1

ALCOHOLS, PHENOLS & ETHERS

ALCOHOLS
CLASSIFICATION OF ALCOHOLS
Alcohols are compounds containing hydroxyl group attached to the alkyl
group.
Example: CH 3  OH Methyl alcohol

CH 3  CH 2  OH Ethyl alcohol

Alcohols are classified as mono, di, tri and polyhydric alcohols depending on
whether they contain 1, 2, 3 or more of hydroxyl groups.

Monohydric alcohols are further classified as primary  1  , secondary  2   or

tertiary  3  alcohols according as the hydroxyl group is attached to a primary,

secondary or tertiary carbon atom.

Monohydric alcohols may also be classified according to the hybridization of

the carbon atom containing the hydroxyl group.
(a) Alcohols containing  OH group attached to sp 3 hybridized carbon:

These are of three types,

(i) Aliphatic alcohols: In these alcohols  OH group is linked to sp 3 carbon.
 2

(ii) Allylic alcohols: In these alcohols, the  OH group is attached to a sp 3

hybridized carbon next to a carbon-carbon double bond.

Example: CH 2  CH  CH 2OH : allyl alcohol

Allylic alcohols are also be 1 , 2  or 3 .

(iii) Benzylic alcohols: In these alcohols, the  OH group is attached to a sp 3

hybridized carbon next to an aromatic ring. They can also be 1 , 2  or 3 .

(b) Alcohols containing  OH group attached to sp 2 hybridized carbon:

These alcohols contain  OH group linked to a carbon-carbon double bond.

They are known as vinylic alcohols and are generally unstable.

Example: CH 2  CH  OH

NOMENCLATURE
According to IUPAC system, alcohols are named by replacing ' e ' in the name
of parent alkane by ' ol ' .

Structure IUPAC Name Trivial Name

CH 3  OH Methanol Methyl alcohol

CH 3  CH 2  OH Ethanol Ethyl alcohol

Isopropyl alcohol Propan-2-ol

CH 3  CH 2  CH 2  CH 2OH Butan-1-ol n  Butyl alcohol

Butan-2-ol sec-Butyl alcohol

 3

2-Methylpropan-1-ol iso-Butyl alcohol

2-Methylpropan-2-ol ter-Butyl alcohol

HO  CH 2  CH 2  OH Ethane-1,2-diol Ethylene glycol

Propane-1,2,3-triol Glycerol

Structure of the functional group:

The oxygen atom of the  OH group in alcohols and phenols is sp 3 hybridized and

the bond angle is slightly less than the tetrahedral angle. The bond

angle is 108.9  in methanol. The slight decrease in bond angle is due to lone pair-
bond pair repulsion. To minimize repulsion from lone pairs, bond pairs move
slightly closer. In phenol, the C  O  H bond angle is 109 .
GENERAL METHODS OF PREPARATION OF ALCOHOLS
(i) From Haloalkanes:
RX  KOH  aq  
 ROH  KCl

(ii) From Carbonyl compounds:

(a) By reduction of aldehydes and ketones
Ni or Pd
R  CHO  H 2   R  CH 2  OH
Ni or Pd
CH 3CHO  H 2  CH 3CH 2OH
NaBH 4
R  CO  R   R  CH  R
|
OH

LiAlH 4
CH 2  CH  CH 2  CHO 
or NaBH 4
 CH 2  CH  CH 2  CH 2 OH

LiAlH 4 and NaBH 4 do not generally affect C  C multiple bonds.

 4

(b) By reduction of acids and esters

Carboxylic acids are reduced to primary alcohols by LiAlH 4
 i  LiAlH 4
R  COOH 
 ii  H 2O
 R  CH 2  OH
( i ) LiAlH 4
CH 3COOH 
( ii ) H 2 O
 CH 3CH 2OH

Esters are reduced to a mixture of alcohols by H 2 / Ni , LiAlH 4 etc.

