Brilliant STUDY CENTRE REPEATERS CHEMISTRY -2022 (ONLINE CLASS NOTES A-NEET)

CHAPTER - 26
ALCOHOLS PHENOLS AND ETHERS

Alcohols are hydroxy derivatives of hydrocarbons. Monohydric alcohols contain one –OH group per
molecules. Dihydric, trihydric and polyhydric alcohols are also there.
Monohydric Dihydric Trihydric Polyhydric

CH 3OH
Eg: 1) CH2 OH Eg : CH2 OH Eg: CH2 OH
C2 H 5 OH etc
CH OH
CH2 OH (CH OH)4
Ethylene glycol
CH2 OH CH2 OH
Glycerol Mannitol (Solid)

Eg: 2) CH3 CH CH2

OH OH
Propylene glycol
Aliphatic saturated monohydric alcohols and ethers have the G.F. CnH(2n+2)O.
1° alcohols contain –CH2–OH grouping
2° alcohols contain CH OH group

3° alcohols have the C OH group

CH3 CH3

CH3 CH OH CH3 C OH
CH 3  CH 2  OH
Propan-2-ol (2°)
Ethanol (1) (Isopropyl alcohol) CH3
2-Methyl propan-2-ol
(Tert : butylalcohol) (3°)
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Alcohols exhibit different types of structural isomerism.
1. Chain isomerism

CH3

Eg: CH3 CH2 CH2 CH2 OH and CH3 CH CH2 OH

Butan-1-ol 2-Methyl propan-1-ol
(n-butyl alcohol) (Isobutyl alcohol)

2. Position isomerism

Eg : CH3 CH2 CH2 OH and CH3 CH CH3

Propan-1-ol
OH
Propan-2-ol
3. Functional isomerism

Eg : CH3 CH2 CH2 OH and CH3 O CH2 CH3

Propan-1-ol Methoxy ethane
(n-propyl alcohol) (Ethylmethyl ether)
4. Ring chain isomerism

OH

CH
Eg : and CH2 CH CH2 OH
(Allyl alcohol)
CH2 CH2 Prop-2-en-1-ol
Cyclopropanol

5. Vinylic alcohols are tautomeric forms of aldehydes or ketones

OH O

Eg :

Cyclohexenol Cyclohexanone

CH2 CH OH CH3 C H
(Vinyl alcohol) (Acetaldehyde ethanal)
ethenol

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Alcohols containing asymmetric carbon can exhibit optical isomerism.

Eg : CH3 CH CH2 CH3

OH
Butan-2-ol
ALLYLIC ALCOHOLS :
Here –OH group is connected to allylic carbon. i.e. sp3 carbon which is directly connected to olefinic
carbon. If the allylic carbon is 1°, the alcohol is 1° allylic. In 2° allylic alcohol, the allylic carbon is 2° and
so on.
Eg : CH2 CH CH2 OH : 1° allylic

OH

CH2 CH CH CH3 : 2° allylic

But-3-en-2-ol

OH

CH2 CH C CH3
: 3° allylic
CH3
2-methyl but-3-en-2-ol

OH

: 2° allylic

Cyclohex-2-en-1-ol
BENZYLIC ALCOHOLS
–OH group is connected to benzylic carbon ie sp3 carbon directly connected to benzene ring.

CH2 OH

 1° benzylic


Phenyl methanol
(Benzyl alcohol)

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OH

CH CH3


 2° benzylic

1-Phenyl ethanol

OH

CH3 C CH3


 3° benzylic

2-Phenyl propan-2-ol

VINYLIC ALCOHOLS (ENOLS)

OH

, CH2 = CH – OH etc

General methods of preparation

1. Hydrolysis of alkyl halides with aqueous alkali or moist Ag2O.

Eg : C 2 H 5 Br  KOH  aq  
 C2 H 5OH  KBr

C 2 H5 Br  AgOH 
 C2 H 5 OH  AgBr
2. Hydrolysis of ethers
dil.H 2SO 4
C 2 H 5  O  C 2 H 5 
heat /pressure
 2C 2 H5 OH
3. Hydrolysis of esters
O

Eg: CH3 C O C2H5 
H 2 O/H
 CH 3COOH  C 2 H 5OH

O
H2O/OH CH3COO + C2H5OH
CH3 C O C2H5

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4. Deamination of aliphatic 1° amines with HNO2

HNO 2
Eg : CH 3CH 2 NH 2   CH 3CH 2  OH  N 2  H 2 O
Major

A small amount of CH2 = CH2 is also formed in this reaction

HNO2 CH3CH2 CH2 OH + CH3 CH CH3 + CH3 CH CH2
Eg: CH3CH2CH2NH2
7% 28%
OH
32%

Here, CH3CH2 CH2 formed rearranges to 2° cation and proton elimination from carbocation
produces alkene. Carbocation combines with nucleophile H2O giving alcohol.
5. Reduction of carbonyl compounds
Aldehydes, ketones, carboxylic acids and acid derivatives like acid chlorides, anhydrides and esters
can be reduced to alcohols.
  H
R  CHO   RCH 2  OH 1 

R
[H]
C O R CH OH (2°)
R
R

O
[H] OH
R C OH RCH2

O O
[H]
R C O C R 2RCH2 OH

O
[H]
R C Cl RCH2 OH

O
[H]
R C O R/ RCH2OH + HOR/
The commonly used reducing agents are
1) LiAlH4 (LAH) (2) B2H6 in THF (3) NaBH4 (4) H2/catalyst (5) Na in ethanol
LAH can reduce all the above six carbonyl compounds. Tetra alkoxy lithium aluminate is formed,
which is then hydrolysed with dil.acid to generate the alcohol.

