SYNTHESIS AND SPECTRAL STUDIES OF NOVEL 2-CHLOROETHYL DIOXA/DIOXATHIAPHOSPHOCINS AND BENZODIAZAPHOSPHOLE 2/6/8-OXIDES

Abstract

Anew class of phosphonates, 2,10-dichloro-l2-trichloromethyl-6-(2-chloroethy1)-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] dioxathiaphosphocin 6-oxide 9 and 2-(2-chloroethy1)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 phosphonyl dichloride I at various temperatures in dry toluene in the presence of triethylamine. Oxidation studies with H₂O₂ (30%) in acetic acid showed interesting results. Compound 9 on oxidation yielded only the corresponding 12-sulphoxide (10) and not its sulphone (11). But similar oxidation of 13 afforded sulphone (14), thus showing that steric and electronic factors control the oxidation process. Alternative approach for the preparation of 11 by oxidation of 7 to sulphone 8 and its cyclocondensation with 1 were unsuccessful due to the existence of strong intramolecular H-bonding. Their IR, ¹H, ¹³C, ³¹P NMR and mass spectral data were analyzed.

Key Words:

• 2-chloroethyl dioxaphosphocins / dioxathiaphosphocins / benzodiazaphospholes
• ¹H, ¹³C and ³¹P NMR analysis
• mass spectral analysis