--%>
Assignment Help - homework help

How haloalkanes are prepared from hydrocarbons?

Alkyl halides can be prepared from alkanes through substitution and from alkenes through addition of halogen acids or through allylic substitution.
    
From alkanes

When alkanes are treated with halogens, chlorine or bromine, in the presence of light or heat, they undergo free radical substitution and a mixture of mono- and poly- substituted products are obtained.

2242_alkyl halide.png 

Although, the substitution beyond monohalogenation may be suppressed by using alkane in excess yet the method is not of much practical use because of the difficulties of separation of such a mixture.

In case of higher alkanes, different isomeric products are formed even when mono-substitution is carried out.

1702_alkyl halide1.png 

In general, the ease of substitution of different types of hydrogen atoms is:

Benzylic, allylic > tertiary > secondary > primary > vinylic, aryl

The iodination of alkanes is reversible and is done by heating with iodine in the presence of oxidising agents like conc. HNO3, HIO4 orHIO3. The function of using such agents is to oxidize HI formed during the reaction to iodine, and hence shift the equilibrium in the forward direction.

264_alkyl halide2.png 

Due to formation of polysubstituted products and isomeric products, this method is not suitable for the laboratory preparation of pure haloalkanes. However, this method can be used for laboratory preparation of certain specific alkyl halides as given below:
    
When all the hydrogen atoms in the alkane are equivalent are equivalent, then it can form only one product on monosubstitution. In such cases this method may be applied.

924_alkyl halide3.png 
    
Allylic and benzylic halides can be prepared from alkenes and arenes respectively by this method because allylic and benzylic hydrogen atoms are substituted much more readily than vinylic and aryl hydrogen atoms.

260_alkyl halide4.png 

In such cases vinylic aryl hydrogens being less reactive do not participate in free radical substitution.

Allylic and benzylic hydrogen atoms are substituted very easily because their substitution proceeds via allylic and benzylic free radicals as intermediates. These intermediates are stabilized by resonance and hence being stable are formed at faster rate.
    
By halide exchange

Iodoalkanes can be obtained by treating bromo or chloroalkanes with a solution of sodium iodine in acetone or methanol. For example,

1778_alkyl halide5.png 

The reaction is known as Finkelstein reaction. This reaction is based on the fact that NaI is soluble in acetone but NaBr and NaCl are not. As a result, equilibrium in the above reaction is very much in favour of forward reaction. The reaction gives best result with primary halides.

Fluoroalkanes are difficult to prepare directly by the action of alkanes with fluorine. It is because fluoride has gor a high reactivity towards the hydrogen. It extracts all the hydrogen atoms from hydrocarbon molecule.

CH4 + 2F2  71_potassium permangnate3.png  4HF + C

However, Fluoroalkanes can be obtained by treating alkyl halides with salts like AgF, Hg2F2, CoF3 or SbF3. This reaction is known as Swarts reaction.

CH3Br + AgF 71_potassium permangnate3.png CH3F + AgBr

2CH3CH2Cl + Hg2F2  71_potassium permangnate3.png  2CH3CH2F + Hg2Cl2

For replacement of two or three halogen atoms at the same carbon CoF3 or SbF3 is used.

67_alkyl halide6.png

   Related Questions in Chemistry

  • 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 : Problem related to molarity Provide

    Provide solution of this question. Increasing the temperature of an aqueous solution will cause: (a) Decrease in molality (b) Decrease in molarity (c) Decrease in mole fraction (d) Decrease in % w/w

    		•
  • Q : Why acetic has less conductivity than

    Illustrate the reason, why acetic has less conductivity than Hcl?

    		•
  • Q : Problem on endothermic or exothermic At

    At low temperatures, mixtures of water and methane can form a hydrate (i.e. a solid containing trapped methane). Hydrates are potentially a very large source of underground trapped methane in the pole regions but are a nuisance when they form in pipelines and block th

    		•
  • Q : Sugar solution The solution of sugar in

    The solution of sugar in water comprises: (i) Free atoms (ii) Free ions (iii) Free molecules (iv) Free atom and molecules. Choose the right answer from the above.

    		•
  • Q : Define Bond Energies - Bond Charges

    Energy changes in some chemical reactions can be used to deduce the energies of chemical bonds. Our understanding of the molecular basis of thermodynamic properties is extended when we ask why the enthalpy change for a reaction is what it is. We deduce,

    		•
  • Q : Problem on physical and thermodynamic

    The shells of marine organisms contain calcium carbonate CaCO3, largely in a crystalline form known as calcite. There is a second crystalline form of calcium carbonate known as aragonite. Physical and thermodynamic properties of calcite and aragonite at 298

    		•
  • Q : Strength of the Hydrochloric acid

    Provide solution of this question. 1.0 gm of pure calcium carbonate was found to need 50 ml of dilute HCL for complete reaction. The strength of the HCL solution is specified by : (a) 4 N (b) 2 N (c) 0.4 N (d) 0.2 N

    		•
  • Q : Hybridization Atomic orbitals can be

    Atomic orbitals can be combined, in a process called hybridization, to describe the bonding in polyatomic molecules. Descriptions of the bonding in CH4 can be used to illustrate the valence bond procedure. We must arrive a

    		•
  • Q : Relative lowering of vapour pressure

    explain the process of relative lowering of vapour pressure

    		•