Reactions of Grignard Reagents with Bis- or Mono-Phosphonium Ions in Situ Generated from Bu_3P and Dicarboxylic Acid Dichlorides or ω-Ethoxycarbonyl Alkanoyl Chlorides as a Novel Method to Obtain Diketones and Ketoesters

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Reactions of Grignard reagents with bis-phosphonium or mono-phosphonium ions in situ generated from Bu_3P and ClCO(CH_2)_nCOCl (5) or ClCO(CH_2)_nCO_2Et (13) as a tool for preparation of symmetrical diketones or ketoesters were examined. Addition of Bu_3P (2.0 eq) to a THF solution of 5 (n=2) at -40℃ followed by addition of n-BuMgCl (2.0 eq) gave the corresponding diketone in good yield. When a mixture of Bu_3P and the Grignard reagent (2.0 eq each) was added to the dichloride solution at the same temperature, a better result was obtained.The latter method not with PhMgBr but with n-BuMgCl or MeMgBr was shown to be useful for preparation of symmetrical alkanediones and keto alkanoates from various 5 (n=2-6) and 13 (n=2 or 3), respectively. For synthesis of α-diketones or α-ketoesters, only PhMgBr entered the reaction, although the yields were not satisfactory. Addition of a mixture of Bu_3P (2.0 eq), MeMgBr (1.0 eq) and BuMgCl (1.0 eq) to a THF solution of 5 (n=4) at -40℃ afforded a mixture of 2,7-undecanedione and the corresponding two symmetrical diketones, with the yield of the unsymmetrical diketone being 36%.
公益社団法人日本薬学会の論文
2000-08-01