Alcohols, phenols and ethers

 Alcohols and phenols are formed when a hydrogen atom in a hydrocarbon,

aliphatic andaromatic respectively, is replaced by –OH group.

 The substitution of a hydrogen atom in ahydrocarbon by an alkoxy or aryloxy

group(R–O/Ar–O) yields another class of compounds knownas ‘ethers’, for example,
CH3OCH3(dimethyl ether).

Classification
Alcohols and phenols may be classified as mono–, di–, tri- orpolyhydric
compoundsdepending on whether they contain one, two,three or many hydroxyl
groups respectively in their structures asgiven below:

Monohydric alcohols may be further classified according to the hybridisation of the

carbon atom to which the hydroxyl group is attached.
(i) Compounds containing C sp3- OH bond: In this class of alcohols,the –OH
group is attached to an sp3 hybridised carbon atom of analkyl group. They are
further classified as follows:Primary, secondary and tertiary alcohols: In these
three types ofalcohols, the –OH group is attached to primary, secondary
andtertiary carbon atom, respectively as depicted below:

Allylic alcohols: In these alcohols, the —OH group is attached toa sp3 hybridised
carbon next to the carbon-carbon double bond,that is to an allylic carbon. For
example

Benzylic alcohols:In these alcohols, the —OH group is attached toa sp3—
hybridised carbon atom next to an aromatic ring. For example
 (ii) Compounds containing C sp2- OH bond: These alcohols contain—OH group
bonded to a carbon-carbon double bond i.e., to avinylic carbon or to an aryl
carbon. These alcohols are also knownas
vinylic alcohols.

Ethers:Ethers are classified as simple or symmetrical, if the alkyl or arylgroups

attached to the oxygen atom are the same, and mixed orunsymmetrical, if the
two groups are different. Diethyl ether,C 2H5OC2H5, is a symmetrical ether whereas
C2H5OCH3 and C2H5OC6H5
are unsymmetrical ethers.

Nomenclature:Cyclic alcohols are named using the prefix cyclo and

consideringthe —OH group attached to C–1.

Phenols: The simplest hydroxy derivative of benzene is phenol.

Dihydroxy derivatives of benzene are known as 1, 2-, 1, 3- and

1, 4-benzenediol.

Ethers: According to IUPAC Alkoxy Alkane e.g. CH3OCH2CH2CH3 1-

Methoxypropane

1-Ethoxy-2-nitrocyclohexane
 .
Preparation of Alcohols:

(i) By acid catalysed hydration: Alkenes react with water in the presence of acid
as catalyst to form alcohols.

(ii) By hydroboration–oxidation: Diborane (BH3)2 reacts with alkenes to give

trialkyl boranes as addition product. This is oxidised to alcohol by hydrogen
peroxide in the presence of aqueous sodium hydroxide.

+ B(OH)3

2. From carbonyl compounds:

(i) By reduction of aldehydes and ketones: Aldehydes and ketonesare reduced to

the corresponding alcohols by addition of hydrogen in the presence of catalysts
(catalytic hydrogenation).

(iii) By reduction of carboxylic acids and esters: Carboxylic acids are reduced to
primary alcohols in excellent yields by lithium aluminium hydride, a strong
reducing agent.
3. From Grignard reagents

Alcohols are produced by the reaction of Grignard reagents with aldehydes and
ketones.
The first step of the reaction is the nucleophilic addition of Grignardreagent to the
carbonyl group to form an adduct. Hydrolysis of the adduct yields an alcohol.

The reaction produces -- a primary alcohol with methanal, a secondary alcohol

with other aldehydes and tertiary alcohol with ketones.

Physical Properties
Boiling Points: The boiling points of alcohols and phenols increase with
increase in thenumber of carbon atoms (increase in van der Waals forces). In
alcohols,the boiling points decrease with increase of branching in carbon
chain(because of decrease in van der Waals forces with decrease in surfacearea).
The –OH group in alcohols and phenols is involved in intermolecularhydrogen
bonding as shown below:

.
The high boiling points of alcohols are mainly due to the presenceof
intermolecular hydrogen bonding in them which is lacking in ethersand
hydrocarbons.

Solubility: Solubility of alcohols and phenols inwater is due to their ability to

formhydrogen bonds with water moleculesas shown. The solubility decreases
withincrease in size of alkyl/aryl (hydrophobic) groups. Several of the
lowermolecular mass alcohols are misciblewith water in all proportions.
Chemical Reactions
Alcohols are versatile compounds. They react both as nucleophiles
andelectrophiles.
Alcohols as nucleophiles:The bond between O–H is broken when alcohols react
as
nucleophiles.

Alcohols as electrophiles:The bond between C–O is broken when they react as

electrophiles. Protonated alcohols react in this manner.

