Alcohols 2

ALCOHOLS
(Part II)
CHEMICAL PROPERTIES OF ALCOHOLS
• Alcohols acts both as nucleophiles as well as electrophiles.
• The bond between O-H is broken when alcohols react as
nucleophiles and the bond between C-O is broken when
they react as electrophiles.
• The chemical properties of any given aliphatic alcohol
depend on the nature of the alkyl group and on the
properties of the hydroxyl group.
• Based on the cleavage of O-H and C-OH bonds, the
reactions of alcohols may be divided into two groups.
(A) Reactions involving cleavage of O-H bond
(B) Reaction involving fission of R—OH bond (cleavage of
C—O bond)
During cleavage of C-O bond Alcohols show following order of
reactivity.
Tertiary alcohol> secondary alcohol> Primary alcohol
and in case of O-H bond cleavage order of reactivity changes to
CH3OH> Primary alcohol> Secondary alcohol> Tertiary alcohol
(A)Reactions involving cleavage of O-H bond :
1. Acylation of alcohol: When alcohol reacts with acyl
halide and anhydride substitution of hydrogen atom by acyl
group is known as acylation of alcohols
2C2H5OH + 2Na 2C2H5ONa + H2
C2H5OH + CH3COOH C2H5COOC2H5 + H2O
C2H5OH + CH3COCl CH3COOC2H5 + HCl
B)Reaction involving fission of R—OH bond
The reactions involving R – OH bond with cleavage of C – O
bond are as follows;
C2H5OH + SOCl2 C2H5Cl + SO2 + HCl
C2H5OH + HNH2 C2H5NH2 + H2O
1. Dehydration (alkene formation):
Alcohols on treating with a protic acid (Con. H2SO4
or H3PO4, or catalysts such as anhydrous ZnCl2
or Al2O3) undergo dehydration to form unsaturated
Hydrocarbon. In this reaction the OH and an H
groups removes from an adjacent carbons. Since water
is removed from the alcohol, this reaction is known as
a dehydration reaction (or an elimination reaction).
The conditions for dehydrating alcohols depend
closely on the structure of individual alcohols. For
primary alcohols, the conditions required are conc.
H2SO4 and temperature of 170oC.
Dehydration of 2o and3o alcohols containing more
than three carbon atoms will give a mixture of alkenes,
the major product can be determined from Saytzeff’s
Rule: When an alkene is produced in an elimination
reaction, the major product is the one with the more highly
substituted double bond i.e., the major product is that contains
the higher number of alkyl groups attached to the C=C bond.
e.g.
Rearrangement of the alkyl groups of alcohols is

very common in dehydration, particularly in the presence of
strong acids, which are conducive to carbocation
formation. Typical examples showing both methyl and
hydrogen migration follow.
Mechanism:
Intermolecular dehydration (forming ether):

When the dehydration is carried out at 140o C with
an excess of alcohol, ether will be formed. This reaction
removes a molecule of water from two alcohol
molecules, causing the two “R” groups to become attached
to an oxygen atom, forming an ether functional group:
2 . Halogenation:
Alcohols can be converted to alkyl halides
using one of three reactions:
a) Reaction with hydrogen halides:

Respective alkyl halides are formed by reacting with
the appropriate hydrogen halide, HCl for chlorination,
HBr for bromination and HI for iodination. The
reaction involves the initial protonation of the hydroxyl
group of the alcohol. This improves the leaving group
ability of the hydroxyl group.
Mechanism:
• Step1: Protonation of
the alcohols:
The alcohol acts as a
weak base and accepts
the proton donated by
the hydrogen halide.
• Step 2: Removal of a
water molecule and
formation of halide
through SN2 mechanism
/ SN1 mechanism as:
(b) Substitution Reactions:
Alcohols give substitution reaction by reacting with
reagents Like phosphorus halides(PCl5,PCl3), HCl or
SOCl2. These Reagents acts as Nucleophile and replace
OH group with Halogen group(X).
Then the chloride will act as the nucleophile in a
second step and displace the oxygen from the carbinol
carbon.
C2H5OH + SOCl2 C2H5Cl + SO2 + HCl
C2H5OH + HNH2 C2H5NH2 + H2O
(c) Reaction with phosphorus halides :

Alcohols will react with phosphorus tribromide or
phosphorus pentabromide to form alkyl bromides.
3 C2H5OH + PCl5 3C2H5Cl + H3PO4
C2H5OH + PCl3 C2H5Cl + POCl + HCl
3. Esterification:
• Alcohol reacts with carboxylic acids, acid
chlorides and acid anhydrides to form esters. The
reaction with carboxylic acid and acid anhydride
is reversible, and therefore, water is removed as
soon as it is formed. Esterification takes place much
faster in the presence of a catalyst such as conc.
H2SO4.
• Alcohols can also react with acid chlorides and

acid anhydrides to form esters. The introduction
of acetyl (CH3CO) group in alcohols or phenols is
known as acetylation.
Reactivity
Distinction between methanol and ethanol
Methanol and ethanol are distinguished by reacting with
iodine in the presence of NaOH, which lead to the
formation of yellow crystals of iodoform that indicates
that alcohol is ethanol while methanol does not form
yellow crystals with iodine.
C2H5OH + 4I2 + 6NaOH CHI3+ HCOONa + NaI
+ H2O
CH3OH + I2 + NaOH No yellow ppt
Distinction between 1o , 2o & 3o alcohol (Lucas Test)
R-OH + HCl    

ZnCl 2
immediatly
 R-Cl + H2O
Primary alkyl halide
(R)2CH-OH + HCl   
ZnCl 2
Heat
 (R) 2CH-Cl + H2O
Secondary alkyl halide ZnCl
(R)3C-OH + HCl 

5 10 min
2
(R) 3C-Cl + H2O

Tertiary alkyl halide
Dihydric alcohols preparation:

Dihydric alcohols are prepared by following different methods:
From ethylene:
CHEMICAL REACTIONS OF VICINAL GLYCOLS
Glycerol molecule is made up of two 1o alcohol groups
joined together. It reacts with Na metal at 50oC to form mono
and dialkoxide at elevated temperature.
Ethylene dichloride is formed in two steps at high temperature
Ethylene dihalides are formed upon reaction with PBr3
TRIHYDRIC ALCOHOL PREPARATION
Glycerol can be synthesized by following different methods:
1.From fats and oil:
On hydrolysis of fats and oils, glycerol and higher fatty acids are
formed
2 . By fermentation of sugars:
Alcoholic fermentation of sugar in the presence of sodium sulphite
gives good yield of glycerol.
Importance and Use of Alcohols
Alcohols are important for its use in
medicine as an antiseptic and disinfectant.
These are applied to skin to disinfect it
before needle stick and before surgery.
These are used (especially methanol) as
solvent for fats, oils, paints and varnishes.
These are used as antifreeze, denaturing
agents, as well as fuel in some areas.
Moreover in pharmaceutical preparations
and as preservative for biological
specimen.

Alcohols 2

Uploaded by

Copyright:

Available Formats

Alcohols 2

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Alcohols 2

Uploaded by

Copyright:

Available Formats

ALCOHOLS

Rearrangement of the alkyl groups of alcohols is

Intermolecular dehydration (forming ether):

a) Reaction with hydrogen halides:

(c) Reaction with phosphorus halides :

• Alcohols can also react with acid chlorides and

(R) 3C-Cl + H2O

Dihydric alcohols preparation:

You might also like

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.