Synthesis and spectral studies of novel 2-chloroethyl dioxa/dioxathiaphosphocins and benzodiazaphosphole 2/6/8-oxides

Anew class of phosphonates, 2,10-dichloro-12-trichlorcomethyl-6-(2- chloroe thyl)- 12H-dibenzo [d,g] [1,3,2]dioxaphosphocin 6-oxide 3a, 2,10-dichloro-6 -(2-chloroethyl) dibenzo [d,g] [1,3,6,2] dioxathiaphosphocin 6-oxide 3b, 8- (2-chloroethyl)-16H-dinaphtho[2,1-d:1,2'-g] 1,3,2-dioxaphosphocin 8-oxide 5 , 2,10-dichloro-6-(2-chloroethyl)-4,8-dinitrodibenzo[d,g] [1,3,6,2] dioxath iaphosphocin 6-oxide 9 and 2-(2-chloroethyl)2,3-dihydro-5-thiophenoxy-1H-1, 3,2-benzodiazaphosphole 2-oxide 13 have been synthesized from reactions of equimolar quantities of diols (2a,2b,4,7)/diamine (12) with 2-chloroethyl p hosphonyl dichloride I at various temperatures in dry toluene in the presen ce of triethylamine. Oxidation studies with H2O2 (30%) in acetic acid showe d interesting results. Compound 9 on oxidation yielded only the correspondi ng 12-sulphoxide (10) and not its sulphone (11). But similar oxidation of 1 3 afforded sulphone (14), thus showing that steric and electronic factors c ontrol the oxidation process. Alternative approach for the preparation of 1 1 by oxidation of 7 to sulphone 8 and its cyclocondensation with 1 were uns uccessful due to the existence of strong intramolecular H-bonding. Their IR , H-1, C-13, P-31 NMR and mass spectral data were analyzed.