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Eg : 4RCOOH + 3LiAlH4 (RCH2O)4 Al Li + 4H2 + 2LiAlO2

(RCH2O)4Al Li + 4HCl 4RCH2OH + AlCl3 + LiCl

LAH (R2CHO)4 Al Li 4H2O

R2CO 4RCH2OH
B2H6 reduces all except RCOCl
H2/Ni reduces all except RCOOH
NaBH4 reduces, Aldehyde, ketone and acid chloride
Na/ethanol reduces, Aldehyde, ketone and ester
Tertiary alcohols cannot be prepared by this reduction method
6. Addion of Grignard reagent to aldehydes or ketones, followed by hydrolysis
H O
Formaldehyde + RMgX 
 Addition product R  CH2  OMgX 
3
 RCH 2  OH
1 Alcohol

Aldehydes other than HCHO gives 2° alcohol

Ketone gives 3° alcohol
Mechanism

O O MgX H

H
+ RMgX  C H H 3O
  R C OH
C
H H
R H
1° alcohol

O
O MgX OH

C + R/MgX 
 R C H H3 O
 R C H
R H
R/ R/
2° Alcohol

O O MgX OH
H3O
C + R MgX 
R C R/ R C R/
R R/
R// R//

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7. Fermentation method for production of ethanol (grain alcohol)

Diastase Maltase Zymase for yeast
i.  C6 H10 O5 n 
(Malt extract )
 C12 H 22O11 
 yeast 
 C 6 H12 O 6   CO 2  C 2 H 5OH
Starch Maltose Glu cose

Invertase Yeast
ii. C H O
12 22 11   C 6 H12 O6  C6 H12 O 6   C2 H 5OH  CO 2 
Sucrose(from molasses) Glu cose Fructose

Ethanol is used as solvent for varnishes. Denatured alcohol is ethanol made unfit for drinking, by
adding some pyridine and CuSO4 solution.
8. Oxo process or hydroformylation of alkene
Alkenes when treated with water gas in presence of cobalt carbonyl hydride gives aldehydes, which
on reduction gives alcohol.

CHO

CoH(CO)4 CHO + CH3 CH CH3

Eg: CH3 CH CH2 + CO + H2 CH3CH2 CH2
(Major) (Minor)
Water gas
Reduction
CH 3CH 2 CH 2  CHO   CH 3CH 2CH 2CH 2  OH

9. Acid catalysed hydration of alkene

Eg: 1. CH3 CH 50% H 2SO4

CH2   CH3 CH CH3

OH
Mechanism :

OH
OH2
H+ H2O H+ CH3 CH CH3
CH3 CH CH2 CH3 CH CH3 CH3 CH CH3

CH3 OH CH3

CH2 dil. H2SO4 C CH3

Eg: 2. CH3 C CH CH3 CH

CH3 CH3
3,3-dimethyl but-1-ene 2, 3-dimethyl butan-2-ol

Mechanism:

OH

H+ CH3 migration (1) H2O

(2) -H+

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Alkenes can be absorbed in con: H2SO4 at 0°C and the alkyl hydrogen sulphate formed on boiling with
water, alcohol is obtained.

Con : H2SO4 CH3 H2O/boil CH3 CH CH3

Eg : CH3 CH CH2 CH3 CH
0°C
OSO3H OH

Isopropyl hydrogen sulphate

(Con: H2SO4 adds in Markownikoff's direction)

10. Hydroboration oxidation of alkene

B2H6/ether 2CH3 CH CH2

CH3 CH CH2 CH3 CH2 CH2 (CH3 CH2 CH2)3 B
H Trialkyl borane
B
H H2O2/OH
Mono alkyl borane

3CH3CH2 CH2 OH

The net result is anti Markownikoff addition of H and OH

11. Oxymercuration-Demercuration of alkene

NaBH4/OH
Hg(OCOCH3)2 + H2O CH3 CH CH3 + Hg + CH3COOH
Eg : CH3 CH CH2 CH3 CH CH2 O

OH Hg CH3 OH
O C

Oxymercurated product

12. Ring opening of epoxide with Grignard reagent followed by hydrolysis

O MgX
O
H3O+ CH2 CH2 OH
+ RMgX 
R CH2 CH2 R

O O MgX OH
+
H 3O
RMgX R CH 2 CH CH 3 R CH2 CH CH 3
CH 2 CH
CH 3
(R from RMgX will attack less hindered carbon)

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13. Commercial production of methanol (Carbinol or wood spirit)

Cr2 O3  ZnO
CO  2H 2  623K
 CH OH 3
Methanol B.P. 65 C

Physical properties
Lower members are colourless liquids. Higher members having more than 12 carbon atoms are wax
like solids.
Eg : Lauryl alcohol C12 H 25  OH M.P = 24.5°C
Cetyl alcohol C16H33 – OH M.P. = 49°C
First three members, methanol, ethanol and propanol are completely miscible with water in all
proportions. i.e. their solubility in water is infinity    . But from butanol onwards, solubility in water
decreases with molecular mass. Among isomeric alcohols, the solubility in water is in the order 3° >
2° > 1°. Boiling point increases with increase in molecular weight.
For isomeric alcohol the boiling point order is 1  2  3 .
Eg : Butan-1-ol (B.P. = 118°C), Isobutanol (B.P. = 108°C), Sec:Butyl alcohol (B.P. = 100°C)
Tert:butyl alcohol (B.P. = 83°C)
Chemical properties
Alcohols can behave as Bronsted acids as well as Bronsted bases.

R OH + NH2 RO + NH3
Acid Base Conjugate base Conjugate acid

R O H + HCl R OH2 + Cl
Base Acid Conjugate acid Conjugate base
Alcohols are neutral to litmus, but they are extremely weak acids, weaker than water pKa of H2O is
15.74, while that of ethanol is  16

CH 3OH H 2O C 2 H 5 OH 2 alcohol 3 alcohol

PK a  15.54 PK a  15.74 PK a  16 PK a  17 PK a  18
Lower the PKa stronger the acid.
The slight acidic character of alcohols is due to the polar nature of O–H bond. An electron releasing
group like –CH3, –C2H5 etc increases the electron density on oxygen and thereby decrease the polarity
of the O–H bond. This decreases the acid strength. So the acidic strength of alcohols follow the order
1° > 2° > 3°.

