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    • 4. 发明授权
    • Process for the preparation of enantiomerically pure (5, 5′-dichloro-6,6′-dimethoxy-biphenyl-2,2′-diyl)- bis(diphenylphosphine oxides)
    • 制备对映体纯(5,5'-二氯-6,6'-二甲氧基 - 联苯-2,2'-二基) - 双(二苯基膦氧化物)的方法
    • US06489513B2
    • 2002-12-03
    • US10010176
    • 2001-11-13
    • Torsten PohlThomas PrinzGuido GiffelsWolfram Sirges
    • Torsten PohlThomas PrinzGuido GiffelsWolfram Sirges
    • C07F953
    • C07F9/5329
    • The invention relates to the preparation of enantiomerically pure bis-diphenylphosphine oxides in a particularly advantageous manner by (1) reacting an aromatic bromine compound with a diphenylphosphinic chloride in a mixture of tetrahydrofuran and an aromatic hydrocarbon to give a diphenylphosphine oxide, which is isolated from a solution in an aromatic hydrocarbon by adding a saturated aliphatic hydrocarbon; (2) metalating the resulting diphenylphosphine oxide in the 6-position and reacting the metalated diphenylphosphine oxide with iodine at temperatures not less than −25° C. in such a way that a small amount of iodine is always present in excess, giving a 2-iodo-diphenylphosphine oxide; (3) preparing a racemic bis-diphenylphosphine oxide from the resulting 2-iodo-diphenylphosphine oxide using copper and an aromatic hydrocarbon solvent and crystallizing the racemic bis-diphenylphosphine oxide from a solution in an aromatic hydrocarbon; and (4) separating isomers using an enantiomerically pure mono- or dicarboxylic acid to obtain a first enantiomer by crystallization from a solution in an aromatic hydrocarbon and obtaining a second enantiomer by hydrolysis and subsequent crystallization from a solution in an aromatic hydrocarbon.
    • 本发明涉及通过(1)使芳族溴化合物与二苯基次膦酰氯在四氢呋喃和芳族烃的混合物中反应得到二苯基氧化膦,特别有利的方法制备对映体纯双的二苯基膦氧化物,得到二苯基氧化膦 通过加入饱和脂肪烃在芳族烃中的溶液; (2)将得到的二苯基氧化膦金属化在6位上,并使金属化二苯基氧化膦与碘在不低于-25℃的温度下反应,使得少量的碘总是存在于过量的中,得到2 碘代二苯基氧化膦; (3)使用铜和芳烃溶剂从所得的2-碘 - 二苯基氧化膦制备外消旋二苯基二氧化膦氧化物,并从外来物质中溶解外消旋双 - 二苯基膦氧化物; 和(4)使用对映异构体纯的单羧酸或二羧酸分离异构体,以通过从芳族烃溶液中结晶获得第一对映异构体,并通过水解并随后从芳族烃溶液中结晶得到第二对映异构体。