6-烷氧基乙氧/硫基-6-氧/硫-双苯并[1,3,2]-二氧磷杂八环的合成与波谱特征

通过双(3,5-二氯-2-羟基-苯基)甲烷(1)分别与POCl₃或PSCl₃在三乙胺存在下关环, 再与单烷氧基乙醇钠作用, 得到了新化合物5或6; 以1与P₄S₁₀及三乙胺关环的产物4与烷氧基溴乙烷反应得到了7. 测试了5, 6和7的¹H, ¹³C和³¹P NMR及MS数据, 并讨论了其特征. 观察到了磷与C¹H (C¹¹H)或C³H (C⁹H)与P的⁵J_PH偶合常数(约为0.9 Hz). 在1与POCl₃关环产物与单甲氧基乙醇反应的产物中, 分离到了一个副产物8并确定了它的化学结构. 1与POCl₃按3∶2的物质的量比在三乙胺存在下反应, 得到收率75%的8.

Synthesis and Spectral Characteristics of 6-O/S-Alkoxyethyl- 12H-[1,3,2]dioxaphosphocin-6-oxides/sulfides

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%.