R
R
O OH > CH O H > R C O H
R CH2
R R
1° 2° 3°

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Strong acids pKa < 1
Moderately strong acid, pKa = (1  5)
Weak acids pKa = (5  15)
Extremely weak acids, pKa > 15
The following equilibrium also shows that alcohols are weaker acids than water.

RO Na + HOH ROH + NaOH

i.e. HOH is a better proton donor than R–OH
See the equilibrium lies mainly to the r.h.s. The position of equilibrium also shows that RONa is a
stronger base than NaOH (or RO is a stronger base than OH
Unprotonated alcohol is a nucleophile, while protonated alcohol behaves as an electrophile.

R O + C 
 R O C R
 O C + H+
E
H H
Nu

R OH + H+ ROH2
Protonated alcohol

Br R O H BrR + H2O

H
Nu E+

REACTIONS OF ALCOHOLS

I. Reactions involving the cleavage of only O H bond

1. With active metals they form alcoholates or alkoxides with the liberation of hydrogen. The
order of reactivity is same as acidic strength order. i.e. 1° > 2° > 3°.

2ROH  2Na 
 2RONa  H 2 
Sodium alkoxide

CH3 CH3

6CH3 C OH + 2Al 2 CH3 C O 3 Al + 3H2

CH3 CH3
Aluminium tert:butoxide

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2. With carboxylic acids, they give esters.

O
* con.H2SO4
RCOOH + HOR/ R C *
O R / + H2 O

Acyl oxygen of the ester is from the acid and alkoxy oxygen is from the alcohol
3. With acid chlorides and acid anhydrides they form esters.
O
Pyridine catalyst
ROH  R COCl  R O C R/ + HCl
Ester

O O

con.H 2SO 4
ROH  (R CO) 2 O  
R O C R/ + R/ C OH
Ester
Note that acyl portion is from acid chloride or anhydride. Alkoxy portion is from the alcohol.
4. With dialkyl sulphates, they form ethers.

O O

RO H + R/ O S O R/ 
R O R/ + R / O S O H
Ether
O O
Alkyl hydrogen sulphate

5. With Grignard reagent they form hydrocarbon

ROH  R MgX 
 R H  R  O  MgX

Eg : 1. CH 3OH  C 2 H 5 MgBr 
 C 2H 6  CH 3  O  MgBr -(Methoxymagnesium bromide)

Mg Br + C2H5 OH + C2H5 O MgBr

2.
Phenylmagnesium bromide Ethoxy magnesium bromide

II. Reactions involving the cleavage of R OH bond

1. Reaction with halogen acids (HX)
The reactivity order of HX is HI > HBr > HCl, while the reactivity order of alcohols towards HX is
3° > 2° > 1° < CH3OH. Allylic and benzylic alcohols are as reactive as 3°.
Here 3° and 2° alcohols react with HX by SN1 pathway while most of the 1° alcohols react by
SN2 mechanism. So among 1° alcohols, methanol show greater reactivity because, no sterric
effect is present with methyl group.
When SN1 mechanism operates in suitable cases, there is a possibility of rearrangement.

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Eg :

CH3 CH3

CH3 CH CH CH3 HBr CH3 C CH2 CH3

OH Br
2-bromo-2-methyl butane
Mechanism:

CH3 CH3 CH3

H+ CH3 CH CH CH3   CH3 CH CH CH3

CH3 CH CH CH3 H O
2

2° C+
OH OH2
Protonated alcohol

CH3 CH3 CH3

Br CH3
CH3 CH CH CH3 H shift CH3 C CH2 CH3 CH3 C CH2

2° C+ 3° C+ Br
But in the following SN1 reaction, there is no rearrangement.

CH3 CH3

CH3 C HBr
OH    CH3 C Br

CH3 CH3

SN2 mechanism
HBr
CH 3CH 2  OH    CH 3 CH 2  Br  H 2O

H+
CH3 CH2 OH CH3CH2OH2

H
H
Br H C OH 2 Br C H + H2 O
CH3
CH 3

Neopentyl alcohol though 1°, it cannot react by SN2 path so it reacts by SN1 path.

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CH3 CH3

CH3 C CH2 OH 
HBr
  CH3 C CH2 CH3 + H2O

CH3 Br
Neopentyl alchol Only product 2-bromo-2-methyl butane

Mechanism

Me Me

Me C CH2 H
OH   Me C CH2 OH2
-H2O
Me Me

Me Br
Me C CH3 gp migration
CH2  Br
 Me C CH2 Me Me C CH2 Me

Me Me Me
2. With PBr3 alcohols give alkyl bromide by SN2 mechanism
3CH 3CH 2 OH  PBr3 
 3CH 3CH 2 Br  H 3 PO 3
Mechanism

Br

CH3CH2 O + P Br CH3CH2 O PBr2 + Br

H Br H

CH3 OH

Br C PBr2 CH3 CH2 Br + P

O
H Br Br
H H

HO  PBr2 can further react with two more molecules of R–OH

CH3 CH3
Cl
PCl3
H OH Cl H + HO P
Cl
Ph Ph
Inverted configuration

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2. With PCl5 1°and 2° alcohols react by SN2 path. 3° alcohols do not react with PCl5 (due to sterric
effect)

H H
PCl4 Cl
H C O H Cl C O PCl4
CH3 H
CH3 H

Cl
H
Cl C H + H O P Cl
CH3 Cl
Cl

Cl
Cl Cl
H O P 
 HCl
O P Cl
Cl
Cl
Cl
For the reaction between a 1° alcohol and HCl, anhydrous ZnCl2 is used as a catalyst (it is a must
otherwise, the reaction will be too slow). But for HBr and HI, ZnCl2 catalyst is not necessary, because

Br and I are stronger nucleophiles than Cl

Alcohols react with thionylchloride SOCl2 producing alkyl chloride by SNi mechanism (Darzen’s
procedure). But if this reaction is carried out in presence of pyridine, the reaction proceeds by SN2
mechanism. When SNi mechanism operates, there is retention of configuration but when SN2 operates,
there is inversion of configuration.
3. With NH3
Al 2O3 ROH ROH
R  OH  NH 3 
350 C  H 2O
RNH 2 
 H 2O
 R 2 NH 
 H2O
 R3N
Vapours of both