H 2 /Ni
CH 3  CH 2  COOC 2 H 5   CH 3  CH 2  CH 2  OH  C 2 H 5OH

(iii) From Grignard Reagents:

Grignard reagent gives addition product with aldehydes and ketones. The
adduct on hydrolysis gives alcohol.

Reaction of formaldehyde with Grignard reagent followed by hydrolysis

gives primary alcohols. All other aldehydes give secondary alcohols and
ketones give tertiary alcohols.
 i  RMgX
HCHO 
 ii  HOH
 R  CH 2  OH 1

alcohol 

R
|
 i  RMgX
RCHO 
 ii  HOH
 R  C H  OH 2 
alcohol 

R
|

RCOR 
i RMgX
 ii  HOH  R  C  OH
|
3 
alcohol 
R
(iv) From Alkenes:
(a) By acid catalysed hydration:
Alkenes react with water in the presence of mineral acid to form alcohols.
Addition of water occurs in accordance with Markovnikov’s rule.

H
CH 3  CH  CH 2  H 2O  CH 3  CH  CH 3
|
OH
Mechanism:
Step 1: Protonation of alkene by attack of H 3O  to form carbocation.

 CH 3  CH  CH 3  H 2O
CH 3  CH  CH 2  H 3O  

Step 2: Nucleophilic attack of water on carbocation.

 5

Step 3: Deprotonation to form alcohol.

(b) Hydroboration-Oxidation:
Alkenes react with diborane to form trialkyl borane. This on oxidation
with alkaline H 2O2 give alcohol. Net reaction is antiMarkownikov

addition of H 2O to double bond.


H 2 O2 /OH
3CH 3  CH  CH 2   BH 3 2  CH 3  CH 2  CH 2 3 B  3CH 3  CH 2  CH 2OH

Commercial preparation of alcohols:

1. Manufacture of methanol:
Cr2O3  ZnO
CO  2 H 2 
573 K , 200 atm
 CH 3OH

Methanol is also called ‘wood spirit’. In small quantities it causes blindness.

Larger quantities cause death. It is used as solvent in paints and varnishes.
2. Manufacture of ethanol:
1. From Molasses: Ethanol is manufactured mainly from molasses.
Molasses is the mother liquor left behind after the crystallization of sugar
from sugarcane juice. It still contains dissolved sugar. Molasses is first
diluted with water to reduce the concentration of sugar to about 10%.
Yeast is then added and the temperature is maintained at about 305 K .

Slow fermentation takes place and a dilute solution of alcohol is obtained.

invertase
C 12 H 22O11  H 2O 
 from yeast   C 6 H 12O6  C 6 H 12O6
Cane sugar Glucose Fructose

Zymase
 from yeast   2C 2 H 5OH  2CO2
C 6 H 12O6 
Glucose or  Ethanol 
Fructose

Alcohol containing 95% ethanol is called rectified spirit. Commercial

alcohol is made unit for drinking by mixing it with poisonous substances
like pyridine, methanol, etc. Some copper sulphate is also added to give it
 6

colour. It is known as denaturation of alcohol and the alcohol so prepared

is called denatured spirit.
2. From Ethene: Ethanol is also manufactured by hydration of ethane.
H2O
CH 2  CH 2  H 2 SO4  CH 3CH 2OSO3 H 
boil
 CH 3CH 2OH  H 2SO4

PHYSICAL PROPERTIES OF ALCOHOLS

1. Alcohol molecules are associated by intermolecular hydrogen bonding. Hence
the boiling points of alcohols are much higher than that of corresponding
hydrocarbons and alkyl halides.
2. Lower alcohols are readily soluble in water. The high solubility of alcohols is due
to the formation of hydrogen bonds with water.

3. Among isomeric alcohols, boiling points show the following trend

Primary alcohol > secondary alcohol > tertiary alcohol
CHEMICAL PROPERTIES OF ALCOHOLS
A. Reactions involving the cleavage of oxygen-hydrogen bond:

Oder of reactivity of alcohols in such reactions is 1  2   3 .

