Document ZnMpd6zaQ976pmV14EDavjOop

A PEROXIDE OP VINYL CHLORIDE By M-jl^derer RECEIVED APR 011974 R. N. WHEE1.FR. JR. Angew. Chemltyl 162 (1959) 1 * v, j Z. LJ HESliArtCM UE^ARTitfErlT AUG 241965 LIBRARY PLEASE DO NOT REMOVE FROM LIBRARY Translated from the German For Union Carbide Corporation, Chemicals Division By The Technical Library Research Service ..Under Purchase Order No. 511-48330-1 TLRS Order No. 3586 n t ucc 03206 ro A PEROXIDE OF VINYL CHLORIDE By Dr. M. Lederer Synthetics Laboratory of the Farbwerke Hoechst A.G. Recently, a report was presented on conversion products of vinyl chloride and oxygen Cl]. We would like to present some of our own results.* When subjected to UV irradiation between -15 and -20C, vinyl chloride forms a peroxide [`OCHg-CHCl-O*] . The compound, pre pared in quantities of 6o-2tO mg, is a colorless, syrupy substance, the halogen atoms are readily split off by hydrolysis. On the 'oasis of active oxygen, we obtained the substance in a purity of 80#. Cryoscoplc molecular weight determinations in dioxane indi cate n =* 2. The compound can be hydrogenated with an excess of LiAlH^ In tetrahydrofuran at 65C Into ethylene glycol (75# of theory) and HC1 (85# of theory). Thermal decomposition in an anhydrous COg-stream at 75C, in part, takes place as follows; * Cl (OCH, -CHC1-O.J -h CH,0 + C-0 CO 4- MCI M, <9\ 4. Th.) (44% 4. Th.) <n% 4. Th.) (39# of theory) (W# of theory) (79# of theory) In the Ng-stream, 1-2# COg are present. At 50C and 60C, the thermal decomposition in dioxane still takes place at a measurable rate* In the hydrolysis with wet ether below 35C, we found HC1 (8^# of theory), glycolaldehyde (20# of theory) and glycolic acid (26# of theory). The peroxide initiates the block polymerization of vinyl chloride above 35C, but only a small quantity of polymer forms. In a similar manner as vinyl chloride, 2-chlorpropylene, its methyl homolog, undergoes a reaction with Og. However, we found UCC 032063 2 only 23# of the anticipated peroxide in the reaction product. In the reduction with LiAlIfy, propylene glycol was formed (18# of theory). Received Jan. 14, 1959 l) G. A. Rasuwajew and K. S. Minsker: J. allgem. Chem. (Russ.) 28. 983 (1958)* ucc 032064