Unit – 11 ALCOHOLS, PHENOLS & ETHERS

The main topics covered in this part are:

Alcohols

1. Classification
2. Nomenclature
3. Preparation
4. Physical properties
5. Chemical properties
6. Test for distinguishing 1o, 2o and 3o alcohols
7. Commercially Important Alcohols
8. Methanol: preparation, properties and uses
9. Ethanol: preparation, properties and uses
10.Denaturation of alcohol

ALCOHOLS:

An alcohol is any organic compound in which the hydroxyl functional group (–

OH) is bound to a saturated carbon atom. For example: methyl alcohol, CH3OH;
ethyl alcohol C2H5OH, etc.

Classification of alcohols:

(i) On the basis of  number of carbons attached to the α-carbon, i.e., the
carbon to which the OH group is attached, alcohols are classified as:

Primary (1o) alcohol:
This type of alcohol has only one carbon atom attached to the α-carbon
atom.

For example:
 Secondary (2o) alcohol:

Here α-carbon has two other carbon atoms attached to it.

For example:

Tertiary  (3o) alcohol:

In such alcohol three other carbon atoms are attached to the α-carbon
atom.

(ii) On the basis of number of hydroxyl groups (−OH) present, alcohols

can be divided into the following categories:

Monohydric alcohols:

They contain only one OH group. They have a general formula C nH2n+2O.

For example: CH3OH, CH3CH2OH, CH3CH2CH2OH, etc.

Dihydric alcohols:

Such alcohol contains two OH groups. For example:

 Trihydric alcohols:

This type of alcohol contains three OH groups. For example:

Polyhydric alcohols:

These are the alcohols that contain more than three OH groups.

Nomenclature of alcohols:

IUPAC naming system:

(i) Select the longest possible chain that contains the α-carbon

(ii) Number the carbon atoms in the chain in such a way that α-carbon gets the
minimum number

(iii) Then identify the hydrocarbon group and name it as per the IUPAC naming
system.

(iv) Now replace the ‘e’ in the end of the parent hydrocarbon name by ‘ol’.
Common naming system:

The Common name of alcohol is alkyl alcohol.

Depending upon the upon the structure of the alkyl group, prefix n, iso, sec, tert
or neo is added to the common name.

‘n’ is added when α-carbon and other carbon atoms make a straight chain.

For example:

          

 ‘Iso’ is added when the ─OH group is attached to

           

For example:

           

‘sec’ is added when the α-carbon is attached to two other carbon atoms.

For example:

            

‘tert’is added when the α-carbon is attached to three other carbon atoms.

For example:

            

‘Neo’ is used when quaternary carbon is present. For example:

            

Preparation of alcohols:

General methods of preparation of alcohols are described below:

(a) From alkenes:

(i) By acid catalysed hydration of alkenes in accordance with

Markownikoffs rule.

(ii) By hydroboration-oxidation of alkenes in accordance with anti-

Markownikoffs rule.

(b) From carbonyl compounds:

(i) By catalytic hydrogenation of aldehydes and ketones.

 Note :  Aldehydes yield primary alcohols whereas ketones give
secondary alcohols.

(ii) By catalytic reduction of carboxylic acids and esters.

(c) Form Grignard reagent, RMgX:

It gives R group as a nucleophile to attack at the partrially positive carbon

atom of carbonyl (–C=O) group.

Physical properties of alcohols:

1. Lower alcohols are liquid at room temperature while higher ones are
solid.
2. The boiling point of alcohols is higher than haloalkanes with the same
number of carbon atoms. This is due to the fact that alcohols are
associated via intermolecular hydrogen bonding. For the same alcohol, as
the branching increases, boiling point decreases due to decrease in
surface area.
3. Lower alcohols are completely miscible in water due to their ability to
form hydrogen bonds with water. Solubility in water decreases with
 increase in molecular mass due to a decrease in the extent of
intermolecular hydrogen bonding.

4. Alcohols are weaker acids than water due to the lower polarity of O – H
bond in alcohols. The acidic strength of alcohols decreases as the number
of electron donating groups increase at carbon.

Chemical properties of alcohols:

(a) Reactions of alcohols involving cleavage of  O – H bond

1. Reaction with metals:

2. Reaction with carboxylic acid (Esterification):

3. Reaction with Grignard reagent:

(b) Reactions involving cleavage of C – O bond:

For the reaction involving cleavage of C – O bond, the reactivity order is

1. Formation of halides:
(c) Oxidation of alcohols:

Depending upon the structure of the alcohol and the type of oxidising
agent used, oxidation of alcohol gives different products.

(d) Dehydration of alcohols:

Dehydration of alcohols with conc. H2SO4 at different temperatures yields

different products.

The ease of dehydration of three alcohols increases in the order

       1o ROH < 2o ROH < 3o ROH

(e) Dehydrogenation of alcohols:

 Dehydration of alcohols takes place in acidic medium. Intra-molecular
dehydration leads to the formation of alkene while inter molecular
dehydration forms ether.

