From bis(3,5-dichloro-2-hydrxy-phenyl)methane (1), the new [1,3,2] dioxaphosphocins 5, 6 and 7 were synthesized. 1 reacted with POCl₃ or PSCl₃ to give cyclic compound 2 or 3, which reacted with monoalkyl-1,2-ethandiol to offer 5 or 6. 7 was prepared by the reaction of 1 with P₄S₁₀ in the presence of triethylamine, and then reacted with 2-alkoxyl ethyl bromide. The ¹H, ¹³C and ³¹P NMR and MS spec-tra of the new compounds were evaluated and discussed. The coupling ⁵J_PH (about 0.9 Hz) of P and C¹H or C³H was observed in the first time. A solid compound 8 was separated from the crude product 5 and its structure was determined. When 1 and POCl₃ reacted at the molar ratio of 3∶2, 8 was obtained in yield of 70%.

Key words: synthesis, NMR, MS, [1,3,2]dioxaphosphocin-6-oxides/sulfide