para positions and m-Cl is
more acid ă strengthening than the p-Cl. Other substituents in this category are F,
Br, I, +NR3.
II. We can compare the relative acid strengths in the following groups :
(a) phenol, m-chlorophenol, m-nitrophenol, m-cresol;
(b) phenol, benzoic acid, p-nitrophenol, carbonic acid
(c) phenol, p-chlorophenol, p-nitrophenol, p-cresol
(d) phenol, o-nitrophenol, m-nitrophenol, p-cresol
(e) phenol, p-chlorophenol, 2, 4, 6 ă trichlorophenol, 2, 4ădichlorophenol
(f) phenol, benzyl alcohol, benzenesulfonic acid, benzoic acid
O
+
(a) N
O
Because NO2 has + on N, it has a greater electron ă withdrawing inductive effect than Cl.
The decreasing order of relative acid strengths
m-nitrophenol > m-chlorophenol > phenol > m-cresol
(b) The decreasing order of relative acid strengths

Benzoic acid > carbonic acid > p-nitrophenol > phenol
(c) The resonance effect of păNO2 exceeds the inductive effect of păCl p-CH3 is electron releasing.
The decreasing order of relative acid strengths
p-nitrophenol > p-chlorophenol > phenol > p-cresol
(d) Intramolecular H-bonding makes the o-isomer weaker than the p-isomer.
The increasing order of relative acids strengths
p-nitrophenol > o-nitrophenol > m-nitrophenol > phenol

QUIZRR 43
(e) The decreasing order of relative acids strengths

2, 4, 6ătrichlorophenol > 2, 4,ădichlorophenol > p-chlorophenol > phenol
(f) The decreasing order of relative acid strengths

benzenesulfonicacid > benzoic acid > phenol > benzyl alcohol
Example 12
Compare acidic order of

OH OH OH OH
CH3
CH3
CH3
ortho meta para
Solution :
· CH3 is electron donating group by inductive effect as well as resonance. Therefore ortho and
para will be least acidic and phenol most. Among ortho & para, inductive effect is greater at ortho
position, therefore it will be less acidic than para.
Therefore
phenol > meta > para > ortho
Example 13
Compare acidity of
OH OH OH OH
NO2
NO2
NO2
Solution :
NO2 is eă withdrawing both by resonance.
Therefore order should be
ortho > para > meta > phenol

44 QUIZRR
but its not the case due to H bonding at ortho position
O·H O
This correct order is

para > ortho > meta > phenol
Example 14
Compare acidity of
OH OH OH OH
Cl
Cl
Cl
Solution :
ă Cl is eă withdrawing by inductive effect
and eă donating by resonance & former dominates over later.
 o > m > p > 
where o · ortho, m · meta, p · para,  · phenol
Example 15
OH OH
H3C CH3
H3C CH3
NO2 NO2
Which is more acidic ?

QUIZRR 45
Solution :
(1) is more acidic than (2)
OH
In (2) repulsion between CH3 groups changes the plane
N of and it doesnÊt undergo resonance as porbitals are

H3C CH3
O O not in same plane.
N
O O
Therefore (1) is more acidic than (2)
Also remember
SO3H COOH OH
> > H2CO3 > (acidity order)
Example 16
OH ONa
+ NaHCO3 + H2CO3
COOH COONa
+ NaHCO3 + H2CO3
Which of the two reactions is feasible ?

46 QUIZRR
Solution :
COOH OH
> H2CO3 > (acidic strength)
Therefore only (2) is feasible.
PREPARATION OF PHENOLS
1. Reaction of Benzene Sulfonic Acid with Hydroxide
SO3H OH
350Ĉ C
NaOH +
Reaction type : Nucleophilic Aromatic Substitution
Mechanism :
SOă3Na+ OăNa+ OH
+
NaOH/350Ĉ C H
ăNa 2SO3
SOă3Na+ OăNa+
NaOH,
fusion
+
H
OH

QUIZRR 47
Note : There an limitations to this method. Firstly, halophenols can not be prepared in this ways
because at high temperature OHă displaces the halogens more readily than the replacement of

SO32 ion. Secondly, a substituent of ă R type which is meta to the sulphonic acid group activates
the ortho and para position for hydride displacement.
2. Base Hydrolysis of Chlorobenzene (Dow’s Process)
Cl OH
350Ĉ C H2O
NaOH +
Reaction type : Nucleophilic Aromatic Substitution
Note :
Ć The reaction occurs via the elimination-addition mechanism via a benzyne intermediate.
Ć Elimination of HCl creates the benzyne that then undergoes addition of H2O to produce the
phenol.
3. Preparation of Phenols from Aryl Diazonium Salts
Benzene or arene diazonium salts on distillation with steam forms phenol or substituted phenols
respectively, with liberation of nitrogen.
+
N2 HO
H2O, H2SO 4

+ N2 + H2SO4
100Ĉ C
Note :
Ć Aryl diazonium salts can be converted into phenols using H2O /H2SO4 / heat
Ć Aryl diazonium salts are prepared by reaction of aryl amines with nitrous acid HNO2.
4. By Distillation of Phenolic Acids with Soda Lime
Phenolic carboxylic acids (ortho, meta or para) on heating with sodalime undergo carboxylation
to give sodium phenoxide, which on acidification gives phenol.

