Utilization of Chlorofluorocarbons (CFCs) : Synthesis of Medicines from Abandoned

本研究的目的是利用氯氟烃(CFCs)，特别是CFC-11在不分解的情况下合成有机中间体、功能材料和生物活性化合物。1998年，我们成功地将CFC-11与三丁基膦反应得到的氟乙烯进行碱性处理，合成了丙炔醇。1999年，由CFC-11与二苯二硫醚反应，以较高的产率合成了二氯氟甲基苯硫醚(1)。1用30%的过氧化氢氧化得到相应的砜2，产率为79%。用锌还原2得到氟甲基苯基砜(3)，它是合成含氟药物如抗病毒药物和抗菌药物的重要有机中间体。其专利申请正在准备中。用相当于锌的锌还原2，以80%的产率得到氯氟甲基苯基砜，它与各种羰基化合物反应，得到有趣的重排和加成产物。这些结果在日本读卖新闻(1999年10月18日和19日)和三洋新闻(1999年10月20日)上都有报道。我们也在亚洲化学大会(台北，1999年11月)上报道了上述结果。

The aim of the present research is the utilization of chlorofluorocarbons (CFCs), especially CFC-11 for the synthesis of organointermediates, functional materials and biologically active compounds without decomposition.In 1998, we succeeded in the synthesis of propargyl alcohols via basic treatment of fluoroethylenes, which were obtained from the reaction of CFC-11 with tributylphosphine.In 1999, dichlorofluoromethyl phenyl sulfid (1) was prepared in a good yield by the reaction of CFC-11 with diphenyl disulfide. Oxidation of 1 with 30% hydrogen peroxide gave the corresponding sulfone 2 in 79% yield. Reduction of 2 with zinc afforded fluoromethyl phenyl sulfone (3) , which is an important organointermediate for the synthesis of fluorine-containing medicines such as antivirus agents and antibiotics.These compounds were prepared by experimentally simple and economical methods. The application of its patent is under preparation. Reduction of 2 with an equivalent of zinc gave chlorofluoromethyl phenyl sulfone in 80% yield, which reacted with various carbonyl compounds, giving interesting rearrangement and addition products.These results were reported to all of Japan in Yomiuri Shimbun (October 18 and 19, 1999) and also in Sanyo Shimbun (October 20, 1999). We also reported the above results in Asian Chemical Congress (Taipei, November 1999).