III. Reactions involving cleavage of alkyl and –OH group

1. Dehydration : Relative ease of dehydration is 3° > 2° > 1°
For dehydration of 1° alcohols, conc:H2SO4 AND 170°C is required.
For 2° alcohols 60% H2SO4 or H3PO4 and 100°C is enough
For 3° alcohols 20% H2SO4 at 80°C, is sufficient for dehydration.
Dehydration is also effected by heating with Al2O3 (Alumina)
For 1° alcohols Al2O3 at 350°C is required
For 2° alcohols Al2O3 at 250°C is enough
For 3° alcohols, Al2O3 at 150°C is sufficient.
con:H SO
Eg : 1. CH 3  CH 2  OH 2
170 C
4
 CH 2  CH 2  H 2O
For acid catalysed dehydration, the most widely accepted mechanism involves the formation of
carbocation intermediate.

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H+ -H+ CH2
Eg : 1. CH CH2 OH CH3CH2 OH2 -H O CH3 CH2 CH2
3 2

CH3 CH3

Eg : 2. CH3 C CH2 OH 

con:H 2SO4
 CH3 C CH CH3 + H2O
170 C
2-methyl but-2-ene
CH3

Mechanism

CH3
CH3 CH3

H+ CH2 OH2 -H O CH3 C CH2 

rearranges

CH3 C CH2 OH CH3 C 2

CH3 CH3
CH3

CH3 C CH2 CH3 

  CH3
C CH CH3
H

CH3 CH3

CH3
CH2 OH CH2 OH CH2
H
con.H 2SO 4 
Eg : 3.  
 
 H2O
 H shift H
 
3° cation

CH3

(Here H+ is lost from CH2 group)

Saytzeff rule is obeyed in dehydrations

(90%)
If H+ is lost from CH3 group in the 3° cation, methylene cyclohexane is formed.

CH2
CH2 H


H
 
Methylene cyclohexane
(Minor product)

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Primary alcohols can undergo dehydration by an E2 mechanism also.

Eg : B CH2 CH2 OH2 CH2 CH2 + H2O + BH

(Base)

Here base B may be HSO4 or H2O.

con. H2SO4
Eg. (4) CH3 - CH2 - CH2 - CH2 - OH CH3 - CH = CH - CH3 + CH3 - CH2 - CH = CH2
170oC
Butan-1-ol but-2-ene 12%
88% but-1-ene

56% trans 32% cis

H+
Mechanism : CH3 - CH2 - CH2 - CH2 - OH CH3 - CH2 - CH2 - CH2 - OH2
-H2O

H shift H+ from CH2

CH3 - CH2 - CH2 - CH2 CH3 - CH2 - CH - CH3 CH3 - CH = CH - CH3
But-2-ene
H+ for CH3 (88%)

CH3 - CH2 - CH = CH2

but-1-ene (12%)

CH3 H CH3 CH3

C C C C
H CH3 H H
trans 2-butene cis 2-butene
so we find that dehydration of butan-1-ol is a regio selective as well as a stereo selective reaction.
2) Dehydrogenation : When vapors of alcohols are passed over heated copper at 300oC, 1o alcohols
yield aldehyde, 2o gives ketone and 3o alcohols produce alkene. (Here 3o undergo dehydration)

R Cu at 300oC
CH O H RCHO + H2

H
Here a C  H bond and O  H bond undergo cleavage and a carbon-oxygen  bond is formed.

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R R
o
R C O Cu at 300 C
H R C O + H2
H ketone
o
2 alcohol

Here also C - H and O - H  bonds undergo cleavage and a carbon-oxygen  bond is formed.

CH3 CH3
Cu at 300oC
CH3 C OH CH3 C + H2O

CH3 CH2

3° alcohol Isobutene (2-methyl propene)

3) Oxidation of alcohols :
Primary alcohol on oxidation, first forms an aldehyde which further undergo oxidation giving a carboxylic
acid, both containing the same number of carbon atoms as in the alcohol.
  O   O
Eg : CH 3CH 2  CH 2  OH   CH 3CH 2CHO   CH 3CH 2 COOH
2° alcohols on oxidation, ketone is formed first. Ketones require vigorous conditions for oxidation and
forms a mixture of two carboxylic acids.

(O) (O)
Eg. CH3 - CH - CH3 CH3 - C - CH3 CH3COOH + HCOOH

OH O
The oxidising agents used for oxidation of alcohols are
  
1) acid dichromate  H Cr O2 
 2 7 

2) acid permanganate H+ / MnO4

3) alkaline KMnO 4 OH- / MnO4

4) dil. HNO3
Tertiarty alcohols cannot be oxidised in alkaline or in neutral media. But they can be oxidised in acid
medium on prolonged heating with oxidising agent.

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CH3 CH3 O
H+ / Cr2O7 (O)
For eg. : CH3 C OH CH3 C CH3 C CH3 + HCOOH
heat
CH3 CH2

O
(O)
CH3 C CH3 CH3COOH + HCOOH
Halogen in aqueous solution will oxidise io alcohol to aldehyde and 2o alcohol to ketone
4) Haloform reaction by alcohols

OH

Alcohols which possess CH3 CH group connected to carbon or hydrogen, on heating with halogen
and alkali, will produce, the corresponding haloform CHCl3 (If Cl2 and alkali are used) CHBr3 (If Br2
and alkali) or CHI3 (iodoform, if I2 and alkali are used)
CHCl3 and CHBr3 are colourless liquids, but CHI3 is an yellow solid. So iodoform test is conducted.

Eg. CH 3CH 2  OH  4I2  6NaOH  CHI3  5NaI  HCOONa  5H 2 O

Yellow ppt.