Order of ease of dehydration is: 3° > 2° > 1°

Test for distinguishing 1o, 2o and 3o alcohols:

Lucas reagent which s a mixture of conc. HCI and anhyd. ZnCl2 is used to
distinguish   and   alcohols.

•    3o alcohol gives cloudiness or turbidity with Lucas reagent immediately.

•    2o alcohol gives cloudiness or turbidity after 5 – 10 min.
•    1o alcohol does not give cloudiness or turbidity at room temperature.

Commercially Important Alcohols:

Two commercially important alcohols are methanol and ethanol.

1. Methanol, CH3OH

Preparation:

Methanol is mainly produced by catalytic hydrogenation of carbon monoxide at

high pressure and temperature and in the presence of ZnO – Cr2O3 catalyst.

Properties:
•    It is a colourless liquid and highly poisonous.
•    It is completely soluble in water.

Uses: It is used as a solvent for paints, varnishes, and for making

formaldehyde.

2. Ethanol, C2H5OH:

Preparation:

Ethanol is mainly obtained commercially by fermentation of sugars. The sugar

sugarcane or fruits such as grapes is converted to glucose and fructose, in the
presence of an enzyme, invertase. Glucose and fructose on fermentation in the
presence of another enzyme, zymase, yield ethanol.

Properties:

•    Ethanol is a colourless liquid.

•    The boiling point of ethanol is higher than methanol.

Uses:

•    It is used as s solvent in paint industry.

•    It is also used in the preparation of a number of carbon compounds.

Denaturation of alcohol:

The commercial alcohol is made unfit for drinking by mixing in it some copper
sulphate and pyridine. This is known as denaturation of alcohol.

PHENOLS:

The main topics covered in this part are:

 1. Classification
2. Nomenclature
3. Preparation
4. Physical properties
5. Chemical properties
6. Kolbe’s reaction, Reimer-Tiemann reaction, Fries rearrangement
7. Uses of Phenol

Phenols are the compounds formed when a hydrogen atom in an aromatic ring,
is replaced by a hydroxyl group (-OH group).
For example:

              

Classification of phenols:

On the basis of number of hydroxyl groups (−OH) present, phenols can be

divided into the following categories:

1. Monohydric phenols:
They contain only one OH group.

For example:

               

2. Dihydric phenols:
Such phenols contains two OH groups.

For example:
             

3. Trihydric alcohols:
This type of phenol contains three OH groups.

For example:

      

Nomenclature of Phenols:

Common naming system:

[A] The simplest hydroxy derivative of benzene is a phenol. Phenol is the

common name as well as an accepted IUPAC name of the compound.

In the case of substituted phenol compounds, the terms ortho (1,2-

disubstituted), meta (1,3-disubstituted) and para (1,4-disubstituted) are
often used as prefixes in the common names.

For example:

[B] IUPAC naming system:

IUPAC names for some important phenolic compounds are given below:
Structure of phenol:

In phenols, the –OH group is attached to sp2 hybridised carbon of an aromatic

ring. The C–O bond length (136 pm) in phenol is slightly less than that in
methanol. This is due to (i) partial double bond character caused by the
conjugation of unshared electron pair of oxygen with the aromatic ring and (ii)
sp2 hybridised state of carbon to which oxygen is attached. The C−O−H bond
angle in alcohols is slightly less than the tetrahedral angle (109°-28′) due to the
repulsion between two lone pairs of electrons present on oxygen.

            

Preparation of phenol:

General methods of preparation of phenols are described below:

(a) From benzene sulphonic acid:

(b) From haloarenes:

(c) From diazonium salt:

Commercial Preparation:

Phenol is prepared commercially by cumene-phenol process in which cumene

(isopropylbenzene) is oxidised to cumene hydroperoxide which on treating
with dilute acid yields phenol and acetones.

Physical properties of Phenols:

1. Phenols are colourless liquids or crystalline solids but become coloured

due to slow oxidation with air.

2. Due to the presence of strong intermolecular hydrogen bonding, phenols

have a higher boiling point than the corresponding hydrocarbon or aryl
halides.

3. Due to their ability to form hydrogen bonds with water, phenols are
moderately soluble in H2O.

4. The phenols are acidic in nature and stronger acids than alcohols. This is
due to the fact that the sp2 hybridised carbon of phenol to which −OH is
attached, is highly electronegative which causes a decrease in electron
density on oxygen. This Increases the polarity of O−H bond and results in
an increase in ionisatlon of phenols than that of alcohols.
Moreover, the phenoxide ion so produced is stabilised by the delocalization of
charge in phenol.

