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出 处:《高等学校化学学报》1991年第6期814-818,共5页Chemical Journal of Chinese Universities
摘 要:通过EPR技术观察到一系列典型的烷基或甲氧基取代的苯基烷基酮ArCOR(Ar=2,5-二甲基苯基(1);2,5-二甲氧基苯基(2);4-叔丁基-2,5-二甲氧基苯基(3))与t-BuMgCl反应中形成的自由基阴离子中间体[ArC(R)OMgCl]。产物分析表明,反应主要生成还原产物[ArCH(R)OH]和1,2-加成产物[ArC(R)(t-Bu)OH]。降低溶剂极性及反应温度都有利于还原产物的生成。对上述反应的可能历程作了简单讨论。We have directly observed twelve ketyl radical intermediates 4~6[Ar C(R)OMgX) formed during the reactions of a series of alkyl aryl ketones 1~3(Ar: 2,5-dimethylphenyl (1); 2,5-dimethoxyphenyl(2); 4-t-butyl-2, 5-dimethoxyphenyl (3)) with t-butyl magnesium chloride by means of EPR technique. The product analysis shows that the major products formed in the reactions of alkyl 2,5-dimethylphenyl ketones l_(a-d) (R:a, Me; b, Et; c, i-Pr; d, t-Bu) are reduction products 7 and 1,2-addition products 8. The lower polarity of the used solvent and the lower reaction temperature would favour the formation of 7. In accordance with these results, the possible mechanisms for the titled reactions are discussed.
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