48 QUIZRR
OH OăNa+ OH
COOH
+
NaOH(CaO), H
ăNa2 CO3
5. From Grignard Reagents
Phenyl magnesium halide or reaction with electrophilic O2 gives a peroxide salt, which on reaction
with another mole of phenyl magnesium halide gives 2 moles of magnesium salt of phenol. This
on acidification gives 2 moles of phenol.
MgBr O ă OMgBr OMgBr OH
+
O2 PhMgBr H
2 2
6. From Cumene Hydroperoxide
This is carried out by oxidising cumene to its hydroperoxide and subsequently decomposing it with
acid into phenol and acetone. The mechanism involves 1, 2-shift of phenyl group.
CH(CH3)2
250Ĉ C
+ CH2 = CHCH3
H3PO 4
Isopropyl benzene
(Cumene)
CH3 CH3
95 ă 135Ĉ C
C6H5 C H + O2 C6H5 C O OH
CH3 CH3
Cumene hydroperoxide

QUIZRR 49
CH3
+
H , H 2O
C6H5 C O OH C6H5 + CH3COCH3
Phenol Acetone
CH3
Cumene hydroperoxide
In the rearrangement, Ph migrates from carbon to oxygen. Most acid-catalyzed rearrangements

require the intermediacy of a positively charged atom to which the group migrates, most of these
positively charged sites were carbocations but in this case it is an O+.
Ph Ph H Ph
H3C + H3C H3C ă
H ăH2O ăPh
C O O H C O O H C O +
+
H3C H3C H3C
An oxonium ion Electronădeficient
intermediate
H3C + H3C
+ ăH2O
C O Ph C O Ph
H3C H3C
Carbocation
+
OH2
H3C H3C OH H3C
+
ăH
C O Ph C C O + PhOH
H3C H3C OPh H3C
Hemiacetal Acetone Phenol
The rearrangement of Ph may be synchronous with the loss of H2O.

50 QUIZRR
R EACTIONS OF PHENOL
+Na
C6H5ONa + H2
as acid
+NaOH C6H5ONa + H2O
+CH3COCl/Pyridine/AlCl3
C6H5COOCH3
ăHCl
Acylation
+(CH3CO2)O/H2SO4/AlCl3
C6H5COOCH3
ăCH3COOH
+ C6H5COCl Benzoylation
C6H5COO6H5 (schotten Baumann
aq. NaOH
reaction)
+ NH3/ZnCl2
C6H5 ă NH2 + H2O
Heat
Zn/
C6H6 + ZnO
C6H5 ă OH
NaOH (CH3)2SO4
C6H5ONa C6H5OCH3
Br2 /(aq)
2, 4, 6 - Tribromophenol
Br2/CS2
Ortho and para bromophenol
Electrophilic
Fuming HNO3 substitution
2, 4, 6 - Trinitrophenol (picric acid)
reactions
dil. HNO3
Ortho and para nitrophenol
293K
CH3Cl
Ortho and para cresol
AlCl3
+
C6H5N2 Clă
HO N=N Coupling
reaction

QUIZRR 51
OH
(i) CHCl3, aq. NaOH CHO Reimer Tiemann

Reaction
(ii) H3O+, 340K
(i) CO3, 400K

C6H5OH ONa + OH Kolbe
(ii) H3 O
Reaction
COOH
OH
HCl + HCN
Gattermann's
AlCl3 Reaction
CHO
(i) Phenol as acid :
Order of acidity for following :
OH
H2O < < HCO3ă < R COOH
Hence,
OH ONa
+ Na
But
OH ONa
+ NaHCO3 + CO2
This reaction does not occur as HCO3 is a stronger acid than phenol.

52 QUIZRR
Now, introducing electronă withdrawing groups increase the acidic strength of phenol in general.
OH
NO2
(a) + NaHCO3
OH ONa
O2N NO2 O2N NO2

(b)
+ NaHCO3 + CO2 + HO2
Now, 2 nitro groups make phenol more acidic than HCO3 .
OH ONa
O2N NO2 O2N NO2
+ NaHCO3 + CO2 + H2O

(c)
NO2 NO2
( ii) Acylation :
O O
AlCl3 ă
R C Cl R C+ AlCl4
O
O O
+ ă
O + ă O C AlCl4 O C R
C ă AlCl4
H R H R
Important Point : It is also known the aryl esters in presence of AlCl3 readily rearrange to form
aryl ketones. This is known as the FRIES REARRANGEMENTS.

QUIZRR 53
The reaction is :
O C CH3 OH OH
COCH3
AlCl3
+
(CS2)
COCH3
Generally low temperature (60Ĉ or less) favours the formation of the p-isomer whereas high
temperature (above 160ĈC) favours the o-isomer.
Mechanism :
ă
Cl2Al + COCH3
O CO CH3 O
Cl
AlCl3
ăClă
ă[ + COCH3]
O AlCl2 O AlCl2
COCH3
+
COCH3
H
Clă
Cl2Al O OH
COCH3 COCH3
H2O

54 QUIZRR
( iii) Bromination :
OH OH
Br Br
Br2
H2O
Br
Mechanism :


Br2 + H2O  HBr + HOBr
H+ (from HBr) 
HOBr 
 H2 O ·· Br
also, OH Oă
+ H+
{phenol in aqueous medium is partially ionized and phenoxide ion is more reactive than phenol
itself towards electrophilic attack}.
Oă Oă Oă
+ ă H+
+
Br OH2 H Br
Br
+
Br OH2
OH Oă Oă
Br Br Br Br Br
+
+
H BrOH2
Br Br Br

QUIZRR 55
But in presence of non-aqueous medium like CS2 or CCl4, only mono-substitution takes place. This
is because phenol is not ionized and hence benzene ring is less activated than that of phenoxide

ion. Also, bromine in Br2 is not as electrophiloic as in Br ·· OH2
OH OH OH
Br
CS2
+ Br2 +
ăHBr
Br
Now, if we have to prepare only the orthobromo phenol, then we wake use of protecting groups.
For example.
OH OH OH
SO3H Br SO3H
H2SO 4 Br2
NaOH
SO3H SO3H
boil H+
Br
OH
The activation of benzene ring in aqueous medium is so strong that derivatives of phenol containing
· SO3H group or · COOH group either at ortho or at para position are displaced by Br in
bromination reaction.

