ALCOHOLS, ETHERS & PHENOLS

Syllabus

Alcohols, Ethers and Phenols: Alcohols (esterification, dehydration and oxidation)

Reactions of alcohols with sodium, phosphorus, halide, ZnCl2/HCl. Phenol, Acidity of
Phenol. Halogenation, Nitration, sulphonation and Reimer Tiemann reaction

CONTENTS INTRODUCTION
 Alcohols We can not go very far into organic
chemistry of almost any kind without
 Ethers encountering alcohols because we could
make every kind of organic compounds
 Phenols
and a host of others. We shall begin our
study of alcohols as the starting point of
organic synthesis. In this connection we
shall learn about the most important – and
simplest – catalytic effect known to organic
chemist : an effect that plays a key role in
the chemistry of compounds of all kinds, in
the test tube and in the living organisms.
Then we shall take up a family of
compounds closely related to alcohols i.e.
ethers and phenols. And with all this we
shall be dealing with alcohols, and their
rich and varied chemistry.

67
 Chemistry : Alcohols, Ethers and Phenols

1. ALCOHOLS
1.1 Introduction: Alcohols are organic compounds containing hydroxyl (—OH) groups.
They are some of the most common and useful compounds in nature, in industry, and around
house. The word alcohol is one of the oldest chemical terms, derived from the easily Arabic al-
kuhl: originally meaning “The powder” and later used as “the essence”. Ethyl alcohol, distilled
from wine, was considered to be “The essence” of wine. Ethyl alcohol (grain alcohol) is found in
alcoholic, beverages, cosmetics, the drug preparations. Methyl alcohol (wood alcohol) is used as
fuel and solvent. Isopropyl alcohol (rubbing alcohol) is used as a skin cleanser for injections and
minor cuts.
Alcohols are synthesized by a wide variety of methods and hydroxyl group may be converted to
most other functional groups. For these reactions, alcohols are versatile synthetic intermeediate.
In this chapter we discuss the physical properties of alcohols and summaries the methods used to
synthesize them.
Structure and classification of Alcohols :
1.4Å
0.96Å 0.96Å
O O
H
H H C H
104.5° H 108.9°
H

water methyl alcohol

The structure of an alcohols resembles the structure of water with an alkyl group replacing one of
the hydrogen atoms of water.

Above figure compares the structure of water and methanol. Both have sp3 hybridised oxygen
atom, but the C—O—H bond angle in water (104.5°) because the methyl group is much larger
than a hydrogen atom. The bulky methyl group counteracts the bond angle compression caused
by oxygen’s nonbonding pairs of electrons. The O—H bond lengths are about the same in water
and methanol (0.96Å), but C—O bond is considerably longer (1.4Å), reflecting the larger
covalent radius of carbon compared to hydrogen.
One way of organizing the alcohol family is to classify each alcohol according to the type of
carbinol carbon atom: the one bonded to —OH group. If this carbon atom is primary (bonded to
one other carbon atom), the compound is a primary alcohol. A secondary alcohol has the —OH
group attached to a secondary carbon atom and a tertiary alcohol has it bonded to a tertiary
carbon. When studied alkyl halides, we saw that primary, secondary and tertiary halides react
differently. The same principle holds for alcohols. We need to learn how these classes are simlar
and under what conditions they react differently. Figure (2) shows examples of primary,
secondary and tertiary alcohols.
Chemistry : Alcohols, Ethers and Phenols

Type Structure Example

Primary H CH3

R C OH CH OH
H3C CH2
H
2-methylpropan-1-ol
H3C CH2 OH
ethanol CH2 OH

benzyl alcohol

Secondary alcohol R' OH

R C OH

H
cyclohexanol
CH3 Me

HC OH
OH
CH2 1-methylcyclopentanol

CH3
2-butanol

Tertiary alcohol R' CH3 Ph

R C OH H3C C OH Ph C OH

R" CH3 Ph
2-methylpropan-2-ol triphenylmethanol

Phenols OH OH
OH

CH3 HO
phenol 2-methyl phenol hydroquinone

1.2 IUPAC Nomenclature

The IUPAC system provides unique name for alcohols based on rules that similar to those for
other classes of compounds. In general, the name carries the —ol suffix, together with a number
 Chemistry : Alcohols, Ethers and Phenols

to give location of the hydroxyl group. The formal rules are summarized in a three-step
procedure.
(i) Name the longest carbon chain that contains the carbon atom bearing the —OH group.
Drop the final-e from the alkane name and add the suffix-ol to give the root name.
(ii) Number the longest carbon chain starting at the end nearest the hydroxyl group, and use
the appropriate number to indicate the position of the —OH group (the hydroxyl group
takes precedence over double and triple bonds.)
(iii) Name all the substituents and give their numbers, as you would for an alkane or an
alkene.
In the following example, the longest carbon chain has four carbons, and the root name is
butanol. The —OH group is in the 2nd C-atom.
The complete IUPAC name is 1-chloro-3, 3 dimethyl-2-butanol.
CH3 OH

H3C C CH CH2 Cl
4 3 2 1
CH3

Cyclic alcohols are named using the prefix cyclo-; the hydroxyl group is assumed to be on C1.
H
6
OH HO CH2 CH3
5 1
4 2
3
Cl
H
trans-2-chloro cyclohexanol 1-ethylcyclopropanol

Illustration 1: Give the systematic (IUPAC) name for the following alcohol.
CH2 I CH2 OH

H3C CH2 CH CH CH CH3

CH3

Solution: The longest chain contains six carbon atoms, but it does not contain the carbon
bonded to the hydroxyl group. The longest chain containing the carbon bonded
to the —OH group is the one indicated by the box, containing 5 carbon atoms.
The chain is numbered from right to left so as to give the hydroxyl bearing
carbon atom the lowest possible number.
CH2 I CH2 -OH

H3C CH2 CH CH CH CH3

CH3
Chemistry : Alcohols, Ethers and Phenols

The correct name for the compound is 3 (iodomethyl) -2-isopropyl-1-pentanol.

In naming alcohols containing double and triple bonds, use-ol suffix after the alkene or alkyne
name. The alcohol functional group takes precedence over double and triple bonds, so the chain
is numbered in order to give lowest possible number to the carbon atom bonded to the hydroxyl
group.

If the numbers are needed to give the location of the multiple bonds the position of the —OH
group is given by putting its number before –ol suffix. Numbers for the multiple bonds was once
given easily in the name, but the 1997 revision of the IUPAC rules puts them next to the –en or
yn suffix they describe. Both the new and old plauments of the numbers are shown below.
OH
OH
1 3 CH3 H3C Cl
5 1
HO 2 4 6 2
5 3
4
trans-2-penten-1-ol or H H
trans-pent-2-ene-1-ol (3Z)-4-chlorobut-3-en-2-ol cyclohex-2-en-1-ol

3
CH2 H CH2 CH2 OH
4 2 OH HO H
5 1
6
O
2-(hydroxymethyl) (1R,3S)-3-(2-hydroxyethyl)
cyclohexanone cyclopentanol

EXERCISE 1: :
1. Give the IUPAC names of the following alcohols.
OH OH
OH
C CH3

a) b) H3C CH3 c)
CH3

Br
CH3

1.3 Common names of alcohols

The common name of an alcohol is derived from the common name of the alkyl group and the
word alcohol. This system pictures an alcohol as a molecule of water with an alkyl group
replacing one of the hydrogen atoms. If the structure is complex the common nomenclature
becomes awkward and IUPAC nomenclature should be used.
 Chemistry : Alcohols, Ethers and Phenols

Common CH3OH CH3CH2CH2OH OH

methyl alcohol n propyl alcohol H3C
name
CH3
isopropyl alcohol
IUPAC name methanol 1-propanol 2 propanol
Common CH2=CH—CH2OH CH3CH2CH2CH2OH CH3
name allyl alcohol n-butyl alcohol
OH
H3C

IUPAC name 2 propene-1-ol 1-butanol 4-methyl-1-butanol

Common OH CH3 CH3
name
CH3 H3C H3C C CH2 OH
H3C
H3C OH
CH3
sec-butyl alcohol t-butyl (alcohol)
Neopentyl alcohol

IUPAC name 2-butanol 2-methyl-2-propanol 2,2 dimethyle propanol

Nomenclature of Diols
Alcohols with two —OH groups are called diols or glycols. They are named like other alcohols
except that suffix diol is used and two numbers are needed to tell where two hydroxyl groups are
located. This is the preferred, systematic (IUPAC) method for naming diols.
OH OH
OH
OH

OH CH3
H3C
OH
1, 2 propane diol 1-cyclohexylbutane-1,3-diol (1R,2R)-cyclopentane-1,2-diol
The term glycol generally means a 1, 2 diol or vicinal diol, with its two hydroxyl groups on
adjacent carbon atoms.
1.4 Physical Properties
Methanol, ethanol, propyl alcohols, and tert butyl alcohol are completely miscible in water. The
remaining butyl alcohols have less solubility in water. The solubility of alcohols in water
gradually decreases as the hydrocarbon portion of the molecule lengthens; long-chain alcohols
are more “alkane like” and are, therefore less like water.
Alcohols have acidities less than that of water. Methanol is to some extent stronger than water
among all, but most alcohols are somewhat weaker acids. Pka values for serial alcohols are listed
below.

Acid Pka
Chemistry : Alcohols, Ethers and Phenols

CH3OH 15.5
H2 O 15.74
CH3CH2OH 15.9
(CH3)3 C—OH 18.0
For example, ethyl alcohol and propane have similar molecular weights, yet these molecules
boiling points differ by about 120°C.
H H

O   1.69D O   1.30D   0.08D

H CH2 CH3 H3 C CH2CH3 H3C CH3

ethanol, MW 46 b.p. 78°C ethyl methyl ether, MW 46 b.p. 25°C propane, MW 44 b.p. - 42°C

Such a large difference in boiling points indicates that ethanol molecules are attracted to each
other much more strongly than propane molecule. Two important intermolecular forces are
responsible: hydrogen bonding and dipole-dipole attraction.
Hydrogen bonding is the major inter molecular attraction responsible for ethanolic high boiling
point. The hydroxyl hydrogen of ethanol is strongly polarized by its oxygen, and it can form a
hydrogen bond with a pair of nonbonding electrons, with the oxygen atom of another alcohol
molecule.
CH3

H2 C H O

O H O CH2 CH3

H CH2 CH3

1.5. Synthesis of Alcohols

(a) From Alkyl Halides
One of the reasons alcohols are important synthetic intermediates is that they can be synthesized
directly from a wide variety of other functional groups. In previous chapters, we examined the
conversion of alkyl halides into alcohols by substitution and the conversion of alkenes to alcohols
by hydration, hydroboration and hydroxylation. These reactions are summarized below.

