Free Radical Chlorination of Alkanes in Supercritical Fluid Solvents

2 Free Radical Chlorination of Alkanes in Supercritical Fluid Solvents 

The free radical chlorination of alkanes represents a classic procedure for the functionalization of alkanes 

Many of the details of this reaction have been understood for more than half a century [60]. In the laboratory, this reaction is initiated by action of visible 

The chlorine atom is a highly reactive species, and exhibits low selectivity in hydrogen abstractions. In solution, 3° C-H (4.2) 2° C-H (3.6) 1° C-H (1.0), on a per hydrogen basis (25 C) [58], absolute rate constants for hydrogen abstraction are just slightly below the diffusion-controlled limit [61]. 

In conventional solvents, the ratio of mono- to polychlorinated products (M/P) has been shown to depend on solvent viscosity [65]. 

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