56 QUIZRR
OH
COOH
Br2
OH
H2O
Br Br
OH
Br2
Br
H2O
COOH
Trisubstitution of benzene is also observed in case of aniline, since aniline has same reactivity
as that of phenoxide ion towards electrophilic attack.
(iv) Nitration
When treated with dilute HNO3, phenol gives o and p-nitrophenol. When treated with nitrating
mixture, phenol gives 2, 4, 6ătrinitrophenol (picric acid) but the yield is poor.
OH OH OH OH
NO2 O2N NO2
dil HNO3 HNO3

+
20Ĉ C H2SO4
NO2 NO2
oăNitrophenol păNitrophenol 2, 4, 6ătrinitrophenol

(Picric acid)
Picric acid can be alternatively prepared as follows :
Cl Cl OH OH
NO2 NO2 O2N NO2
HNO3 aqueous HNO3
H2SO4 Na2CO3 H2SO4
NO2 NO2 NO2

2, 4, 6ătrinitrophenol
(Picric acid)
QUIZRR 57
(v) Reaction with HNO 2 (Nitrosation)

OH OH OH
NO
+ HNO2 +
NO
păNitrosophenol
dil. HNO3
Ć Here NO+ is electrophile.
Ć In 2nd step oxidation of Nitrogen in OH
p-nitrosophenol takes place.
NO2
(vi) Reaction with H2SO 4 (SULPHONATION)
OH OH OH
SO3H
+ H2SO4 +
SO3
(ortho) (para)
At 25ĈC ortho will be major as it is kinetically controlled product.

At 100ĈC (high temperature) para will be major as it is thermodynamically controlled product.
(vii) Oxidation by KMnO 4
Phenol can easily be oxidised by KMnO4 and ring is broken
OH
CH(OH) · COOH
KMnO4

CH(OH) · COOH
Meso tartaric acid

58 QUIZRR
Oxidation with Air
Ph · OH + O2
O
Benzoquinone
( viii) Action with bisulphate ion
ă
OH
Ph OH + K2S2O8 HO OH
păquinol
Mechanism :
O O O O
Oă S O O S Oă Oă S O+ +Oă S Oă
O O O O
OH O
OH OH O
H
+ ă
OH H OSO3 OSO3
+
H
ortho

QUIZRR 59
Similarly a para product can also be formed.
OH
OH
(major)
Example 17
OH
O
LiAlH4
+ H3C S Cl ?
Solution :
OH
O O
LiAlH4
+ H3C S Cl H3C Ph S O
O O
LiAlH4 is source of hydride Hă.
O
ă ||
O · S · Ph · CH3 is very good leaving group. Therefore it will leave very easily on attack
||
O
of Hă.

60 QUIZRR
Exmaple 18
Which has more B.P.
OH OH
C CH3 Or
C CH3
O
(a) (b)
Solution :
(a) has less b.p. than (b) due to intramolecular hydrogen bonding in (a) & intermolecular
hydrogen bonding in (b)
O·H O O H O H
C CH3
Intermolecular
Hydrogen bonding
O C O C
CH3 CH3
Intermolecular
H bonding
(ix) Reimer–Tiemann Reaction
The Reimer–Tiemann reaction is a chemical reaction used for the ortho-formylation of phenols.
In the simplest case, the product is salicylaldehyde :
OH OH O
CHCl3 H
+ 3NaCl + 2H2O
3 KOH

QUIZRR 61
R eaction mechanism
Chloroform (1) reacts with strong base to form the chloroform carbanion (2), which will quickly
alpha-eliminate to give dichlorocarbene (3). Dichlorocarbene will react in the ortho-and para-
position of the phenate (5) to give the dichloromethyl substituted phenol (7). After basic hydrolysis,
the desired product (9) is formed.
Cl Cl Cl
Cl KOH Cl
H ă
Cl Cl Cl
1 2 3
Cl
OH Oă O
Cl Cl
Cl
ă
KOH 3
H
4 5 6
H
OH O Oă Oă
Cl
O
Cl Cl
KOH
H H H
9 8 7
Ć oăhydroxy and p-hydroxy benzaldehyde are formed, which are separated by steam distillation.
Ć If oăpositions are blocked, p-hydroxy benzaldehyde is the main product.
When phenol is refluxed with CCl4 in alkaline medium, salicylic acid is formed.
OH OH
CO2H
+ CCl4 + NaOH + 4NaCl + 2H2O

62 QUIZRR
(x) Carboxylation of Phenols (Kolbe-Schmitt reaction)
ONa OH
1. CO2/125Ĉ C, 100 atm
2. H+
CO2H
Ć Heating the nucleophilic phenolate salt with carbon dioxide under high pressure / temperature
results in ortho-substitution.
Ć This process is also known as the Kolbe-Schmitt synthesis.
Ć o-hydroxybenzoic acid is more commonly known as salicyclic acid.
O
H The geometry allows for
ă an intramolecular
O
C hydrogen bond
Mechanism :
OH OăNa+
NaOH
Now, ă
O O
O
H Oă
C
C
O
O
tautomerize
OH OH
COOH CO2
+
H
(salicylic acid)