R R R
HO
X HO C X HO +X
H H
H H H H

Example
 Chemistry : Alcohols, Ethers and Phenols

H Br HO H
C KOH
  C
H3C CH2 CH3 H3C CH2 CH3

(2S)-2-bromobutane (2R)-butan-2-ol 100% inverted

configuration (plus elimination products

(b) From Alkene

Acid catalysed hydration

H
CC  H 2 O   —C—C—
H OH
Oxymercuation-demercuration

H2O NaBH 4
CC  Hg(OAc)2   — C — —C —   —C — —C —
HgOAc OH H OH
markonikov orientation

Example
H3C CH3 CH3 OH CH3 OH

Hg(OAc)2 NaBH

H 2O
 H C C CH3 
4
H C CH3

H CH3 H CH3
Hg(OAc) CH3

Hydroboration - Oxidation

(1) BH 3 . THF
CC  H 2 O 
(2) H 2 O 2 .NaOH
 C C (anti-Markonikov orientation)

H OH
CH3 CH3 CH3
H H 2 O2
H
BH 3 . THF
  
NaOH

BH2 OH
H H H
1-methylcyclopentene (1S,2S)-2-methylcyclopentanol

Hydroxylation: synthesis of 1, 2 diols from alkene.

OsO4 ,H 2 O2
CC   C C (syn hydroxylation)
or KMnO .OH –
4
cold dilute
OH OH
Example
Chemistry : Alcohols, Ethers and Phenols

CH2 CH3 CH2 CH3 CH2 CH3

H CH2 CH3 H H OH
O O
KMnO4 –
H OH
 Mn OH
  
H2O
O O OH H OH
H CH2 CH3 H
CH2 CH3 H
CH2 CH3
CH2 CH3
meso-3, 4 hexane
diol (60%)
OH
O

R C OOH
CC   C C (anti hydroxylation)
H2O

OH
CH2 CH3
H CH2 CH3 H CH2 CH3 H OH
HCO3H H2O
  O  
CH2 CH3
H CH2 CH3 H CH2 CH3 HO
H
(3S,4S)-hexane-3,4-diol

CH2 CH3

H OH

HO H

CH2 CH3

Organometallic Reagents
Organometallic compounds contain covalent bonds between carbon atoms. Organometallic
reagents are useful because they have nucleophilic carbon atoms, in contrast to the electrophilic
carbon atoms of alkyl halides. Most metals (M) are more electropositive than carbon and the C-
M bond is polarized with a partial +ve charge on the metal and partial negative charge on the
carbon atom:
Grignard Reagents
Organometallic compounds of lithium and magnesium are most frequently used for synthesis of
alcohols. The organometallic halides of empirical formula R—Mg—X, are called Grignard
reagents in honor of the French Chemist Victor Grignard, who discovered this utility around
1905 and received the Nobel Prize in chemistry in 1912. Grignard reagents result from the
reaction of an alkyl halide with magnesium metal.
This reaction is always carried out in an ether solvent, which is needed to solvate and stabilize
the Grignard reagent as it forms. Although we write the Grignard reagents as R—Mg—X, the
actual species in solution usually contains two, three, or four of these units associated together
with several molecules of the ether solvent. Diethyl ether, CH3CH2—O—CH2CH3, is the most
common solvent for these reactions although other ethers are also used:
 Chemistry : Alcohols, Ethers and Phenols

 – – 
CH3 CH 2 —O—CH 2 CH3
R — X  Mg   R — Mg— X
organometallic halide(Grignard reagent )

(X = Cl, Br or I)
Grignard reagents may be made from primary, secondary and tertiary alkyl halides as well as
from vinyl and aryl halides. Alkyl iodides are the most reactive halides followed by bromides and
chlorides. Alkyl fluorides generally do not react.
Reactivity R — I > R — Br > R — Cl > > R — F
The following reactions show the formation of some typical Grignard reagents
ether
CH3 — I  Mg   CH 3 — Mg — I
iodomethane methyl magnesium iodide

Br MgBr
ether
 Mg 

H H
bromocyclohexane cyclohexyl magnesium bromide

ether
CH 2  CH — CH 2 — Br  Mg   CH 2  CH — CH 2 — MgBr
alkyl magnesium bromide

Organolithium Reagents
Like magnesium, lithium reacts with alkyl halides, vinyl halides, and aryl halides to form
organometallic compounds. Ether is not necessary for this reaction; organo lithium reagents are
made and used in a wide variety of solvents.

 Li  X –  R — Li
R — X  2Li 

Organo lithium reacts like R – : Li 

Example
hexane
CH3CH 2CH 2CH 2 — Br  2Li   CH 3CH 2CH 2CH 2 Li  LiBr
n  butyl bromide n butyl lithium

pen tan e
CH 2  CH — Cl  2Li  CH 2  CH — Li  LiCl
vinyl Chloride

ether
Br  2Li   Li + LiBr

bromobenzene phenyllithium

(c) Preparation of alcohols by Grignard’s reagents: addition of

organometallic reagents to carbonyl compounds.
Because the Grignard reagents resemble carbanions, Grignard and organolithiuim reagents are
strong nucleophiles as well as strong bases. Their most useful nueleophilic reactions are addition
Chemistry : Alcohols, Ethers and Phenols

to carbonyl (>C=O) groups much like we saw acetylide ions ( H — C  C – ) in hydrocarbons

chapters. The carbonyl group is polarized, with a partial +ve charge on carbon atom and a partial
negative charge on oxygen. The positively charged carbon is electrophile; attack by a nucleophile
places a negative charge on oxygen atom. The positively charged carbon is electrophile.
 –
R CO 
 R C O

The product of this nucleophilic attack is an alkoxide ion, a strong base. The addition of water or
a dilute acid protonates the alkoxide ion to give the alcohol.

R C O H O H 
 R C OH + OH

alkoxide

Either a Grignard reagent or an organo metallic reagent can serve as the nucleophile in the
addition to carboxyl group. The following discussions refer to Grignard reagents, but they also
apply to organometallic reagents.
R R R X
– 
ether 
R' MgX  C O   R' C H3 O
O MgX   R' C OH  Mg

R R R OH

(i) Preparation of Primary Alcohols

H

ether H3 O
R MgX  C O   R CH2 O MgX  R CH2 OH
H
Grignard reagent formaldehyde

H3C H H3C
(1) ether
CH MgBr  C O   CH CH2 OH
(2) H O 
3

H3C H H3C

(ii) Preparation of Secondary Alcohols


ether H3 O
R MgX  R' CH O   R' CH O MgX   R' CH OH
Grignard's aldehyde
reagent R R

O OH
Br
(1) ether
H3C Mg  C H 
( 2) H O 
 C H
3

ethyl magnesium
bromide benzaldehyde H2C CH3
1-phenylpropan-1-ol
 Chemistry : Alcohols, Ethers and Phenols

(iii) Preparation of Tertiary Alcohols

Br
H O
H3C Mg  3

ethyl magnesium O
bromide H3 C
CH2 H3C CH2 C O H3 C CH2 C OH
phenyl-ethyl ketone
H2 C CH3 H2 C CH3
3-phenylpentan-3-ol
O R

(1) ether
R MgX  R' C Cl 
( 2) H O 
 R' C OH
3
acetyl chloride
R
tertiary alcohol
O OH
(1) ether
R MgX  R' C OR" 
(2) H O
 R' C R
3
ester
R
tertiary alcohol

Addition of the first equivalent of the Grignard reagent produces an unstable intermediate that
expels a chloride ion (in the acid chloride) or an alkoxide ion (in the ester), giving a ketone. The
alkoxide ion is a suitable leaving group in this reaction because on leaving stabilizes a negatively
charged intermediate in a strongly exothermic step.
Attack on an acid chloride
R' R' R'

R MgX C O 
 R C O MgX 
 C O + Cl
Cl R
Cl
acid chloride intermediate ketone

Attack on an ester
R' R' R' X

R MgX C O 
R C O MgX 
 C O + Mg

R" O R OR''
O R"
ester intermediate ketone

The ketone, thus produced reacts with a second equivalent of the Grignard reagent, forming the
magnesium salt of a tertiary alkoxide. Protonation gives a tertiary alcohol with one of its alkyl
groups derived from the acid chloride or ester, and the other two derived from the Grignard
reagent.
Chemistry : Alcohols, Ethers and Phenols

R' R' R'


R MgX C O 
 R C O H 3O
MgX   R C OH

Grignard R
R R
(second ketone
equivalent) intermediate alkoxide tertiary alcohol

(iv) Addition of Grignard Reagents to Ethylene Oxide

Grignard reagents usually do not react with ethers, but epoxides are usually reactive ethers
because of their ring strain. Ethylene oxide reacts with Grignard’s reagents to give after
protonation, primary alcohols with two additional carbon atoms. Notice that the nucleophilic
attack by Grignard reagents opens the ring and relieves the ring strain.
O MgX OH
O

ether H3 O
R MgX H2 C CH2   R CH2 CH2   R CH2 CH2
ethylene oxide alkoxide primary alcohol

O O MgBr OH

(H3 C) 2 HC MgBr H2 C CH2  H2 C
 CH2 H3 O
  H2 C CH2
Butyl magnesium ethylene oxide
bromide CH(CH3 ) 2 CH(CH3 )2
3-methyl-butan-1-ol

Reactions with Acidic Compounds

Grignard and organolithium reagents react vigorously and irreversibly with water. Therefore, all
reagents and solvents used in these reactions must be dry.
OH
– 
R — MgX  H — O — H 
 R — H  Mg
X

For example, consider the reaction of ethyl lithium with water.

– 
 CH 3CH 2 — H  Li  — OH
CH3 — CH 2 — Li  H — O — H 
ethane

The products are strongly favoured in the reaction. Ethane is a very weak acid (pKa of about
10–50). So the reverse reaction (abstraction of a proton from ethane by lithium hydroxide) is
unlikely. When ethyl lithium is added to water ethane is instantly bubbled to the surface.
Why would we want to add an organometallic reagent to water? This is a method for reducing an
alkyl halide to an alkane.
 Chemistry : Alcohols, Ethers and Phenols

OH
H2O
R — X  Mg 
ether
 R — MgX   R — H  Mg
X

H2O
R — X  2Li 
 R — Li  LiX   R — H  LiOH
The overall reaction is a reduction because it replaces the electronegative halogen atom with
hydrogen atom. In particular, this reaction provides a way to “label” a compound with deuterium
at any position where a halogen to present.
The Grignard reagent is a very powerful base as it contains a carbanion. Thus, it is
not possible to prepare a Grignard reagent from an organic compound that contains an acidic
hydrogen atom. We can not, for example, prepare Grignard reagent from a compound containing
an —OH group, an —NH — group, an —SH group, a —COOH group, or an SO3H group. If we
were to attempt to prepare a Grignard reagent from an organic alkyl halide containing any of
these groups, the formation of the Grignard reagent would simply fail to take place because the
Grignard reagent that would be produced on the 1st step, it would immediately react with an
acidic group.
Since Grignard reagents are powerful nucleophiles, we cannot prepare a Grignard reagent from
any organic halide that contains a carbonyl, epoxy, nitro or cyano (—CN) group. Compounds
containing the following groups can not be used to prepare the Grignard reagent, —OH, —NH2,
O O O

—NHR, —COOH, —SO3H, —SH, —C  C — H , CH, C R, C OR,

O

C NH2, —NO2, —C  N .

