SYNTHESIS OF HLOROMETHYL-12H-DIBENZO[D,G][1,3,2]DIOXAPHOSPHOCIN AND HLOROMETHYL-12H-DIBENZO[D,G][1,3,2]DIOXAPHOSPHOCIN 6-OXIDES - X-RAY-DIFFRACTION ANALYSES OF HLOROMETHYL-12H-DIBENZO[D,G][1,3,2]DIOXAPHOSPHOCIN 6-OXIDE AND TRIETHYLAMMONIUM 2-METHYLPHENYL '-HYDROXYL-5''-CHLOROPHENYL))ETHYL]-4-CHLOROPHENYL PHOSPHATE

6-Aryloxy- and hloromethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-ox ides were synthesized and characterized by IR, H-1, C-13, P-31, and ma ss spectral analyses for the first time. The H-1 chemical shifts for H (12) at the carbon bridge occurred between delta 6.15 and 6.40 which s uggested a common environment and one conformer, but the presence of m ore than one conformer in each example cannot be entirely eliminated. Obviously the trichloromethyl groups attached to C(12) induces a signi ficant downfield shift of H(12). An X-ray diffaction analysis of solid hloromethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxide (3j) shows it is a boat-chair with the trichloromethyl group in a pseudo equator ial arrangement and with the phosphoryl group in a ''down arrangement' ' of a boat-chair conformer. An interesting by-product, namely triethy lammonium 2-methylphenyl 2-[{2',2',2'-trichloro-1'-(2 ''-hydroxyl-5 '' -chlorophenyl)}ethyl]-4-chlorophenyl phosphate (5), was isolated when attempts were made to purify a crude sample of 3b. Thus, it appears th at either the initial ring closure did not occur between 1 and 2b or, in the purification process for 3b, the ring was opened in the presenc e of residual triethylamine. System 5 was also confirmed by X-ray anal ysis.