ALCOHOL

Introduction

It is an organic compound in which a hydroxyl group (–OH)

is attached to an alkyl group. General molecular formula of alcohol is
CnH2n+1OH and structurally it can be represented as

The hydroxyl group is functional group and all chemical properties

of alcohol depend on it.

Nomenclature and Structures

Alcohols are named based on alkyl group to which hydroxyl

group is attached. Some of the alcohols with their common name,
IUPAC name and their structure are listed below
 Alcohols are classified as 10, 20, or 30 depending upon the type of
carbon to which hydroxyl group is attached. Alcohols are also named
as monohydric, dihydric or trihydric depending upon the number
hydroxyl groups attached to the alkyl group.
Physical properties

Lower alcohols such as methanol ethanol etc are colorless

toxic liquids with characteristic smell.

The boiling points of the alcohols increase as the number of

carbon atoms increases. The patterns in boiling point reflect the
patterns of intermolecular forces and it is same as alkanes.

The boiling point increases with the increase in molecular

mass. The boiling point decreases with increase in branching.

The boiling point of an alcohol is always much higher than

that of the alkane with the same number of carbon atoms. This is due
to hydrogen bonding.

Alcohols are more soluble in water in comparison to alkane.

This is again due to hydrogen bonding. Other wise solubility also
shows the same trend as shown by alkane.

Hydrogen bonding occurs between molecules where there

is a hydrogen atom attached to one of the very electronegative
elements - fluorine, oxygen or nitrogen.

In case of alcohols, hydrogen bonds are set up between the

slightly positive hydrogen atoms and lone pairs on oxygen in other
molecules.

Synthesis of Alcohols

Alcohol can be prepared by various methods. Any one of the

methods listed below can be used depending on the type and yield of
alcohols required.
Reduction of carbonyl group:

Carbonyl group is present in aldehydes, ketones and

carboxylic acids. All these compounds can be reduced by either using
direct hydrogen in presence of a catalyst or by using a reducing
agent.

Both NaBH4 and LiAlH4 can be used to reduce aldehyde and ketones.
Reduction of aldehydes will give primary alcohols while reduction of
ketones will give secondary alcohols.

In all the four reaction shown above hydride ion acts as a

nucleophile.
 Reducing agent attacks carbonyl carbon, breaks the double
bond on oxygen, and forms alcohol. The hydride ion preference to
carbonyl carbon is based on the electron donating tendency of the
group attached to carbonyl carbon. More easily the electron is
donated less likely the hydride ion gets attacked and forms alcohol.
The tendency to form alcohol can be graded as

Reduction using Grignard Reagents(R – MgX)

Grignard reagent is an organometallic compound

having general formula as R – MgX (X = F,Cl, Br, I) These are highly
polarized species due to polar bond between the metal and carbon.
Carbon is more electronegative than the magnesium hence carbon
becomes partially negative. The polarized carbon metal bond and a
partially negative charge on the carbon make it a strong nucleophile
and a base. Grignard reagent also reacts with C = N, S = O, N = O. It
deprotonates O – H, N – H, S – H. Grignmard reagent is made in
ether.

Carbon of carbonyl is positively charged as

oxygen of carbonyl group is more electronegative than carbon. Thus
it acts as an electrophile. The incoming nucleophile carbon of
Grignard reagent attacks the carbonyl group carbon.

While adding to carbonyl group, organic part of

Grignard reagent attaches itself to carbon and magnesium to oxygen
of carbonyl group. The product is a weak salt of acidic alcohol which
is easily converted to alcohol by giving it an acidic bath.

Primary alcohol is produced by the reaction between

formaldehyde and Grignard reagent.
Secondary alcohol is obtained by treating Grignard reagent with all
other aldehydes other than formaldehyde.

Tertiary alcohol is produced due to the reaction between Grignard

reagent and ketones.
 In all the above reactions carbon chain is extended by one
carbon. Grignard reagent therefore can be used to synthesize organic
compounds in ascending order. i.e. methane to ethane or propane to
butane etc.

Several other methods for synthesis of alcohol such as

hydration of alkene , oxymercuration-demercuration, hydroboration,
and nucleophilic substitution have been discussed in the section of
alkenes.

Acidic Nature of Alcohol

The alcohols have polar structure in which oxygen has

excess of electrons and the hydrogen of alcohols can be released. This
is the reason why proton making alcohols are acidic in nature.
However alcohols are weaker acids than water. Acidity of alcohols in
descending order is methyl > i0 > 20 > 30
 Methyl group is better electron donor when compared to
hydrogen. As alkyl group increases, electron density on oxygen atom
increases making it more and more negative.
The increasing negative charge makes release of proton
more difficult and acidic nature of alcohols reduces.

Oxidation of Alcohol

Oxidation is addition of oxygen, addition of halogens or loss

of hydrogen while reduction is loss of oxygen, addition of hydrogen,
or loss of halogen. Although there are other definitions as well but for
the time being we will stick to these definitions.