Planning A Grignard Synthesis

By using Grignard synthesis skillfully one can synthesize almost any alcohol we wish. In
planning a Grignard synthesis we must simply choose the correct Grignard reagent and the
correct aldehyde, ketone, ester or epoxide. We do this by examining the alcohol we wish to
prepare and by special attention to the groups attached to the carbon atom bearing the —OH
group. Many time there may be more than one way of carrying out the synthesis. In these cases
our final choice will probably be dictated by the availability of starting compounds. Let us
consider the following example.

Suppose we want to prepare the following compound.

H3C CH3

CH

H3C OH
2, 3 dimethyl -2-phenyle butane-2-ol
Chemistry : Alcohols, Ethers and Phenols

This means we can synthesize this compound in several different ways.

(i) We can use a ketone with isopropyl group and methyl group (3-methyl 2 butanol) and
allow to react with phenyl magnesium bromide.
C6 H5 H3C O

H3C CH C CH3  CH C CH3 + C6 H5 Mg Br

CH3 OH H3C

(ii) We can use a ketone containing an ethyl group and a phenyl group (ethyl phenyl ketone)
and allow of to react with ethyl magnesium bromide
C6 H5 C6 H5

H3C CH C CH3  H3C CH C + CH3 Mg Br

CH3 OH CH3 O

(iii) We can use an ester of benzoic acid and allow it to react with one equivalent of methyl
magnesium bromide and one equivalent ethyl magnesium bromide
C6 H5 C6 H5

H3C CH C CH3  + (CH3)2 CH Mg Br + CH3 Mg Br

O OCH3
CH3 OH

Illustration 2: Using an alcohol of no more than four carbon atoms as your only starting
material, outline a synthesis of A:
O

H3C CH CH2 C CH CH3

CH3 (A) CH3

Solution: CH3

H3C
C CH3

OH
CH3 O
CH3
(A)
H3C CH2 MgBr

 CH3

CH3
O

(B) (C)

Synthesis
 Chemistry : Alcohols, Ethers and Phenols

H3C O H3C CH3

(1) Et O H 2 CrO4
CH CH2 MgBr  H C CH CH3  2
(2) H O
 CH CH2 CH HC   (A)
2

H3C CH3 H3C OH CH3

EXERCISE 2:
Starting with bromobenzene and any other needed reagents, outline a synthesis of the
following ketone.
O

CH3

Synthesis
O
(i )
Mg
Br   MgBr 

(ii ) H3O 
CH2 CH2 OH
Dry ether

PCC
CH2Cl2
O CH3
K 2Cr2O7 (i) CH MgBr
CH2 C CH3   CH2 C OH  3
 CH2 CHO
(ii) H O 3

Reaction of grignard reagents to α, β unsaturated aldehydes

and ketones
When Grignard reagents (RMgX) react α-β unsaturated adehydes and ketones, they do so in two
ways. They may react by a simple addition that is one in which the nucleophile adds across the
double bond of the carbonyl groups; or they may react by a conjugate addition. These two
processes resemble the 1, 2 and the 1, 4 addition reaction of conjugated dienes.
O OMgBr

H3C CH CH C CH3  CH 3 MgBr  H3C CH CH C CH3

CH3 simple or 1, 4 addition

product (18%)


OMgBr

H3C CH CH C CH3

CH3

conjugate addition or 1, 2
addition product (72%)
Chemistry : Alcohols, Ethers and Phenols

When organolithium compounds made to undergo the afore-said reaction with conjugated
aldehyde or ketone, they yield 1, 2 addition pdt in much higher percentage (almost exclusively)
as compared with the Grignard reagents.

(d) Alcohols by Reduction of Carbonyl Compounds

Primary and Secondary alcohols can be synthesized by reduction of variety of compounds that
contain the carbonyl group several general examples are shown here,
O

[H ]
C   R CH2 OH
R H
1° alcohol
acetaldehyde

O R
[H] CH OH
C  
R R'
R' 2° alcohol
ketone

[H] R CH2 OH
C 
R OH
1° alcohol
Acid

[H]
C   R CH2 OH + R'OH
R OR'
1° alcohol
ester

The two most useful hydride reagents, sodium borohydride (NaBH4) and Lithium aluminum
hydride (LiAlH4) reduce carboxyl groups in excellent yields. These reagents are called complex
hydrides because they do not have a simple hydride structure such as Na+ H– or Li+ H–. Instead,
their hydrogen atoms, bearing partial negative charges, are covalently bonded to boron and
aluminum atoms. This arrangement makes the hydride a better nucleophile while reducing its
basicity.
H H
+ +
Na H B H Li H Al H

H H

Of these reducing agents, lithium aluminium hydride (LiAlH) is much stronger and more difficult
to work with LAH as reacts explosilvely with water and alcohols, liberating hydrogen gas and
sometimes initiates fires. Sodium boronhydride reacts slowly with alcohols and with water as
long as the pH is high (basic). Sodium borohydride is a convenient and highly selective reducing
agent.
 Chemistry : Alcohols, Ethers and Phenols

(i) Uses of Sodium Borohydride

Sodium borohydride (NaBH4) reduces aldehydes to primary alcohols, and ketones to secondary
alcohols. The reactions take place in a wide variety of solvent including alcohols, ethers, and
water. The yields are generally excellent.
O

C CH2 OH
NaBH 4
H  

cyclohexanecarbaldehyde

O OH

NaBH 4
H3C C CH2 CH3  H3 C CH CH2 CH3
CH 3 OH
butan-2-one butan-2-ol
(100%)

Sodium borohydride is selective; it usually does not react with carbonyl groups that are less
reactive than ketones and aldehydes. For example, carboxylic acids and esters are unreactive
towards borohydric reaction. Sodium borohydride can reduce a ketone or an aldehyde in the
presence of an acid or ester.
O
O HO CH2 C OCH3
NaBH 4
O CH2 C OCH3 

H H

(ii) Uses of Lithium Aluminium Hydride

Lithium aluminium hydride (LiAlH4, abbreviated as LAH) is a much stronger reagent than
sodium borohydride. It easily reduces ketones and aldehydes and also the less reactive carboxyl
groups e.g. those in acids, esters, and other acid derivatives. LAH reduces ketones to secondary
alcohols and aldehydes, acids and esters to primary alcohols. LAH reduces both keto and ester
group in a compound like;
O

O CH2 C OCH3

O HO CH2 CH2 OH
(1) LiAlH 4
O CH2 C OCH3  
(2) H O 
2

H H

Catalytic hydrogenation of ketones and aldehydes.

O OH

Raney
C —  H 2 
Ni
 — CH
Chemistry : Alcohols, Ethers and Phenols

The conversion of acetone or an aldehyde to an alcohol involves adding two hydrogen atoms
across the C=O group. This addition can be accomplished by catalytic hydrogenation commonly
using Raney Nickel as the catalyst. If any unsaturation (double bond) present in addition to
aldehyde or ketone will get reduced by this reagent.
CH3 O
CH3
Raney H3C CH2 CH2
H2C CH CH C 

Ni
CH2 OH
CH3 H
CH3
2,2-dimethyl-4-entenal
2,2-dimethylpentan-1-ol

NaBH4

CH3

H2C CH2 CH2 C CH2 OH

CH3
2,2-dimethylpent-4-en-1-ol

(e) From Amines

When 1° aliphatic amines are treated with nitrous acid, the —NH2 group gets converted into —
OH group and alcohols are formed; Nitrous acid is very unstable and usually it is prepared in situ
by treating aqueous and dilute sodium nitrite solution with dilute acids, HCl, H2SO4, acetic acid
etc.
R — NH 2  HNO2   R — OH  N 2   H 2O
Mechanism :
 HNO 2  NaCl; HO — N  O  H 
NaNO2  HCl 
H

+ R — NH 2 +
R N N O NO H O N O

H H

—H 

H — N2
R N N OH R N N OH2 R
H 2O :

– H +
R — OH R O H

However, carbonium ions being the intermediates of the reaction, several side products and
rearranged products are obtained as shown below.
 Chemistry : Alcohols, Ethers and Phenols

HX NaNO2
CH3CH 2 CH 2 — NH 2 CH 3CH 2CH 2 — N   N

H
H CH2 H O
CH2  H3C CH2 CH2 OH
2
H3C CH
CH2  – H

H2 C
CH3 CH 2CH 2 X CH3 — CH  CH 2
 –
H2O X
CH3 CH(OH) CH 3   CH 3 — CH— CH3 
SN
 CH3 — CH(X) CH 3

Thus, in this reaction, isomeric alcohols are obtained through the nucleophilic attack by water on
the carbonium ions; they may undergo the nucleophilic attack by the x – to form inorganic esters.
Isomeric alkenes also form through the E1 reactionof the carbonium ions; alkenes and esters are
the side products of the reaction. Besides these, a small amount of cycloalkene is also obtained.

(f) From Ethers: When ether is warmed with dilute H2SO4, under pressure, an alcohol is
obtained.
Dil H 2SO4 Dil. H 2SO 4
R 2 O 
Pr essure
 2ROH; CH 3CH 2OCH 2CH 3 
Pr essure
 2CH3 CH 2 OH
 
H  +
R — O — R   R O R OH2 R O R

H2O : H H

H
+
R O  R — OH 2ROH

EXERCISE 3:
Which reducing agent would you use to carry out the following transformation
a)
H3C COOH H3C CH2 OH

b) O OH

H3C C COOH H3C CH COOH

c) O O

H C C OCH3 HO CH2 CH2 OH

Chemistry : Alcohols, Ethers and Phenols

1.6 Reactions of Alcohols

(a) Substitution Reaction of Alcohols: An alcohol cannot undergo a nucleophilie
substitution reaction because it has a strongly basic group ( OH – ) that can not be displaced by a
nucleophile.

CH 3 — OH  Br – 
 CH3 Br  OH –
stronger base (bad leaving group)

In order for an alcohol to undergo a nucleophilic substitution reaction, the —OH group has to be
converted into a weaker base. One way of converting it into a weaker base is to protonate it.
Protonation changes the leaving group from OH – (a strong base) to H2O (a weak base). The
water can then be displaced by a nucleophile. The substitution reaction is slow and requires heat
for it to take place in a reasonable period of time.
 –
CH3 — OH  H  Br
CH3 — O H 2 

CH 3Br  H 2O

Because the OH group of the alcohol has to be protonated before it can be displaced by a
nucleophile, only weakly basic nucleophiles (I–, Br–, Cl–) can be used in the substitution reaction.
Moderately and strongly basic nucleophiles (NH3, R—NH2, CH3O–) would be protonated in the
acidic solution and, once protonated would no longer be neucleophiles or would be poor
nucleophiles. Primary, secondary and tertiary alcohols can all undergo nucleophilic substitution
reactions with HI, HBr and HCl to form alkyl halides.

