--%>

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.

   Related Questions in Chemistry

  • Q : Strength of dilute acid of Sulfuric acid

    Select the right answer of the question.10ml of conc.H2SO4 (18 molar) is diluted to 1 litre. The approximate strength of dilute acid could be: (a)0.18 N (b)0.09 N (c) 0.36 N (d)1800 N

  • Q : Excel assignment I want it before 8 am

    I want it before 8 am tomorow please. I am just wondering how much is going to be ?

  • Q : Problem on decinormal strength Can

    Can someone please help me in getting through this problem. How many grams of dibasic acid (having mol. wt. 200) must be present in 100ml  of its aqueous solution to provide decinormal strength: (i) 1g  (ii)2g  (iii) 10g  (iv) 20g<

  • Q : Molarity of HCl solution 20 ml of HCL

    20 ml of HCL solution needs 19.85 ml of 0.01M NaOH solution for complete neutralization. Morality of the HCL solution is:  (i) 0.0099 (ii) 0.099 (iii) 0.99 (iv) 9.9 Choose the right answer from above.

  • Q : Concentration of urea Help me to go

    Help me to go through this problem. 6.02x 1020 molecules of urea are present in 100 ml of its solution. The concentration of urea solution is: (a) 0.02 M (b) 0.01 M (c) 0.001 M (d) 0.1 M (Avogadro constant, N4= 6.02x 1023mol -1)<

  • Q : Molecular energies and speeds The

    The average translational kinetic energies and speeds of the molecules of a gas can be calculated.The result that the kinetic energy of 1 mol of the molecules of a gas is equal to 3/2 RT can be used to obtain numerical values for the

  • Q : Raoults law Give me answer of this

    Give me answer of this question. Provide solution of this question. Which one of the following is the expression of Raoult's law: (a) P-P1/P = n/n+N (b) P1-P/P = N/ N+n (c)P-P2/P1= N/ N-n (d) P1-P/P2= N-n/N

  • Q : Describe First Order Rate Equation The

    The integrated forms of the first order rate equations are conveniently used to compare concentration time results with this rate equation. Rate equations show the dependence of the rate of the reaction on concentration can be integrated to give expressions fo

  • Q : Vapour pressure of methanol in water

    Give me answer of this question. An aqueous solution of methanol in water has vapour pressure: (a) Equal to that of water (b) Equal to that of methanol (c) More than that of water (d) Less than that of water

  • Q : What do you mean by the term dipole

    What do you mean by the term dipole moment? Briefly describe it.