QUIZRR 63
Note : Salicylic acid is used for preparation of Asprin, oil of winter green (methyl salicylate) and
Salol (phenyl salicylate)
OH OH OCOCH3
CO2Me CO2H CO2H
MeOH (CH3CO)2O
Conc. H2SO4 NaOH
Aspirin
PhOH
Conc. H2SO4
OH
CO2Ph
(Phenyl salicylate)
Example 19
Find the final product
OH
CO2, OH
ă +
H /CH3 · C · Cl
[A] ?
Solution :
We know
OH Oă
CO2, OH
ă COOă
Kolbe Reaction
O
ă
O OH O C CH3
O
O
C Oă H
+ COOH CH3 · C · Cl C OH
O
Aspirin

64 QUIZRR
( xi) Oxidation of Phenols
Ć Oxidation can achieved by reaction with silver oxide (Ag2O) or chromic acid (Na2Cr2O7), or
other oxidising agents.
Ć Particularly important are the oxidation of 1,2-and 1,4-benzenediol (pyrocatechol and

hydroquinone, respectively) and their derivatives :
OH O OH O
OH O
Ag2O Na2Cr2O7
ether H2SO4, H2O
,
CH3 CH3 OH O
* WITH HNO3
OH O
HNO3
O
Benzoquinone
(xii) Claisen Rearrangment of Aryl Allyl Ethers :
O OH
heat
Summary
Ć Aryl allyl ethers undergo a thermal rearrangement to give ortho-allylphenols.
Ć This reaction is an intramolecular process.

QUIZRR 65
Ć Note how closely the mechanism of this reaction resembles that of the Diels-Alder reaction :
Claisen Diels-Alder
Caution : Do no confuse this reaction with the Claisen condensation of esters.
Mechanism :
O O tautomerize to form OH
more stable anomatic enol
( xiii) Dakin Reaction
C CH3 OH
O
+ CH3 C OH
H2O2/OH ă
OH OH
Mechanism :
Step 1 : Formation of hypoperoxide ion

H2O2 + OH   O · O · H + H2O

66 QUIZRR
Step 2 : Attack on carbonyl group
OH
O O
ă
C CH3 O C CH3
OH OH
Step 3 : Shift of phenyl group.
O
+
O OH2 C CH3
H3C C Oă O
OH OH
Setp 4 :
OH
O
O
C O OH H2O
+ CH3 C OH
CH3
OH

QUIZRR 67
Example 20
OH
O
NaOH
CH3 + CHCl3 S, (Product), Product S, is

OH
O
CH3
Solution :
COH
(xiv) Reaction with Formaldehyde
OH OH OH
O CH2OH
+
H
H C H +
CH2OH
Mechanism :
Step 1 : +
O H+ OH OH
H C H H C H H C H
+
Step 2 : OH OH OH
OH
CH2
+
OH
OH C H
H C H
+ H

68 QUIZRR
(xv) Gattermann Aldehyde Synthesis
When phenol is treated with liquid HCN and gaseous HCl in presence of anhydrous AlCl3,
product formed is hydrolysed Ph ă hydroxy benzaldehyde
OH CHO
AlCl3
+ HCN + HCl
Phenol OH
Mechanism :
Step 1 : Formation of electrophile
+
H
H C N H C NH
+
Step 2 : Electrophulic substitution Reaction an Phenol
OH
OH
H C NH
+
C NH
H
Step 3 :
OH OH
+
H
Hydrolysis
C NH C O
H H

QUIZRR 69
T est of Phenol
1. Phenol reacts with FeCl3 solution to form red and violet coloured solution.
OH
6 + FeCl3 [Fe · (O · C6H5)]3ă+ 3HCl + 3H+

Red or Violet
Ć This is also test for enol form.
2. Liebermann Test :
When phenol is dissolved in concentrated sulphuric acid and a few drops of aqueous sodium
nitrite is added, a red colour is obtained on dilution and turns blue when aqueous sodium
hydroxide is added.
Example 21
CH2
MgBr
NBS NaCN
X Y Z1 + Z2
OH
Solution :
Br CN CN
X= , Y= , Z1 = , Z1 =
OH OH OMgBr

70 QUIZRR
Example 22
Prepare (a) Picric acid (2, 4, 6-trinitrophenol), and (b) 2, 4-dichlorophenol from benzene.
Solution :
Even through the NO2Ês are in the o, o, p positions where OH directs electrophilic substitution,
phenol cannot be nitrated because the ring is susceptible to oxidative ring cleavage by
nitric acid. Instead, we take advantage of a nucleophilic addition ă elimination.
Cl Cl
NO2
Cl2 HNO3 1. NaOH
Fe H2SO4 2. H3O+
NO2
2,4-Dintrochlorobenzene
OH OH
NO2 O2N NO2
HNO3
H2SO4
NO2 NO2
2,4-Dintrophenol Picric acid
PhCl cannot be trinitrated because the Cl and two NO2Ês deactive the ring toward further
electrophilic substitution. 2, 4-Dintrophenol can be nitrated because the two deactivating NO2Ês
prevent ring oxidation. (b) Phenol cannot be chlorinated because the ring is susceptible to oxidation
by Cl2. Again nucleophilic addition ăelimination is used.
Cl OH
Cl Cl
3Cl2 / Fe OHă
PhH
Cl Cl
1,2,4-Trichlorobenzene 2,4-Dichlorophenol
The displaced Cl is ortho to one other Cl and para to the other and is activated by both. Each
of the other ClÊs is meta to at least one deactivating Cl.