CH CH CH OH  HI 
3 2  CH 3CH 2CH 2 I  H 2O
2
1 propanol a primary alcohol 1iodo propane

OH Br


+ HBr   + H2O

cyclohexanol (a bromo cyclohexane

secondary alcohol)

CH3 CH3
OH Cl
+ HCl 
 H3C + H2O
H3C

CH3 CH3
2-methylbutan-2-ol 2-chloro-2-methylbutane
(a tertiary alcohol)

The mechanism of the substitution reaction depends on the structure of the alcohol. Secondary
and tertiary alcohols undergo SN1 reaction.
The carbonation intermediate formed in the SN1 reaction has two possible fates: Either it can
combine with a nucleophile or it forms a substitution product
As tertiary carbonations are easier to form than secondary carbocation, tertiary alcohols undergo
substitution reactions with hydrogen halides faster than secondary alcohols.
 Chemistry : Alcohols, Ethers and Phenols

Mechanism of SN1 mode of reaction

CH3 CH3 CH3

H3C C OH + H—Br H3C C  H3C

OH2  C + H2O

CH3 CH3 CH3

tert butyl alcohol a
tertiary alcohol
Br

CH3 CH3

H3C C H3C Br

CH2 CH3
elimination product substitution product

The reaction of a hydrogen halide with a tertiary alcohol proceeds readily at room temperature,
whereas the reaction of a hydrogen halide with secondary alcohol requires heat.
CH3 CH3

H3C C CH2 CH3 + HBr 

 H3C C CH2 CH3 + H2O

OH Br

H3C CH CH2 CH3 + HBr 


 H3C C CH2 CH3 + H2O

OH Br
1
Primary alcohols can not undergo SN reactions because primary carbocations are too unstable to
be formed. Primary alcohols, therefore, undergo SN2 reaction.
Mechanism of the SN2 mode of reaction

Br
H3C CH2 + H — Br H3C CH2 OH   CH3CH2Br + H2O
H
OH
ethyl alcohol a
primary alcohol

Only the substitution product is obtained. No elimination product is formed because the halide
ion, although a good nucleophile, is a weak base.
A strong base is needed in an E2 reaction to remove a proton from a β-carbon.
When HCl is used instead of HBr or HI the SN2 reaction is slower because Cl– is a poorer
nucleophile than Br– or I – . The rate of the reaction can be increased by using ZnCl2 as a catalyst
because the Zn2+ cation is a Lewis acid that complexes strongly with the nonbonding electrons on
oxygen atom. This weakens the carbon-oxygen bond and creates a better leaving group.
ZnCl2
CH 3CH 2 CH 2OH  HCl   CH 3CH 2CH 2Cl  H 2O
Chemistry : Alcohols, Ethers and Phenols


CH3 CH 2 CH 2 OH  Zn 2 
 CH 3CH 2 CH 2 — O H
Zn

Cl

CH 3CH 2 CH 2Cl  Zn(OH)2

The Lucas Test: Whether an alcohol is primary, secondary or tertiary can be determined by
taking advantage of the relative rates at which the three classes of alcohols react with HCl/ZnCl2.
This is known as Lucas test. The alcohol is added to a mixture of concentrated HCl and ZnCl2
(the lucas reagent) low molecular weight alcohols are soluble in the Lucas reagent, but the alkyl
halide products are not, so the solution turns cloudy as the alkyl halide is formed. When the test
is carried out at room temperature, the solution turns cloudy immediately if the alcohol is tertiary,
in about 5 minutes if the alcohol is secondary and remains clear if alcohol is primary. Because
the test relies on the complete solubility of the alcohol in the Lucas reagent, it is limited to
alcohols with lesser than six carbon.
Because the reaction of a secondary or a tertiary alcohol with hydrogen halide is an SN1 reaction,
a carbocation is formed as an intermediate. Therefore, we must check for the possibility of a
carbocation rearrangement when determining the product of substitution reaction. A carbocation
rearrangement would only occur if it leads to formation of more stable carbocation. For example,
the major product of the reaction of 3-methyl-2-butanol with HBr is 2-bromo-2-methyl butane
because a 1, 2 hydride shift converts the initially formed secondary carbocation into a more
stable tertiary carbocation.
CH3 CH3

H3C CH CH CH3 + H Br H3C CH CH CH3

OH OH2
3-methylbutan-2-ol
– H2O

CH3 CH3

H3C C
1,2 hydride
CH2 CH3  shift
 H3C C CH CH3
2°-carbocation
3°-carbocation H

Br Br

CH3
(H3 C)2 CH CH CH3
H3C C CH2 CH3
Br
Br
2 bromo-3-methyl butane
2-bromo-2-methylbutane
(major product)
(minor product)
 Chemistry : Alcohols, Ethers and Phenols

EXERCISE 4: i) CH3 

HCl

OH
CH3
ii)
HCl
CH CH OH 

CH3

Better yields of alkyl halides are obtained and carbocation rearrangements can be avoided if a
phosphorous trihalide (PCl3, PBr3 or PI3) or phosphorous pentahalide (mainly PCl5) or SOCl2 is
used to convert alcohols into alkyl halides. These reagents all act in the same way they convert an
alcohol into an intermediate with a leaving group that is readily displaced by a halide ion. For
example, phosphorous tribromide converts the strongly basic leaving group of an alcohol into a
weakly basic bromophosphite group that can be displaced by a bromide ion.
Br
+
H3C CH2 P Br H3C CH2 O PBr2

OH Br H
Phosphorous
tribromide
N

H3C CH2 O PBr2

a bromo phosphite
Br group

CH3CH2—Br OPBr2

Thionyl chloride coverts an OH group into a chlorosulfite leaving group that can be displaced by Cl – .
H3C H3C
CH OH SOCl 2
  CH Cl

Retention of configuration

H3C H3C
CH OH SOCl2
  CH Cl

Inversion of configuration

Detailed mechanism of the reaction had been discussed in alkyl and aryl halides chapter.
Chemistry : Alcohols, Ethers and Phenols

(b) Dehydration of Alcohols: The dehydration of alcohols requires an acid catalyst and
heat. Sulfuric acid (H2SO4) and phosphoric acid (H3PO4) are the most commonly used acid
catalysts for this purpose.
CH3 CH3
H 2SO4 + H2O
H3C H3C

OH
OH CH3 CH2
H3C

H 2SO 4

 + H2O

93% 7%
CH3 CH3 CH3
H2 SO4
H3C C CH2 CH3 H3C C CH CH3 H2C C CH2 CH3 + H2O
84% 16%
OH
Dehydration of secondary and tertiary alcohols involved the formation of a carbocation
intermediate, so be sure to check the structure of the carbocation for the possibility of
rearrangement. The carbocation will rearrange if rearrangement produces a more stable
carbocation.
CH3 CH3

H3 PO4 / 
H3C C CH CH3 H3C C CH CH3

CH3 OH CH3
secondary carbocation
CH3 —H
1, 2, methyl shift
H3C C CH CH2
CH3
CH3
H3C C CH CH3
3, 3 dimethyl -1- butene
(3%)
CH3

—H

CH3

H3C C C CH3 H2C C CH2 CH3

CH3 CH3 CH3

2, 3 dimethyl-2-butene 2, 3 dimethyl-1-butene
(33%) (33%)

Alcohols can be dehydrated by use of POCl3 in presence of pyridine.

 Chemistry : Alcohols, Ethers and Phenols

CH3 CH3
POCl3
H3C 
pyridine, 0 C
 H3C

OH
Reaction with POCl3 converts the OH group of the alcohol into OPOCl2, a good leaving group.
Because of the mildly basic reaction conditions, an E2 reaction is not formed, so we do not have
to be consumed with carbocation rearrangements. Pyridine serves as a base to prevent the
formation of HCl and to remove the proton in the elimination reaction.
H3 C O CH3 O
Cl
+
OH P H3 C CH O P
Cl Cl
Cl
H3 C Cl H

CH3 O
Cl
H2 C CH CH3 H2 C CH O P
Cl
+2 + OPOCl2 H
N
N
H
Illustration 3: Propose a mechanism for the following reaction.
H3 C CH3 H3C CH3
CH3 CH3

OH H OH2
 

CH3
H3C CH3
H3 C 2 2 CH3
Me 3 1
1
4 7
5 6

tertiary carbocation

H3 C CH3
2 CH3
1
CH2

primary carbocation
Chemistry : Alcohols, Ethers and Phenols

Solution: H2 O H CH2 CH2

2 CH3 2 CH3
H3C 1 H3C 1
H3 O

EXERCISE 5:
Convert i) n — CH3CH 2 CH 2 CH 2OH 
 MeC  C — Me
ii) H3C CH3

n — CH3CH 2CH 2OH 

 C C

H H
iii) O O
OH OH



Because the starting material contains a seven membered ring unstable and the final product has
a six member ring, a ring contraction rearrangement must occur.
(c) Oxidation of Alcohols

The reagent most commonly used to oxidize alcohols is chromic acid (H2CrO4), which is formed
when chromium trioxide (CrO3) or sodium dichromate (Na2Cr2O7) is dissolved in aqueous acid.
H3 C H3 C
CrO3
CH3 
H 2SO4 O

HO H3C
OH O

Na 2 Cr2 O7

H2 SO 4


OH H2 CrO4 O


H3C H3C
secondary alcohols ketone

Primary alcohols are initially oxidized to aldehydes by these reagents. The reaction, however
does not stop at the aldehyde. The aldehyde is further oxidized to a carboxylic acid.
H3C H3C

H3C OH 
H 2 CrO 4
O 
further oxidation
 O

HO HO
 Chemistry : Alcohols, Ethers and Phenols

Therefore in most laboratory preparations we must rely on special conditions to prepare

aldehydes from primary alcohols. A variety of reagents is available. An excellent reagent for this
purpose in pyridinium chlorochromate (abbreviated PCC), the compound when CrO3 is dissolved
in hydrochloric acid and then treated with pyridine.
+ -
CrO3  HCl  
 N CrO 3 Cl
N
pyridine Pyridinium chlrochromate

PCC when dissolved in CH2Cl2 will oxidize a primary alcohol to an aldehyde and stop at this stage.
H3C H3C
CH 2Cl2
 PCC 
25 C

H3C OH H3C O
2-methylpropan-1-ol
Pryidinium chlorochromate also does not attack double bond.
The reason for oxidation by PCC leads to only aldehyde stage is that the oxidation can be carried
out in solvent such as CH2Cl2 in when PCC is soluble. Aldehydes are not as easily oxidized as
the aldehyde hydrates, R – CH(OH)2 that form when aldehydes are dissolved in water, the usual
medium for oxidation by chromium compounds.
R  CHO  H 2 O R  CH(OH)2
Mechanism of chromate oxidations
The mechanism of chromic acid oxidations of alcohols has been investigated thoroughly. It is
interesting because it shows how change in oxidation states occurs in a reaction between an
organic and an inorganic compound. The 1st step is the formation of a chromate ester of the
alcohol. Here we show the step using a 2° alcohol.
H O
Step 1: H3C
C  O Cr OH
OH
H3C H O
Cromic acid
Sec-propyl alcohol –H2O
Step (i)
H2O
H
H3C O
C
O Cr OH
H3C
Alkyl Chromate
O (Cromate ester)

H3C
 
C O  HCrO 3  H 3O

H3C
Acetone
Chemistry : Alcohols, Ethers and Phenols

The chromium atom departs with a pair of electrons that formerly belonged to the alcohol; the
alcohol is thereby oxidized and the chromium reduced.
If we consider the oxidation of 1° alcohol to aldehyde. The aldehyde initially formed from the 1°
alcohol reacts with water to form an aldehyde hydrate. The aldehyde hydrate can their react with
HCrOH– (and H+) to form a chromate ester, and that can then be oxidized to the carboxylic acid.
In the absence of water (i.e. using PCC in CH2Cl2), the aldehyde hydrate does not form, therefore
further oxidation does not take place.
R O H R R
O HCrO4-, H+ O
+
O R O H H
H H
H O H H O O
H O
H O
H H Cr
H O
HO

HO

O  HCrO 3  H 3O 

In case of oxidation of 3° alcohol, the chromate ester is formed in the 1st step, the ester does not
bear a hydrogen atom that can be eliminated, and therefore, no oxidation takes place.