OH O I O
I2 3I2
Mechanism CH 3 CH H CH 3 C H I C C H
-2HI -3HI
ethanol ethanal I

I O
Hydrolysis
I C C H CHI3 + HCOONa
NaOH
I
tri iodo ethanal

I O
OH
I C C H CI3 + HCOOH
I
proton transfer

CHI3 + HCOO

About iodoform reactions of alcohols

1) Ethanol is the only 1o alcohol that answers iodoform test

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2) No tertiary alcohol will answer this test

OH

3) Only those secondary alcohols having CH3 CH group will answer this test.

O OH

NB : Haloform reaction is given by compounds having either CH3 C group or CH3 CH

group connected to carbon or hydrogen.
Pentan-2-ol and pentan-3-ol can be distinguished by iodoform test
OH
I2 + NaOH
CHI3 (yellow ppt.)
heat

I2 + NaOH
No yellow ppt. CHI3
heat
OH

How many structural isomers of C5 H12 O will answer iodoform test ? Answer is 2

OH

OH
pentan-2-ol
3-methyl butan-2-ol

NB : C5 H12 O has 8 structurally isomeric alcohols and 6 structurally isomeric ethers. Out of these
fourteen structural isomers only two will answer iodoform test.
Methods to distinguish between 1o, 2o and 3o alcohols
1) Dehydrogenation test
o
1o 
Cu at 300 C
Aldehyde  H 2
o
2o 
Cu at 300 C
Ketone  H 2
o
3o alcohol 
Cu at 300 C
 Alkene  H 2O
2) Lucas test (Lucas reagent is con. HCl + anhy. ZnCl2)
1o alcohol + Lucas reagent 
Room temp.
 No turbidity
2o alcohol + Lucas reagent 
Room temp.
 Turbidity appears slowly

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(approx. 5 minutes time)
3o alcohol + Lucas reagent Room temp.
 Turbidity appears immediately
(NB : If heated with Lucas reagent 1o will also give turbidity)

CH2OH

Exceptional cases CH2 - CH - CH2 - OH and as well as CH2 - OH will

(cyclo propyl methanol)

give a turbidity even at room temperature .
3) Acid dichromate test
Room temp.
1o alcohol  acid dichromate so ln.   Green colour  Cr 3 
 orange colour 
Room temp.
2o alcohol  acid dichromate so ln .   Green colour  Cr 3 
 orange colour 
Room temp.
3o alcohol  acid dichromate so ln.   No colour change
 orange colour   orange colour persists 
4) Victor Meyer’s Test

During victor meyer’s test 10 alcohol gives a red colour

20 Blue colour
0
3 Colourless solution

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10 20 30

R
RCH2 OH R CH OH R C OH
R
P + I2 R
P + I2
P + I2
RCH2 I
(R)3 C I
AgNO2
(R)2 CH I
AgNO2
R CH2 NO2 AgNO2
(R)3 C NO2
HNO2
(R)2CH NO2 HNO2

R CH NO2 HNO2
No reaction
NO NO2 NaOH solution
R C
Tautomerises NO Colourless solution
R
Pseudonitrole
R C NO2
NaOH solution
N OH
Nitrolic acid
Blue Colour
NaOH solution

R C NO2

N O Na
Red colour

NB : Only 10 and 20 nitroalkanes can react with nitrous acid, 30 nitroalkane cannot.

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PHENOLS
Phenols are hydroxy derivatives of aromatic hydrocarbons in which the OH group is directly attached
to the carbon atom of the aromatic ring. The natural source of phenol is the middle oil fraction during
the fractional distillation of coal tar.

OH OH OH
OH OH

OH
Phenol or carbolic acid Catechol Pyrogallol
(monohydric phenol) Benzene-1,2-diol Benzene 1,2,3-triol
(Dihydric phenol) (Trihydric phenol)

OH OH OH

OH HO OH

Resorcinol OH
quinol or hydroquinone Phloroglucinol
The hormone adrenaline contains catechol unit
HO OH

HO CH CH2 NH CH3

Adrenaline

Laboratory method of preparation of phenol

ONa OH
SO3Na
2 NaOH dil. HCl
1)
Fusion at 632 K

Sodium benzene sulphonate

N2 Cl OH

heat + N2 + HCl
2)
+ H2O

Benzenediazoniumchloride
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ONa OH
OH

COONa heat H+
3) + NaOH + CaO

Soda lime
Sodiumsalicylate

Mg Br O Mg Br OH
Br

Mg/ether 1/2 O2 H+ /H2O

4)

OH

5) Fenton’s reagent +

Fenton’s reagent is a mixture of freshly prepared FeSO4 solution and H2O2.

H 2O 2  Fe2  Fe3  OH  OH
The OH radical attacks the benzene ring.
Manufacture of phenol
1) Dow process

Cl ONa OH
10 % NaOH
3500 C H+
300 atm

This reaction is an aromatic nucleophilic substitution that occur by elimination-addition mechanism

and involves the formation of benzyne intermediate (also called benzyne mechanism)

OH OH
Cl
OH (Dow conditions) OH H+ from solvent
(3500 C, 300 atm)
H
benzyne

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2) Cumene hydroperoxide process (Most widely used method)

CH3
CH3 CH3
H 3C C O O H OH
CH O

O2 dil. H2SO4 C
+ CH3 CH3
heat
Acetone
(Cumene) Cumene hydroperoxide
Isopropylbenzene

Here acetone is a valuable by product.

Physical properties of phenol
Pure phenol is a colourless crystalline solid. M.P. = 430 C. But due to atmospheric oxidation. Phenol
turns slightly coloured pink and finally the colour turns brown. The colour is due to the formation of
phenoquinone.

O H O O H O

Phenoquinone
Phenol is moderately soluble in cold water. Phenol is a weak acid, when phenol ionises, the resulting
phenoxide ion is more resonance stabilized than unionised phenol.

OH O

+ H2O  + H+

Phenoxide ion

O O O O O

Phenol is more acidic than alcohols, but much less acidic than carboxylic acids. Carboxylic acids are
much less acidic than mineral acids like HCl acid. Consider the following compounds and their pKa
values.

