ALCOHOL

Introduction:-
In chemistry, an alcohol is any organic compound in which a hydroxyl group (-OH) is
bound to a carbon atom of an alkyl or substituted alkyl group. The general formula for a simple
acyclic alcohol is CnH2n+1OH. In common terms, the word alcohol refers to ethanol, the type of
alcohol found in alcoholic beverages.

Ethanol is a colorless, volatile liquid with a mild odor which can be obtained by the
fermentation of sugars. (Industrially, it is more commonly obtained by ethylene hydration-the
reaction of ethylene with water in the presence of phosphoric acid.) Ethanol is the most widely
used depressant in the world, and has been for thousands of years. This sense underlies the
term alcoholism (addiction to alcohol).

Other alcohols are usually described with a clarifying adjective, as in isopropyl alcohol
(propan-2-ol) or wood alcohol (methyl alcohol, or methanol). The suffix -ol appears in the
"official" IUPAC chemical name of all alcohols.

There are three major subsets of alcohols: primary (1), secondary (2) andtertiary (3),
based upon the number of carbon atoms the C-OH group's carbon is bonded to. Ethanol is a
simple 'primary' alcohol. The simplest secondary alcohol is isopropyl alcohol (propan-2-ol), and
a simple tertiary alcohol is tert-butyl alcohol (2-methylpropan-2-ol).

Structure of alcohol:-
Alcohols are compounds of the general formula ROH, where R is any alkyl or substituted
alkyl group. The group may be primary, secondary, or tertiary; it may be open-chain or cyclic; it
may contain a double bond, a halogen atom, or an aromatic ring. For example

All alcohols contain the hydroxyl (-OH) group, which, as the functional group,
determines the properties characteristic of this family. Variations in structure of the R group
may affect the rate at which the alcohol undergoes certain reactions, and even, in a few cases,
may affect the kind of reaction.

Compounds in which the hydroxyl group is attached directly to an aromatic ring are not
alcohols; they are phenols, and differ so markedly from the alcohols that we shall consider
them separately.

Classification of alcohol:-
Monohydric alcohols: Containing two OH grp e.g. CH3OH methyl alcohol

Dihydric alcohols: Containing two OH grp e.g. HO-CH2-OH

Polyhydric alcohols: Containing more than two OH grp e.g. CH2OHCHOHCH2OH

If two or more hydroxyl groups attached to same carbon atom, the compounds is
usually unstable and lose a molecule of water to give a stable and therefore two or more
hydroxyl groups must be present on different carbon atoms.

We classify a carbon atom as primary, secondary, or tertiary according to the number of

other carbon atoms attached to it. An alcohol can further classified according to the kind of
carbon that bears the -OH group:

One reaction, oxidation, which directly involves the hydrogen atoms attached to the
carbon bearing the -OH group, takes an entirely different course for each class of alcohol.
Usually, however, alcohols of different classes differ only in rate or mechanism of reaction, and
in a way are consistent with their structures. Certain substituents may affect reactivity in such a
way as to make an alcohol of one class resemble the members of a different class. Benzyl
alcohol, for example, though formally a primary alcohol, often acts like a tertiary alcohol. We
shall find that these variations, too, are consistent with the structures involved.

Allylic alcohols: In these alcohols, the OH group is attached to a sp3 hybridized

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 to a sp3 hybridised
carbon atom next to an aromatic ring. For example

Vinylic alcohols: These alcohols contain OH group bonded to a carbon-carbon double

bond i.e., to a vinylic carbon or to an aryl carbon.

Structure of alcohols:-
In alcohols carbon as well as oxygen both show sp3 hybridization. In carbon all the four
sp3 hybridized orbitals have on electron in each orbital whereas in oxygen two of the four
sp3 hybridized orbitals have one electron & rest two orbitals have on electron pair in each.
These two completely filled orbitals in oxygen atom do not take part in bonding and give rise to
contraction in bond angles due to lone pair effect and therefore the bond angle C-O-H is
105o which is lesser than the normal tetrahedral structure.

Nomenclature of alcohol:-
For the simpler alcohols the common names, are most often used. These consist simply
of the name of the alkyl group followed by the word alcohol. For example:
 We should notice that similar names do not always mean the same classification; for
example, isopropyl alcohol is a secondary alcohol, whereas isobutyl alcohol is a primary alcohol.

Finally, there is the most versatile system, the IUPAC. The rules are:

1. Select as the parent structure the longest continuous carbon chain that contains the -OH
group; then consider the compound to have been derived from this structure by
replacement of hydrogen by various groups. The parent structure is known as ethanol,
propanol, butanol, etc., depending upon the number of carbon atoms; each name is
derived by replacing the terminal -e of the corresponding alkane name by -ol.