R O
O R O
O
H  O Cr OH  H+ Cr  H2O
R' R' OH
R" O R" O
3° alcohol
This chromate ester cannot
undergo elimination of H2CrO3

Oxidation of primary alcohols by KMnO4

Primary alcohols can be oxidized to carboxylic acids by potassium permanganate. The reaction is usually
carried out in basic aqueous solution from which MnO2 participates as the oxidation takes place.
R  OH  - +
KMnO 4 
H 2 O, heat
 R COO K  MnO 2
OH
H 3O 

OH

(d) Periodic Oxidation: Oxidative cleavage of polyhydroxy compounds:

Oxidation by periodic acid or lead tetraactate: Periodic acid or lead tetraacetate breaks C(OH)—
C(OH) bond oxidatively and forms 2 moles of carbonyl compounds; in this reaction, a 1°
carbionl C gives formaldehyde, a 2° carbinol C forms aldehyde other than formaldehyde and a 3°
carbinol C forms a ketone. If there are three OH groups on three adjacent C atoms, the middle C
 Chemistry : Alcohols, Ethers and Phenols

atom gets converted to formic acid. However, the reaction is widely used in oxidative
degradations. The size of the ring of a sugar can be determined through the oxidative degradation
reaction involving periodic acid.
CH2 OH H3C CHOH
HIO4 HIO4 or

or Pb(OAC)
 2HCHO; 
Pb(OAC)4
 CH 3CHO  (CH 3 ) 2 C  O
4
CH2 OH H3C COH

CH3

CHOCH3 CHOCH3 CHOCH3 CHOCH3

CHOH CHO CHOH O CHO O

2HIO4
 CHO  HCHO
CHOH 2HIO4
O   HCOOH O ; CHOH

CHOH CHO CH CH

CH CH CHOH CHO

CH2 OH CH2OH CH2 OH

In the reaction n molecules of HIO4 are required per (n + 1) OH groups on (n + 1) adjacent

carbon atoms and (n — 1) molecules of formic acid form.

The mechanism of lead tetraacetate oxidation is:

C OH C O Pb(OAC)3 C O OAC
– ACOH
 Pb(OAC) 4 –ACOH Pb
C OH C O H C O OAC

Pb(OAc)2

C O O C

i) The rate of the reaction = k [substrate] [Pb(O—AC)4] which is in conformity with the
given mechanism.

ii) When acetic acid is added, the reaction retards which supports the reversibility of the
reaction.
iii) Cis-diols react much faster than the trans-diols.
This is a strong evidence in favour of the cyclic intermediate.
Chemistry : Alcohols, Ethers and Phenols

The mechanism of periodic acid oxidation is similar to tht of the lead tetraacetate:

O
C OH C O
–H O
O I OH 
2
 I O3 H 
 HIO3  — C  O  — C  O
C OH C O
O

EXERCISE 6:

Write down the periodic oxidation products of

H2 C OH

HC OH

C O

HC OH

HC OH

CH3

(e) Haloform Reaction

O O
|| ||
Compounds containing  C CH 3 group or on oxidation gives  C CH 3 group when treated
with dilute alkali and halogen gives haloform (CHX3) [where X = Cl, Br or I].
Haloform is an oxidizing agent, an alcohol can give a positive iodoform test, it is oxidized to
methyl ketones. The haloform reaction can convert such an alcohol to a carboxylic acid with one
less carbon atom.
HO O HO
excess X 2
CH3  I 2 
 CH3  2HI 
 – OH O  CHX3
R R R
(one less carbon)

H3C H3C H3C I

I2 I2

 OH 
  I
OH

OH O O I

H3C H3C O
hexan-2-ol hexan-2-one
 Chemistry : Alcohols, Ethers and Phenols

Mechanism
R X
R R
Step 1: O H

OH
  CH2
X X
  
 X

O HO X O X
R

enolisation

CH2

Step 2: O X O X

X 
R X
OH

R X OH X

X O O X O X

H 3O
X  R 
R  X 
 O  X

X OH O X R H X

1.7 Identification tests of Alcohols

(a) Reaction with sodium : Alcohols react with Na (as well as Ca and Al) to form
alkoxide and evolve hydrogen gas.

 2RO – Na   H 2
2ROH  2Na 

(b) Lucas Test: Already discussed.

(c) Oxidation: When treated with dichromate and conc. sulphuric acid, the solution turns
blue green opaque a few seconds; 3° R—OH does not give the test.

1 or 2 alcohol  H 2 CrO4 
 blue green opaque

orange, transparent
Chemistry : Alcohols, Ethers and Phenols

(d) Victor Meyer’s Test: This test involves the following sequential reactions

In the case of
1° ROH—blood red soln.

HI AgNO 2 HNO2
Aqueous In the case of
ROH   RI   R — NO 2   So ln . 
alkali


2° ROH—blue soln.

In the case of
3° ROH—colourless

Since in this reaction 1°, 2° and 3° ROH give red, blue and colourless solutions respectively, this
test is also called red-blue-white test.

2. ETHERS

2.1 Introduction

Ethers have the general formula R—O—R or R—O— R  , where R  may be an alkyl (or phenyl)
group different from R. The bond angle at the oxygen atom of an ether is only slightly larger than
that of water. Thus ether has same geometry as water

R R H3C

O O 110° O

R R H3C



general formula of an ether Dimethyl ether
(a typical ether)

C—O—C linkage is called ethers linkage: An O atom flanked by two hydrocarbon groups or
their derivatives constitute the ether linkage. Compounds containing ether linkage are called
ethers. Depending on the nature of the hydrocarbon groups the ethers may be classified as :
dialkyl ethers, alkyl aryl ethers, diaryl ethers, alkyl allyl ethers etc.

2.2 Structure and physical properties of Ethers

Ether linkages have angular shapes; the C—O—C bond angles are usually 110° to 118°. The O
atom holds 2 lone-pairs of electrons, Owing to the greater electronegativity of O atom than that
of C atom, C—O bonds are polar. Since the shape is angular and since bonds are polar, ether
molecules have dipole moments of the order 1.12—1.18D.
 Chemistry : Alcohols, Ethers and Phenols

–
O

 –
R R
110°–118°  = 1.12—1.18D
The O atom may be in sp2 or sp3 hybridised state. In an alkyl ether it is in sp2 hybridised state, the
two lone-pairs of e.’s occupy two sp3 A.O.s; while in an aryl, or aryl alkyl ether the O atom may
assume sp2 hybridized state and as a consequence one of the two lone-pairs of e.’s occupy a p-
A.O. and undergo p-π conjugation with π bonds of the aryl part.

O O O

etc.

Since there is no O—H bond (e.g. alcohols and phenols) in an ether, it cannot form H-bond and
as a result of which ether molecules do not associate amongst themselves; but they experience
dipole-dipole interaction (because of their dipolar nature) which is weaker than the H-bonding
force. Hence ethers are low melting, low boiling and highly volatile. Their m.p.s and b.p.s are
much lower than those of alcohols of comparable molecular weights e.g., methyl ether (b.p.–
24°C); propane (b.p.–42°C) and ethanol (b.p. 78°C). The m.p. and b.p. increase with increasing
molecular weight.

However, they can form H-bond with water molecules and for this reaction lower members are
slightly soluble in water; the solubility decreases with the increasing molecular weight.

The structure of an ether molecule tells us that it will be weakly basic and it will form salt with
acids; this also tells us that an ether can undergo reactions involving C—O bond cleavage and the
cleavage requires a protonic or Lewis acid since OR is a bad leaving group. As the O atom draws
electrons from the alkyl group, the α-H atoms are expected to be slightly acidic and hence they
can be substituted by electrophiles. The acidity order of the α-H atoms is 1° > 2° > 3°. Since in
aryl ethers p-π conjugation takes place, an aryl ether undergoes electrophilic substitution
reactions besides C—O bond breaking reactions. Since the ether linkage has a + R effect, it is an
o-, p-directing group. We shall discuss the general reactions of the ether linkage on the basis said
above.

2.3 IUPAC Nomenclature: Ethers are compounds in which an oxygen atom is bonded to
two alkyl substitutents. If the alkyl substituents are identical, the ether is a symmetric/simple
ether. If the substituents are different, the ether is an asymmetrical/complex ether.

R —O—R R — O — R
a symmetricalether an asymmetrical ether
Chemistry : Alcohols, Ethers and Phenols

The common name of an ether is obtained by citing the names of the two alkyl substituents (in
alphabetic order) followed by the word “ether”. The smallest ethers are almost always named by
their common names.

