α-羰基烯酮环二硫代缩醛化学(Ⅹ)——β,β-1,5-亚丙二硫基-α,β-不饱和酮与烯丙基Grignard试剂加成物的酸催化反应取向研究  

The Chemistry of α-Oxo Ketene Cyclic Dithioacetals( X ) --Studies on the Orientation of Acid Catalyzed Reaction to the Adducts of α-Oxo Ketene Cyclic Dithioacetals with Allyl Grignard Reagents

作　　者：刘群[1] 朱再明[1] 杨智蕴[1] 胡玉兰[1] 景凤英[2] 孝延文 

机构地区：[1]东北师范大学化学系,长春130024 [2]中国科学院长春应用化学研究所

出　　处：《高等学校化学学报》1993年第11期1538-1542,共5页Chemical Journal of Chinese Universities

基　　金：国家教育委员会优秀年轻教师基金

摘　　要：β,β-1,5-亚丙二硫基-α,β-不饱和酮2b和2-甲基烯丙基氯化镁加成可得醇3b.在BF_3·Et_2O催化下,3b经分子内环合芳构化生成芳硫醚5b.2和烯丙基溴化镁反应得醇4,4在BF_3·Et_2O催化下经β-消除脱水生成共轭多烯类化合物6.二硫缩醛基以环和非环结构及环的大小对2与烯丙基Grignard试剂加成物在酸催化下的反应取向有重要影响.Addition of aliphatic title compounds 2b with 2-methyl allyl Grignard reagent afforded the corresponding carbinols 3b. Catalyzed by BF3 · Et2O, 3b were converted to the arylthio ether 5b via a cyclization-aromatization process. When water or methanol was present in the reaction mixture, 3b were converted to the phenols or arylether 5'b via a substitution-cyclization aromati-zation process under similar conditions as above. The adducts 4 formed by the addition of 2 with magnesium allyl bromide, were converted to the conjugate polyenes 6 under the above conditions either in the presence or in the absence of the nucleophile. The mechanism was discussed according to the effects of different dialkylthio groups to the carbon cation intermediates 12, 13 and 14.

关 键 词：羧基烯酮 二硫代缩醛 烯丙基试剂 

分 类 号：O623.541[理学—有机化学]