QUIZRR 71
Example 23
Compound (A), C9H13O3N shows optical isomerism when 1, 2-dihydroxybenzene is treated

with chloroethanoyl chloride in the presence of POCl3, compound (B), C8H7O3Cl, is obtained
which upon treatment with methyl amine gives compound (C), C9H11O3N. Reduction of (C)
with Pd/H2 yields (A). Compound (B) when heated with NaOI and subsequent treatment of
the product formed with dilute acid solution yields 3, 4-dihydroxybenzoic acid. Deduce the
structure of (A).
Solution :
OH OH OH OH O
OH OH OH OC CH2Cl
ClCH2COCl
Or Or
POCl3
C · CH2Cl CH2COCl
O (I) (II) (III)
1, 2ădihydroxybenzene may undergo ring acylation or ring alkylation or esterification to form

compound (B).
Since (B) gives haloform test, the only possibility is (I).
OH OH OH
OH OH OH
NaOI +
H
CHCl2 +
C · CH2Cl COONa COOH
O (B) 3,4-dihydroxybenzoic acid
OH OH OH
OH OH OH
CH3NH2 H2/Pd
C · CH2Cl C · CH2NHCH3 *CH(OH)CH2NHCH3
O O (C) (A)

72 QUIZRR
Example 24
Write mechanism for the oxidation of a 2Ĉ alcohol with Cr (VI) as HCrO 4ă .

Solution :
A chromate ester is formed in the first step :
O O
fast +
H
R2C OH + Cr OH R2C O Cr OH
H2O
ă
H O O H O
Chromate ester
H O
H2O
R2C O Cr OH R2C = O + H3O+ + HOCr · Oă [Cr(IV)]
slow
O O
E2 elimination
The Cr(IV) and Cr(VI) species react to form 2Cr(V), which in turn also oxidizes alcohols giving
Cr(III) with its characteristics colour.
Example 25
(a)
CHCl3 H2O2/OH
A B+C D+E
KOH solution 
followed by
acidification
H2O2 /OH
catechol + E

followed by
acidification
Identify A to E.
(b) Carryout the following transformations.
Br
OH
(i)

QUIZRR 73
(ii)
NH2 CH2COOH
(iii)
Solution :
OH OH OH OH
CHO
(a) A= ; B= ; C= ; D= ; E = HCO2H
CHO OH
Br
OH
(b) (i) alcoholic (i) B2H6
KOH (ii) H2O2/OH
O O
O OH OH
(ii) CH2MgBr CH3MgBr OH
+
H3O+ H3O

74 QUIZRR
(iii) NH2 N2Cl
NaNO2 + HCl H3PO2

OĈ ă5Ĉ C
HCl + CO
anhydrous AlCl3
CH2Cl CH3 CHO
Cl2 HCl
ZV Zn ă Hg
KCN
CH2CN CH2COOH
+
H3O
Example 26
Give a simple test tube reaction that distinguishes between the compounds in each of the
following pairs. What would you do, see and conclude ?
(a) t-butyl and n-butyl alcohol,
(b) ethyl and n-propyl alcohol,
(c) allyl and n-propyl alcohol,
(d) benzyl methyl ether and benzyl alcohol
(e) cyclopentanol and cyclopentyl chloride.
Solution :
2ă
(a) Add Acid Cr2O7 (orange). The 1Ĉ n-butyl alcohol is oxidized; its solution changes colour to
green Cr(III). The 3Ĉ t-butyl alcohol is unchanged. Alternatively, when Lucas reagent
(HCl + ZnCl2) is added, the 3Ĉ ROH quickly reacts to form the insoluble t-butyl chloride that
appears as a second (lower) layer or a cloudiness. The 1Ĉ ROH does not react and remains
dissolved in the reagent.

QUIZRR 75
(b) Add I2 in OHă until the I2 colour persists. A pale yellow precipitate of CHI3 appears,
indicating that ethyl alcohol is oxidized. n-Propyl alcohol does not have the · CH(OH) CH3
group and is not oxidized.
(c) Add Br2 in CCl4; as the Br2 adds to the C = C of the colorless allyl alcohol, its orange colour
disappears. The orange colour persists in the unreactive n-propyl alcohol.
2ă
(d) Add acid Cr2O7 . It oxidizes the alcohol, and the colour changes to green. The ther is
unreactive. Alternately, if the two compounds are absolutely dry, add a small piece of Na
to each. H2 is released from the alcohol; the ether does not react.
(e) The simplest test is to add conc. H2SO4 to each dry compound. There will be only one layer
as the alcohol dissolves, evolving some heat. The layers will be discernable for the chloride,
which is not soluble in H2SO4.
Example 27
A compound (A), C10H12O2, is soluble in aqueous NaOH, but does not dissolve in aqueous
NaHCO3. When (A) is treated with dimethyl sulphate and aqueous NaOH, compound (B),
C11H14O2, is formed with hot HI (A) gives methyl iodide and with hot and concentrated base,
compound (C) C10H12O2 is obtained. Compound (B) is insoluble in aqueous NaOH but readily
decolourises KMnO4 solution. When treated with hot and concentrated base, compound (B)
produces (D), C11H14O2. Ozonolysis of C produces a compound, which is isomeric with 4-
hydroxy-3-methoxybenzaldehyde. Ozonolysis of (D) gives a compound, which is also obtained
by treating 4-hydroxy-3-methoxybenzaldehyde with di-methyl sulphate. Deduce the structure
of A with proper reasoning.
Solution :
Since (A) is soluble in aqueous NaOH, it is phenolic compound. Methylation with (CH3)2SO4/
NaOH introduces ă CH3 group.
 (B) is C11H14O2
(A) is C10H12O2
A difference of ăCH2 also indicates phenolic group in (A). (A) is cleaved with hot HI to produce
CH3I, indicating the presence of second oxygen.
That ozonolysis yields 4ăhydroxy-3-methoxybenzaldehyde, indicates that (A) is trisubstituted
benzene ring.
C10H12O2(A) C10H 11O C9H 8