(i) Reaction with active metals  Na , K , Al  .

2 ROH  2 Na 
 2 RONa  H 2

2C 2 H 5OH  2 Na 
 2C 2 H 5ONa  H 2

This reactions shows the acidic nature of alcohols. The acid strength of
alcohols follow the order 1  2   3 . But alcohols are less acidic than
water.
 7

(ii) Reaction with organic acids (Esterification)

Alcohols react with carboxylic acids, in presence of a few drops of conc.
H 2 SO4 , to form esters. This reaction is known as esterification.


conc. H 2SO4
R  COOH  HOR  RCOOR  H 2O


2conc. H SO
CH 3COOH  HOC 2 H 5 
4
CH 3COOC 2 H 5  H 2O

Alcohols also form esters when treated with acid chloride or acid
anhydride. The reaction with acid chloride is carried out in presence of a
base such as pyridine to remove HCl formed in the reaction.
O
||
pyridine
CH 3  COCl  C 2 H 5OH 
 CH 3  C  OC 2 H 5  HCl
O
||
CH 3CO 2 O  C2 H 5OH 
 CH 3  C  OC 2 H 5  CH 3COOH

B. Reactions involving cleavage of carbon-oxygen bond:

Order of reactivity of alcohol in such reactions is 3  2   1 .

(i) Reaction with hydrogen halides:
Order of reactivity of HX is HF  HCl  HBr  HI
anhy. ZnCl2
CH 3CH 2OH  HCl g   
CH 3CH 2Cl  H 2O

(ii) Reaction with phosphorous halides:

CH 3CH 2OH  PCl5 
 CH 3CH 2Cl  POCl3  HCl

3ROH  PX3  3 R  X  H 3 PO3

(iii) Reaction with thionyl chloride:

pyridine
R  OH  SOCl2   R  Cl  SO2  HCl

Product alkyl chloride will be pure as the by-products are volatile gases.
C. Reactions involving both alkyl and hydroxyl groups:
(i) Dehydration of alcohols:
Alcohols undergo dehydration when heated with conc. H 2 SO4 or H 3 PO4 .
 8

H 2 SO4
CH 3  CH 2OH 
443 K
 CH 2  CH 2  H 2O

Ease of dehydration of alcohol 1  2   3 .

Secondary and tertiary alcohols are dehydrated under milder condition.

Mechanism of dehydration of alcohol:

Step 1: Protonation of alcohol.

Step 2: Formation of carbocation.

It is the slowest and rate determining step.

Step 3: Elimination of a proton to form alkene.

(ii) Oxidation of alcohols:

 Primary alcohols are easily oxidized first to aldehyde and then to the
carboxylic acids both having the same number of carbon atoms as the
parent alcohol.
K 2Cr2O7 K 2Cr2 O7
CH 3CH 2OH 
H 2SO4
 CH 3CHO 
H 2 SO4
 CH 3COOH

Mild oxidizing agent such as CrO3 in anhydrous medium will oxidize

primary alcohols to aldehydes.

CrO3
R  CH 2OH   R  CHO
 9

Pyridinium chlorochromate (PCC) is a better reagent for oxidation of

1 alcohols to aldehydes. PCC does not affect carbon-carbon double
bond.
PCC
CH 3  CH  CH  CH 2 OH   CH 3  CH  CH  CHO

 Secondary alcohols undergo oxidation to form ketones.

Ketones undergo oxidation only under vigorous conditions.

 Tertiary alcohols do not easily undergo oxidation. They undergo
oxidation only at high temperature with strong oxidizing agents.

