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烷二胺中的LDA或n-BuLi使炔醇的内炔键异构化

ISOMERIZATION OF THE INTERNAL TRIPLE BOND OF ALKYN-1-OL WITH LDA OR n-BuLi IN THE ALKYLDIAMINES

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【作者】 周维善张学海吴培君谈忠兴

【Author】 ZHOU WEI-SHAN;ZHANG XUE-HAI;WU PEI-JUN;TAN ZHONG-XING Shanghai Institute of Organic Chemistry, Academia Sinica

【机构】 中国科学院上海有机化学研究所中国科学院上海有机化学研究所

【摘要】 <正> 分子中的内炔键移至末端的反应在有机合成中有着重要的用途,因为末端炔键可用以延长碳链或转化为其它功能团,它已在长碳链脂肪酸和昆虫性信息素以及其它天然产物的合成中得到应用。已经报道炔-2异构化为炔-1要用很强的碱:钠(4.5小时,100℃,伴随有聚合物产生),在芳烃中的NaNH2(1.5~2小时,160℃),KNH2-

【Abstract】 Migration of the internal triple bond of alkyn-1-ol to the terminal one could beaffected by LDA or n-BuLi in APA (1), AIPA (2) or AEA (3). The efficiency of triplebond migration using LDA in 1 is better than that in 2 or 3, but the reaction inLDA-1 system is slower than that in NaH-1, NaH-2 or NaH-3 system. Furthermore,the isomerization is usually incomplete, e. g. Ⅶ was obtained in the isomerizationof Ⅰ in 20 hours (Table 1, in the Chinese Text). The migration reactions in LDA-2 orLDA-3 system are always incomplete, even with increasing reaction time. The yieldsof the migration products in these two systems are also much lower than that inLDA-1 system. The yields of the migration product in n-BuLi-1, 2 or 3 systems arealso much lower than that in LDA-1, 2 or 3 systems and the migration is alwaysincomplete.

  • 【文献出处】 化学学报 ,Acta Chimica Sinica , 编辑部邮箱 ,1984年06期
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