ăOH ăOCH 3 ăC6H 3 (Trisubstituted aromatic ring)
C10H 11O C9H 8 C3H 5

76 QUIZRR
The residual group, C3H5 corresponds to an unsaturated side chain.
Treatment of (A) with strong and hot base results into isomerisation to C.
HO ă HO
HO
C6H3 · CH2 · CH = CH2  C6H3CH = CH · CH3
CH3O (A) CH3O (C)
C10H12O2 C10H12O2
The same isomerisation occurs when (B) is treated with hot and concentrated base.
CH3O ă CH3O
HO
C6H3 · CH2 · CH = CH2  C6H3CH = CH · CH3
(B) (D)
CH3O CH3O
C11H14O2 C11H14O2
Orientation in the compounds can be worked out as follows :
CHO CHO
O3 (CH3)2SO4
(D) ă
HO
OCH3 OCH3
OCH3 OH
CH2CH = CH2
OCH3
CH2CH = CH2 CH = CH ă CH3 CHO
OH
(A) (CH3)2SO4 HO
+
O3
(or) HO
ă

OCH3 OCH3 OCH3
CH2CH = CH2
OCH3 OCH3 OCH3

(B) (D)
OH
OCH3
(A)

QUIZRR 77
(C) has the same orientation of groups as (D). Hence the only possible isomer of 4-hydroxyă3ă
methoxybenzaldehyde that can be formed by cleavage of (C) is the one in which the ăOH and
ăOCH3 groups are reversed.
CHO
O3
(C) (isomer of 4ăhydroxyă3ămethoxybenzaldehyde)
OH
OCH3
Thus, A is
CH2CH = CH2 CH = CH · CH3 CHO
ă
OH O3
OH  OH OH
OCH3 OCH3 OCH3

(A) (C) (D)

78 QUIZRR
ETHERS
Ethers have a general formula R·O·R´. The groups R and R´ may be same or different and
accordingly ethers are known as simple or mixed respectively. The general IUPAC name of ethers
is alkoxy alkane
CH3 · O · CH3 CH3 · O · C2H5 CH3CH2CH2 · OC2H5

Methoxy methane Methoxy ethane Ethoxy propane
(Dimethyl ether)
CH2 = CH · OC2H5 OCH3

ethoxyethene
Methoxy benzene
(anisole)
Physical Properties
Ć The polar nature of the CăO bond (due to the electronegativity difference of the atoms)
results in intermolecular dipole-dipole interactions.
Ć An ether cannot form hydrogen bonds with other ether molecules since there is no H to be
donated (no ă OH group)
Ć Ethers can be involved in H-bonding with systems able to donate H (e.g. water).
Ć The implications of these effects are :
lower melting and boiling points compared to analogous alcohols.
solubility in aqueous media similar to analogous alcohols.
Ć Ethers have a definite dipole moment. This is due to the bent structure of their molecule.
Ć They are lighter than water. Their density incolases with increase in molecular mass.
Reactivity :
Ć The ethereal O atom is a region of high electron density due to the lone pairs.
Ć Ether oxygen atoms are Lewis bases.
Ć Like an alcohol ă OH group, the ă OR group is a poor leaving group and needs to be
converted to a better leaving group before substitution can occur.
Ć The most important reaction of ethers is their cleavage by strong acids such as HI or HBr.
Methods of Preparation :
1. By Williamson Synthesis :
R · X  RÓNa  R · O · R´ + NaX

QUIZRR 79
Here ăX can be halides, sulphates (ăOSO2OR) or sulphonates (ăOSO2R). Also, the temperature
should be low for this reaction.
The alkyl halide used in this reaction should preferably be primary because in case of secondary
and tertiary alkyl halides, the elimination reaction predominates resulting in the formation of
alkene as the major product.
CH3 CH3
| |
C2 H5 Br + NaO · C · CH3  C2 H5 · O · C · CH3  NaBr
| |
CH3 CH3
Whereas,
CH3 CH3
| |
CH3 · C · Br  C2 H5 ONa  CH3 · C  CH2  NaBr + C2 H5 OH
| (major product)
CH3
Note : (1) For aromatic ethers generally alkyl sulphates are used.
(2) The reaction is SN2.
2. Dehydration of alcohols
2 4 conc. H SO
2C2H5OH   C2H5 · O · C2 H5 + H2O
413 K
(excess)
2 3 Al O
2C2 H5OH   C2H5 · O · C2H5 + H2O
Dehydration of alcohols to ether is an example of nucleophillic substitution. However, it can be

used only to prepare symmetrical ethers only, otherwise we get a mixture of ethers. For example,
2 4conc. H SO
R · OH + HOR    R · OR + RÓR + RÓR´
140Ĉ C, 

80 QUIZRR
3. Alkoxy Mercuration - Demercuration of Alkenes
1. Hg(OAC)2 / ROH
C C H C C OR
2. NaBH4
Note : 1. Product is formed following MarkownikovÊs rule.

2. Reaction proceeds via the formation of a cyclic mercurinium ion
+ +
C C
Hg +
AcO
4. Preparation of epoxides
RCO3H
(a) C C C C + RĆO2H
O
RCO3H is peroxy acid.
(b) epoxides can also be prepared by internal SN2 reaction of chlorohydrin
Cl Cl
ă ă
OH ă Cl
CH2 CH2 CH2 CH2 CH2 CH2
+
O
OH Oă
Example 28
(a) Upon treatment with sulphuric acid, a mixture of ethyl and n-propyl alcohols yield a
mixture of three ethers. What are they ?
(b) On the other hand, a mixture of tert-butyl alcohol and ethyl alcohol gives a good yield
of a single ether. What ether is this likely to be ? How do you account for this good
yield ?