(iii) Dehydrogenation of alcohols:

When alcohol vapours are passed over hot copper, primary and secondary
alcohols are dehydrogenated to form aldehydes and ketones respectively
while tertiary alcohols are dehydrated to form olefins.
Cu
R  CH 2  OH 
573 K
 R  CHO
Cu
CH 3CH 2 OH 
573 K
 CH 3CHO  H 2
 10

METHODS IN DISTINGUISH PRIMARY, SECONDARY AND TERTIARY

ALCOHOLS
Lucas Test: Addition of alcohol to Lucas reagent (a mixture of conc. Hydrochloric
acid and anhydrous zinc chloride) forms corresponding alkyl halide. Since alkyl
halides are insoluble, their formation is indicated by turbidity in the reaction
mixture. Tertiary alcohols react immediately with Lucas reagent producing
turbidity in the reaction mixture. Secondary alcohols give turbidity within 5 minutes
and primary alcohols do not give turbidity at room temperature.
Dehydrogenation reaction and Oxidation reactions can also be used to distinguish
the three types of alcohol.

PHENOLS
CLASSIFICATION OF PHENOLS

METHODS OF PREPARATION OF PHENOLS

1. Alkali fusion of benzene sulphonic acid:
Benzene is heated with fuming sulphuric acid to form benzene sulphonic
acid. This is then heated with solid NaOH to form the sodium salt of phenol.
 11

2. From Diazonium salts:

Diazonium salt is prepared by treating aromatic primary amine such as
aniline with NaNO2 and dilute HCl (or HNO2 ) at 273  278 K .

Diazonium salts on warming with water give phenols.

Commercial preparation of Phenols:

1. Dows process:

2. From Cumene:
Cumene is oxidized by air to cumene hydroperoxide which on treating with
dilute acid gives phenol and acetone.

PHYSICAL PROPERTIES OF PHENOL

Boiling point of phenol is higher than that of corresponding hydrocarbon and
haloarenes. This is due to association of phenol molecules by intermolecular
hydrogen bonding.
 12

CHEMICAL PROPERTIES OF PHENOL

1. Acidic character: Phenols are weakly acidic. They ionize in aqueous solution to
give H  ions. They react with active metals liberating H 2 gas.

2C 6 H 5OH  2 Na 
 2C 6 H 5ONa  H 2

Phenol also react with strong alkalies to form salts.

C 6 H 5OH  NaOH 
 C 6 H 5ONa  H 2O
sodium phenoxide

Note: Since phenols are only weakly acidic, they do not decompose carbonates
and bicarbonates.
Explanation for the acidic nature of phenol:
In phenol,  OH group is attached to sp 2 hybridized carbon atom of the benzene

ring. Due to greater electronegativity of sp 2 hybridized carbon, the electron

density on oxygen in phenol is reduced. This increases the polarity of O  H

bond and favours the ionization of phenol.
The acidic character of phenol is also explained by the greater resonance
stabilization of phenoxide ion. Both phenol and phenoxide ion are stabilized by
resonance. But phenoxide ions is more established than phenol by resonance. So
phenol ionizes and behaves as an acid.

Effect of substituents on acidity of phenol:

Presence of electron with drawing groups such as NO2 , CN , halogens, etc.,

increase the acid strength of phenol. This is because such groups stabilize the
phenoxide ion by dispersing the negative charge. The effect is more prominent
 13

when these groups are in the ortho and para positions. On the other hand,
electron donating groups such as  R (alkyl), OCH 3 (methoxy), etc., decreases

the acid strength of phenol.

2. Acetylation of phenols (formation of esters): The introduction of acetyl group

in phenols (or alcohols or amines) is known acetylation. Phenol reacts with
acetyl chloride in presence of bases to form esters.

Acetylation can also be carried out with acetic anhydride in presence of a small
amount of conc. H 2 SO4 . Salicylic acid when heated with acetic anhydride in

presence of small amount of conc. H 2 SO4 gives acetyl salicylic acid (aspirin).

