Alcohols, Phenols, & Ethers

Indroduction :
Alcohols are organic compounds containing hydroxy (– OH) groups attached to a saturated (sp3 hybridised)
carbon atom. The compound in which the – OH group is attached to an unsaturated (sp2 hybridised) carbon
atom are called enols. The compounds in which – OH group is attached to aromatic ring are called phenols.
For example :

Ethers are regarded as dialkyl derivatives of H2O. The general formula of ethers is CnH2n + 2O which is the
same as it is for monohydric alcohols. Its structure is R – O – R, where R and R may be alkyl groups or aryl
(benzene ring) groups.

When R = R, it is called a symmetrical ether.

When R  R, it is called an unsymmetrical ether.

For example :

Structure :
The structure of an alcohol and ether resembles the structure of water like bent structure.

Bonding in ethers is readily understood by comparing ethers with water and alcohol. Vander Waals strain
involving alkyl groups causes the bond angle at oxygen to be larger in ethers than in alcohol, and larger in
alcohols than in water. An extreme example is di-tert-butyl ether, where steric hindrance between the tert-
butyl groups is responsible for a dramatic increase in the C – O – C bond angle.

As the groups bonded to O increase in size, the repulsive Vander Waals forces between them increase
causing an expansion of the angle.

RESONANCE Alcohols, Phenols, & Ethers - 1

Ex.1 Arrange the following in decreasing orders.

O O O
H a H CH3  H CH3 
CH3
(a) (Bond angles)
(I) (II) (III)

(b) CH3 – CH3 CH3 – CH2OH CH3 – O – CH3 H–O–H (Polarity)

(I) (II) (III) (IV)

O
Sol. (a) III > II > I ,
H 104.5° H

B.A. = As size of substituent increases bond angle at central atom increases.

(b) IV > II > III > I , > > > CH3  CH3

0D

Reason : As bond angle increases, vector sum of individual bond moments decreases.

Classification of Alcohols
Alcohols are classified into two ways.
(a) Degree of an alcohol : Nature of alcohol based on – OH group attached to the type of carbon.
(i) 1° alcohol : Those alcohols in which – OH group is attached to 1°carbon atom.
(ii) 2° alcohol : Those alcohols in which – OH group is attached to 2° carbon atom.
(iii) 3° alcohol : Those alcohols in which – OH group is attached to 3° carbon atom.
CH3
|
e.g. Primary alcohol CH3  CH  CH2  OH and CH2 – OH
2  Methyl  1  propanol
Benzyl alcohol

e.g. Secondary alcohol CH3  CH2  CH  CH3 and

|
OH
2  Bu tan ol

CH3 Ph
| |
e.g. Tertiary alcohol CH3  C  OH and Ph  C  OH
| |
CH3
Ph
Triphenyl methanol
2  Methyl  2  propanol

(b) Nature of alcohol based on number of – OH groups present in an alcohol molecule.

(i) Monohydric alcohols : Those alcohols in which only one – OH group is present in their molecule are
known as monohydric alcohols
(ii) Dihydric alcohols : Those alcohols in which two –OH groups are present in their molecule are known
as dihydric alcohols
(iii) Trihydric alcohols : Those alcohols in which three -OH groups are present in their molecule are
known as trihydric alcohols
(iv) Polyhydric alcohols : Those alcohols in which more than three -OH groups are present in their mol
ecule are known as polyhydric alcohols.
RESONANCE Alcohols, Phenols, & Ethers - 2
 Examples of alcohols of different categories.

Physical Properties
(1) Boiling point :
(a) Alcohols show increase in boiling point with increase in molecular weight amongst homologues.
(b) Alcohols have higher boiling point than hydrocarbons of the same molecular weight. The reason for higher
boiling point is the intermolecular H-bonding present in alcohols.

Intermolecular H bonds in alcohol

(c) The boiling points of isomers decrease with increase in branching, due to decrease in surface area and
decrease in Vander Waal forces of attraction.

e.g.(i) CH3 OH < C 2H5 OH < H3 C  CH2  CH2  OH< H3 C  CH2  CH2  CH2  OH< H3 C  CH2  CH2  CH2  CH2  OH(B.P.).)
(Methanol ) (Ethanol ) (Propan  1  ol) (Bu tan  1  ol) (Pen tan 1  ol)

CH3
|
e.g.(ii) H3 C  CH2  CH2  CH2  OH > H3 C  CH  CH2  OH > H3 C  CH  CH2  CH3 > H3 C  C  CH3 (B.P.)
.)
(n  Butylalcoh ol) | | |
CH3 OH OH
(Isobutylal cohol ) (sec  butylalcohol) ( tert  butylalcoh ol)

RESONANCE Alcohols, Phenols, & Ethers - 3

Ex. 2 Which of the following alcohol has higher B.P.
(i) Ethylene glycol (ii) Glycerol

Sol. H2C  CH  CH2 > CH2  CH2

| | | | |
OHOH OH OH OH
( glycerol) (ethylene glycol)
B.P. 290C B.P. 198C

As number of– OH groups increases, the extent of intermolecular H-bonding increases.

(2) Solubility in water :

As molecular weight increases solubility in water decreases. The lower alcohols are miscible with water.
This is due to intermolecular hydrogen bonding between alcohol and water molecules.

Intermolecular H bond between water & alcohol molecules

But this is true only for the lower alcohols, where the – OH group constitutes a large part of the molecule. As
the alkane like alkyl group becomes larger water solubility decreases. For practical purpose we consider
that the borderline between solubility and insolubility in water occurs at about four to five carbon atoms for
normal primary alcohols.
Polyhydroxy alcohols provide more than one site per molecule for hydrogen bonding and their solubility is
appreciable till seven carbon atoms molecules. Amongst isomers, as branching increases, the surface area
of hydrocarbon part (hydrophobic part) decreases so solubility increases.
It follows the order : 3° alcohol > 2° alcohol > 1° alcohol.

Ex.3 Write the decreasing order of water solubility of all isomers of C4H10O.
Ans. Decreasing order of water solubility of all isomers of C4H10O is :

CH3 CH3 CH3

| | |
CH3  C  OH > CH3  CH2  CH  OH > CH3  CH  CH2  OH > CH3 – CH2 – CH2 – CH2 – OH
|
CH3

CH3
|
~ CH3 – CH2 – O – CH2 – CH3 > CH3  CH  OCH3 > CH3 – CH2 – CH2 – OCH3

Ex.4 Arrange following compounds in decreasing order of solubility in water

(i) CH3CH2OH , CH3CH2CH2OH , CH3CH2CH2CH2OH

(ii) ,

Sol. (i) CH3CH2OH > CH3CH2CH2OH > CH3CH2CH2CH2OH

(ii) > ; Phenol has planar structure, so extent of H-bonding is more.

