ALCOHOLS

Introduction

Alcohols are the compounds in which a hydroxyl (-OH) group is attached to saturated carbon atom.

The hydroxyl group is the functional group of alcohols. Alcohols containing one hydroxyl group are called
Monohydric Alcohols. Alcohols with two, three or more hydroxyl groups are known as Dihydric alcohols,
Trihydric Alcohols and Polyhydric Alcohols respectively.

Some examples of Alcohols are,

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 Monohydric Alcohols

Monohydric alcohols contain one –OH group attached to a saturated carbon. These are represented as R-OH.

Primary (10), Secondary(20) and Tertiary(30) Alcohols

Monohydric alcohols are classified as primary, secondary or tertiary alcohols, depending upon whether the –
OH group is attached to a primary, a secondary or a tertiary carbon.

Structure of Monohydric Alcohols

Consider methyl alcohol (CH3OH) as an example. In methyl alcohol, both oxygen and carbon are sp3
hybridised. Two of the sp3 orbitals of oxygen are completely filled and cannot take part in bond formation.
The C-O bond in methyl alcohol is formed by overlap of an sp3 orbital of carbon and an sp3 orbital of oxygen.
The O-H bond is formed by the overlap of an sp3 orbital of oxygen and s orbital of hydrogen. The C-O-H
bond angle is 1050. It is less than the normal tetrahedral angle. This is because the two completely filled sp3
orbitals of oxygen repel each other. This results in reduction of the bond angle.

Nomenclature of Monohydric Alcohols

Alcohols are named by three systems :

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 Common System : In this system, alcohols (R-OH) are named as ‘Alkyl Alcohols’. The alkyl group attached
to the –OH group is named and ‘alcohol’ is added as a separate word. As we go higher in the series, it
becomes necessary to indicate whether a particular alcohol is primary, secondary or tertiary. The prefix
secondary is abbreviated as sec-. the prefix tertiary is abbreviated as tert- or t-.

(1) Carbinol System : In this system, alcohols are considered as derivatives of methyl alcohol which is called
Carbinol. The alkyl group attached to the carbon carrying the –OH group are named in alphabetic order. Then
the suffix –carbinol is added.

(2) IUPAC system : In this system, alcohols are named as ‘Alkanols’. The IUPAC rules are,
a. Select the longest continuous carbon chain containing the –OH group.
b. Change the name of the alkane corresponging to this chain by dropping the ending –e and adding the suffix –
ol.
c. Number the chain so as to give the carbon carrying the –OH group, the lowest possible number. The position
of the –OH group is indicated by this number.
d. Indicate the positions of other substituents or multiple bonds by numbers.

Methods of Preparation of Monohydric alcohols

Alcohols are prepared by the following methods :

(1) Hydrolysis of Alkyl Halides : Alkyl Halides react with aqueous sodium hydroxide to form alcohols.

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(2) Reduction of Aldehydes and ketones : Aldehydes and ketones can be reduced with H2/Ni or lithium
Aluminium hydride to form the corresponding alcohols. Aldehydes give primary alcohols, ketones give
secondary alcohols.

Distinguish test between 10, 20, 30 alcohols

The following tests are used to distinguish between primary, secondary and tertiary alcohols.

(1) Lucas test : In this test, alcohols are treated with a solution of HCl and zinc chloride(Lucas reagent) to form
alkyl halides. Zinc chloride serves as a catalyst.

The three types of alcohols undergo this reaction at different rates. Tertiary alcohols react with lucas reagent
very rapidly. Secondary alcohols react slower. Primary alcohols react with lucas reagent even more slowly.
The lucas test is carried out as follows : An alcohol is mixed, at room temperature, with concentrated
HCl and ZnCl2. The alkyl chloride, which is formed, is insoluble in the medium. It causes the solution to
become cloudy before it separates as a distinct layer.
(a) With tertiary alcohols, cloudiness appears immediately
(b) With secondary alcohols,cloudiness appears in 5 minutes
(c) With primary alcohols, the solution remains clear. (This is because primary alcohols do not react with lucas
reagent at room temperature. High temperatures are needed.)
(2) Victor-Meyer Method :
The Victor Meyer test is used to differentiate between primary, secondary and tertiary alcohols, using the
colour of the solutions they each produce after a series of reactions.
In the test, the alcohol being tested is first converted into an iodide with either red phosphorus and
iodine or concentrated HI. Then, the resulting iodide is converted into a nitroalkane (R-NO2) using AgNO2 as

