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How haloalkanes are prepared 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:
    
Reaction by Halogen Acids: alcohols can be converted into haloalkanes by action with halogen acids. The reaction, in general, can be represented as
2262_haloalkanes.png 

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.
2263_haloalkanes1.png 

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  2078_electrode potential.png  KHSO4 + HBr

C2H5OH + HBr  2078_electrode potential.png  C2H5Br + H2O


The reaction can also be carried out with conc. Solution (48%) of hydrobromic acid. Iodoalkanes are obtained by heating alcohols withKI and 95% H3PO4 (phosphoric acid).

1945_haloalkanes3.png 

C2H5OH + HI  2078_electrode potential.png  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 particular reaction is: tertiary > secondary > primary

It is because of the fact that greater the number electron releasing groups on 535_amines with aldehydes3.png-carbon atom of alcohol more is the polarity of C-OH bond. Consequently greater is the ease with which it cleaves.
    
Reaction by phosphorus halides: Chlorolakanes are obtained by reaction of alcohols with PCl3 or PCl5.
1701_haloalkanes4.png 


1170_haloalkanes5.png 

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 accumulated for long periods. For example,

              
P4 + 6Br2  2078_electrode potential.png  4PBr3

2315_haloalkanes7.png  
                   
P4 + 6I2  2078_electrode potential.png  4PI3    

94_haloalkanes6.png 

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.
    
Reaction by 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.

1733_haloalkanes8.png

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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