RESONANCE Alcohols, Phenols, & Ethers - 4

Q.1 Which member of each pair will be more soluble in water
(a) 1-Hexanol and cyclohexanol (b) 1-Hexanol and 4-Methyl phenol
(c) 3-Ethyl -3-hexanol and 2-Octanol (d) 2-Hexanol and Cyclooctane-1,4-diol

Q.2 Sucrose (C12H22O11) has a large carbon chain yet it is highly soluble in water. What functional group in
sucrose may lead to it’s high solubility ?

(3) Melting point (M.P.) :

Melting is the change from the highly ordered arrangement of particles in the crystalline lattice to the more
random arrangement that characterises a liquid. Melting occurs when a temperature is reached at which the
thermal energy of particles is great enough to overcome the inter crystalline forces that hold the molecules
together in the solid state. The effect of branching on melting point is difficult to predict. Generally branching
that produces highly symmetrical structures results in abnormally high melting points.
Ex-5 Which member of each pair will have higher M.P.
(a) Phenyl methanol and diphenyl methanol
(b) 1-hexanol and cyclohexanol

Sol. (a) Ph2 CHOH > Ph – CH2– OH ; The first member has higher molecular weights.
M.P. (69ºC) M.P. (– 15ºC)

(b) Cyclo hexanol > 1– hexanol ;

M.P. (25ºC) M.P. (– 52ºC)

Preparation of alcohols
(1) From alkenes
(a) By acid catalyzed hydration of alkenes :
Formation of carbocation intermediate (Markovnikov addition, rearrangement possible)
General reaction :

CH3  CH  CH3
|
OSO 3H
H2SO4 + CH3  CH  CH3
|
OH
(b) By Oxymercuration-demercuration process :
(Markovnikov addition, no rearrangement possible)
(1) Oxymercuration involves an electrophilic attack on the double bond by the positively charged mercury
species. The product is a mercurinium ion, an organometallic cation containing a three-membered ring.
(2) In the second step, water from the solvent attacks the mercurinium ion to give (after deprotonation) an
organomercurial alcohol.
(3) The second step is demercuration to remove the Hg. Sodium borohydride (NaBH4, a reducing agent)
replaces the mercuric acetate fragment with hydrogen.
General reaction :

CH3  CH  CH2 CH3  CH  CH2 CH3  CH  CH3

Prop  1  ene | | |
OH Hg(OAc ) OH
Propan  2  ol

(c) By Hydroboration - oxidation process : (Forms anti-Markovnikov alcohol, no

rearrangement)

General reaction : R – CH = CH2 R – CH2 – CH2 – OH

RESONANCE Alcohols, Phenols, & Ethers - 5

Q.3 Identify P, Q & R in following reaction :

(2) From alkyl halides : By nucleophilic substitution reactions

1. By SN2 mechanism (second-order substitution) : Given by primary (and some secondary) halides

KOH
General reaction : R – CH2 – Br  
 R – CH2 – OH
H2O

2. By SN1 mechanism : Given by tertiary and some secondary halides

R R
| |
Aceton e / water R  C  R
General reaction : R  C  R      
Heat |
|
Cl OH

Ex.6 Write the structure of product ‘P’

KOH / DMSO
 P
    
H2O

Ans. Inversion of configuration is possible

Q.4 Give the structure of the major product in the following reaction

(3) From Grignard reagents

(3.1) From air
A Grignard reagent may be used to synthesize an alcohol by treating it with dry oxygen and decomposing
the product with acid :
O2 RMgX H O
General reaction RMgX   RO2MgX  2ROMgX 3 2ROH

O2 C2H5MgX H O
e.g. C2H5MgBr   C2H5O2MgX     2C2H5OMgX 3 2C2H5OH + MgBr(OH)

RESONANCE Alcohols, Phenols, & Ethers - 6

(3.2) From ethylene oxide (oxirane)
Addition of Grignard reagent to ethylene oxide gives a primary alcohol (with two carbon atoms added)

H O
General reaction  RCH2CH2OMgX 3 RCH2CH2OH

e.g. + C2H5MgBr  C2H5CH2CH2OMgBr C 2H5 CH2CH2 OH + MgBr(OH)

Butyl alcohol

(3.3) From carbonyl compounds :

Nucleophilic addition to the carbonyl groups by Grignard reagent

General reaction  
 + Mg(OH)X
ether

(3.3a) Addition of formaldehyde gives a primary alcohol

General reaction Ether RCH2 – OH

 


(1) ether solvent CH3  CH2  CH2  OH

e.g. CH3 CH2MgBr + H2C = O      
(2) H3O 1  propanol
Ethylmagnesium bromide

(3.3b) Addition to an aldehyde gives a secondary alcohol

O
||
General reaction Ether
R  C  H + RMgX  

O
||
(1) ether solvent
e.g. + CH3  C  H      
acetaldehyde (2) H3O

(3.3c) Addition to a ketone gives a tertiary alcohol

R
|
(1) ether
General reaction    R  C  OH  MgX(OH)
( 2) H3O |
R

(1) ether
e.g. CH3CH2MgCl +   
( 2) H3O

RESONANCE Alcohols, Phenols, & Ethers - 7

 (3.3d) Addition to an acid halide or an ester gives a tertiary alcohol
Esters on treatment with Grignard reagent first form ketones which then react with second molecule of
Grignard reagent and form tertiary alcohol.
General reaction
- + O
O MgX
| ||
R – C – OR R  C  R2 +
|
R2

R
|
R2  C  R2
|
OH
tertiaryalcohol

e.g.

Ex.7 Write the product of the following reaction

CH3COCH3

Ans. (CH3)3C – OH

Ex.8 Show how you would synthesize the following alcohol from compounds containing not more than five carbon
atoms.

Ans. This is a tertiary alcohol ; any one of the three alkyl groups might be added in the form of a Grignard reagent.
We can propose three combinations of Grignard reagents with ketones :

+ CH3CH2MgBr

+ CH3MgBr

Any of these three synthesis would probably work but only the third begins with fragments containing no
more than five carbon atoms. The other two synthesis would required further steps to generate the ketones
from compounds containing no more than five carbon atoms.
RESONANCE Alcohols, Phenols, & Ethers - 8
Ex.9 Identify A to E in the following reaction
O
||
HO 
H O
(a) + 2CH3CH2MgBr 3 
 A (b) Ph  C  Cl + 2 3 
 B

O
|| H O H O
(c) + 2CH3CH2MgBr 3 
 C (d) + 3 
 D
H  C  O  Et
H O
(e) (C2H5O)2CO + 3CH3MgBr 3 
 E

Ans. (A) : (B) : (C) :

(D) : (E) : (CH3)3COH

Ex.10 What combination of ester and Grignard reagent could you use to prepare each of the following tertiary
alcohols.