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 the reagent.The resulting nitroalkane is then treated with nitrous acid (prepared in the situ itself).Then, the
resulting product is made alkaline, using KOH as the reagent, which changes the colour of the solution.

Test for Hydroxyl Alcohol

(1) Formation of Alkoxide : Reaction with active metals : Alcohols react with sodium or potassium to form
alkoxides with the liberation of hydrogen gas. The metal replaces the hydrogen atom in the alcohol group
forming a salt and hydrogen gas.

The above reaction shows that the alcohols are acidic in nature. The reason for this is that the O-H bond in
alcohols is polar and allows the release of the hydrogen atom as proton. However, alcohols are weaker acids
than water. This is because the alkyl groups in alcohols have a +I effect. They release electrons towards the
oxygen atom so that it becomes negatively charged. This negative charge on oxygen makes the release of the
proton more dissicult.
Tertiary alcohols are less acidic than secondary alcohols. The secondary alcohols are less acidic than
the primary alcohols. This is because the +I effect would be maximum in tertiary alcohols, as they contain
three alkyl groups attached to the carbon bearing the –OH group.
Note : Alcohols are not acidic enough to react with aqueous NaOH or KOH.
(2) Esterification :
Esterification is the process of combining an organic acid (RCOOH) with an alcohol (ROH) to form an ester
(RCOOR) and water; or a chemical reaction resulting in the formation of at least one ester product. Ester is
obtained by an esterification reaction of an alcohol and a carboxylic acid.
When primary alcohol is treated with a carboxylic acid in the presence of sulphuric acid a compound
is formed. This compound has a sweet smell. The compound obtained is called ester. The chemical
reaction occurring in the formation of the ester is known as an esterification reaction.

CH3COOH + CH3CH2COOH → CH3COOCH2CH3

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 Dihydric alcohols

Compounds which contain two –OH groups on different carbons are called Dihydric alcohols or
Diols. Compounds with two –OH groups on one carbon are rare. This is because they are unstable
and undergo spontaneous decomposition to give the corresponding carbonyl compound and water.
Diols are commonly called as Glycols, since they have a sweet taste.

Nomenclature
Diols have both common and IUPAC names are obtained by adding the suffic –diols to the name of
the parent alkane. Numbers are used to indicate the positions of the two –OH groups.

Preparation of Glycol from alkene

By the oxidation of ethylene with cold dilute potassium permanganate solution, glycol is prepared.

Oxidative cleavage of glycol using lead tetraacetate and periodic acid

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 Lead tetraacetate is used cleave a carbon-carbon bond in a vicinal diol (glycol).
This reaction is useful in the formation of ketones and aldehydes and involves a favourable five-membered
cyclic intermediate.

The oxidation cleavage of 1,2-diol by a periodic acid or periodic salt to give corresponding
carbonyls is known as Malaprade oxidation. Vicinal diols can also be oxidized to form aldehydes and ketones
by lead tetraacetate. This oxidation cleavage is analogous to malaprade oxidation and is known as Criegee
oxidation.

Uses of Ethylene glycol

a. Ethylene glycol is used as an antifreeze for car radiators.
b. It is used as deicing fluid for aeroplane wings.
c. It is used in the manufacture of dacron and ethylene oxide.

Trihydric Alcohols

Compounds which contain three –OH groups are called as Trihydric Alcohols or Triols. The introduction of
the third –OH group in a diol molecule raises the boiling point by about 1000C, increasing the viscosity and
makes the alcohol more sweet. An increase in the number of –OH groups also enhances the hydrogen bonding
ability and association, thereby raising the boiling point.

