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Halogenation of Alkanes

Introduction: 

  • Halogenation of alkanes is a chemical reaction where hydrogen atoms in an alkane are replaced by halogen atoms through a free radical mechanism.

  • This process is crucial in organic chemistry for the functionalization of alkanes and the synthesis of halogenated compounds.

Mechanism: 

The reaction proceeds in three steps: initiation, propagation, and termination.

1. Initiation:

  • UV light or heat breaks the diatomic chlorine molecule into two chlorine radicals.

Cl2 + UV light/heat → 2Cl•Cl2 ​+ UV light/heat → 2Cl•

2. Propagation:

  • A chlorine radical abstracts a hydrogen atom from the alkane, creating a carbon-centered radical and hydrochloric acid.

R-H + Cl• →R• + HClR-H + Cl• → R• + HCl

  • The carbon-centered radical reacts with another chlorine molecule, forming the chlorinated alkane and another chlorine radical.

R• + Cl2 → R-Cl + Cl•R• + Cl2 ​→ R-Cl + Cl•

3. Termination:

  • The reaction stops when two radicals recombine to form a stable molecule.

  • Possible reactions include:

    • Two chlorine radicals forming a chlorine molecule.

    • A carbon-centered radical and a chlorine radical forming a chlorinated alkane.

    • Two carbon-centered radicals forming a new alkane.


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