Hydrogen migration in 1,1-dichloroalkyl radicals

Synthesis of Polychloroalkanes

“…Terminal CCl 3 groups in polychloroalkanes can be easily converted to CHCl 2 groups by reaction with EtMgBr [63] or by reduction in the presence of Fe(CO) 5 and a hydrogen donor (dimethylformamide, hexamethylphosphotriamide, isopropanol) [64][65][66][67]. Hydrodechlorination with EtMgBr is accompanied by dimerization (Fig.…”

“…44). [64] Internal CCl 2 groups can also easily and selectively be reduced to CHCl [69,70] on Fe, Mo, and Mn carbonyls in the presence of a hydrogen donor. The best yields (up to 90%) are reported for Mo 2 (CO) 10 and Et 3 SiH system [70] (Fig.…”

“…Hydrolysis of telomeric a,a,a,o-tetrachloroalkanes followed by electrolysis of o-chloroalkancarboxylic acids is a good synthetic pathway to a,o-dichloroalkanes up to 1,24-dichlorotetracosane [64] (Fig. 47b).…”

“…Addition of CoCl 2 to reaction mixture increases the yield of 1,5,5,6,6,10-hexachlorodecane and decreases the yield of 1,1,5-trichloropentane. Fe(CO) 5 allows selective reduction of the CCl 3 group into CHCl 2 in the presence of CHCl and CH 2 Cl groups in molecules with chain lengths of up to 11 carbon atoms [64,65,67,68] (Fig. 42).…”

“…Distillation gave 16.6 g (74%) of 1,1-dichloroundecane with b.p. 101-102 C (2 mm) and a fraction containing, according to GLC data, 3.2 g (16%) of a mixture of 1,1,5-and 1,1,6-trichloroundecanes, which were identified by GLC with reference to samples obtained by an independent method [64]. 1,1,3-Tetrachlorooctane, 1,1,1,3-Tetrachlorononane, 1,1,1,3,6,8,8,8Octachlorooctane (Fig.…”