(a) C 6H5  C  (CH2 CH3 )2 (b) (c) (C2H5)3COH

|
OH
O
||
Ans. (a) C 6H5  C  OCH3 and CH3CH2MgBr

(b) and C6H5MgBr

O
||
(c) C 2H5  C  OC 2H5 and C2H5MgBr
In all cases ester and Grignard reagents are taken in 1 : 2 molar ratio.
Q.5 Alcohol containing least number of carbon which can be prepared using Grignard reagent is :
(A) (CH3)2CHOH (B) (CH3)3COH (C) CH3OH (D) CH3CH2OH

3 H O
Q.6 RMgBr + X   CH CH CH OH
3 2 2

R and X are :

(A) CH3CH2–and HCHO (B) CH3–and (C) Both are correct (D) None is correct

Q.7 What is the end product of the following reaction

Mg / ether HCHO H O
   
   2 


(A) (B)

(C) (D)

RESONANCE Alcohols, Phenols, & Ethers - 9

Q.8 In the following reactions alcohols have been synthesized using carbonyl compounds and Grignard reagent.

(a) + H O
3 


(b) + H O
3 


Give alternate alkyl / aryl part for the synthesis of X & Y

(4) By reduction of carbonyl compounds

4.1. Catalytic hydrogenation of aldehydes and ketones
General reaction :
2 H / Ni R 2C  O 
H2 / Ni R 2CH  OH
R  CHO   R  CH2OH ; 
Ketone 2 Alcohol
Aldehyde 1 Alcohol
4.2 Lithium aluminium hydride reduction of aldehydes and ketones :
By LiAlH4 : Lithium aluminium hydride (LiAlH4) is the most versatile reagent. It reduces most functional
groups, but does not normally reduce the olefinic bond (C = C bond). An unusual feature of this reagent is its
reduction of the carboxyl group to primary alcohol.

R 2C  O R 2CH  OH
LiAlH 4
(i) R  CHO  LiAlH 4
 R  CH2OH (ii) Ketone   2 Alcohol
Aldehyde 1 Alcohol

4 LiAlH LiAlH
4
(iii) RCOOH + 4H    RCH2OH + H2O (iv) R  C  Cl + 4H    RCH2OH + HCl
||
O

4 LiAlH
(v) R  C  O  R    R – CH2OH + ROH
||
O
4.3 By NaBH4 (sodium borohydride) :
It is insoluble in ether and is used in aqueous ethanolic solution to reduce carbonyl compounds. It does not
reduce esters and acids.
(i) Reduction of an aldehyde gives a primary alcohol

O
||
NaBH4
R  C  H    R – CH2 – OH
(ii) Reduction of a ketone gives a secondary alcohol

4NaBH
  

4.4. Bouveault-Blanc reduction :

The reduction of aldehydes, ketones or esters by means of excess of sodium and ethanol or n-butanol as the
reducing agent.

RESONANCE Alcohols, Phenols, & Ethers - 10

 General reaction
Na
(i) Aldehyde RCHO  RCH OH
EtOH 2

Na
(ii) Esters RCO2R2  RCH OH + R2OH
EtOH 2

Na
(iii) Ketones R2CO  R CHOH
EtOH
2

The Bouveault-Blanc reduction is belived to occur in steps involving the transfer of one electron at a time.

Q.9 Identify end products in the following reactions :

4NaBH NaBH
4
(A)    (B)   
CH3OH CH3OH

(5) By reaction of nitrous acid on aliphatic primary amines

Reactions of amines with nitrous acid (H – O – N = O) are particularly useful for synthesis of alcohol HNO2
is unstable, it is generated in sites (in the reaction mixture) by mixing sodium nitrite (NaNO2) with cold, dilute
HCl.
2 NaNO / HCl
General reaction R – NH2 + HONO     R – OH + N2 + H2O

Mech.
HNO 2 HO 
R – NH2   2 ROH + N2 + H

e.g. (i) C2H5NH2 + HNO2  C2H5OH + N2 + H2O

CH3 CH3
| |
NaNO 2 / HCl
(ii) CH3  CH2  C  CH3 + HONO  CH  CH  C  CH3  N2  H2O
  3 2
| |
NH2 OH

Ex.11 HNO2 forms an alcohol on reaction with :

(A) (CH3)2NH (B) CH3NH2 (C) C6H5NHCH3 (D) C6H5NH2
Ans. B

Ex.12 Ethyl amine on treatment with HNO2 produces :

(A) CH3CHO (B) C2H5OH (C) CH3COOH (D) C2H5NO2
Ans. B

2 NaNO
Ex.13 CH3CH2CH2NH2 HCl
  A (Mixture) Mixture can contain :

(A) CH3CH2CH2OH (B) CH3  CH  CH3 (C) CH3  CH  CH3 (D) CH3 – CH = CH2
| |
OH Cl
Ans. A, B, C, D

Q.10 The major product formed on treatment of 1–propanamine with sodiumnitrite in dilute hydrochloric acid is
2–propanol. Explain :

RESONANCE Alcohols, Phenols, & Ethers - 11

 CH3
|
Q.11 HNO 2
CH3  C  CH2NH2   A (major product) ;
 A is :
|
CH3

CH3 CH3
CH3 CH3
| | | 
|
(A) CH3  C  CH2 OH (B) CH3  C  CH2 CH3 (C) CH3  C  CH2N2 (D) CH3  C  CH  CH2
| | |
CH3 OH CH3

HNO 2
Q.12 CH2NH2  
 Products. What can be possible products ?

(6) Hydroxylation : Forms vicinal diols (glycols)

Converting an alkene to a glycol requires adding a hydroxy group to each end of the double bond. This
addition is called hydroxylation of the double bond.

(a) Syn hydroxylation, using KMnO4 / NaOH or using OsO4 / H2O2

General reaction :
| |
CC ... (Syn addition)
| |
HO OH

KMnO 4
e.g.     
cold
(dilute )

(b) Anti hydroxylation, using per acids

... (Anti addition)

Ex.14 Write the product of the following reaction

HCO H
 3


RESONANCE Alcohols, Phenols, & Ethers - 12

Q.13 Identify major product

Q.14 Which is the incorrect reaction ?

