SYNTHESIS OF 6-ARYLOXY- AND 6 p-TOLYLTHIOXY 2,10-DICHLORO-12-TRICHLOROMETHYL-12H-DIBENZO[d,g]-[1,3,2]DIOXAPHOSPHOCIN 6-OXIDES

Abstract

6-Aryloxy- and 6-p-tolylthioxy-2,10-dichloro-12-trichloromethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxides were synthesized and characterized by IR, ¹H, ¹³C, ³¹P, and mass spectral analyses for the first time. The ¹H chemical shifts for H(12) at the carbon bridge occurred between δ 6.15 and 6.40 which suggested a common environment and one conformer, but the presence of more than one conformer in each example cannot be entirely eliminated. Obviously the trichloromethyl groups attached to C(12) induces a significant downfield shift of H(12). An X-ray diffraction analysis of solid 6-(4′-chlorophenoxy)-2,10-dichloro-12-trichloromethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxide (3j) shows it is a boat-chair with the trichloromethyl group in a pseudo equatorial arrangement and with the phosphoryl group in a “down arrangement” of a boat-chair conformer. An interesting by-product, namely triethylammonium 2-methylphenyl 2-[[2′,2′,2′-tichloro-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 that 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 presence of residual triethylamine. System 5 was also confirmed by X-ray analysis.

Key Words:

• 6-Aryloxy- and 6-p-tolylthioxy-2,10-dichloro-12-trichloromethyl-12H-dibenzo[d,g][1,3,2]-dioxaphosphocin 6-oxides
• triethylammonium 2-methylphenyl 2-[{2′,2′2′-trichloro-1′-(2″-hydroxyl-5″-chlorophenyl}ethyl]-4-chlorophenyl phosphate
• boat-chair conformer
• NMR analysis
• mass spectral analysis
• conformational analysis
• X-ray diffraction analysis