Oxidizing agents are the species with excess of oxygen while

reducing agents have less oxygen atoms but high amount of
hydrogen. Examples of oxidizing agents are K2Cr2O7, O2, Br2, H2CrO4
and reducing agent are H2, NaBH4, LiAlH4

Sequence of oxidation and reduction of various functional

groups is given below:
Nucleophilic reactions of Alcohol

The oxygen atom on alcohol has lone pair of electron which

makes it basic as well as nucleophilic. In presence of strong acid,
alcohol acts as a base and accepts proton.
 Protonation of alcohols converts –OH into H2O which is a
better leaving group. It also makes carbon atom more positive and
more susceptible to nucleophilic attack and so SN2 as well as SN1
reaction become possible.

The reaction is used to synthesize alkyl halide using SN2

mechanism by primary and secondary alcohol.

Halide ion shown in the above reaction comes from acid. The
function of the reaction is to produce a substrate in which leaving
group is a weakly basic water rather than a strongly basic hydroxide
ion.

Tertiary alcohols use SN1 mechanism. Reaction between tert-

butyl alcohol and hydrochloric acid is taken as example.
 In the first step, alcohol accepts a proton from the acid
forming a protonated alcohol. It then dissociates in to water and
forms a carbocation.

Carbocation in third step reacts with nucleophile and halide ion. The
acid in this case helps in the formation of carbocation.
The reaction is carried out in presence of acid and high concentration
of halide ion. The large quantity of halide ions helps stabilization of
carbocation.

The alcohols can be converted to alkyl halide by PCl5, PBr3 ,

PI3 by SN2 mechanism. The result with tertiary alcohols is poor.
Alkyl halide can also be produced by thionyl chlorides to obtain
additionally sulfur dioxides.

Preparation of Mesylates and Tosylates

A sulfonate ion is an ion that contains the -S(=O)2-O−

functional group. The general formula is RSO2O−, where R is some
organic group. They are conjugate bases of sulfonic acids. Sulfonates,
being weak bases, are good leaving groups in Sn1, Sn2, E1 and E2
reactions.
Alcohols react with sulfonyl chlorides to form ester called sulfonate.
These reaction involves cleavage of O – H bond of alcohols. The
reaction is nucleophilic substitution of type SN2 where alcohol acts as
nucleophile.
 The tosylates and mesylates are very good leaving
groups, and weak bases. The reactions in which tosylates and
mesylates act as a leaving group follow SN1or SN2 mechanism.

A nucleophile alcohol shows elimination reaction as well

as addition reaction. Addition reaction has been discussed in alkene
section and elimination will be discussed in subsequent section.

Pinacols Rearrangement

These are dihydric alcohols which are completely substituted such

as 2, 3 dimethyl 2, 3 butanediol. These result from the dehydration by
mineral acid and subsequent rearrangement form ketones. The
reaction is known as pinacol rearrangement. The reaction takes the
following steps.

In first step the hydroxyl group is protonated and removed by acid to

form carbocation.

In second step protonated hydroxyl group is removed as water and

carbocation is formed.
Carbocation rearranges it self and gets attached to different carbons
forming protonated ketone.
Ketone is formed by loss of proton from protonated ketone.

Ethers

Ethers are compounds in which two groups are attached to

oxygen atom. To name the ether we name the two groups attached to
oxygen followed by the word ether.
Properties of Ether

a) Di-methyl ether and ethyl-methyl ether are gases at room

temperature. Rests all are liquids with pleasant order.
b) Lower ethers are volatile and highly flammable.
c) Boiling point follow the trend of alkane, alkene etc.
d) Boiling point is lower than the corresponding alcohol
due to lack of hydrogen bonding.
e) Ethers are slightly soluble in water. Ether can form
hydrogen bonding with water as well as with other compounds
which contain a hydrogen atom attached to N, O, F atom.
f) Ethers are very good organic solvents.
g) Chemically ether reacts with concentrated HI and HBr to
give alcohol and alkyl halide.

The concentration of acid should be proper, because

excess of acid will react with alcohol and form alkyl halide.
h) Ether can be oxidized to peroxides.
 i) In general ethers highly nonreactive compounds.

Epoxides (Oxiranes)

Epoxides are cyclic ethers with ethereal oxygen as part of

three membered ring.

Epoxides are more reactive than ethers due to strain created by small
ring.

An epoxide is protonated by acid. The protonated epoxide can then

be attacked by any of the nucleophile reagents.
 The protonated epoxide now can be used to synthesize a
compound with two functional groups such as glycol by treating
protonated epoxide with water. The reaction is anti-addition.
The protonated epoxide reaction with alcohol yields a compound
which is ether along with alcohol.

The protonated epoxide reaction with HBr which is a compound

having a bromine and alcohol as functional group.
Relative Acidity of Functional Group

Acidic character of various functional groups in increasing

order is as follows:

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