Processes for the production of chlorinated alkanes are provided. The present processes comprise dehydrochlorinating one or more trichloroalkanes having from 3-6 carbon atoms and vicinal chlorine atoms, followed by a series of sequential chlorination and/or further dehydrochlorination steps. Because the trichloroalkane is first dehydrochlorinated, rather than being first chlorinated, greater specificity to desired tetra- and pentachloroalkanes can be seen.