(A) KMnO 4 / KOH (B) HCO 3H

    
HO OH
CH3
H3C H
H OH
(C) OSO 4 / H2 O 2 (D) KMnO / OH
    4 

H OH
H3C H
CH3
Q.15 Identify the X & Y in the following reaction :
HCO 3H KMnO 4
(Y)     (X)
Cold
trans

Chemical reactions of alcohols :

1. Reaction with hydrogen halides
A common method is to treat the alcohol with a hydrohalic acid, usually HCl or HBr. These acids are used to
convert alcohols to the corresponding alkyl halides.
Genral reaction :
R – OH + HX  R – X + H2O (R may rearrange)
Reactivity of HX : HI > HBr > HCl
Reactivity of ROH : allyl, benzyl > 3° > 2° > 1°

e.g. NaBr, H SO
2 4
CH3 (CH2 )2  CH2 OH     
  CH3 (CH2 )2  CH2Br
1  bu tan ol 1  bromobutane
(90%)
Protonation converts the hydroxy group to a good leaving group, but ionization to a primary carbocation is
unfavourable. The protonated primary alcohol is well suited for the SN2 displacement.
Secondary alcohols also react with HBr to form alkyl bromides usually by the SN1 mechanism.
e.g. Cyclohexanol is converted to bromocyclohexane using HBr as the reagent

HBr


Lucas Reagent :
(1) A mixture of concentrated hydrochloric acid and zinc chloride is called the Lucas reagent.
(2) Whether an alcohol is primary, secondary or tertiary is identifed by the Lucas test, which is based upon the
difference in reactivity of the three classes of alcohol towards hydrogen halides.
(3) Alcohol (of not more than six carbons in their molecule) are soluble in the Lucas reagent. The corresponding
alkyl chlorides are insoluble.
(4) Formation of a chloride from an alcohol is indicated by the cloudiness that appears when the chloride
separates from the solution hence, the time required for cloudiness to appear is a measure of the reactivity
of the alcohol.
(5) A tertiary alcohol reacts immediately with the Lucas reagent, a secondary alcohol reacts within five minutes
and a primary alcohol does not react appreciably at room temperature.

RESONANCE Alcohols, Phenols, & Ethers - 13

Ex.15 Write the structure of the product ‘X’.
ZnCl 2 / HCl
CH3  CH2  CH  CH2  CH3     X
|
OH

Ans. X is CH3  CH2  CH  CH2  CH3

|
Cl
3  Chloropentane

Ex.16 Explain the mechanism and type of reaction :

Ans. It follows SN1 mechanism followed by rearrangement

H 
H O
2
  

Q.16 Why is ZnCl2 (Lewis acid) required with HCl in its reaction with 1° and 2° alcohol. Where as reaction with HBr
proceeds without any Lewis acid.
Q.17 Make distinction between following pairs of substances by using Lucas reagent or H2CrO4.

2. Reaction with phosphorus trihalides

(1) Several phosphorus halides are useful for converting alcohols to alkyl halides. PBr3, PCl3, & PCl5 work
well and are commercially available.
(2) Phosphorus halides produce good yields of most primary and secondary alkyl halides, but none works
well with ter. alcohols. The two phosphorus halides used most often are PBr3 and the P4 / I2 combination.
General reaction :

3R – OH + PX3 3R – X + H3PO3

RESONANCE Alcohols, Phenols, & Ethers - 14

3. Reaction with thionyl chloride
Thionyl chloride (SOCl2) is often the best reagent for converting an alcohol to an alkyl chloride. The by
products (gaseous SO2 and HCl) leave the reaction mixture and ensure that there can be no reverse reaction.
O
||
Heat
R – OH + Cl  S  Cl  
 R – Cl + SO2 + HCl

4. Dehydration of alcohols :
Dehydration requires an acidic catalyst to protonate the hydroxyl group of the alcohol and convert it to a good
leaving group. Loss of water, followed by loss of proton, gives the alkene. An equilibrium is established
between reactants and products.

| | | |
acid
 C  C     C  C  + H2O (Rearrangement may occur)
| |
H OH

Mechanism :

Step 1 :

In this step, an acid-base reaction a proton is rapidly transferred from the acid to one of the unshared electon
pairs of the alcohol.
In step 2 the carbon oxygen bond breaks. The leaving group is molecule of water :

Step 2 : +

Finally,in step 3 the carbocation transfers a proton to a molecule of water. The result is the formation of a
hydronium ion and an alkene.

Step 3 +

Reactivity of ROH : 3° > 2° > 1°

Ex.17 The dehydration of a butanol with acid gives a mixture of 1- and 2-butene ; which predominates ? Explain by
mechanism.
H H
Ans. CH3CH2CH2CH2OH 
 


RESONANCE Alcohols, Phenols, & Ethers - 15

Ex.18 Me3CCH2OH + B

Identify A and B

CH2  CCH2Me
Ans. A : Me2C = CHMe B: |
Me

Ex.19 H SO , 
2  
4


Explain mechanism

Migration
H of bond H 
Ans. 
    

Ex.20 H SO 4 , 
2    A

Identify A

Ans.

Q.18 What are dehydration products of ?

+
O OH H
|| | A, What is A ?

Q.19 - O
OH ||

Q.20 H SO 4 , 
2    A (Major) + B

5. Reaction with metals

We learned to remove the hydroxy proton from an alcohol by reduction with an “active” metal such as Na or
K. This reaction generates a Na or K salt of an alkoxide ion and hydrogen gas.
The reactivity of alcohols toward Na and K decreases in the order. Methyl > 1° > 2° > 3°. Sodium reacts
quickly with primary alcohols and some secondary alcohols. K is more reactive than Na and is commonly
used with tertiary alcohols and some secondary alcohols.

RO – H + M  + M = Na, K, Mg, Al, etc.

Reactivity order of ROH : CH3OH > 1° > 2° > 3°

RESONANCE Alcohols, Phenols, & Ethers - 16

 CH3 CH2OH
e.g. Na
Ethyl alcohol 

CH3 CH3
| | 3
Al (CH3  C  O)3 Al + H 
CH3  C  OH 
 2 2
| |
H
H
Alu min ium Isopropoxide
Isopropyl aochol

CH3
|
K
CH3  C  OH 
|
CH3
tert  Butyl alcohol

6. Ester formation
Replacing the – OH group of a carboxylic acid with the – OR group of an alcohol gives a carboxylic ester. The
following reaction, called the Fischer esterification. Because the Fischer esterification is an equilibrium
(often with an unfavourable equilibrium constant), some techniques are often required to achieve good yields
of esters.
General reaction

+ R OH + H2 O
Alcohol

e.g. + H2 O

7. Oxidation reactions
(1) Oxidation of primary alcohols
Oxidation of a primary alcohol initially forms an aldehyde. Obtaining the aldehyde is often difficult, since
most oxidizing agents strong enough to oxidize agents strong enough to oxidize primary alcohols also
oxidize aldehydes. CrO3 acid generally oxidizes a primary alcohol of all the way to the carboxylic acid

(2) Oxidation of secondary alcohols

Sec. alcohols are easily oxidized to give excellent yields of ketones. The chromic acid reagent is often best
for laboratory oxidations of secondary alcohols. The active species in the mixture is probably chromic acid,

H2CrO4, or the acid chromate ion, .