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SO3H COOH OH

HCl H2CO3 H2O C2H5OH

pKa = - 7 pKa = - 6.5 pKa = 4.19 pKa = 6.4 pKa = 9.98  10 pKa = 15.74 pKa = 16

Acidic strength decreases as pKa value increases

Presence of electron withdrawing groups like ––NO2, ––CN, halogens (X) etc. increases the acidic
strength of phenol where as electron donating groups like ––CH3, ––OCH3 etc decreases the acidic
strength of phenol.

OH OH
OH OH OH OH OH
O2 N NO2
NO2
CH3

CH3 NO2
Cl
CH3
pKa = 9.98 pKa = 7.23 pKa = 9.38 pKa = 0.38
pKa = 10.2 pKa = 10.08 pKa = 10.28

2,4,6 trinitrophenol called picric acid is a strong acid.

COOH

will dissolve in NaHCO3 solution, but phenol will not. Why ?

COOH

Benzoic acid is a stronger acid than H2CO3. Therfore can displace H2CO3 from the salt

NaHCO3.

COOH COONa

i.e., + NaHCO3 + [H2CO3] H2O + CO2

So we observe brisk effervescence.

But phenol is a weaker acid than H2CO3. So it cannot displace H2CO3 from NaHCO3.

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OH

+ NaHCO3 solution No reaction

So phenol and benzoic acid can be distinguished by NaHCO3 solution. But NaOH cannot distinguish
these two. Both will dissolve in NaOH solution.

COOH COONa

+ NaOH + H2O

ONa Acid base reactions

OH

+ NaOH + H2O

When NaHCO3 solution is added to benzoic acid and phenol separately they behave differently. Benzoic
acid will dissolve in NaHCO3 solution. So the visible change is evolution of CO2, when benzoic acid is
added to NaHCO3 solution and due to the formation of sodium benzoate, benzoic acid dissolves in
NaHCO3 solution. But phenol will not dissolve in NaHCO3 solution. Picric acid 2,4,6 trinitrophenol is a
strong acid and it will dissolve in NaHCO3 solution. pKa of picric acid is 0.38.
Reactions of phenol
A. Reactions due to the –OH group
1) with FeCl3 solution a violet colour is produced
3
 Fe  C6 H5O  
 6 complex

2) Phenol reacts with alkyl halide in presence of alkali to form alkyl aryl ether (Williamson’s reaction)

OH + NaOH ONa + H2O

ONa + CH3 Br O CH3 + NaBr

Anisole
This is a nucleophilic substitution reaction.

Phenoxide ion displaces Br

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O Na + CH3 CH2 I O CH2 CH3 + NaI

Phenetole

OH O
2 NaOH CH2 + 2NaI
CH2I2
OH O
3) Ester formation : Phenol reacts with acid chlorides or acid anhydrides in presence of alkali to form
phenyl esters.

O
NaOH
OH + CH3COCl O C CH3
Phenyl acetate
Acetylchloride

O O
NaOH
OH + C Cl O C

Benzoyl chloride Phenyl benzoate

This benzoylation of phenol is Schotten Baumann reaction.

4) When distilled with Zn dust phenol gives benzene

OH

heat
+ Zn + ZnO

OH
CH3 CH3
Zn dust
+ ZnO
heat
Toluene

Anhy.ZnCl2
5) OH + NH3 NH2 + H O
heat 2

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B. Reactions of benzene nucleus
Electrophilic substitutions
1) Bromination of phenol with Br2/CS2 gives a mixture of ortho and para bromo phenols.

OH OH
OH
Br
Br2/CS2 + + HBr

 20% Br
 80%

2) With Br2 water, 2,4,6 tribromophenol is formed

OH OH
Br Br
Br2/H2O + 3HBr
+ 3Br2

Br
white ppt.

OH OH
COOH Br Br
Br2/H2O
+ CO2

salicylic acid Br

3) Nitration with dil.HNO3 gives ortho and para - nitrophenols

OH OH
OH
NO2
dil.HNO3 +
0
25 C

(30 - 40%) NO2

(15%)

Ortho and para isomers can be separated by steam distillation, since ortho isomer is steam volatile.

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4) With conc. HNO3 picric acid is produced

OH
OH
O2N NO2
conc.HNO3

NO2
Picric acid
2,4,6 - trinitrophenol

But the yield is low, due to oxidation of phenol, so, picric acid is prepared as follows.

OH
OH OH
O2N NO2
SO3H
conc. H2SO4 conc. HNO3

NO2
SO3H

5) Reimer-Tiemann reaction

ONa ONa
OH
CHO
0
60 C +
+ CHCl3 + NaOH

(major) CHO
(minor)

ONa OH

CHO CHO
H+

ONa OH

H+

CHO CHO

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Mechanism of Reimer-Tiemann reaction
Here the attacking electrophile is dichlorocarbene: CCl2, which is formed as an intermediate by the
action of NaOH on CHCl3.

Cl
OH
H C Cl CCl3
- H2O
Cl

CCl3 C Cl
- Cl
Cl

O O O
H H
H+ from solvent H
CCl2
C Cl C Cl

Cl Cl

Tautomerises

OH O Na O Cl
CHO CHO CH
H+ NaOH Cl
hydrolysis
gemdihalide

Similarly para attack by CCl2 gives a small amount of p-hydroxy benzaldehyde.

When phenol is heated with CCl4 and NaOH at 700 C salicylic acid is obtained. This is also Reimer-
Tiemann reaction. But here mechanism is different. No carbene intermediate is formed here.
6) Kolbe-Schmidt reaction
Sodium phenoxide on heating with CO2 at 130 - 1400 C and a pressure of 6 atm. Salicylic acid is
produced.