The only important member of the class is glycerol or 1,2,3-propanetriol.

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Manufacture of Glycol from Spentlye

In soap manufacture, the fat is hydrolysed by boiling with alkali solution. The carboxylic acids
produced by hydrolysis react with the alkali to form solid soap while the glycerol is left in the solution. The
soap is filtered out. The filtrate is called Spent Lye.

Spent lye contains.4 to 6% glycerol unused alkali.Soluble salts, soaps and suspended impurities. It is
allowed to stand in a tank where most of the suspended impurities settle down.The clear solution is
transferred to a new tank where it is first treated with.HCl to neutralize.Excess alkali.It is then treated
with aluminium sulphate and steam.The remaining excess alkali is precipitated as aluminum
hydroxide, and the soluble soaps are converted into insoluble aluminium soaps.These impurities are
filtered out.The filtrate is next concentrated under vacuum when most of the sodium chloride
separates out.This is filtered and the filtrate is treated with animal charcoal to remove colored
impurities.After filtration, it is again subjected to vacuum distillation.The glycerol thus obtained is
90% pure.To obtain pure glycerol, it is redistilled under vacuum.

Synthesis of glycerol from Propene

Step 1 : .Propaee is treated with chlorine at 6000 Celsius to give allyl chloride.
Step 2 : Allyl chloride is treated with dilute NaOH to give allyl alcohol.
Step 3: Allyl alcohol is treated with dilute hypochlorous acid to give a chlorohydrin.The addition of
HOCl to the carbon-carbon double bond takes place according to the Markovnikov's rule.
Step 4 : The chlorohydrin is treated with dilute enough to yield glycerol.

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 Alternative Method: Propane may be oxidized with oxygen in the presence of CUO at 350 degrees
Celsius to give acrolein.Acrolein is then treated with hydrogen.Peroxide followed by reduction to
produce glycerol.

Reactions of glycol with oxalic acid at different temperatures

Glycerol reacts with oxalic acid in two ways :
0
1. At 110 C, glycerol reacts with oxalic acid to form glycerol monoformate. Glycerol monoformate on
hydrolysis gives formic acid and glycerol is regenerated.

2. At 2600C, glycerol reacts with oxalic acid to form allyl alcohol.

Reaction of glycerol with PCl5

Glycerol reacts with PCl5 to form glyceryl trichloride. All these –OH groups are
replaced by Cl atoms.

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 Reaction of glycerol with fatty acids

Glycerol reacts with fatty acids to yield triglyceride and water.

Uses of Glycerol

a. Glycerol is non-toxic and an excellent humectant.

b. It is used.In bakery products, hand lotions, vanishing creams, shaving soaps and toothpastes.
c. Glycerol is used in the production of plastics, synthetic fibers and surface coatings.
d. It is used in the manufacture of explosives like dynamite and cordite.

Preparation of Nitroglycerine
Nitroglycerin is obtained when glycerol reacts with cold mixture of conc. sulphuric acid and nitric
acid.

Composition and Uses of Cordite and Dynamite

Composition of Cordite is 37 parts of guncotton, 57.5 parts of nitroglycerin, and 5 parts of mineral
jelly together with 0.5 percent of acetone. Cordite was also used for large weapons, such as tank guns,
artillery, and naval guns.
Dynamite contains nitroglycerine, sodium nitrate, and a combustible absorbent. Nobel created
dynamite to help people in building and mining, but he and others also used dynamite to make bombs, canons,
and rockets used in wars.

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 PHENOLS
Introduction & Nomenclature :
Phenols are compounds containing an -OH group attached directly to an aromatic ring.Like alcohols,
there may be monohydric or polyhydric according to the number of -OH groups that they contain.
Phenols are usually named by common system or as derivative of the present phenol(C6H5OH).
Some examples are,

Compounds which contain an –OH group in a side chain attached to an aromatic ring are not phenols. They
are called Aromatic Alcohols.
Eg: Benzyl Alcohol

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 Preparation of Phenols
Phenol is obtained by the following methods:
1. From Chlorobenzene (Dow Proces) : This process was first introduced in 1928 by the Dow Chemical
company of U.S.A. This involves the hydrolysis of chlorobenzene with aqueous NaOH at high temperatures
and pressure followed by the treatment with dilute HCl.

