双(4-氯甲酰苯基)苯基氧化膦的合成与表征

Synthesis and Characterization of Bis (4-chloroformyl) Phenylphosphine Oxide

苯基硫代膦酰二氯与甲苯通过Friedel-Crafts反应形成双(对甲苯基)苯基硫化膦(BMPPS),继而用KMnO4作氧化剂分别在吡啶、KOH的水溶液中经两步氧化制得关键中间体双(对羧苯基)苯基氧化膦(BCPPO).再将BCPPO和氯化亚砜反应以较高产率合成了聚合单体双(4-氯甲酰苯基)苯基氧化膦.该方法具有原料价廉、反应温和、毒性不强、操作简单等优点,有利于工业化生产.

Treatment of phenylthiophosphonic dichloride (DCPPS) with toluene by Friedel-Crafts reaction afforded bis(4-methylphenyl)phenylphosphine sulfide (p-BMPPS), which was oxidated into key intermediate, bis(4-carboxyphenyl)phenylphosphine oxide (p-BCPPO) in the presence of KMnO_4 in aqueous solution of pyridine and potassium hydroxide in two step, respectively. And then reaction of bis(4-carboxyphenyl)phenylphosphine oxide(p-BCPPO) with sulfur oxychloride yielded polymerization-grade monomer bis(4-chloroformyl)phenylphosphine oxide in good yields. The present method has the advantage of ready availability of starting materials, mild reaction condition, convenient manipulation and low toxicity for the industrial preparation of bis(4-chloroformyl)phenylphosphine oxide.