(3) Resistance of tertiary alcohols to oxidation

Oxidation of ter-alcohol is not an important reaction in organic chemistry. Ter-alcohols have hydrogen atoms
on the carbinol carbon atom, so oxidation must take place by breaking C – C bonds. These oxidations
require severe conditions and result in mixtures of products.
RESONANCE Alcohols, Phenols, & Ethers - 17
 Primary

R R
| 
|
Secondary K 2Cr2O7 or CrO3 / H R C O
R  CHOH         
A ketone
R
| KMnO 4
Tertiary  no reaction
R  C  OH   
|
R
Q.21 (a) What are the oxidation products of the following using Jones reagent (chromic acid in aqueous acetone
solution)
(i) CH3CH = CHCH(OH)CH3

(ii)

(b) Following compounds are oxidised with MnO2 ; write the products in each case
(i) CH3CH2CH = CHCH2OH (ii) PhCH2OH (iii) PhCH(OH)CH2CH2OH

(iv) CH3CH = CHCH2CH2CH2OH (v)

Q.22 Identify the product in the following reaction :

CH3CH2CH2OH

SOLUTIONS OF UNSOLVED PROBLEMS

1. (a) 1-Hexanol < cyclohexanol (b) 1-Hexanol < 4-methyl phenol
(c) 3-Ethyl -3-hexanol > 2-octanol (d) 2-Hexanol < cyclo octane-1,4-diol

2. It has many OH groups capable of H-bonding.

CH3 H CH3 CH3 CH3
| | | | |
3. P = CH3  C  C  CH3 Q = CH3  C  CH2  CH2  OH R = CH3  C  C  CH3
| | | | |
CH3 OH CH3 OH H

4. 5. D 6. C

7. B 8. (a) CH3MgBr + ; (b) +

RESONANCE Alcohols, Phenols, & Ethers - 18

9. (A) (B)

10. The reaction take place through the formation of diazonium salt which changes to carbocation.
NaNO2  HCl 
1,2hydride shift 
CH3CH2CH2NH2   CH3CH2CH2 CH3 CH2 CH2       CH3 CHCH3
1º carbocation 2º carbocation
(more stable than 1º)

– H2O

CH3 CH  CH3
|
OH
(2– propanol)
1º carbocation formed changes to more stable 2º carbocation by 1, 2–hydride shift, hence major product is
2–propanol.

11. B

12. CH2OH, CH2

C H3, CH3,
OH

13. P = CH3  CH  CH  CH3 (meso isomer)

| |
OH OH

14. C

15. (X) X, formed by syn addition is racemic mixture

CH3
H OH
(Y) Y, formed by anti addition is meso compound
H OH
CH3
(X) and (Y) compounds are enantiomers.
16. Because the chloride ion is a weaker nucleophile than bromide or iodide ions. HCl does not react with 1° or
2° alcohols unless zinc chloride or some similar Lewis acid is added to the reaction mixture as well. ZnCl2 is
a good Lewis acid, forms a complex with alcohol through association with on unshared pair of electrons on
the oxygen atom. This provides a better leaving group for the reaction than H2O.

RESONANCE Alcohols, Phenols, & Ethers - 19

17. Lucas H2CrO4

(a) (II) gives white turbidity immediately (I) gives green colour
(b) (II) gives white turbidity after 5-7 minute (I) & (II) both give green colour
(c) (II) gives white turbidity after 5-7 minute (I) gives green colour
(d) (II) gives white turbidity immediately No reaction
(e) (I) gives white turbidity after 5-7 minute (I) gives green colour

18. 19. 20. A: B:

O
Jones reagent
21. (a) (i) CH3CH = CHCH(OH)CH3  ||
    CH CH  CHCCH
3 3

(ii) Jones reagent

    
(Jones reagent oxidises 1° alcohol to aldehyde and 2° alcohol to ketone without affecting C = C bond)

2 MnO
(b) (i) CH3CH2CH = CHCH2 OH    CH3CH2CH = CHCHO
(allylic )
MnO2
(ii) PhCH2OH    PhCHO
(benzylic)

2 MnO
(iii) PhCH(OH)CH2 CH2 OH    PhCCH2CH2 OH
(benzylic ) ||
O
2 MnO
(iv) CH3CH = CHCH2CH2CH2OH    no reaction

MnO
2
(v)   

(MnO2 oxidises only benzylic and allylic 1° and 2° alcohols to aldehydes and ketones respectively).

-
22. CH3CH2 COO + MnO2 + H2O

Alfred Nobel
Alfred Nobel was born in Stockholm (Sweden) on October 21.1833. Alfred developed interest in
Literature and basic sciences. In order to widen Alfred’s horizons his father sent him abroad for
training in chemical engineering. During a two year periodm, Alfred Nobel visited Sweden, Germany,
France and the United States. In Paris, the city he liked the best, he worked in a private laboratory
of Professor T.J. Pelouze, a famous chemist. There he met the young Italian chemist who, three
years earlier, had invented a highly explosive liquid, nitroglycerine, produced by mixing glycerine
with sulphuric and nitric acids. It was considered too dangerous to be of any practical use.
After his return to Sweden from St. Petersburg in 1863, Alfred Nobel concentrated on developing nitroglycerine as an
explosive. Alfred Nobel experimented with different additives and soon found that mixing nitroglycerine with silica
would turn the liquid into a paste which could be shaped into rods of a size and form suitable for insertion into drilling
holes. In 1867 he patented this material under the name of dynamite.

RESONANCE Alcohols, Phenols, & Ethers - 20

 Ethers
Common Use of Ether
Diethyl ether is a colourless liquid having b.p. 34.5°C. It is fairly soluble in water and is miscible with ethanol
in all proportions. It is highly inflammable and forms explosive mixtures with air ; this is a great disadvantage
in its use as an industrial solvent for oils, fats, gums, resins etc., and as an extracting solvent. It is also used
in surgery as an anaesthetic and is the usual solvent for carrying out reactions of Grignard reagent. In the
presence of air and light, ether forms ether peroxide (CH3CH(OOH)OC2H5) which is a heavy pungent, oily
liquid, and is explosive. Since its boiling point is higher than that of ether, it is left in the residue after many
distillations and may cause explosions. Addition of a small amount of a cuprous compound e.g. cuprous
oxide has been recommended for avoiding the formation of ether peroxide. The chief impurity in ether is
ethanol and this has the property of preventing the formation of ether peroxide.
Di-isopropyl ether is a colourless liquid having b.p. 69°C. It is used as an industrial solvent for extraction
operations, and for decreasing the knocking properties of petrol when mixed with di-isopropyl ether, petrol
acquires a high octane number.
Di-n-butyl ether having b.p. 142°C, is manufactured by heating n-butanol with concentrated sulphuric acid. It
is used as an industrial solvent and as a solvent in reaction of Grignard reagent for which higher temperatures
are required than can be obtained by using diethyl ether.
Di-isoamyl ether, [[(CH3)2CHCH2CH2 –]2O], is prepared by the action of concentrated sulphuric acid on
isopentanol. It is a colourless liquid having b.p. 172°C and has a pear-like odour. It is used as an industrial
solvent, and as a solvent in reactions of Grignard reagent.
Ether is used as a volatile starting fluid for diesel and gasoline engines.
Ether is much less toxic than chloroform because ether degrades to ethanol which the body can oxidize.
Diethyl ether was found to be a much safer surgical anesthetic than chloroform.