Note:  The presence of electron withdrawing group like NO2 group,

increases the acidic strength whereas the electron donating groups
 like an alkyl group decreases the acidic strength. Therefore, the
acidic strength order is:

Chemical properties of phenols:

Eelectrophilic substitution reactions:

The presence of OH group on benzene increases the electron density on the

benzene ring making it more susceptible to attack by an electrophile. The
reactions involving benzene ring are electropnilic substitution reaction. The
presence of OH group makes the orthoand para carbon of benzene more
electron rich than meta position. The OH group is called o ‒, p ‒  directing
group.
Reactions of phenol involving the cleavage of O–H bond:

Kolbe’s reaction:

Reimer-Tiemann reaction:

Fries rearrangement:

Esters of phenol gives phenolic ketones on rearrangement in the presence of

anhydrous AlCl3. This reaction is called fries rearrangement.

Acetylation:
Nitration:

(i) Reaction with dilute HNO3:

(ii) Reaction with conc. HNO3:

Halogenation:

Bromination in solvents of low polarity like CS2:

Reaction of phenol with bromine water:

Reactions of phenol involving cleavage of C−O bond:

1. Reaction with zinc dust:

2. Reaction with ammonia:

Uses of phenol:

1. It is used as an antiseptic.
2. It is used as a disinfectant in household cleaners.
3. It is used in the preparation of resins, dyes, explosives, lubricants,
pesticides, plastics, drugs, etc.

ETHERS:
The main topics covered in this part are:

1. Classification
2. Nomenclature
3. Structure
4. Preparation
5. Physical properties
6. Chemical properties
7. Uses of Ethers

Ethers are the organic compounds in which an oxygen atom is connected to

two alkyl or aryl groups. These are represented by the general formula R-O-R'
where R and R' may be alkyl or aryl groups.
For example:

Classification of Ethers:

On the basis of similarity or dissimilarity of alkyl or aryl groups attached to the

central oxygen atom, ethers are classified into the two following categories:

Simple or Symmetrical ethers:

If R = R', then the ether is called simple or symmetrical ether. For example:

Mixed or Unsymmetrical ethers:

If R ≠ R’, then ether is called mixed or unsymmetrical ether. For example:

Nomenclature of Ethers:

[A] Common naming system:

First identify the alkyl or aryl groups attached to the central oxygen atom.

Then arrange the alkyl or aryl groups alphabetically and write a suffix ether

[B] IUPAC naming system:

In the IUPAC system, ethers are regarded as ‘alkoxy alkanes’ in which the
ethereal oxygen (to which the two alkyl or aryl groups are attached) is
taken along with smaller alkyl group while the bigger alkyl group is
regarded as a part of the alkane.
The oxygen atom is sp3 hybridised and the two bond pairs and two lone pairs of
electrons on oxygen are arranged approximately in a tetrahedral arrangement.
The R−O−R’ bond angle is more than the typical tetrahedral angle of 109°. This
is due to the interaction between the two bulky (–R) groups. The C–O bond
length (141 pm) is almost the same as in alcohols.

Preparation of Ethers:

General methods of preparation of ethers are described below:

(a) By dehydration of 1° alcohols (SN2 reaction):

This method can be used to prepare ethers having primary alkyl groups only.
2° and 3° alcohols on dehydration gives alkenes but not ethers.

(b) By Williamson's synthesis (SN2 reaction):

For example:

Ethers containing substituted alkyl groups (2° or 3°) may also be prepared by
this method.

On the other hand alkyl halides (RX) yield only alkenes as main product.
Physical properties of Ethers:

1. Ethers are polar in nature and have a net di-pole moment even if the two
R and R' groups are similar. This is due to their bent structure.

2. Ethers have a lower boiling point than alcohols which is due to their
inability to associate via intermolecular hydrogen bonding.

3. Lower ethers (containing up to three carbon atoms) are completely

miscible in water. The solubility of ethers decreases as the number of
carbon atoms increases.

4. Due to the presence of electron donating R groups and the lone pair on
oxygen atoms, ethers act as Bronsted bases as well as Lewis bases.

Chemical properties of Ethers:

(a) Reactions of ethers involving C−O bond cleavage:

1. Reaction with hydrogen halides (HX):

For symmetrical ethers:

R ‒ O ‒ R + HX → 2RX + H2O

For asymmetrical ethers:

R ‒ O ‒ R’ + HX → RX + R’‒OH

For a given ether, the reactivity of hydrogen halides follows the order:

HCl < HBr < HI

 For aromatic ethers:

In case of aromatic ether, reaction with HI results in the cleavage of R−O

bond due to the stability of aryl-oxygen bond.

When one of the alkyl group is a tertiary group, the halide formed is a
tertiary halide. This is due to the formation of more stable 3° carbonium
ion.

(b) Electrophilic substitution:

The alkoxy group (-OR) on benzene ring is o- and p-directing and activates
the aromatic ring towards electrophilic substitution.

Some of the important electrophilic substitution reactions of aromatic

ethers are:

1. Halogenation:
2. Nitration:

3. Friedel-Crafts reaction:

Uses of Ethers:

1. Dimethyl ether is used as refrigerant and as a solvent at low temperature.

2. Diethyl ether is used as an anesthesia in surgery.
3. Diethyl ether is also used as a solvent for oils, gums, resins etc.
4. Phenyl ether is used as a heat transfer medium because of its high boiling
point.

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