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ONa OH OH
COONa COOH
0
140 C H+
+ CO2
6 atm

Here the attacking electrophile is CO2

O OH
O
H COO
Tautomerises
+ C O C O

O O
H+

OH
COOH

7) Gattermann’s aldehyde synthesis

OH OH
OH
CHO
1) anhy.AlCl3 +
+ liquid HCN + conc. HCl
2) hydrolysis

CHO (minor)
(major)

Mechanism
H  C  N  H  Cl  HN  CH  Cl
imido formyl chloride


AlCl
3  HN  C H
HN  CH  Cl 
imido formylcation

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OH
OH OH OH
CHO
H CH NH hydrolysis
HN CH
CH NH - H+

para attack gives para isomer

8) Oxidation of phenol

O
OH

K2Cr2O7
+ conc. H2SO4

O
para benzoquinone
(yellow powder)

9) Coupling reaction
Phenol couples with benzene diazonium chloride in faintly alkaline medium, producing an azo dye.

faintly
alkaline
N2 Cl + H OH N N OH

orange coloured dye

10) Phenol condenses with HCHO to form Bakelite
Here the first reaction is Lederer-Manasse reaction that produces ortho and para hydroxy benzyl alcohols.
O
H+
H C H CH2 OH

OH OH
OH
H CH 2 OH
+
CH 2 OH -H
CH 2 OH

Similarly para attack gives p-hydroxy benzyl alcohol, hydroxy benzyl alcohols condenses to form a
linear polymer called Novolac resin, which on further heating with HCHO, under pressure produces,
cross-linked 3-dimensional network polymer Bakelite.
Phenolphthalein formation
heat
Phenol + Phthalic anhydride + few drops of conc. H 2 SO 4   colourless solution
NaOH solution
 pink colour..

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O
O
C
O Phthalic anhydride C
O
C conc. H2SO4
C
O OH
H OH
H

phenolphthalein
OH

OH NaOH solution

Pink colour

SOME IMPORTANT DERIVATIVES OF SALICYLIC ACID

O C CH3

COOH
1. Aspirin (Acetylsalicylic acid)

Preparation

OH O CO CH3
 CH CO
3 O
 2
CH3COOH
COOH COOH
Salicylic acid is acetylated with a mixture of acetic anhydride and acetic acid.
Aspirin has analgesic, antipyretic and antiblood clotting properties
Aspirin is a solid M.P. = 135°C
2. Methylsalicylate (Oil of winter green)

OH
COOCH3
It is prepared by esterification of salicylic acid with methanol.

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OH
OH
COOH
CH 3OH

con:H 2SO4

COOCH3
It is a pleasant smelling liquid. b.p. = 224°C. It is used in rubbing liniments (used in Rheumatic pains)

OH
3. Phenyl salicylate (salol)
COO

Prepared by heating salicylic acid with phenol in presence of phosphoryl chloride POCl3.

*
OH OH
OH
POCl3
+  
*
COOH C O

O
It is a white solid. m.p. = 42°C. It is used as intestinal antiseptic.
ETHERS
Ethers are named, in substitutive IUPAC nomenclature as alkoxy derivatives of alkanes. Functional
class IUPAC names of ethers are derived by listing the two alkyl groups in the general structure ROR 
in alphabetical order as separate words, and then adding the word ‘ether’ at the end. When both the
alkyl groups are the same, the prefix di-precedes the name of the alkyl group.

Substitutive IUPAC name CH 3  CH 2  O  CH 2  CH3 CH 3  CH 2  O  CH 3

Ethoxy ethane Methoxy ethane

Functional class IUPAC name diethyl ether Ethyl methyl ether

Ethers are described as symmetrical or unsymmetrical depending on whether the two groups bonded
to oxygen are the same or different. Symmetrical ethers are also called simple ethers and unsymmetrical
ethers are called mixed ethers.
Preparation
1. Dehydration of primary alcohols by heating with conc. H2SO4 at 1400 C.
conc. H 2SO4
eg : 2CH3CH 2  OH   CH3CH 2  O  CH 2  CH3
0 140 C

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Mechanism

H+
CH3 CH2 OH CH3CH2 OH2

CH3 CH2 O CH2 OH2 SN2 process

CH3 CH2 O CH2 CH3
H CH3
H
Nu E protonated ether
(diethyl oxonium ion)

- H+

CH3 CH2 O CH2 CH3

2. Williamson’s method
Alkoxide  Alkyl halide  ether

Eg : C2H5 O Na + CH2 I C2H5 O CH2 CH3 + NaI

CH3

Limitation of this method

This method fails with tert. alkyl halides, because they undergo elimination.

CH3 CH3
eg : CH3ONa + CH3 C Br CH2 C + CH3OH + NaBr
CH3
CH3
Isobutene
So to prepare tert. butyl methyl ether, tert. butoxide and methyl halide are allowed to react

CH3
CH 3
I CH 3 C O CH 3 + KI
CH3 C OK + CH 3

CH 3 CH3

Intramolecular williamson’s reaction can produce cyclic ethers.

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 O
Na
Cl  CH 2  CH 2  CH 2  CH 2  OH  Cl  CH 2  CH 2  CH 2  CH 2O Na
THF

Cl
CH2
O CH2 O
Tetrahydrofuran O Na
(THF) CH2
CH2

3) Action of dry Ag2O on alkyl halide

R X + Ag O Ag + X R R O R + 2AgX
4) Addition of alcohols to alkenes, in presence of dil. H2SO4

O C2H5
H2SO4
CH3 C CH2 + C2H5OH CH3 C CH3

CH3 CH3
2 - ethoxy 2-methyl propane

Mechanism

C2H5 H
O H O
H+ C2H5
CH3 C CH2 CH3 C CH3
CH3 C CH3
CH3 CH3
CH3

H+

O C2H5

CH3 C CH3

CH3

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General properties of ethers

The lower members are gases or volatile liquids and their vapours are highly inflammable. Their boiling
points are much lower than those of the alcohols containing the same number of carbon atoms, and
this is due to the fact that ethers cannot associate through hydrogen bonding. All the ethers are less
dense than water in which they are not much soluble. Just as in alcohols and phenols oxygen is sp 3
hybridised in ethers also.