Note: Phenol reacts with benzoyl chloride in presence NaOH to form phenyl
benzoate. This benzoylation is known as Schotten-Baumann reaction.
3. Action of zinc dust: Phenol on distillation with zinc dust gives benzene.
C 6 H 5OH  Zn 
 C 6 H 6  ZnO

4. Electrophilic substitution reactions: The  OH group attached to the benzene

ring activities it towards electrophilic substitution.  OH group is an ortho-para

direction group.
(i) Nitration:
(a) With dilute HNO3
 14

o-nitrophenol forms intramolecular hydrogen bond. So it is steam

volatile. p-nitrophenol has higher boiling point due to intermolecular
hydrogen bonding.

(b) With conc. HNO3

(ii) Bromination:
(a) Bromine in non-polar solvent.
 15

(b) Bromine water.

Some special reactions of Phenol:

1. Kolbe’s reaction:
When sodium phenoxide is heated with CO2 under pressure sodium salicylate is

formed. This on acidification gives phenol.

2. Reimer-Tiemann reaction:
When phenol is heated with chloroform in presence of aqueous NaOH ,
salicylaldehyde is obtained as the major product.

Note: If carbon tetrachloride is used instead of CHCl3 in Reimer-Tiemann

reaction, salicylic acid is formed as the major product.

 16

3. Oxidation:
Oxidation of phenol with chromic acid gives benzoquinone.

4. Reaction with ferric chloride:

Phenols give violet colour with neutral Fe2Cl3 solution.

DISTINCTION BETWEEN ALCOHOLS AND PHENOLS

Alcohols Phenols

(a) Alcohols do not react with sodium Phenols from salts with NaOH
hydroxide solution. solution.

(b) Alcohols do not give any Phenols give characteristic colour

characteristic colour with neutral (generally violet) with neutral ferric
ferric chloride solution. chloride solution.

(c) Alcohols do not give azodyes with Phenols give azodyes with diazonium
diazonium salt. chloride in alkaline medium.

(d) Alcohols do not react with litmus Phenols turn blue litmus to red.
solution.

ETHERS
INTRODUCTION
Ethers are the alkoxy derivatives of alkanes with general formula ROR . If R
and R are same they are simple or symmetrical ethers while if R and R are
different they are mixed or unsymmetrical ethers.
Simple or symmetrical ethers
CH 3  O  CH 3 , C2H5  O  C2H5
 Dimethyl ether   Dimethyl ether 

Mixed or unsymmetrical ethers

 17

NOMENCLATURE OF ETHERS
There are 2 systems of naming ethers are given below:
(i) Common system: Common names are derived from the name of alkyl (aryl)
groups attached to the oxygen atom arranged in the alphabetic order followed
by the word ether.
(ii) IUPAC system: In the IPUAC system, ethers are considered as hydrocarbon
derivatives. The group having greater number of carbon atoms is taken as the
parent alkane and other group along with oxygen is taken as the alkoxy
group.

Compounds IUPAC name Common name

1. CH 3OC2 H 5 Methoxy ethane Ethyl methyl ether

2. C 2 H 5OC2 H 5 Ethoxy ethane Diethyl ether

3. Phenoxy benzene Diphenyl ether

4. Ethoxy benzene Ethyl phenyl ether

Some aromatic ethers have special common names

GENERAL METHODS OF PREPARATION OF ETHERS

There are two ways of preparing ethers.
(a) Dehydration of alcohols:
Symmetrical ethers can be prepared by the dehydration of alcohol with conc.
H 2 SO4 at 413 K . In this method a large excess of alcohol is heated with conc.

H 2 SO4 413 K . The temperature of reaction must be properly controlled because

at higher temperature the alcohols get dehydrated to alkenes.

 18

The above method is mainly used for the preparation of ethers having primary
alkyl groups only. Secondary and tertiary alcohols give alkenes as major
products under the reaction conditions.
Mechanism: The formation of ether by dehydration of alcohols using protic acid
is a nucleophilic bimolecular substitution reaction  SN 2  .

