Oxidative addition reactions of cyclic chlorophosphites and arsenites with diols and 1,2-quinones: X-ray structure of the phosphocin (ClCH < inf > 2 < /inf > CMe < inf > 2 < /inf > CH < inf > 2 < /inf > O)P(O) {(O-2,4-(t-bu) < inf > 2 < /inf > C < inf > 6 < /inf > H < inf > 2 < /inf > ) < inf > 2 < /inf > CH < inf > 2 < /inf > }

Abstract

The phosphorinane ring opens when CIP(OCH2CMe2CH2O) (1) is treated with diols and N-chlorodiisopropylamine (NCDA) or with quinones. X-ray structure of one such product, the phosphocin oxide, (ClCH2CMe2CH2O) P(O) {(O-(2,4-(t-bu)2C6H2)2CH 2} (3) reveals a 'symmetrical anti' (chair) conformation of the eight membered ring. The phenylene phosphorochloridite CIP(O2C6H4) by contrast gives pentacoordinated phosphoranes in similar reactions. The arsorinane ClAs(OCH2CMe2CH2O) (9) on treatment with 2,2-dimethyl-1,3-propanediol-NCDA affords an arsorane formulated as ClAs(OCH2CMe2CH2O)2; no reaction was apparent when 9 was treated with quinones. © 1994.