Ethers as Polar Solvents

Nonpolar substances tend to be more soluble in ethers than in alcohols because ethers have no hydrogen-
bonding network to be broken up by the nonpolar solute.
Polar substances tend to be nearly as soluble in ethers as in alcohols because ethers have large dipole
moments as well as the ability to serve as hydrogen bond acceptors.
Ethers are nonhydroxylic (no hydroxyl group) and are normally unreactive towards strong base. For this
reason, ethers are frequently used as solvents for very strong polar bases (like the Grignard reagent). The
four ethers shown here are common solvents for organic reactions.

Crown Ethers
The polar nature of C – O bonds and the presence of unshared electron pairs on oxygen atoms allow ethers
to form complexs with metal ions.

The strength of this oxygen-metal bond depends on the structure of ether. A class of polyethers, also known
as crown-ethers are known to form more stable complexes with metal ions than simple ethers. Crown
ethers are cyclic polyethers containing four or more ether linkages in a ring of twelve or more atoms. Crown
ethers were given this name because their molecular models resemble crowns. A crown ether binds certain
metal ions depending on the size of the cavity.

RESONANCE Alcohols, Phenols, & Ethers - 21

 In this reaction, the crown ether is the ‘host’ and the species it binds is the ‘guest’. The crown-guest complex
is called an inclusion compound. The crown ethers allow inorganic salts to dissolve in non-polar solvents.
For example, potassium ion of potassium permanganate forms a complex with the crown ether, thereby
making KMnO4 soluble.

Q.1 What is a crown ether ?

Q.2. Give the structural formula for :
(i) 12-Crown-4 (ii) 18-Crown-6
Ex.1 Explain the structure of ether and n-pentane on the basis of boiling point. (for ether 34.6°C, & for n-pentane
36°C.)
Ans. Because ethers are weakly polar, their intermolecular forces of attraction are about as weak as are those of
the hydrocarbons. Hence, the boiling points are about the same :

Ex.2 Why ethers are soluble in water rather than hydrocarbons.

Ans. Ethers are much more soluble in H2O because of H-bonding between the O of ether and the H of water.
Hydrocarbons do not participate in H-bonding

True / False
Q.3 Bond angle in ether and bond angle in water are equal ( = 104.5°) due to lone-pair lone-pair
repulsion.

Q.4 The polar nature of C – O bonds and the presence of unshared electron pairs on oxygen atoms allow ethers
to form complexes with metal ions.

Q.5 Assertion (A) Boiling point of ether is smaller than that of isomeric alcohol.
Reason (R) : Solubility of ether in water is due to H-bonding.

Physical properties of ethers

1. Comparison of boiling points of ethers & alcohols
Pure ethers cannot engage in hydrogen bonding because they have no O – H groups. Although ethers do
have large dipole moments, resulting in dipole-dipole attractions, but these attractions appear to have rela-
tively little effect on their boiling points.

A molecule of water or an alcohol can serve as both a hydrogen bond donor and acceptor. Ether molecules
have no hydroxyl groups, so they are not hydrogen bond donors. If a hydrogen bond donor is present, ethers
can serve as hydrogen bond acceptors so ethers molecules are not held together by hydrogen bonds.

RESONANCE Alcohols, Phenols, & Ethers - 22

Table 1 : Comparision of the boiling points of ethers, alkanes and alcohols of almost similar molecular weights.

Method of Preparation of Ether

(1) Williamson synthesis
General reaction
RX + R  R – OR

nPr Br
e.g. (i)  CH3 CH2 CH2O  CH2CH2 CH3
n-PrOH  
Di  n  propyl ether

Na PhCH Br CH2 – O – CH3

(ii) MeOH 
 2
   
Benzylmethyl ether

(iii) Na
t-BuOH  EtBr
   t-Butyl ethyl ether

(This reaction produces a poor yield of ether because of the bulkiness of t-BuO¯)

Ex.3 Give the decreasing order of reactivity of alkyl halides in the Williamson reaction.
(CH3 )3 CCH2Br ClCH2CH  CH2 (C)ClCH2CH2CH3 BrCH2 CH2CH3
(A) (B) (C) (D)
Ans. B>D>C>A

RESONANCE Alcohols, Phenols, & Ethers - 23

Ex.4 Identify the product (A) in the following reaction :

(A)

CH3
|
Ans. (A) = CH3CH2 – O – C – CH3 + NaBr
|
CH3
Ethyl ter. Butyl ether

Ex.5 Identify the product in the following reactions :

(i)  (ii) (CH3)3CONa + C6H5CH2Br 

(iii) CH2 = CHCH2Br + (CH3)2CHONa  (iv) 

Ans. (i) (ii) (CH3)3COCH2C6H5

(iii) CH2 = CHCH2OCH(CH3)2 (iv)

Q.6 To prepare t-butyl ethyl ether, t-butyl bromide and sodium ethoxide is not taken ; instead ethyl bromide
sodium t-butoxide is taken. Explain ?

2. Williamson’s Continuous Etherification process or by Dehydration of Alcohols

Ethers may be prepared from alcohols in acidic medium. Generally accepted mechanism for 1° primary
alcohols is SN2 with alkyl hydrogen sulphate intermediate.
3° proceed by SN1 mechanism
1°, 2° by proceed SN2 mechanism

General Reaction :

Mechanism

Step-1 :
This is an acid-base reaction in which the alcohol accepts a proton from the sulfuric acid

Step-2 :
Another molecule of the alcohol acts as a nucleophile and attacks the protonated alcohol in an SN2 reaction.

Step-3 :

RESONANCE Alcohols, Phenols, & Ethers - 24

 Another acid-base reaction converts the protonated ether to an ether by transferring a proton to a molecule
of water (or to another molecule of the alcohol).

140°C Ethanol

• • Condenser

Ethanol • Ether
(2vol.)
+
• H2SO4 Water
(1vol)
Water
ice+water

Only one combination of alkylhalide and alkoxide is appropriate for the preparation of each of the following
ethers by Williamson ether synthesis. What is the correct combination in each case ?

Ex.6 Identify the product (ether) when dehydration of mixture of CH3OH and CH3CH2OH takes place in presence of
conc. H2SO4.
Ans. CH3COCH3 , CH3OCH2CH3 & CH3CH2OCH2CH3

Q.7 Would it be possible to form Di-t-butyl ether from dehydration of t-butyl alcohol ?
Q.8 Mixture of (CH3)3C18OH and CH3CH2OH undergoes dehydration in presence of conc. H2SO4 to form ether.
Identify major product with exact location of isotopic oxygen - 18.
Q.9 Identify the end product of the following reaction

A B

Name the reaction and the side product formed.