2. From Cumene : This involves air-oxidation of cumene (Isopropylbenzene) followed by treatment with
dilute HCl.

3. From Benzenediazonium chloride : This process requires warming a solution of benzenediazonium

chloride, prepared from aniline, on a water bath at 500C.

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 Acidity of Phenols
Phenols are much more acidic than alcohols but less so than carboxylic acids or even carbonic
acid. This is indicated in order of acidity constants :
Compounds Formula Ka
Phenols Ar-OH 10-19
Alcohols R-OH 10-18
Carboxylic acids R-COOH 10-5
Carbonic Acid H2CO3 10-7

Phenols are acidic due to the formation of stable phenoxide ions in aqueous solutions.
For Example, Phenol itself gives phenoxide ion on dissociation.

The Phenoxide ion is stable due to resonance :

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 In Phenoxide ion, the engative charge is spread throughout the benzene ring and thereby effectively dispersed.
This charge delocalization is a stabilizing factor in the phenoxide ion. No resonance is possible in alkoxide
ion (RO-) derived from alcohols. The negative charge is concentrated or localized on a single oxygen atom.
Thus, alcohols are much weaker acids than phenols.

Effect of substituents on Acidity of Phenols

(1) Effect of Electron-withdrawing substituents : An electron withdrawing group (eg. –NO2, -Cl, -CN, -CHO, -
COOH) on the aromatic ring is acid-strengthening. It enables the ring to withdraw more electrons from the
phenoxy oxygen. This stabilizes the phenoxide ion further and results in a stronger acid.
Eg. P-nitrophenol is more acidic than phenol

(2) Effect of Electron-releasing substituents : An electron-releasing group (eg. –CH3, -OCH3,-NH2) on the
aromatic ring is acid-weakening. It strengthens the negative charge on phenoxy oxygen and inhibits the
charge delocalization due to resonance. This destabilizes the phenoxide ion and results in a weaker acid.
For eg. p-cresol is less acidic than phenol

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 Reactions of Phenols
(1) Fries Rearrangement :
It is an organic rearrangement reaction in which an aryl ester is transformed into a hydroxy aryl ketone with
the help of a Lewis acid catalyst and an aqueous acid. In this reaction, an acyl group belonging to the phenolic
ester migrates to the aryl ring.

Mechanism :

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(2) Claisen Rearrangement : A Claisen rearrangement is a reaction which is specific to ally aryl ethers
and allyl vinyl ethers. Heating an allyl aryl ether to 250 oC causes an intramolecular rearrangement to
produce an o-allylphenol.

(3) Riemerr-Tiemann Reaction : The Reimer Tiemann reaction is an organic chemical reaction where
phenol is converted into an ortho hydroxy benzaldehyde using chloroform, a base, and an acid
workup.

Mechanism :

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(4) Lederer-Manasse Reaction : Lederer-Manasse Reaction is defined as the condensation of phenol
(ArOH) with Formaldehyde,in the presence of acid or base. It gives ortho Benzyl alcohol as minor
Product and para Benzyl alcohol as major Product. This reaction can occur in the acidic medium as
well in the alkali medium.

Mechanism :

Synthesis of Phenolphthalein :

Phenolphthalein is an organic compound having the chemical formula C₂₀H₁₄O₄ that is used as a ㏗
indicator in acid-base titrations.

Phenolphthalein can be synthesized by condensation of phthalic anhydride with two equivalents of

phenol under acidic conditions.

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Mechanism :

Synthesis of Salicylaldehyde :

Salicylaldehyde is prepared from phenol and chloroform by heating with sodium hydroxide or
potassium hydroxide in a Reimer–Tiemann reaction.

Mechanism :

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Synthesis of Vanillin :

Synthesis of o-benzoquinone :

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