QUIZRR 81
Solution :
(a) CH3CH2OH (ethyl alcohol) and CH3CH2CH2OH (n-propyl alcohol) by dehydration make a
mixture of three ethers since each alcohol is 1Ĉ and follow SN2 reaction
H2SO4
CH3CH2OH + CH3CH2OH 
 CH3CH2OCH2CH3 + H2O
H 2SO4
CH3 CH2 CH2 OH + CH3 CH2 CH2 OH 
 CH3 CH2 CH2 OCH2 CH2 CH3 + H2 O
H 2SO 4
CH3 CH2OH + CH3 CH2CH2OH 
 CH3CH2CH2OCH2 CH3 + H2O
CH3 CH3 CH3

+ +
(b) CH3 C OH + H+ CH3 C OH2 CH3 C
CH3 CH3 CH3

(3) most stable carbonium ion
CH3 CH3
CH3 C + + CH3CH2OH CH3 C OCH2CH3 + H+
CH3 CH3
Since pr ot onat ed 3° alcohol (t er t -but yl alcohol) can make most st able car bonium ion, hence
t his leads t o t he single et her in good quant it y.
R EACTIONS OF ETHERS
Ethers are relatively inert compounds and do not react with alkalies, reducing agent, oxidizing
agents and reactive metals. Because of their inertness ethers are frequently used as solvents. They,
however, undergo cleavage under acidic conditions.
1. Cleavage by acids
On reaction with conc. HBr or conc. HI, ethers undergo cleavage to form an alcohol or phenol and
an alkyl halide.
C2H5 · O · C2H5 + HX  C2H5 X + C2H5OH
Ć The order of reactivity of halogen acids is
HI > HBr > HCl

82 QUIZRR
Ć In case of excess acid, product formed is only alkyl halide
C2H5 · O · C2H5 + 2HX  C2H5 X + H2O

excess
Mechanism :
Step I : R · O · R´ + HX R · O · R´ + Xă
+
H H
SN2
Setp II : R · O · R´ + Xă X · R · O´ · R´ RX + RÓH
+ +
SN1
ă
+X
R·X R + + RÓH
So, reaction can go by SN1 or SN2 depending upon the conditions employed and the structure of
ether. When both the alkyl groups are methyl or 1Ĉ, it will follow SN2 pathway and when atleast
one of the alkyl group is 3Ĉ, it follows SN1 pathway.
For example,
H
HI
(a) CH3 · OC2H5
+
SN2
Here, CH3CH2 · O  is a good leaaving group and CH3 is also not hindered. Therefore,
|
H
CH3I is formed.

QUIZRR 83
But
ă CH3
I
+ This is also a good leaving
C´ O CH3 group but not as good as
+
H H H C2H5O ă H and C´ is also hindered
Hence, this product is not formed.
CH3
HI +
(b) CH3 C O CH2CH3 (CH3)3C O CH2CH3
CH3 H
1
SN
CH3 CH3
I
C Iă C
+
+ CH3CH2OH
H3C CH3 H3C CH3
{stable carbocation}
Note : When the reaction follows SN2 mechanism (R > R´) then Iă attacks R´ and forms RÍ and
ROH.
But, if SN1 mechanism is followed than RI and RÓH is formed.
In acidic medium, in case of cleavage of ether, if strong nucleophile is used, then reaction takes
place by SN2 mechanism.
Example 29
HI
CH3 CH CH2 ?
O
strong
+ ă
nucleophute
Solution : H I
CH3 CH CH2 CH3 CH CH2 CH3 CH CH2I
O OH
+ OH
ă
I
I
CH3 CH CH2
I
84 QUIZRR
Ć Strong nucleophile will attack at less hundered carbon.
But if we use CH3OH instead of HI
OCH3
+
H CH3 · O ·H
CH3 CH CH2 CH3 CH CH2 CH3 C CH2
O OH OH
+
Ć In case of weak nucleophile, we break up the ring according to carbocation stability but
actual carbocation is not formed.
Example 30
O +
H
CH2 C CH3 ?
CH 3OH
CH3
Solution :
H a good leaving
group
+
O O
+
H
CH2 C CH3 H2C C CH3
CH3 CH3
O
H3C H
OH CH3 OH CH3
+
H
H2C C CH3 H2C C CH3
OCH3 +O H
CH3

QUIZRR 85
Example 31
O ă
CH3O
CH2 C CH3 ?
CH3OH
CH3
Solution :
this is a stronger base than
ă
CH3O , hence it will obstract the proton
ă
O +
Oă
+
1CH2 2
C CH3 2 H2C C CH3
SN
CH3 Cleavage would be OCH3 CH3
ă at 1 not at 2 because
CH3O
of hindrance
CH3OH
OH
H2C C CH3
H3CO CH3
Example 32
*
O +
(1) H CH3OH
ClH2C* CH C CH3 ?
(2) Base
CH3

86 QUIZRR
Solution :
H
*
O +
O*
H
ClH2C* CH C CH3 ClH2C* CH C CH3
CH3 CH3
O
* CH3
CH2 CH C CH3 CH3 ă O
OCH3 H
ă *
O CH3 CH3
ă
* OH * *
Cl CH2 CH C CH3 Cl CH2 CH C CH3
ă H2O
OCH3 *O H OCH3
Example 33
(a) Give SN2 and SN1 mechanisms for the cleavage of ethers with HI.
(b) Why does SN2 cleavage occur at a faster rate with HI than with HCl.
Solution :
+
(a) Step 1 R O R´ + HI R O R´ + Iă
H
base1 acid2 acid1 base2
H
slow
Step 2 for SN2 Iă+ R O R´ RI + HOR´(Rís 1Ĉ )
+
H
slow
Step 2 for SN1 R O R´ R+ (R is 3Ĉ ) + RÓH
+

QUIZRR 87
Setp 3 for SN1 R   I   RI
(b) The transfer of H+ to ROR´ in step 1 is greater with HI, which is a stronger acid, than with
HCl. Furthermore, in step 2, Iă, being a better nucleophile than Clă, reacts at a faster rate.
2. Reaction with PCl5 /SOCl2
Ethers on heating with PCl5 or SOCl2 undergoes cleavage to form alkyl chlorides.