CH 3 — OCH 2 — CH 3 CH 3 — CH 2 — OCH 2 — CH3

ethyl methyl ether diethyl ether after called ethyl ether

CH3 H3C

H3C CH O CH CH2 CH3 CH O

CH3 H3C

sec-butyl isopropyl ether cyclohexyl isopropy ether

The IUPAC system names an ether as an alkane that has an RO substituent. The substituents are
named by replacing the “yl” ending in the name of the alkyl substituent with “Oxy”.
H3C O H3C O
CH 3O — CH 3CH 2 O — CH
methoxy ethoxy CH2 HC
CH3 CH3
isopropoxy sec butoxy

CH3 OCH3
H3C CH2
(CH 3 )3 C — O — CH CH3 H2 C CH2 CH2
tert butoxy
CH CH2
OCH3
2-methoxy butane H3C
1-methoxy-4-methylhexane
CH3

O CH3
H3C O

1,4-diisopropoxybutane CH3

Cyclic ethers can be named in several ways, one simple way is to use the replacement
nomenclature in which we relate the cyclic ether to the corresponding hydrocarbon ring system
and use the prefix oxo to indicate that an oxygen atom replaces a CH2 group. In another system, a
cyclic three membered ether is named oxirane and a four membered ether is called oxetane.
Several simple cyclic ether.
Since the reaction usually takes place in a quantitative yield, valuable information can often be
gained by measuring the number of molar equivalents of carboxylic acid that also have the
common names are given in paranthesis. The trahydro furan (THF) and 1, 4 dioxane are useful
solvents.
 Chemistry : Alcohols, Ethers and Phenols

O O

Oxocyclopropane or oxirane Oxacyclobutene or oxetane

(ethyleneoxide)

O
O
Oxocyclopentane 1, 4 Dioxocyclo hexane
(tetrahydrofuran) (1, 4 dioxane)

2.4. General Methods of Preparation of Ethers

(a) When an alcohol is heated with concentrated H2SO4 at an elevated temperature an ether is
formed by the loss of one molecule of water from two molecules of alcohol. In this case
unsaturated acid not only catalyses the reaction but it also absorbs the water. Since an ether is
formed from an alcohol by the loss of water molecule, this is also called the anhydride of the
latter.
conc.
R — OH  HO — R 
H 2SO 4
 R 2O  H 2 O

   
H
R — OH R — O H2 R O  R — O H2 R O R OH2

H H

H
R — OH R — O H2
R O R  OH 2

H
slow 
R  H 2O ROR  H 

R  HSO –
R O   R O R 
4
 R — O — R  H 2SO 4

H H

The drawback of the particular reaction is that we can only produce a simple ether (R—O—R)
from R—OH alcohols. If we need to produce an ether like R — O — R from alcohols R—OH
and R  — OH respectively, besides of this ether ( R — O — R ), A mixture of ethers R—O—R
and R’—O—R’ will also be obtained.
(b) The Williamson Synthesis
This is the best method for the preparation of unsymmetrical and symmetrical dialkyl and aryl
alkyl ethers. This involves the treatment of an alkyl halide with sodium alkoxide or phenoxide
respectively.
Chemistry : Alcohols, Ethers and Phenols


R — X  N a OR  
 R — O — R

R — X  N a O R 
R—O—R

R — X  N a O Ar 
 R — O — Ar
Since in aryl halides C—X bond has a double bond character, they do not react with alkoxides or
phenoxides.
It is better to choose 1° alkyl halide for the reaction since 2° and 3° alkyl halides undergo E2
reaction in the presence of strong alkoxide or phenoxide, bases. The alkoxide ion may be 2° and
3° but 3° alkoxides react very slowly. It is here important to note that Ar3C—X gives carbonium
ion readily and therefore, in this case the reaction is SN1. In the case of a 1° R—X, the reaction is
SN2.
– –
R O –  R — X 
 R  O .... R .... X 
 R — O — R

Another reason for non-participation of 3° R—X is that the T.S. will have to bear high steric
strain because of the bulk of the 3° R group; this means that the T.S. will be of high energy and
therefore, it will be difficult to form T.S.
CH3

Illustration 4: Choose the appropriate reagent to prepare H3C C OCH3 by

CH3
williamson’s reaction.
Solution: If we will have to prepare Me3C—OCH3, the choice left for us are either (i)

(CH3)3C—Br and CH 3O – N a or (ii) (CH3)3C—O–Na+ and CH3—Br. If we
opt for the first choice, Me3C—Br being 3° alkyl halide will not participate in
SN2 type substitution owing to the T.S. will have to bear a high steric strain as
well as the back side attack by the nucleophile CH 3O – will be very much
resisted due to steric crowding rather it will go for E2 reaction leading to an
alkene as the product.
CH3 CH3
–
H3C C X H3C C X (CH 3 ) 2 C  CH 2  CH3OH

H CH2 H CH2
–
CH 3O – H3CO

Hence the 2nd choice i.e. (CH 3 )3 C — O – Na  and CH—Br is the only choice
which will lead to the desired product (CH 3 )3 C — OCH 3 though the rate of
the reaction would be slow.
 Chemistry : Alcohols, Ethers and Phenols

(CH 3 )3 C — O – Na  CH3 — Br

 (CH3 ) 3 C — OCH 3

(c) The Ullmann diaryl ether synthesis

When aryl bromides or iodides are heated with phenoxides in the presence of copper powder,
diaryl ethers are formed and the reaction in called the Ullmann diaryl ether synthesis.


Cu
Br  N a O CH3  O CH3

(d) From alcohol and alkyl p-toluenesulphonate

When an alcohol is refluxed with metallic sodium and an alkyl p-toluene sulphonate, a diaryl
ether is formed.
O

Na
R — OH   RO – Na  ; RO –  R' O S Me

R — OR   Me C6 H 4 SO3– Na 

(e) Conversion of an alcoholic —OH group to a methoxy group

When alcohols are treated with diazomethane in the presence of a Lewis acid, e.g. anhydrous
AlCl3 or BF3, a methyl ether is formed.
AlCl3
R — OH  CH 2 N 2   ROCH 3  N 2

(f) Conversion of phenolic —OH group to methoxy group by di-methyl

sulphate

A methyl aryl ether is formed when alkaline solution of dimethyl ether is allowed to react with
phenol
–
OH
ArOH  (CH 3 )2 SO 4   ArOCH 3  CH 3HSO 4

(g) In presence of acids alcohols as well as phenols add to C=C double bond to form dialkyl
ethers as well as alkyl aryl ethers. The reaction with phenols is slower than that with alcohols.
Chemistry : Alcohols, Ethers and Phenols

R H
O H3C

CH 3 — CH  CH 2  H  H3C CH CH3 CH OR

H3C

CH 3 — CH  CH 2  H  H3C CH CH3

O
Ph H

H3C H3C
+
CH O Ph CH O Ph

H3C H3C H

Epoxides or Oxiranes
Oxiranes or epoxides contain 3-membered rings in which two are C-atoms and one is an O atom
and hence oxiranes may be called derivatives of ethylene oxide they may also be called
expoxides or alkene oxides.
O O O

H3C
H2 C CH2 H3C HC CH2 CH2

Ethylene oxide Propylene oxide H3C

Isobutylene oxide
Preparations
1. Per acid C C (already discussed
C C   in hydrocarbon
R O H
O O chapter)
O

2. – (already discussed
C C OH
  C C in alkyl ary halides
chapter)
OH X O

2.5 Reaction of Ethers


(a) Formation of oxonium salts: The ethers are basic (pKa of R 2 O H is
approximately –35). They form salts with protonic and Lewis acids at a low temperature. If a
solution of hydrogen chloride in dry diethyl ether is cooled to a low temperature, a crystalline
oxonium salt is obtained.
 Chemistry : Alcohols, Ethers and Phenols

CH3 — O — CH3  HCl 

 H3C O CH3 Cl (m.p. – 97°C)

 Et
Et — O — Et  HCl  O Et Cl (m.p. – 92°C)

Et — O — Et  2HCl 
 Et O Et 2Cl – (m.p. – 88°C)

R — O — R  BF3 R O BF3

R — O — R  H 2SO4 R 2 O— HHSO 4–

(b) Reaction with dil. sulphuric acid: When ethers are heated with dilute sulphuric
acid under pressure, alcohols are obtained.
dil. H 2SO4
R 2 O  H 2 O  press
 2ROH

R R H R
H 3O 
R O R O H  H 2 O 
 O R O H

R H R


–H O R O H
ROH  H O  ROH 
 

H
H

(c) Reaction of hydrohaloacids: When ethers are treated with hydroiodic acid or
hydrobromic acid in cold, an alcohol and an alkyl halide is formed.
R — OR 1  HI(HBr) 
R — I(RBr)  R 1OH

Ar — OR 1 HI 
 ArOH  R 1I
Usually methyl iodide is formed when one of the hydrocarbon group is methyl; however, if there
is a 3° alkyl group, a 3° alkyl iodide and methyl alcohol are formed. In this connection it is
important to note that HI is more reactive than HBr. The reaction may follow the SN1 or the SN2
pathway.
Chemistry : Alcohols, Ethers and Phenols

 
slow
 R 2 O HI – ; R 2 O H
R 2 O  HI  ROH  R  ; R   I – 
 RI
R H
–
I– R O H I R O R I — R  ROH


When ethers are heated with HI (HBr) two moles of alkyl iodides (bromides) are obtained; at first
an acohol and an alkyl iodide is formed and then the alcohol changes to the alkyl iodide again
either by the SN1 or by the SN2 pathway.
R — OH  HI 
 RI  H 2O
Ethers are also readily cleaved by Lewis acids.

 R 2O
R 2 O  AlCl3 
 R 2 O— AlCl3   RCl  R — O — AlCl2   RCl

R 2O
RCl  (RO)3 Al   R — O — A lCl — OR
Triphenyl phosphine dibromide also splits ethers
125 C
R 2 O  Ph 3PBr2   2RBr  Ph 3PO
(d) Oxidation: Strong oxidizing agents like potassium permanganate and sulphuric acid or
dichromate and sulphuric acid oxidize an ether to a carbonyl compounds. The alkyl groups
present in the ether determine the nature of the carbonyl group to be formed.
K 2 Cr2 O7
CH 3CH 2 — OCH(CH3 ) 2 
H 2SO4 (conc.)
 CH 3CHO  (CH 3 ) 2 C  O  H 2O  H.
The ether linkage is a very unreactive functional group. Ethers have similarities with
hydrocarbons. Ethers do not react with metallic sodium and phosphorus halides; whereas
isomeric alcohols (ethers are structural isomers of alcohols) react with them. On the other hand
ethers are soluble in concentrated sulphuric acid at a low temperature whereas hydrocarbons are
insoluble in concentrated sulphuric acid.

EXERCISE 7:
Me anh HI A

Me C O CH3

Me conc. HI B

Identify A and B with proper explanation.

2.6 Uses of Ethers

Ethers are mostly used as solvents and extracting agents for organic compounds. Methyl ether,
ethyl ether, is-propyl ether, iso-amyl ether, tetrahydrofuran, dioxane and diglime deserve mention
in this respect. Methyl ether is also used as a propellant for aerosol sprays. Others are used as
solvents for the Grignard reagents. dichloroethyl ether is used as a selective solvent for removing
sludgeforming materials from lubricating oils.
 Chemistry : Alcohols, Ethers and Phenols

3. PHENOLS
3.1 Introduction: Compounds that have a hydroxyl group directly attached to a benzene
ring are called phenols. Thus, phenol is the specific name for the hydroxyl benzene, and it is the
general name for the family of compounds derived from hydroxyl benzene. Phenols are having
the general formula ArOH, where Ar is phenyl, substituted phenyl, or some other aryl group.
OH OH OH COOH
Cl

CH3
phenol O-chlorophenol m-cresol
OH
p-hydroxybenzoic acid

OH OH Cl
OH

OH OH
pyrocatechol resorcinol OH OH
hydroquinone 4-chlorophenol

Br
NO2

OH
OH
2-nitrophenol 3-bromophenol

3.2 Structure and Physical Properties of Phenols

The simplest phenols are liquids or low melting solids; because of H-bonding, they have quite
high boiling points. Phenol is somewhat soluble in water (9g per 100 g of water) presumably
because of H-bonding with water; most other phenols are essentially insoluble in water. Unless
some groups capable of producing colour is present, phenols themselves are colourless.
The O atom of the phenolic OH group is in sp2 hybridised state. It holds two lone pairs of
electron one in a pA.O and the other on sp2 AO; the OH group lies on the plane of the ring. The p
A.O. is parallel to the p A.Os of the aromatic ring and perpendicular to the ring. The p electrons
of the —OH group, therefore undergo p-π conjugation and delocalise over the ring. Thus, the
structure of phenol is supposed to be a resonance hybrid of the following resonating structures.
O OH O OH OH OH
Chemistry : Alcohols, Ethers and Phenols