2. Indicate by a number the position of the -OH group in the parent chain, generally using
the lowest possible number for this purpose.

3. Indicate by numbers the positions of other groups attached to the parent chain.

Alcohols containing two hydroxyl groups are called glycols. They have both common
names and IUPAC names.
 Nomenclature : Common name Carbinol name IUPAC name

CH3OH methyl alcohol carbinol methanol

CH3CH2OH ethyl alcohol methyl carbinol ethanol

CH3CH2CH2OH n-propyl alcohol ethyl carbinol propanol-1

CH3CHOHCH3 isopropyl alcohol dimethyl carbinol propanol-2

CH3CH2CH2CH2OH n-butyl alcohol propyl carbinol butanol-1

(CH3)2CHCH2OH isobutyl alcohol isopropyl carbinol 2-methylpropanol-1

CH3CH2CHOHCH3 sec.butyl alcohol ethylmethylcarbinol butan-2-ol

(CH3)3COH t-butyl alcohol trimethyl carbinol 2-methylpropan-2-ol

Preparation of Alcohols:-
By hydrolysis of haloalkanes :

R-X + aq. KOH ROH +KX

By reduction of Carbonyl compounds

By the action of Grignards Reagent on aldehydes, ketones and esters

 By Aliphatic Primary Amines:

RCH2NH2 + HNO2 RCH2OH + N2 + H2O

Hydration of alkenes:

Oxymercuration-demercuration:

Hydroboration-oxidation:

Hydroxylation of alkenes:

Physical Properties of Alcohol:-

Lower alcohols are liquid at room temperature while higher ones are solid.

High boiling point due to presence of intermolecular hydrogen bonding. Order of Boiling
Point: primary > secondary > tertiary
 Solubility in water decreases with increase in molecular mass due to decrease in extent
of intermolecular hydrogen bonding.

Chemical Properties of Alcohol:-

Alcohol's reaction with metal: ROH + Na2RO+Na + H2

Formation of Halides:

3ROH + P + I2 3RI + H3PO3

ROH + SOCl2/PCl3/PCl5 RCl

ROH + HX RX

ROH + NaBr, H2SO4R-Br

ROH + Zn+ HCl R-Cl

R2C-OH alcohol + HCl R2CCl

Reaction with HNO3: R-OH + HO-NO2 R-O-NO2

Reaction with carboxylic acid (Esterification) : R-OH + R-COOH + H+ R-COOR

Reaction with Grignard reagent: R'OH + RMgX RH + R'OMgX

Reduction of alcohol : ROH + 2HI + Red P RH + I2 + H2O

Dehydration of Alcohol: Dehydration of alcohols takes place in acidic medium. Intra-

molecular dehydration leads to the formation of alkene while inter molecular
dehydration which forms ether. Ease of dehydration: 3 > 2 > 1

Satyzeffs Rule : Elimination through b carbon containing minimum b hydrogen

 Oxidation of Alcohol:
RCH2-OH + [O] RCHO RCOOH
RCH2-OH + [O] +PCC RCHO

Haloform Reaction: Compound containing CH3CO- group (or compound on oxidation

gives CH3CO group) which is attached with a C or H, in presence of halogen and mild
alkali gives haloform.CH3-CH2-COCH2-CH3, CH3-CO-Cl, CH3COOH will not respond to
haloform reaction wile CH3CH2OH will respond to haloform Reaction.

Test for Alcohols:-

1. Lucas Test:

Alcohols + ZnCl2 + HCl

1o Alcohol: RCH2OH + ZnCl2 + HCl No reacMon at room temperature

20 Alcohol: R2CHOH + ZnCl2 + HCl R2CHCl white turbidity after 5-10 min.

30 Alcohol: R3CHOH + ZnCl2 + HCl R3CHCl white turbidity instantaneously.

2. Victor Meyer Test:

 Phenols
Introduction:-
Phenols are aromatic compounds containing hydroxyl group directly attached to the
nucleus. Phenols are compounds of the general formula ArOH, where Ar is phenyl, substituted
phenyl, or some other aryl group (e.g., naphthyl). Phenols differ from alcohols in having the OH
group attached directly to an aromatic ring.

Both phenols and alcohols contain the OH group, and as a result the two families
resemble each other to a limited extent. In most of their properties, however, and in their
preparations, the two kinds of compounds differ so greatly that they well deserve to be
classified as different families.

Physical Properties of Phenols:-

Phenol is a colorless, toxic, corrosive, needle shaped solid.

Phenol soon liquifies due to high hygroscopic nature.