C2 H5 + O + C2 H5 + Cl + PCl3 + Cl  2C2 H5 Cl + POCl3
O
|| 
C2 H5 + O + C2 H5 + Cl + S  Cl  2C2 H5 Cl + SO2
The cleavage by PCl5 or SOCl2 is and to distinguish metameric ethers as their cleavage.
3. Oxidation of Ether by Air
When ethers are exposed to oxygen for a long time they are oxidised to ether hydroperoxides
(solid) which explodes on slightest heating or on rubbing.
R · CH2 · CH2 · O · CH2 · CH2 · R + O2  RCH2 · C H · OCH2 CH2 R

|
O · OH
Ethers are purified by extraction with excess of FeSO4 solution, which reduces the ăOOH gap to
the non-explosive, innocuous · OH group.
4. Test of Peroxide ion

CH3 · O · CH · CH3 + Fe2  Fe 3  Fe (SCN)3
SCN
| Red Colour
O
|
OH
When ether hydroperoxide is reduced with Fe+2, it oxidises Fe+2 to Fe+3 which can easily be
detected by thiocyanide ion producing green colour.

88 QUIZRR
5. Halogenation of ether
Cl2
CH3CH2 O CH2 CH3 CH3CH O CH2CH3
Cl
Cl2
CH3 ă CH O CH CH3
Cl Cl
6. Epoxidation
Ag2O
CH2 CH2 + O2 300Ĉ C
CH2 CH2
7. Formation of aryl ether
OH ONa
NaOH
+ CH3 · OSO2OCH3
OCH3
+ CH3 · OSO2ONa
(Anisole)

QUIZRR 89
As discussed earlier, methyl sulphonates are better leaving group than halogens, hence are better
for this kind of substitution.
Aryl halides cannot be used in the william sonÊs synthesis because of their low reactivity towards
nucleophilic substitution. There can be two combination of reactants for the preparation of alkyl
aryl ether, but one can usually be ruled out.
+ ă
CH3CH2Br + Na O
CH3CH2CH2 · O
CH3CH2Oă Na+ + Br

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ALCOHOLS, PHENOLS & ETHERS

Ć Due to the electronegativity of the O atoms, alcohols are slightly acidic

2 RăOăH + 2 Na  2 NaOR + H2

2 HăOăH + 2 Na  2 NaOH + H2

EXCEPTION : Few exception to the above point can be noted.

ALCOHOLS, PHENOLS & ETHERS

(2) Oă HOH

(3) Trihydric alcohols : three ăOH groups present.

ALCOHOLS, PHENOLS & ETHERS

Explain the following :

A summary of all the methods of preparation is given below.

ALCOHOLS, PHENOLS & ETHERS

Organometallics with Aldehydes

Reduction of Carboxylic LiAlH4 + C H C R´

ALCOHOLS, PHENOLS & ETHERS

C2H5Br + KOH (aq)  C2H5OH + KBr

CH3 C Br + KOH CH3 C CH2 + KBr + H2O

2.1 Hydration of Alkenes

CH3 CH CH2 + H2O CH3 CH CH3

H3C C CH2 + CH3 H3C C CH2 CH3

ALCOHOLS, PHENOLS & ETHERS

2 .2 Hydroboration / oxidation of Alkenes

CH3 CH CH2 CH3 CH2 CH2

Now, let us also see the mechanism of the following reaction.

Here lone pair - lone pair

ALCOHOLS, PHENOLS & ETHERS

Some Important Points :

CH = CH2 CH2 CH2 BH2 CH2 CH3

ALCOHOLS, PHENOLS & ETHERS

Alkenes can be converted into alcohols by oxymercuration-demercuration reaction. In this

CH3 CH CH2 CH3 CH CH2

ALCOHOLS, PHENOLS & ETHERS

CH3 CH3 HgOCOCH3

3. FROM ALDEHYDES AND KETONES

3.1 By using Grignard Reagents

ALCOHOLS, PHENOLS & ETHERS

Products formed by Grignard synthesis :

ALCOHOLS, PHENOLS & ETHERS

(2) For compounds like CH2 CH2 , the reaction is :

CH2 CH3 CH2 CH2 OMgCl

(3) Reaction of RMgX with epoxide ring

ALCOHOLS, PHENOLS & ETHERS

{1Ĉ alcohol will be formed because of the allylic nature of 2Ĉ carbon}

(f)  RCO 2 O 4LiAlH

ALCOHOLS, PHENOLS & ETHERS

(ii) Using NaBH4

Note : Hydrogenolysis (cleavage by hydrogen) of an ester requires more severe conditions

ALCOHOLS, PHENOLS & ETHERS

CH3  CH2 14 COOC2H5  CH3  CH2 14 CH2 OH

 Ethyl hexadecanoate  1Hexadecanol

ALCOHOLS, PHENOLS & ETHERS

4. CHEMICAL PROPERTIES OF ALCOHOLS

1. Reactions involving the cleavage of oxygen hydrogen bond.

ALCOHOLS, PHENOLS & ETHERS

I. Reactions involving cleavage of oxygen-hydrogen bond.

ă the order of acidic strength of different types of alcohol is

CH3OH > 1Ĉ > 2Ĉ > 3Ĉ