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Lucas test

Differentiate between 1ry, 2ry and 3ry alcohols

Lucas reagent (conc. HCl + ZnCl2) is added to the


alcohol at room temperature. Alkyl chlorides formed
produce turbidity.
3ry alcohols react immediately.
2ry alcohols react within few minutes.
1ry alcohols do not react at room temperature.
B- Reaction with phosphorus halides:
Alcohols react with phosphorus trihalides (PX3) or
pentahalides (PX5) to yield alkyl halides.

3ROH + PX3  3 R - X + H3PO3

ROH + PX5  R – X + HX + POX3

1ry alcohols react by SN2 mechanism without


rearrangement.
2ry alcohols react by SN1 and undergo rearrangement.
C- Reaction with thionyl chloride:
ROH + SOCl2  ROSOCl + HCl  RCl + SO2
chlorosulfite

Mechanism (SNi substitution nucleophilic internal):

The reaction leads to retention of configuration


In the presence of a base e.g. pyridine, HCl liberated is
converted to pyridinium cation and Cl- which readily
attacks the alkyl group from the back with the expulsion
of -OSOCl leading to SN2 mechanism and inversion of
configuration.
4- Dehydration:
Alcohols are dehydrated to alkenes by heating in the
presence of an acid, usually sulfuric acid.

CH3CH2OH + H2SO4 Heat CH2=CH2 + H2O

Mechanism (E1):

The ease of dehydration is 3ry > 2ry > 1ry alcohol


The reaction proceeds to form the most stable alkene
(Saytzeff's rule).

The cabocation ion intermediate may undergo rearrangement.


5- Oxidation:
Oxidizing agents used for oxidation of alcohols are:
1- Aqueous acid dichromate (alternatively chromic acid CrO3 in
glacial acetic acid).
2- Acid or alkaline permanganate.

3ry alcohols are resistant to oxidation in neutral or alkaline


solutions but in acidic medium, they are dehydrated to alkenes
which are then oxidized.
Hot permanganate oxidation of 2ry alcohols leads to
breaking of carbon-carbon bonds and production of a
mixture of carboxylic acids each containing fewer carbon
atoms than the original alcohol.
Oxidation of glycols with strong oxidizing agents e.g.

permanganate, dichromate or periodic acid result in

fission of carbon-carbon bond to give aldehydes, acids

and/or ketones.
Pinacol-Pinacolone rearrangement:
Pinacol (2,3-dimethyl-2,3-butanediol) when treated with an
acid is converted into pinacolone.

Mechanism:
b. IUPAC system:
Ethers are regarded as alkoxy derivatives, the larger
group is chosen as the parent one, e.g.
Preparation of ethers
1- From alcohols (dehydration):
Limited to the preparation of symmetrical ethers and
large scale production.

Dehydration to ethers rather than to alkenes is


controlled by adjusting the temperature of the reaction.
Mechanism:
SN2 (for straight chain primary alcohols)
SN1 (for tertiary alcohols)
2- Williamson synthesis:
Prepare all types of ethers (Symmetrical or Asymmetrical).
R – O- Na+ + R`- X  R – O – R` + NaX
N.B: Use 1ry alkyl halide with the 3ry alkoxide and not
the reverse, otherwise elimination takes place.
For the preparation of alkyl aryl ethers, we have to use
a phenoxide with an alkyl halide and not the reverse
because of the low reactivity of aryl halides towards
nucleophilic substitutions.

e.g. preparation of anisole

C6H5-O- Na+ + CH3-Br  C6H5OCH3

C6H5Br + CH3–O- Na+  no reaction


Physical properties of ethers
Ethers are weakly polar molecules which cannot
associate through hydrogen bonding.
Their boiling points are about the same as those of
alkanes having comparable molecular weights (e.g. ethyl
ether 35oC).
They could form hydrogen bonds with water, that is
why they are slightly soluble in it (ethyl ether and n-
butanol are soluble to the extent of 8%).
Hazards of ethers
1.Lower members are gases or volatile liquids and are
highly inflammable.
2. Most alkyl ethers contain traces of peroxides due to
air oxidation; these may cause explosions during
distillation of the ethers.
The presence of peroxides is indicated by formation of a
red color when the ether is shaken with an aqueous
solution of ferrous salt and potassium thiocyanate.

Peroxides are removed either by washing


the ether with solutions of ferrous ions or
by distillation from conc. H2SO4.
Chemical reactions of ethers
Ethers are relatively un-reactive compounds therefore they
are widely used as solvents for different chemical reactions.

Cleavage in strong acid medium:


Conc. HI or HBr is used and the products depend mainly
on the temperature of the reaction.
Mechanism:
SN1 or SN2 depending upon conditions and the
structure of the alkyl groups (1ry SN2 and 3ry SN1).
Aryl alkyl ethers undergo this reaction in one direction

Conc. HI/Heat
C6H5OCH3  C6H5OH + CH3I

Zeisel method:
Used to determine the number of methoxyl or ethoxyl
groups in the molecule.