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Catalytic hydrogen-chlorine exchange between chlorinated hydrocarbons under oxygen-free conditions.

Chlorinated hydrocarbons (CHCs) remain important industrial chemical intermediates and solvents, especially for the exploration of the potential of La-based materials for the conversion of chlorinated waste compounds.[1] The production of industrially important CHCs frequently occurs with concurrent formation of less desirable side-products. For example, mixtures of chlorinated C1 and C2 hydrocarbons are still formed as by-products in industrial processes such as the production of vinyl chloride monomer (VCM).[2, 3] Another example is carbon tetrachloride (CCl4) formation in the production of chloroform (CHCl3) and other chlorinated methanes. The United States Clean Air Act and the Montreal Protocol limit the production and sale of CCl4,[4,5] therefore methods to effectively recycle chlorinated side-products, in particular CCl4, would be advantageous. The hydrogen– chlorine exchange of CCl4 with other CHCs, such as CH2Cl2, for the recycling of less desirable compounds into valuable products would be of particular interest.