(i) There is no doubt that owing to the –I effect of the –OH group, the ring is somewhat
deactivated; where as the +R effect of the –OH group activates the ring to a great extent
eliminating the deactivating effect due to –I effect. Therefore the net result of –I and +R
effects of the –OH group is the activation of the ring.
(ii) Phenol has a dipolemoment 1.70D, the negative end of the dipole points towards the ring.
Thus the O—C bond has some double bond character; the O atom also bears a small
amounts of +ve charge while two o- and the p-carbons bear very small amounts of
negative charge; the o-atom being +vely charged, it draws electrons of the O—H bond
appreciably and thus makes the H atom to bear reasonable amount of positive charge.
Further more, a phenol (except 1, 3, 5 trihydroxy benzene) does not exhibit keto-enol
tautomerism; because the keto form does not possess Huckel number of π electrons and
therefore it is not aromatic and possess high amount of internal energy. So a phenol does
not show properties of ketone.
Since the ring of a phenolic compound is activated one, it will undergo aromatic
electrophillic substitution reaction more readily than benzene but nucleophilic
substitution reactions less readily; for the same reason ring will rupture very readily by
the oxidizing agents. The presence of activating groups will increase this character.
However, if there are electron withdrawing groups e.g. nitro, carboxyl etc. at the o- and p-
positions, they will deactivate the ring and as a consequence nucleophilic substitution,
instead of electrophilic, will be favoured and the ring will be resistant towards oxidation.
Since o-and p-positions are partially negatively charged, the electrophilic substitution in
phenol will occur at o- and p-position.
(iii) Simplest phenols are liquids or low-melting solids; because of hydrogen bonding, they
have quite high boiling points. This is due to the fact that the phenol molecules associate
among themselves through intermolecular H-bonding.
Ph Ph

O O O
Ph H H H

(iv) Phenol itself is somewhat soluble in water, presumably because H-bonding with the
water; most other phenols are essentially insoluble in water.
(v) An important point emerges from a comparison of the physical properties of the isomeric
nitro phenols. We notice that o-nitrophenol has a much lower boiling point and much
lower solubility in water than its isomers; it is the only one of the three that is readily
steam distillable. How can these differences be accounted for? This is due to the fact that
the there is extensive intermolecular H-bonding in o-nitro phenol whereas there are
intermolecular H-bonding in m-and p-nitro phenols.
 Chemistry : Alcohols, Ethers and Phenols

O O H O
O N
N O

H
O
N
H O O O

3.3 Preparations of Phenols

(a) Hydrolysis of Chlorobenzene (Dow Process): In this process chlorobenzene is

heated at 350°C (under high pressure) with aqueous sodium hydroxide. The reaction products
sodium phenoxide, which on acidification, yields phenols. The mechanism for the reaction
probably involves the formation of benzyne (discussed in alkyl aryl halides).
- +
Cl O Na
350°C
 2NaOH 
(high pressure)
  NaCl + H 2 O

- +
O Na OH

 HCl  NaCl

(b) Alkali Fusion of Sodium Benzene Sulfonate: Sodium benzene sulfonate is

melted (fused) with sodium hydroxide (at 350°C) to produce sodium phenoxide. Acidification
then yields, phenol.
- +
O Na
- +
SO3 Na
350°C
+ 2NaOH   + Na 2SO3 + H 2O

Sodium benzene
sulfonate

CH3 CH3 CH3

NaOH (72%)_ 

 KOH(28%)
 H 3O
 
300 350C

- + - +
SO3 Na O Na OH
Sodium p-toluene
sulfonate
Chemistry : Alcohols, Ethers and Phenols

(c) From Cumene Hydroperoxide: Most of the world wide production of phenol is
now based in this method. The synthesis begins with Friedel-Crafts alkylation of benzene with
propene to produce cumene (isopropyl benzene).
H3C CH3

H2C 250C

H 3PO4

CH3
cumene

The cumene is oxidized to cumene hydroperoxide.

CH3 CH3
95 135 C
 O 2   O
CH3 CH3 O H
Cumeme hydroperoxide

Finally, when treated with 10% sulfuric acid, cumene hydroperoxide undergoes a hydrolytic
rearrangement that yields phenol and acetone.
OH
CH3 H3 C
H3 O 
O 
  O
50 90 C
CH3 O H
H3 C

Mechanism
CH3 H3C CH3
H3C H O PO3 H 2

H2C H3PO 4  H3PO 4

  
  H3C 

CH3 CH3

the second reaction is a radical chain reaction. A radical initiator abstracts the benzylic hydrogen
atom of cumene, then producing a 3° benzylic radical. Then a chain reaction with oxygen
produces cumene hydroperoxide chain initiation.

Step 1: CH3 CH3

H5 C6 H R H5 C6  R H
CH3
CH3
Chain propagation
 Chemistry : Alcohols, Ethers and Phenols

Step 2: CH3
CH3

H5 C6  OO H5 C6 O

CH3 CH3 O
Step 3: CH3 CH3 CH3 CH3

H5 C 6 O  H C 6 H5 H5 C 6 O  H5 C6

O CH3 O H CH3
CH3 CH3
CH3
Step 4: CH3 H3C H
 H 2O H2O +
O  H  OH 2   O   O O
loss of water and concurrent
phenyl migration with an
CH3 OH2 electron pair on oxygen H3C C 6H5 H C6 H 5
CH3

H3C CH3
 H 3O 
C 6 H 5 OH + O  O O

H3C H CH3 C6 H 5
H2O

EXERCISE 8:

O2N Me

H 2O / H
C  ?
Me2 N O OH

(d) Aromatic Nucleophilic Substitution

When p-chloro nitro benzene as well as (or m or p) is heated with aqueous sodium hydroxide p-
nitro phenol is formed.
- +
Cl O Na

 2NaOH 
  NaCl  H 2 O

NO2 NO2

(e) Hydrolysis of Diazonium Salts: When benzene diazonium sulphate solution is

steam distilled, a phenol is produced.

ArN 2 HSO14  H 2O 
 ArOH  N 2  H 2SO 4
Chemistry : Alcohols, Ethers and Phenols

Distillation of phenolic acids with soda lime produces phenols e.g. sodium salicylate gives
phenol.
- +
CH3 O Na

 NaOH(CaO) 
  Na 2 CO3
- +
COO Na

3.4 Reaction of Phenols

(a) Oxidation:
OH O

O2

CrO3 or HNO3


(b) Reduction:
OH OH

Ni / H 2

175 C,1atm


(c) Like R—OH, phenols do not react with HX, PX3, SOCl2 etc. Phenols can be converted
into benzene by distillation with Zn dust.
OH

Zn  dust

distilation
  ZnO

When phenol is treated with an aldehyde in presence of an acid, an electrophilic substitution

takes place leading to ortho and para phenol alcohols (Laderer Manasse reaction).

 
R — CH  O  H  
 R — CH  O H 
 R — CH — OH

OH OH OH


 

R

HC HO H
R R OH
OH
 Chemistry : Alcohols, Ethers and Phenols

Based catalysed
O O O


 


H R
O R OH
R

(d) The Kolbe’s Schmidt Reaction

Carboxylation of phenoxides by carbon dioxide at an elevated temperature under pressure is

called the Kolbe Schmidt reaction. Salicylic acid, (o-hydroxy benzoic acid), is commercially
prepared by the reaction. A small amount of p-hydroxy benzoic acid also forms.
- + - + O O
O Na O Na OH

O OH
220 C HCl
 CO 2 
6 7 atm
 

Mechanism
+
Na
O O
- + + +
O Na ONa ONa H
O H O
H O

 C 

O
O

- +
O Na
COO

When potassium salt of phenol is used, perhaps chelation does not happen to occur of high
volume and low positive charge density on the metal ion; owing to the absence of chelation in the
case of potassium salt, the o-product is not the major product. Since chelation brings stability to
the complex of sodium phenoxide and carbon dioxide, the o-product is formed in large excess
over the p-product.
Acetyl salicylate (aspirin), an analgetic and antipyretic, is prepared by heating salicylic acid,
acetic anhydride and glacial acetic acid.
Chemistry : Alcohols, Ethers and Phenols

OH OAc
AcOH
 Ac2 O 
 
O O

OH OH
Aspirin

(e) Nitration: Phenols are very susceptible to oxidation for the reason they cannot be
nitrated by nitric acid and sulfuric acid mixture. However, they can be nitrated by dilute
nitric acid.
(f) Nitrosation: When phenols are treated with nitrous acid, p-nitro phenols are obtained.

HNO2 H   NO 2

H  O  N  O  H H  OH  N  O H 2O  NO 

+ H + H
OH O O OH OH


 
 


H NO H NO
NO N
O

(g) Mercuration: When phenol is refluxed with aqueous mercuric acetate, usually o-
acetoxy mercuric phenol is formed as a predominant product. This mercuric compound
can be converted to iodophenol.
OH OH OH OH
HgOAC HgCl I
Hg(OAC) 2 Aq. NaCl I 2 / CHCl3

reflux
 
 


(h) Reimer-Tiemann Reaction: Formylation of phenols by the reaction with

chloroform in strong and aqueous base (e.g. NaOH) is known as Reimer Tiemann
reaction. When phenol is subjected to the reaction, sodio salts of o-hydroxy benzaldehyde
(major) and p-hydroxy benzaldehyde are formed in the ratio 4:1; the hydroxyl aldehydes
are obtained on acidification of sodio salts.
Mechanism
Initial step: Formation of dichlorocarbene
Cl Cl Cl

HO  + H Cl  H2O +
 Cl 
 C  Cl

Cl Cl Cl
 Chemistry : Alcohols, Ethers and Phenols

Step 1: Electrophilc attack on the o and p – C of the phenol by dichlorocarbene.

OH O O O O


OH
  
 
 


Step II: Aromatisation of A to B by H+ shift

O O Cl
H Cl
Cl


Cl

Step III:
O Cl O OH

Cl - O H 3O  O
1.OH

2. 
  

salicylaldehyde

Similarly,
O O O O OH

- H 3O
1.OH
CCl2
  
 
2. 
  

H H Cl
Cl Cl O O
Cl

dilute nitric acid.

When p-methyl phenol is subjected to the Reimer-Tiemann reaction, among other products
compound D is formed. This supports the aromatization step of the mechanism as shown above.

OH O O O O

 
OH
  
 CCl2
  H 3O
 

CCl2 H3C Cl H3C Cl

CH3 CH3 CH3
Cl Cl
(C) (D)
Chemistry : Alcohols, Ethers and Phenols

Since there is no H-atom at the para position, aromatization of (C) cannot occur. Furthermore,

because of the special congestion and insolubility of (C), the hydrolysis of  C Cl2 group to
–CHO does not take place under reaction conditions.