Phenol is less soluble in water, but readily soluble in organic solvents.

Simplest phenols, because of hydrogen bonding have quite high boiling points.

o-nitrophenol is, steam volatile and also is less soluble in water because of
intramolecular hydrogen bonding.
Preparation:-

Chemical Properties of Phenols:-

a) Formation of Esters

Phenyl esters (RCOOAr) are not formed directly from RCOOH. Instead, acid chlorides
or anhydrides are reacted with ArOH in the presence of strong base
 (CH3CO)2O + C6H5OH + NaOH CH3COOC6H5 + CH3COONa + H2O

Phenyl acetate

C6H5COCl + C6H5OH + NaOH C6H5COOC6H5 + Na+Cl + H2O

Phenyl benzoate

e) Electrophilic Substitution: The OH and even more so the O(phenoxide) are strongly
activating ortho , para - directing

Special mild conditions are needed to achieve electrophilic monosubstituion in phenols

because their high reactivity favors both polysubstitution and oxidation.
 Ethers
Introduction:-
Ethers are compounds of the general formula ROR, ArOR, or ArOAr.

To commonly name ethers we usually name the two groups that are attached to
oxygen, and follow these names by the word ether:

If one group has no simple name, the compound may be named as an alkoxy derivative:

If the two groups are identical, the ether is said to be symmetrical (e.g., diethyl ether,
diphenyl ether), if different, unsymmetrical (e.g., methyl tert-butyl ether, anisole).

Nomenclature:-
Ethers are supposed to have no functional group and thus IUPAC nomenclature does not
provide their suffix name. These are named (in IUPAC) as alkoxy alkane, the smaller alkyl group
along with oxygen is called alkoxy substituent.
 Formula Trivial Name IUPAC Name

CH3OCH3 Dimethyl ether Methoxymethane

CH3OCH2CH3 Methyl ethyl ether Methoxyethane

CH3OCH2CH2CH3 Methyl propyl ether 1-Methoxypropane

Methyl isopropyl ether 2-Methoxypropane

CH3CH2OCH2CH3 Diethyl ether Ethoxyethane

Isomerism of ethers:-
Ethers show functional isomerism with alcohols.

CH3OCH3 & CH3CH2OH

Ethers with at least four carbon atoms show metamerism due to different alkyl gps
attached on bivalent O atom.

Structure of Ether:-
In CH3OCH3, the central oxygen atom is sp3 hybridized with two completely filled
sp3 orbitals having lone pair of electrons and two half-filled sp3hybridized orbitals. Also carbon
atoms are sp3 hybridized and both the half-filled sp3orbitals of O atom from strong s (C-O)
bonds with half-filled sp3 orbitals of two adjacent carbon atoms of alkyl grps.

The C-O-C bond angle is about 110oC which is quite closer to 109o 28' of sp3hybridized
nature, inspite of the fact that lone pair of electrons must result in contraction in bond angles.
This is because of the fact that presence of alkyl grps on O atom counterbalances the repulsion
between the lone pair - bond pair electrons and leads to the bond angle nearer to 109o 28'.
Physical Properties of Ethers:-
Physical state, color and odor: Dimethyl ether and ethyl methyl ether is gas at ordinary
temperature while the other lower homologues of ethers are colorless liquid with
characteristic 'ether smell'.

Dipole nature: Ethers have a tetrahedral geometry i.e., oxygen is sp3 hybridized. The C
OC angle in ethers is 110. Because of the greater electronegativity of oxygen than
carbon, the CO bonds are slightly polar and are inclined to each other at an angle of
110, resulting in a net dipole moment.

Bond angle of ether is greater than that of tetrahedral bond angle of 10928'.

Solubility and boiling point: Due to the formation of less degree of hydrogen bonding,
ethers have lower boiling point than their corresponding isomeric alcohols and are
slightly soluble in water.

Preparation of Ethers:-
a) From alcohols:

Order of dehydration of alcohol leading to formation of ethers: 1 > 2 > 3

b) Williamson's synthesis:

R-X + Na+ -O-R' R-O-R' + Na+ X-

In case of tertiary substrate elimination occurs giving alkenes.

 From alkenes:.

From Grignard reagent: Treating - halo ethers with suitable Grignard reagents.

On standing in contact with air, most aliphatic ethers are converted slowly into unstable
peroxides. The presence of peroxides is indicated by formation of a red colour when the ether
is shaken with an aqueous solution of ferrous ammonium sulfate and potassium thiocyanate
i) Reaction with acid chlorides and anhydrides:
j) Electrophilic substitution reactions

Epoxides or Oxiranes preparation:-

a) Oxidation of ethylene :