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Haloalkanes from Alcohols
This is the common method for preparing haloalkanes in laboratory.
Alcohols can be converted to haloalkanes by substitution of – OH group with a halogen atom.
Different reagents can be used to get haloalkanes from alcohols as described below:
By reaction with Halogen Acids: alcohols can be converted into haloalkanes by treatment with halogen acids. The reaction, in general, can be represented as

Chlorolakanes are obtained by treating alcohols with HCl in the presence of anhydrous zinc chloride. The anhydrous ZnCl2 acts as dehydrating agent and thus favours the forward reaction (Le Chateliar principle). The mixture of HCl and anhydrous ZnCl2 is known as Lucas reagent.

Bromoalkanes can also be obtained in an identical manner by heating alcohols with KBr or NaBr and conc. H2SO4.HBr is generated in situ (during the reaction) by reaction of KBr or NaBr with conc. H2SO4.
KBr + H2SO4
KHSO4 + HBr
C2H5OH + HBr
C2H5Br + H2O
The reaction can also be carried out with conc. Solution (48%) of hydrobromic acid. Iodoalkanes are obtained by heating alcohols with KI and 95% H3PO4 (phosphoric acid).

C2H5OH + HI
C2H5I + H2O
The reaction can also be carried out with conc. solution (57%) of hydroiodic acid.
Reactivity of halogen acids towards this reaction is: HI > HBr > HCl
It is because of the fact that the bond dissociation energy of HI is less than that of HBr which in turn is less than that of HCl.
Reactivity of alcohols towards this reaction is: tertiary > secondary > primary
It is because of the fact that greater the number electron releasing groups on
-carbon atom of alcohol more is the polarity of C-OH bond. Consequently greater is the ease with which it cleaves.
By reaction with phosphorus halides: Chlorolakanes are obtained by reaction of alcohols with PCl3 or PCl5.


Bromo and iodo alkanes are obtained by reaction of alcohols with a mixture of red phosphorus and Br2 or I2. The function of red phosphorus and Br2 or I2 is to get PBr3 and PI3 during the course of the reaction. PBr3 and PI3 being relatively unstable have to be prepared either in situ or just before use. They cannot be stored for long periods. For example,
P4 + 6Br2
4PBr3

P4 + 6I2
4PI3

The alkyl halides are obtained in excellent yield (80%) in the reaction. The phosphorus halide method is better than halogen acid method because
Certain alcohols such as, secondary and tertiary alcohols tend to dehydrate in the presence of halogen acids.
Intermediate carbocation formed can undergo rearrangement in the presence of acids.
By reaction with Thionyl Chloride: in this method the alcohol is refluxed with thionyl chloride in the presence of a small amount of pyridine. Refluxing is the process of heating a volatile liquid in a flask fitted with condenser so that the vapours are condensed back into the flask.
The reaction of straight chain primary alcohols in the presence or absence of pyridine is called Darzen’s procedure. Pyridine is used in the reaction to neutralize hydrogen chloride in the reaction.

The above methods cannot be applied for conversion of phenols to aryl halides because carbon-oxygen bond in phenols has partial double bond character due to resonance and hence is stronger and difficult to break.
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Alcohols can be converted to haloalkanes by substitution of – OH group with a halogen atom.
Different reagents can be used to get haloalkanes from alcohols as described below:
By reaction with Halogen Acids: alcohols can be converted into haloalkanes by treatment with halogen acids. The reaction, in general, can be represented as
Chlorolakanes are obtained by treating alcohols with HCl in the presence of anhydrous zinc chloride. The anhydrous ZnCl2 acts as dehydrating agent and thus favours the forward reaction (Le Chateliar principle). The mixture of HCl and anhydrous ZnCl2 is known as Lucas reagent.
Bromoalkanes can also be obtained in an identical manner by heating alcohols with KBr or NaBr and conc. H2SO4.HBr is generated in situ (during the reaction) by reaction of KBr or NaBr with conc. H2SO4.
KBr + H2SO4
C2H5OH + HBr
The reaction can also be carried out with conc. Solution (48%) of hydrobromic acid. Iodoalkanes are obtained by heating alcohols with KI and 95% H3PO4 (phosphoric acid).
C2H5OH + HI
The reaction can also be carried out with conc. solution (57%) of hydroiodic acid.
Reactivity of halogen acids towards this reaction is: HI > HBr > HCl
It is because of the fact that the bond dissociation energy of HI is less than that of HBr which in turn is less than that of HCl.
Reactivity of alcohols towards this reaction is: tertiary > secondary > primary
It is because of the fact that greater the number electron releasing groups on
By reaction with phosphorus halides: Chlorolakanes are obtained by reaction of alcohols with PCl3 or PCl5.
Bromo and iodo alkanes are obtained by reaction of alcohols with a mixture of red phosphorus and Br2 or I2. The function of red phosphorus and Br2 or I2 is to get PBr3 and PI3 during the course of the reaction. PBr3 and PI3 being relatively unstable have to be prepared either in situ or just before use. They cannot be stored for long periods. For example,
P4 + 6Br2
P4 + 6I2
The alkyl halides are obtained in excellent yield (80%) in the reaction. The phosphorus halide method is better than halogen acid method because
Certain alcohols such as, secondary and tertiary alcohols tend to dehydrate in the presence of halogen acids.
Intermediate carbocation formed can undergo rearrangement in the presence of acids.
By reaction with Thionyl Chloride: in this method the alcohol is refluxed with thionyl chloride in the presence of a small amount of pyridine. Refluxing is the process of heating a volatile liquid in a flask fitted with condenser so that the vapours are condensed back into the flask.
The reaction of straight chain primary alcohols in the presence or absence of pyridine is called Darzen’s procedure. Pyridine is used in the reaction to neutralize hydrogen chloride in the reaction.
The above methods cannot be applied for conversion of phenols to aryl halides because carbon-oxygen bond in phenols has partial double bond character due to resonance and hence is stronger and difficult to break.
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