EXERCISE 9:
OH
OH

Convert 
 CH (Not more than 3 steps)

OH

Illustration 5: Give the mechanistic steps of the following reaction.

O
OH OH

1. NaOH/ OH
 CCl 4 
2. H O

3

Solution: OH
O O O

OH
  
 


O O O O
OH 

 
 Cl 
 OH
H
H Cl
Cl OH
Cl Cl Cl HO
Cl
Cl Cl

Cl OH O O
H3 O OH
O

 

O O

OH O OH
 Chemistry : Alcohols, Ethers and Phenols

(i) Sulphonation: When phenol is treated with cold concentrated sulphuric acid at 0°C, a
mixture of o- and p-phenolsulphuric acid are obtained; at a higher temperature p-product
is formed as major product o- and p- halophenols can be prepared from haloarenes, via
sulphonation.
OH OH OH OH

SO3 H
100 C 0 C
H 2SO 4

H 2SO 4


SO3 H SO 3 H

(j) Friedel Craft’s Alkylation of Phenols

O

Friedel Craft’s akylation or alylation of phenol with R—X/ AlCl3 or R C X/AlCl3 gives
very poor yield of (conc.) because AlCl3 gets coordinated with o-atom of phenol.
OH
CH CH  CH 2 H 2SO4
C 6 H5 OH   3 
or HF
 o  and p  C6 H 4  H 2O
 (CH3 ) 2 CHOH
CH(CH 3 ) 2
(k) Fries Rearrangement: When phenol is treated with acid chloride it gets converted
to an ester which on treatment with anh. AlCl3 converted into o-and p-acyl phenol (o-product
being major owing to intra molecular H-bonding).
O

OH O O R OH O OH

R Cl R
 AlCl3

heat
 

O R

Mechanism
O
Cl O Cl
Cl Cl
Al + Al +
R O AlCl3 O R O O OH O
Cl Cl
R
H H 2O
R

 
  

(h) Halogenation: Chlorine and bromine form the precipitate of 2,4,6-trihalo phenol
immediately when they are treated with phenol in aqueous medium. In water phenol ionizes to
phenoxide ion, the PhO– ion has no –I effect but has a strong +R effect. Owing to the strong +R
effect, the ring of the phenoxide ion is highly activated and can undergo electrophilic substitution
Chemistry : Alcohols, Ethers and Phenols

reaction readily (much readily than phenol itself). When chlorination or bromination is carried
out in non-aqueous solvents of (e.g. in carbon disulfide halogenation, the ring (being less
activated than phenoxide ion ring owing to the –I effect and low +R effect of the –OH group), the
ionization of phenol does not occur and mono-halogenation takes place.
OH O O
Br Br
H 2O + 
  Br2(aq) 


 H 3O  Br
OH OH OH
X

 X 2 (Cl 2 or Br2 )  CS2 

However, phenols can be indirectly halogenated via diazonium ion.

(m) Preparation of Ethers from Phenol
(i) Reaction with diazomethane: A methyl ether is formed when diazomethane or
dimethyl sulfate is allowed to react with phenols. No Lewis acid is required for the reaction.

+ +
O  H2 C N 
 O  H3C N

H N
N

O
CH3

O
O
Base
OH 
 O H3C S
O
O
CH3

O  O S O
CH3 CH3
O

(ii) The Williamson synthesis and the Ullmann reaction: When alkyl halides
are treated with sodio salt of phenols, alkyl aryl ethers are formed. Diaryl ethers may be prepared
by the Ullmann reaction.
 Chemistry : Alcohols, Ethers and Phenols

ArO Na  R  Cl 
 ArOR  NaCl

Ph
  Cu powder
ArO Na  Cl NO2  150 C
O NO2

(properly in 2,6-dimethyl-4-nitrophenol which is a stronger acid than 3,5-dimethyl-4-

nitrophenol).

(n) Ester formation: When phenols are warmed with aryl halides or acid anhydrides,
they form esters; but the reaction is much slower than esterification of alcohols by the same
reagents. Phenol can not react directly with acid (e.g CH3COOH or CH3CH2COOH) to produce
ester. The reaction follows the mechanism where phenols act as nucleophiles. Since the lone pair
of electrons on the o atom in phenol gets delocalized through p –  overlapping , they are not
readily available for nucleophilic attack and consequently the reaction takes place slowly.

R Ph R Ph O
+
Ph O  O 
 O O 
 R

H Cl H Cl O

O O
O O Ph O
Ph O  O  Ph
 +


O R
H R O R CH3
O
H
H3C

(o) The Diazonium Coupling Reaction

Aromatic diazonium ions combine with phenoxide ions and aromatic tertiary amines to form a
large number of azodyes and this sort of reactions are known as the diazonium coupling reaction.
In this reaction the diazonium salt is called the primary component and the compound with which
the diazonium ion couples is called the secondary component. Benzene diazonium ion couples
with sodium phenoxide in cold alkaline medium and forms an azodye.

Example

N N ONa N N ONa

Primary component Secondary component Azodye

Chemistry : Alcohols, Ethers and Phenols

Mechanism:

N N
O N N O
H

HO N N

3.5 Acidity of Phenols

Although phenols are structurally similar to alcohols, they are much stronger acids. The pKa
values of most alcohols are of the order of 18.
(a) Reaction with Grignard Reagent: Since the phenols are acidic, they will react
with the Grignard reagent to form hydrocarbons.
ArOH  RMgX 
 ArOMgX  RH
Furthermore, if there is steric inhibition of resonance involving either the +R effect of the
phenolic OH group or the electron with drawing –R effect of the phenolic OH group, the acidity
of the phenol decreases. The pKa values of the following phenols support the explanation as
stated above.
pKa Reason
OH 7.14 –I and –R effects of the NO2 group pull is 1 electron of the –OH

NO2
OH 7.22 –I and –R effects of the NO2 group pull electrons of the OH and
H3C CH3 +I effect of the two Me group push the electrons.

NO2
OH 8.25 Since two Me groups and the NO2 group are very close to each
other, they cannot lie in the same plane owing to their bulk. The
NO2 group rotates around the C – N bond to avoid steric strain.
Thus, the aromatic ring cannot involve itself properly in the p–
H3C CH3 conjugation, hence it cannot withdraw the lone pair of electrons
NO2 of the hydroxyl group appreciably and as a consequence the
acidity of 3,5-dimethyl-4-nitrophenol is less than our
expectation.
 Chemistry : Alcohols, Ethers and Phenols

However the acidity of phenol increases as the presence of electron withdrawing groups at o- and
p- positions increases; while the acidity decreases as the presence of electron releasing groups
increases in the ring.

Name pKaq (in H2O at 25°C)

Phenol 9.89

2-methyl phenol 10.20

3-methyl phenol 10.17

2-chloro phenol 10.01

3-chloro phenol 8.11

4.-chloro phenol 9.20

o-nitrophenol 7.23

p-nitrophenol 7.14

m-nitro phenol 8.35

2,4-dinitro phenol 3.96

2,4,6-Trinitro phenol (Picric acid) 0.38

(b) Reaction with Bases: PhOH is weakly acidic, its pKa value is 10. Any base whose
conjugate acid is weaker than phenol will react with the latter to form salt. Thus NaOH, KOH
etc., react with phenol to form Na or K phenoxide and water; water is the conjugate acid of the
base NaOH or KOH which is a weaker acid than phenol.
ArOH  NaOH ArO Na   H 2O

Since carbonic acid (pKa = 6) is a stronger acid than phenol, sodium bicarbonate does not form salts
with phenols (except di and trinitro phenols). This fact has been utilized to differentiate carboxylic
acids from phenols. Carboxylic (pKa = 4.5) being stronger than carbonic acids, the former compounds
react with sodium bicarbonate to form sodio salt and evolve carbon dioxide. If a saturated aqueous
solution of sodium bicarbonate evolves CO2 on treatment with organic sample is either a carboxylic
acid or a sulphuric acid. However, alcohols are weaker acid than phenols.

PhOH  NaHCO3 PhO Na   H 2 CO3

(carbonic acid )

The conjugate bases of alcohols are RO–, the alkoxide ions; the negative charge on O atom has
no scope to delocalize and so they are strong bases and naturally alcohols are very weak acids.
On the other hand the negative charge on O atom of the phenoxide ion, conjugated.

Illustration 6: Identify A and B on the following reactions are also

Chemistry : Alcohols, Ethers and Phenols

OH

conc. HBr

HNO3
A  B

Solution: OH O OH

conc. HBr

HNO3
   
Br
O OH
benzo-1,4-quinone

Mechanism

O OH OH OH


H
  
Br  

H
Br
Br
O O O OH

EXERCISE 10:
Find the product and explain the mechanism
HO CH3


H
 ?
H3C
O

3.6 Claisen Rearrangement

This is the rearrangement of alkyl aryl ethers to alkyl phenols. No catalyst is required and it
occurs when the substrate is heated alone to about 200°C or in some inert solvent eq. diphenyl
ether. Alkyl group migrates to the o-position if one is free, but if ortho positions are occupied
then migration occurs to p-position, e.g.,
 Chemistry : Alcohols, Ethers and Phenols

CH2

O OH
CH2 (exclusive)
200C
 

O OH
CH2
H3C CH3 H3C CH3
200 C
  (85%)

H2C CH CH2

The mechanism of the claisen rearrangement has been the subject of a great deal of work. The
intramolecular nature of the rearrangement has been demonstrated by the fact that of two different
ethers are heated together, they rearrange independently. If the alkyl group labeled with 14C at the r-
carbon atom, also showed that the rearranged product contained the tracer to the nucleus.
CH2

O OH
CH2 CH2

Mechanism:
O
O O CH3
CH2
slow
slow
CH2 CH CH2

fast

OH
CH2

The mechanism of the p-rearrangement is believed to occur in two stages each one with reversal
and thus final product will not be reversed.
Chemistry : Alcohols, Ethers and Phenols

CH2

H2CO OH
H3C CH3 H3C CH3

CH2

The Sigmatropic Rearrangement : The thermal or photochemical converted step

rearrangement involving cyclic T.s. in which  -bond, flanked by one or two  -orbitals shift
intramolecularly from one atom to another with the conversation of orbital symmetry is known as
sigmatropic rearrangement. The claisen rearrangement is a thermal sigmatropic rearrangement
involving [3, 3] shift.
3.7 Identification of Phenol
When a few drops of freshly prepared ferric chloride solution are added to an aqueous solution or
alcoholic solution of a phenol, violet or green or blue colour water is observed, the color may be
transient or permanent. Fe3+ has a coordination no. 6 and six phenoxide ions may coordinate with
the Fe (III) to form hexacoordinated complex which may impart the colour or it may be that
ferric ion oxidizes the phenol and oxidation product exhibits the colour or it may be that both
complexation and redox reaction occur at a time. However enols give colouration with ferric
chloride; in fact phenols being enols, they also undergo the reaction.
OH O

 H 2O  H3O ;

Fe3   [Fe(OC 6 H5 ) 6 ]3– 


2
OFe