3. From alkenes
(3-a) By addition of alcohols in alkenes
When alcohol is added to alkenes in presence of acid, we get ethers.
General reaction
(I) Me2C = CH2 + H (H2SO4)  Me3 C 

(II) Me3 C  + EtOH Me3COEt

(3-b) Alkoxymercuration-demercuration

e.g.
(i) Hg( OCOCF )
3 2
(i) RCH = CH2 + ROH   
(ii) NaBH
 RCH(OR)CH
3
4

CH3 CH3
| |
(i) Hg( OCOCF3 )2
(ii) CH2 = CHCH3 + CH3CH(OH)CH3       CH  CH  O  CH  CH
(ii) NaBH 3 3
4

CH3 CH3
| |
(iii) (i) Hg(OCOCF3 )2
CH3CH = CHCH3 + CH3CH(OH)CH2CH3      CH3  CH 2  CH  O  CH  CH2  CH3
(ii) NaBH4

RESONANCE Alcohols, Phenols, & Ethers - 25

Ex.7 Out line synthesis of following ethers by solvomercuration-demercuration of alkenes

(A) C 6H5 CHOCH2 CH2 CH3 (B) CH3  CHCH2 CH2 CH2 CH3
| |
CH3 OCH2 CH3

(C) (CH3 )3 CCHCH3 (D)

|
OCH3

Ans. Alkene product (ether)

Alkene Alcohol
(a) C6H5CH = CH2 CH3CH2CH2OH

(b) CH3C = CHCH2CH2CH3 CH3CH2OH

(c) (CH3)3CCH = CH2 CH3OH

(d) CH3CH2OH

Ex.8 Identify A and B in the following reactions :

(a) A (b) B

Ans. It is alkoxy mercuration demercuration reaction

A is B is

4. From alkylhalide

2R – X + Ag2O  R – O – R + 2AgX
5. Industrial method
Al2O3
523 K
R – O – H + HO – R   R – O – R + H2O

Ether vapours are dried over fused CaCl2. If the temperature is 653K, instead of ether, ethene is obtained.

6. Miscellaneous reaction
4 HBF
ROH + CH2N2  
  R – O – CH3 + N2

conc. H SO
e.g. (i) 2PrOH   2 
4
 Pr – O – Pr + H2O

conc. H SO
(ii) HOCH2CH2CH2CH2 – OH   2 
4


Ex.9 Predict the product of the reaction between 2-Methyl-1, 3-propanediol and Al2O3 at 620 K.

Ans.

RESONANCE Alcohols, Phenols, & Ethers - 26

Chemical reactions of ethers
1. With HX
Ethers are unractive toward most bases, but they can react under acidic conditions. A protonated ether can
undergo substitution or elimination with the expulsion of an alcohol. Ethers react with conc. HBr and HI
because these reagents are sufficiently acidic to protonate the ether, while bromide iodide are good nucleo-
philes for the substiution.
Mechanism

Br
|
 CH  C  H +
3
|
H
ethyl bromide
CH3CH2Br

(i) excess HBr

   

(ii) 

H
(iii) CH3CH2 – O – CH3 



Ex.10 A series of dialkyl ethers was allowed to react with excess of HBr with the following results. Identify the ether
in each case.
(a) One ether gave a mixture of bromocyclopentane and 1-bromobutane
(b) Another ether gave only benzyl bromide
(c) A third ether gave one mol of 1, 5-dibromopentane per mol of ether

Ans. (a)

(b) (c)

Ex.11 Di-tert-butyl ether is rapidly cleaved by even HCl at room temperature forming tert-butyl chloride.

HCl
Ans. (CH3)3COC(CH3)3  (CH3 )3 C O C(CH3 )3
|
H

 (CH3 )3 C + (CH3)3COH



 (CH3)3CCl

(CH3)3COH + HCl  (CH3)3CCl + H2O

RESONANCE Alcohols, Phenols, & Ethers - 27

Q.10 Explain why ArOR ethers are cleaved to give RI and ArOH rather than ArI and ROH ?

Q.11 Account for the following observations.

CH3 CH3 CH3

| | anhydrous ether |
conc. HI        CH I  CH C  OH
CH3OH + CH3  C  I     CH3C  OCH3 ( I ) HI 3 3
| SN1 | |
( 2) CH3
SN2 CH3
CH3
( I)

Q.12 Assertion : In the cleavage of ether bond (– O –) by HI, the halide formed is a tertiary halide when one of the
alkyl groups is a tertiary group.
Reason(R) : Stability of 3° carbocation is maximum.

Q.13 Following reaction takes place as given :

(CH3)3C – O – CH3 + HI  (CH3)3COH + CH3I

Q.14 Predict the product of the following reactions. An excess of acid is available in each case.
(a) Ethoxycyclohexane + HBr
(b) Tetrahydropyran + HI
(c) Anisole + HBr

(d) + HI

(e) Ph  O  CH2 CH2  CH  CH2  O  CH2 CH3  HBr

|
CH3

2. Reaction with sulphuric acid

Ethers dissolve in concentrated solutions of strong inorganic acids to from oxonium salts, i.e. ether behave
as bronsted Lowry bases.
+ - 
R2O + H2SO4 (R – O – R) HSO4  R – OH + R  O  SO 2 OH
| alkyl hydrogen
H sulphate

When heated with dilute H2SO4

2 dil H SO
4
R2O + H2O    2ROH


e.g. C2H5OC2H5 + H2SO4  C2H5OH + C2H5OHSO4 C2H5OH + H2SO4

3. Autoxidation of ethers :
When ethers are stored in the presence of atmospheric oxygen, they slowly oxidize to produce hyroperoxides
and dialkyl peroxides, both of which are explosive. Such a spontaneous oxidation by atmospheric oxygen is
called an autoxidation.
General reaction

OOH
excess O 2 |
     R  O  CH  R + R  O  O  CH2  R
( Slow ) dialkyl peroxide
Hydroperoxide

RESONANCE Alcohols, Phenols, & Ethers - 28

 H3C CH3
excess O CH – O – O – CH
Ex.12 (i)      2 
 +
( weeks or months ) H3C CH3
Diisopropyl peroxide

OOH
|
(ii) CH3 CH2  O  CH2CH3 h
 CH3  CH  O  CH2 CH3
Diethyl ether 1  Ethoxyethyl hydroperoxide

4. Reaction with acid chlorides and anhydrides

Reagent ZnCl2 , AlCl3 etc.
3 AlCl
General reaction (i) R – O – R + R – CO – Cl  
  R – Cl + RCOOR

Mech.
RCOCl + AlCl3 RCO+ + AlCl4–

AlCl
R2O + RCO+  R1 – RCOOR1 +  
4
 R2Cl + AlCl3

Anhydrous
e.g. C2H5OC2H5 + CH3COCl    C2H5Cl + CH3COOC2H5
ZnCl2

(ii) R2O + ZnCl 2

  2 CH3COOR

anhydrous
e.g. C2H5OC2H5 + (CH3CO)2O AlCl
3  2CH3COOC2H5

5. Reaction with carbon monoxide :

Ether react with CO at 125–180ºC and at a pressure of 500 atm, in the presence of BF3 plus a little water.
BF3
500 atm
R2O + CO   RCOOR
125 –180 º C

6. Reaction with halogens :

When treated with chlorine or Br, ethers undergo substitution, the extent of whioch depends on the
conditions.
Cl2 Cl2
CH3CH2OCH2CH3   CH3CHClOCH2CH3  CH3CHClOCHClCH3
In presence of light
2Cl
(C2H5)2O 

hv


Mech.
The reaction proceeds by a free–radical mechanism, and –substitution occurs readily because of
resonance stabilization of the intermediate radical
•
– C HR 2
•
R1 – CH2R2 
 R
Cl 1
R1 Cl2
= CHR  R
1
– CHClR2 + Cl•, etc.

