1,1,1,2,2,2-Hexachloro-ethane reaction

Tetrakis(phenyldifluorophosphine)nickel-(0) could also be obtained, using arsenic trifluoride in the presence of catalytic amounts of antimony pentachloride, or zinc fluoride as fluorinating agents. Yields as high as 50% could be obtained, but sizable decomposition on the process of fluorination of the chlorophosphine nickel-(0) complexes in solution could not be entirely suppressed. The marked instability of zerovalent nickel-phosphine complexes in solution in organic solvents, even under strictly anhydrous and anaerobic conditions, has been noted by several workers (16,20), but is still lacking a detailed explanation. A closer examination of the system carbon tetrachloride-tetrakis(trichlorophosphine)nickel-(0) (23) showed the main pa h of the reaction to consist in the formation of hexachloro-ethane with conversion of zerovalent into bivalent nickel, while the coordinated... 

Thus, the thermal decomposition of tetramethyldibismuthine in the presence of bromotrichloromethane may take place via the following chain mechanism, (i) Tetramethyldibismuthine decomposes first into two dimethyl-bismuth radicals, (ii) These radicals react with bromotrichloromethane to form bromodimethylbismuthine bromide and a trichloromethyl radical, (iii) The trichloromethyl radical reacts with the dibismuthine to form dimethyl(trichlor-omethyl)bismuthine and dimethylbismuth radical. The termination step is the self-combination of the trichloromethyl radicals. In fact, the major product of the reaction is bromodimethylbismuthine bromide and the second product is dimethyl(trichloromethyl)bismuthine. Trimethylbismuthine, hexachloro-ethane and tetrachloroethylene are also formed in smaller quantities [830M1859]. 

The products of the reaction between alkyldiphenylphosphines and hexachloro-ethane in the presence of a tertiary amine are the ylide (88) and the a-chloro-alkylphosphine (89), which are interchangeable, constitutional isomers that interconvert via an intramolecular reversible 1,2-chlorine shift from phosphorus to carbon. Application of the triphenylphosphine-hexachloroethane reagent for the self-condensation polymerization of / -aminobenzoic acid has been studied in detail. Related reactions between dicarboxylic acids and diamines, conducted in the presence of pyridine, involve the cationic phosphorane (90) as a key intermediate. Replacement of hexachloroethane by hexabromoethane or... 

Reactions of zinc or aluminum with organic halogen compounds as used in certain white smoke formulations also fall into the intermediate (0.5—1.0 kcal/g) range. In order to present meaningful figures, the considerable heat of vaporization of the aluminum (III) chloride (Aids) and the still higher one of zinc chloride (ZnClj must be considered. The reaction of aluminum with hexachloro-ethane (CaClg) furnishes 0.98 kcal/g in standard states but only 0.88... 

Polychlorides. An ice-cooled mixture of perchloroethylene and water satd. with chlorine, then with continued stirring and introduction of chlorine a soln. of divinylacetylene, as initiator, in perchloroethylene added dropwise during ca. 1 hr. at such a rate so as to keep the temp, at 15-30° during the exothermic reaction, which starts after an induction period of 5-10 min. hexachloro-ethane. Y 96% based on startg. m. consumed. F. e., also in the absence of water, and initiators s. A. N. Akopyan, A. M. Saakyan, and A. A. Safaryan, X. 32, 1098 (1962) C. A. 58, 2355b. 

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