Spange Stefan, Bauer Mirko, Walfort Bernhard, Lang Heinrich
Department of Polymer Chemistry, Institute of Chemistry, Chemnitz University of Technology, D-09111 Chemnitz, Germany.
J Org Chem. 2006 Sep 29;71(20):7850-3. doi: 10.1021/jo061196+.
Activation of different benzophenone derivatives with triflic anhydride for electrophilic aromatic substitution of 5-phenylbarbituric acids leads to regioselective formation of the ortho-substituted product. The resulting triphenylmethylium salt can be isolated when the Michlers ketone is used. More electrophilic cations form cyclic enol ethers such as 1-n-butyl-9,9-diaryl-1,9-dihydro-10-oxa-1,3-diazaphenanthrene-2,4-diones. Alternatively, supramolecular complex formation with 2,6-diacetamido pyridine as well as carbenium ion generation have been studied. Although in dilute acid only protonation of one of the carbonyl oxygens occurs, ring opening of the cyclic enol ether toward the carbenium ion is observed in 96% sulfuric acid.
用三氟甲磺酸酐活化不同的二苯甲酮衍生物,用于5-苯基巴比妥酸的亲电芳香取代反应,可区域选择性地生成邻位取代产物。当使用米氏酮时,可以分离得到生成的三苯甲基鎓盐。亲电性更强的阳离子会形成环状烯醇醚,如1-正丁基-9,9-二芳基-1,9-二氢-10-氧杂-1,3-二氮杂菲-2,4-二酮。另外,还研究了与2,6-二乙酰氨基吡啶形成超分子配合物以及生成碳正离子的情况。尽管在稀酸中仅一个羰基氧发生质子化,但在96%的硫酸中观察到环状烯醇醚向碳正离子的开环反应。