(b) Williamson’s ether synthesis:

This is the most important and widely used method for the preparation of both
symmetrical and unsymmetrical ethers. It is carried out by treating on alkyl or
substituted alkyl halide with sodium alkoxide or sodium phenoxide.
RONa  RX 
 R  O  R  NaX

C 2 H 5ONa  C 2 H 5 I 
 C 2 H 5  O  C 2 H 5  NaI

Mechanism: The reaction involves the nucleophilic substitution of halogen atom

by the alkoxide group.
 
  

R  X  OR 
  RO   R    X  
 R  O  R  X
 
 19

Limitation of Williamson’s synthesis:

Williamson’s synthesis has limitation when a tertiary alkyl halide is used as a
reactant. The basic nature of an alkoxide catalyses elimination reaction is tertiary
alkyl halides leading to the formation of an alkene.
Therefore for the preparation of ether containing primary and tertiary alkyl
groups, tertiary alkoxide must be treated with primary alkyl halide.

If we use tertiary butyl chloride and sodium ethoxide as reactants, the major
products would be 2-methyl propene and ethanol.

PHYSICAL PROPERTIES OF ETHERS

1. Lower members are gases and higher members are low boiling liquids.
2. Ethers do not show intermolecular hydrogen bonding. Hence ethers have boiling
points lower than that of isomeric alcohols.
3. Ethers show nearly the same solubility in water as isomeric alcohols. The
solubility of ethers is due to the capability of their molecules to form hydrogen
bond with water molecules.

4. Ethers are freely soluble in organic solvents. The solubility of ethers in water
decreases from lower members to higher members due to the increase in size of
the alkyl group which decreases the tendency to form hydrogen bonding.
5. Bond angle in ethers.
The hybridization of oxygen in ether is sp 3 . The C  O  C bond angle in ethers is

slightly greater than the tetrahedral angle due to repulsive interaction between
the two bulky alkyl  R  groups. The bond angle in CH 3  O  CH 3 is 111.7  .
 20

CHEMICAL REACTIONS OF ETHERS

(i) Reaction with HX :
On heating with halogen acids such as HBr or HI , ethers undergo cleavage
in which one of the C  O  C bond breaks to form an alcohol or phenol and
an alkyl halide.
C 2 H 5  O  C 2 H 5  HI  C 2 H 5 I  C2 H 5OH
In the presence of excess acid, the alcohol formed reacts with halogen acid to
form alkyl halide.
R  O  R  2 HX  RX  RX  H 2O
The order of reactivity of halogen acids in this reaction is HI  HBr  HCl .
Mechanism of the reaction: The reaction involves protonation of ether by the
acid followed by nucleophilic attack by halide ion on the protonated ether to
form alcohol and alkyl halide.

In the case of unsymmetrical ethers, the alkyl iodide and alcohol formed will
depend upon the nature of the alkyl group. When primary or secondary alkyl
groups are present, it is the smaller alkyl group that forms alkyl iodide.
For example: CH 3  O  C 2 H 5  HI 
 CH 3 I  C 2 H 5  OH

CH 3  O  CH CH 3  2  HI 
 CH 3 I  CH 3  2 CHOH

If one of the attached groups is tertiary, tertiary halide is formed by SN 1

reaction.
CH 3  O  C CH 3 3  HI 
 CH 3 3 CI  CH 3OH

In the case of aryl alkyl ethers, the cleavage leads to formation of phenol and
alkyl halide. Phenol does not react with HI .

(ii) Reactions of aromatic ethers:

Aromatic ethers undergo electrophilic substitution reactions.
Alkoxy group is ortho para directing.
 21

(1) Nitration:

(2) Halogenation:

(3) Friedel-craft’s reaction:

(a) Alkylation

(b) Acylation

USES OF ETHERS
1. Diethylether is used as a solvent.
2. It is used as a refrigerant.
3. It is used in the reaction medium in LiAlH 4 reduction and Grignard synthesis.

4. As a general anaesthetic in surgery.