(a) Reactions involving cleavage of O–H bond

1. Acidity of alcohols:The acidic character of alcohols is due tothe polar nature

of O–H bond. An electron-releasing group(–CH3, –C2H5) increases electron density
on oxygen tending todecrease the polarity of O-H bond. This decreases the
acidstrength. For this reason, the acid strength of alcohols decreasesin the
following order:

Alcohols are, however, weaker acids than water. This can beillustrated by the
reaction of water with an alkoxide.

This reaction shows that water is a better proton donor (i.e.,stronger acid) than
alcohol. Also, in the above reaction, we notethat an alkoxide ion is a better proton
acceptor than hydroxideion, which suggests that alkoxides are stronger bases
(acids and bases are always stronger than their conjugate counterparts). Hence,
sodium ethoxide is a stronger base than sodium hydroxide
Alcohols act as Bronsted bases as well. It is due to thepresence of unshared
electron pairs on oxygen, which makesthem proton acceptors.
(ii) Reaction with metals: Alcohols react with activemetals such as sodium,
potassium and aluminium to
yieldcorresponding alkoxides and
hydrogen.
 The above reactions show that alcohols and
phenols areacidic in nature. In fact, alcohols and
phenols are Brönstedacids i.e., they can donate a proton to a stronger base (B:).

2. Esterification: Alcohols react with carboxylic acids, acid chlorides andacid

anhydrides to form esters.

The reaction with carboxylic acid and acid anhydride is carriedout in the
presence of a small amount of concentrated sulphuricacid. The reaction is
reversible, and therefore, water is removed assoon as it is formed. The reaction
with acid chloride is carried out inthe presence of a base (pyridine) so as to
neutralise HCl which isformed during the reaction.

(b) Reactions involving cleavage of carbon – oxygen (C–O) bond in alcohols:

The reactions involving cleavage of C–O bond take place only inalcohols. Phenols
show this type of reaction only with zinc.

1. Reaction with hydrogen halides: Alcohols react with hydrogenhalides to

form alkyl halides ROH + HX → R–X + H2O
The difference in reactivity of three classes of alcohols with HCldistinguishes
them from one another (Lucas test). Alcohols are solublein Lucas reagent (conc.
HCl and ZnCl2) while their halides are immiscibleand produce turbidity in solution.
In case of tertiary alcohols, turbidityis produced immediately (within 1 minute) as
they form the halides easily. Secondary alcohols,produced turbidity (within 5
minute). Primaryalcohols do not produce turbidity at room temperature since there
is no reaction.

2. Reaction with phosphorus trihalides: Alcohols are converted toalkyl

bromides by reaction with phosphorus tribromide C 2H5 OH + PBr3 C2H5- Br +
H3PO3.
 3. Dehydration: Alcohols undergo dehydration (removal of a molecule of water)
to form alkenes on treating with a protic acid e.g., concentrated H2SO4 or H3PO4,
or catalysts such as anhydrous zinc chloride or alumina.
Thus, the relative ease of dehydration of alcohols follows the followingorder:
Tertiary>Secondary > Primary

Primary alcohol (Ethanol) undergoes dehydration by heating it with strong

oxidising agent concentratedH2SO4 at 443 K.

Secondary and tertiary alcohols are dehydrated under milderconditions. For

example:

Mechanism of Dehydration e.g. ethanol

Step 1:Formation of protonated alcohol.

Step 2:Formation of carbocation: It is the slowest step and hence, therate

determining step of the reaction.

Step 3:Formation of ethene by elimination of a proton.

 The acid used in step 1 is released in step 3. To drive the equilibriumto the
right, ethene is removed as it is formed.
4. Oxidation: Oxidation of alcohols involves the formation of a carbonoxygen
doublebond with cleavage of an O-H and C-H bonds.

Such a cleavage and formation of bonds occur in oxidationreactions. These are

also known as dehydrogenation reactions asthese involve loss of dihydrogen from
an alcohol molecule. Dependingon the oxidising agent used, a primary alcohol is
oxidised to analdehyde which in turn is oxidised to a carboxylic acid.
Strong oxidising agents such as acidified potassium permanganateare used for
getting carboxylic acids from alcohols directly. CrO3 inanhydrous medium is used
as the oxidising agent for the isolationof aldehydes.A better reagent for oxidation
of primary alcohols to aldehydes in good yield is pyridinium chlorochromate (PCC),
a complex of chromium trioxide with pyridine and HCl.

Secondary alcohols are oxidised to ketones

by chromic anhydride (CrO3).

Tertiary alcohols do not undergo oxidation

Catalytic dehydrogenation:
When the vapours of aprimary or a secondary alcoholare passed over heated
copper
at 573 K, dehydrogenationtakes place and an aldehyde ora ketone is formed while
tertiary
alcohols undergo dehydration.