RESONANCE Alcohols, Phenols, & Ethers - 29

 SOLUTIONS OF UNSOLVED PROBLEMS
1. The crown ether is a hetero cyclic polyether, usually with atleast four O-atoms. Repeating unit is – OCH2CH2 –
2. In 12-crown-4-ether (or 18-crown-6-ether) first number indicates total number of carbon & oxygen atoms and
second one no. of O-atoms.

3. False 4. True 5. C

6.

(CH3)3CBr changes to stable 3° carbocation which can form alkene in presence of strong nuclephile

SN 2
(CH3)3CBr  

In the reverse case, reaction is SN2 which does not involve formation of carbocation and required ether is
formed predominatly.

S 2
N (CH3)3COCH2CH3

CH3 CH3 CH3

| | |
 H2O (CH3 )3  C  OH
7. CH3  C  OH  H  CH3  C  OH 2  
  CH3  C       
| | |
CH3 CH3 CH3
3 carbocation

In this reaction, t-butyl alcohol can’t solvate the 3° carbocation readily because of steric hindrance. Hence
formation of di-t-butyl is not possible.

8. (CH3)3C18OH behaves as a base while CH3CH2OH as an acid. Under the given condition stable 3° carbocation
is formed from (CH3)3C18 OH.
+
H
(CH3)3C18OH (CH3 )3 C (CH3)3COCH2CH3
18
– H2O
This ether does not have 18O. Instead it goes with H2O18.

9.  +

It is intramolecular cyclisation of Williamson synthesis (by SN2 reaction). Side product is

RESONANCE Alcohols, Phenols, & Ethers - 30

10. 



SN2 attack on a carbon of a benzene ring does not occur nor does the (phenyl) of high energy form

by an SN1 reaction. Hence, ArI can’t be formed.

11. In (I) ether is the solvent. Being less polar, it favours SN2 reaction and the nucleophile I¯ attacks the 1°
carbon of CH3.

CH3
|
S 2
N CH3I + CH3  C  OH
|
CH3

In reaction (2), H2O is the solvent. Being highly polar, it favours SN1 reaction giving 3° carbocation.

CH3
|
SN1 CH3  C  I
  CH3OH + |
CH3

12. A 13. CH3I +

14. (a) + C2H5OH (b) IH2C – CH2 – CH2 – CH2 – CH2I

1, 5-diiodopentane

(c) + CH3Br (d) 

(e) + C2H5Br + BrCH2CH2 CHCH2Br

|
CH3
1, 4  dibromo  2  methylbu tane

RESONANCE Alcohols, Phenols, & Ethers - 31

 Phenols
Preparation of phenols :
1. Phenols may be prepared by fusion of sodium arylsulphonates with sodium hydroxide :
ArSO3– Na+ + 2NaOH  ArO– Na+ + Na2SO3 + H2O
2. When a diazonium sulphate solution is steam distilled, a phenol is produced :
ArN2+ HSO4– + H2O  ArOH + N2 + H2SO4

3. Phenols are formed when compounds containing an activated halogen atom are heated with aque-
ous sodium hydroxide ; e.g., p-nitrophenol from p-chloronitrobenzene :

+ 2NaOH 

 + NaCl + H2O

4. Distillation of phenolic acids with soda-lime produces phenols e.g. sodium salicylate gives phenol :

5. Phenols may be prepared by means of a Grignard reagent :

ArMgBr
ArMgBr 2ArOMgBr 2ArOH
O2 / 

6. By Cumene-Hydroperoxide method

C6H6 + CH3CH = CH2 C6H5CH(CH3)2 (CH3)2 O – OH C6H5OH + CH3COCH3

Mechanism :

RESONANCE Alcohols, Phenols, & Ethers - 32

Properties of phenol :
These are characteristic of monohydric pheonls. Phenol is a colourless crystalline solid, m.p. 43°, b.p.
182°C, which turns pink on exposure to air and light. It is moderately soluble in cold water, but is readily
soluble in concentrated sulphuric acid (Liebermann reaction), when phenol is dissolved in concentrated
sulphuric acid and a few drops of aqueous sodium nitrite added, a red colour is obtained on dilution and turns
blue when made alkaline with aqueous sodium hydroxide.
Phenol is used as an antiseptic and disinfectant and in the preparation of dyes, drugs, bakelite, etc.

Chemical Reactions of Phenols :

Phenol generally gives electrophilic substitution with electrophlile

(1)

(2)

(3) (Major is oxidative cleavage of ring) + Picric acid (small amount)

(4)

(5) Reimer-Tiemann formylation reaction :

Mechanism : 
Step (I) CHCl3 + NaOH CCl3 : CCl2

Step (II)

attack of :CCl2 is the slow step (i.e. rate determing step)

RESONANCE Alcohols, Phenols, & Ethers - 33

 (6) Reimer-Tiemann carboxylation reaction :

(7) Kolbe carboxylation reaction :

(8) Fries Rearrangement :

(9) (polymer)

(10)

(11)

(12)

Test of Phenol :
(1) Phenols turn blue litmus red. Phenols behave as acids because of the presence of polar O–H group
in them. they ionise in aqueous solutions to give H+ ions.

RESONANCE Alcohols, Phenols, & Ethers - 34

 (2) Reaction with Ferric Chloride
Phenol gives a violet-coloured water soluble complex with ferric chloride.
6C6 H5 OH + FeCl3 [Fe(OC6 H5)6]–3 + 3H+ + HCl
Violet complex
(3) Libermann’s test
When a sodium nitrite (NaNO2) is added to a phenol dissoved in conc. sulphuric acid red or brown
colouration is produced. The colour changes to blue or green by the addition of a strong alkali. This
test can be used to distinguish phenols from alcohols.
2NaNO2 + H2SO4 2HNO2+Na2SO4
Sodium nitrite Nitrous acid

HNO
2
 

Summary of Preparation & Chemical Reactions of Phenol :

RESONANCE Alcohols, Phenols, & Ethers - 35

 (minor) + [Major is oxidative
cleavage]

(1)
(2) 

ArOH

(Kolbe's schmidt Reaction)

Phthalic

(Fries Rearrangement)

CHCl3 / NaOH / 

RESONANCE Alcohols, Phenols, & Ethers - 36