136 pm
142 pm
O 96 pm O 96 pm O O 141 pm
H
H 104.50 H R H 1090 CH 3 111.7 0 CH 3
108.9 0

O CH3
H 3C
C 1300 C CH3
H 3C
H 3C CH3

CH 3  O  CH3 B.P  240 C

CH 3  O  C 2 H5 B.P  8C
C2 H 5  O  C 2H 5 B.P  350 C
Chemical properties of ethers
1) Oxonium salt formation
Ethers dissolve in conc. solutions of strong inorganic acids to form oxonium salts. So ethers behave
as Bronsted base.

O + H2SO4 O HSO4
R R R R

  
00 C
C2 H 5  O  C2 H5  conc.H 2SO 4 
  C2 H 5 2 O H  HSO 4
eg :  
Diethyloxonium hydrogen sulphate

2) Clevage of C  O bond in ether

Ethers are the least reactive of the various functional groups. The cleavage of C  O bond in ethers
takes place under drastic conditions with excess of halogen acids. Among the halogen acids HI is
most effective. Usually conc. HI or HBr is used at high temperature.

R  O  R  HI 
 ROH  RI
1:1molar ratio

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Brilliant STUDY CENTRE REPEATERS CHEMISTRY -2022(ONLINE CLASS NOTES A-NEET)
heat
R OR  HI 
 2RI  H 2O
 excess HI

  ROH  R  I  or  RI  R  OH  ?
R  O  R  HI 
mixed ether
1:1ratio 
To answer this question, the following rules are helpful.
1) If both the alkyl groups are 10 or 20, then smaller alkyliodide is formed by an SN2 mechanism.

eg : CH  O  CH  CH  HI
3 2 3  CH3I  CH3  CH 2  OH
1:1ratio 
Mechanism

H+ from HI CH2 CH3

CH3 O CH2 CH3 CH3 O

SN2
I CH3 O CH2 CH3 I CH3 + O CH2 CH3

H H

i.e. ether gets protonated first and then I will attack the protonated ether from the back side of the
smaller alkyl group.
2) If one alkyl group is tertiary then tertiary alkyl iodide is formed and mechanism is SN1.

CH3 CH3
HI
CH3 C O CH3 CH3 C I + CH3 OH
eg : (1 : 1 ratio)
CH3 CH3

Mechanism

CH3 CH3
H+ from HI
CH3 C O CH3 CH3 C O CH3

CH3 CH3 H

CH 3 CH 3
CH3

CH3 C O CH 3 CH3 C + O

CH 3 H CH 3 H

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
I
 CH3 3 C    CH 3 3 C I
NB : Even if one alkyl group is tertiary, SN1 cannot operate, if the solvent is non polar.

CH3 CH3
anhy. HI
For eg : CH3 C O CH3 CH3 C OH + CH3I
CCl4 solvent
CH3 CH3

Using anhydrous HI in non polar solvent, SN1 cannot operate, and cleavage is by SN2 path, so smaller
alkyl iodide is formed.
Rule 3
Aryl alkyl ether always gives phenol and alkyl iodide not phenyl iodide, because bond between benzene
ring and oxygen is very strong. Irrespective of the mechanism, i.e, whether SN1 or SN2, phenol and
alkyl iodide are formed.

HI
O CH3 OH + CH3I

HI
O CH3 O CH3

H H

I CH3 O ICH3 + O

Rule 4 : Diaryl ethers cannot be cleaved by halogen acid

HI
O No reaction
heat
Hydroperoxide formation
Ethers having  -hydrogens will undergo atmospheric oxidation and forms ether hydroperoxides which
are explosive compounds.

H
O
O
O2 CH O CH2 CH3
CH3 CH2 O CH2 CH3 CH3
  hydroperoxide

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Brilliant STUDY CENTRE REPEATERS CHEMISTRY -2022(ONLINE CLASS NOTES A-NEET)
So before using ether for an experiment, make sure that it is free from hydroperoxide. To test the
presence of hydroperoxide, the ether sample is shaken with freshly prepared FeSO4 solution and then
KCNS solution is added. If a blood red colour is formed it indicates the presence of hydroperoxide
ether hydroperoxide will oxidise Fe 2 to Fe3 and thiocyanate ions combine with Fe3 forming ferric
thiocyanate (blood red colour)
Crown ethers
Crown ethers are macrocyclic polyethers containing at least four oxygen atoms.

These crown ethers can bind certain metal ions specifically and the resulting complexes are called
guest - host complexes or inclusion complexes. 12 - crown - 4 can bind Li  ions. 15 - crown - 5 can

bind Na and 18 - crown - 6 can bind K  ions.

O O
Li

O O

Electrophilic substitution in aromatic ethers

The alkoxy group  OR  is ortho, para directing and activates the aromatic ring towards electrophilic
substitution.

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Brilliant STUDY CENTRE REPEATERS CHEMISTRY -2022 (ONLINE CLASS NOTES A-NEET)

R O R O R O R
O R O

1. Halogenation

OCH3 OCH3 OCH3

Br
Br2 / CH3COOH
+

2 - bromoanisole
Anisole Br
4 - bromoanisole  10 %

 90 %

OCH3
OCH3
Br Br
FeBr3
+ Br2  
2, 4, 6 tribromo anisole

Br

2. Friedel-Crafts Alkylation and acylation

OCH3

OCH3
OCH3
CH3
Anhy:AlCl
+ CH3Cl 
CS2
3
 +
CH3
(Minor) 4-methoxy toluene
(Major)

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Brilliant STUDY CENTRE REPEATERS CHEMISTRY -2022(ONLINE CLASS NOTES A-NEET)

OCH3 OCH3 OCH3

COCH3
Anhy:AlCl3 +
+ CH3COCl
Ethanoyl chloride
2-Methoxy acetophenone
(Acetylchloride) COCH3
(Minor)
4-Methoxyaceto phenone
(Major product)

3. Nitration

OCH3 OCH3 OCH3

NO2
con:H 2SO 4  con:HNO3

 +

2-Nitroanisole
(Minor) NO2
4-Nitroanisole
(Major)

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