OXIDATIVE ADDITION-REACTIONS OF CYCLIC CHLOROPHOSPHITES AND ARSENITESWITH DIOLS AND 1,2-QUINONES - X-RAY STRUCTURE OF THE PHOSPHOCIN (CLCH2CME2CH2O)P(O) ((O-2,4-(T-BU)(2)C6H2)(2)CH2)

The phosphorinane ring opens when CIP(OCH(2)CMe(2)CH(2)O) (1) is treat ed with diols and N-chlorodiisopropylamine (NCDA) or with quinones. X- ray structure of one such product, the phosphocin oxide, (ClCH(2)CMe(2 )CH(2)O) p(O) {(O-(2,4-(t-bu)(2)C6H2)(2)CH2} (3) reveals a 'symmetrica l anti' (chair) conformation of the eight membered ring. The phenylene phosphorochloridite ClP(O2C6H4) by contrast gives pentacoordinated ph osphoranes in similar reactions. The arsorinane ClAs(OCH(2)CMe(2)CH(2) O) (9) on treatment with 2,2-dimethyl-l,3-propanediol-NCDA affords an arsorane formulated as ClAs(OCH(2)CMe(2)CH(2)O)(2); no reaction was ap parent when 9 was treated with quinones.