METALATION OF PYRROLE, 1-METHYLPYRROLE, AND 1-PHENYLPYRROLE WITH n-BUTYLLITHIUM
METALATION OF PYRROLE, 1-METHYLPYRROLE, AND 1-PHENYLPYRROLE WITH n-BUTYLLITHIUM
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吡咯、1-甲基吡咯和1-苯基吡咯与正丁基锂的金属化
DOI：
10.1021/jo01120a012
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发表时间：
1955
影响因子：
3.6
通讯作者：
P. Roussel
中科院分区：
文献类型：
--
作者：
D. A. Shirley;B. Gross;P. Roussel
1-苯基吡咯与约3摩尔正丁基锂的金属化反应在碳酸化后不产生任何二羧酸。相反，除了一些一元羧酸之外，还获得了含有羰基的亮黄色化合物，其通过分析和分子量测定表明是5-酮基吡咯并[1，2-a]吲哚（III）。该化合物可能是由1-苯基吡咯在2-和2 '-位的二金属化，然后与二氧化碳形成分子内酮而产生的。酮通常作为反应性有机金属化合物与二氧化碳作用的副产物形成，但在这种情况下，环酮是从二金属化中分离出的唯一产物。这无疑是由于一分子二氧化碳反应后官能团的有利空间排列。在1-苯基吲哚（1）的双金属化反应中也遇到了类似的情况，尽管这里也可以分离出一些二羧酸。
Metalation of 1-phenylpyrrole with about three moles of n-butyllithium to one of thepyrrole did not yield any dicar boxy lie acid subsequent to carbonation. Instead there was obtained, in addition to some monocarboxylic acid, a bright yellow compound which contained a carbonyl group and which was indicated by analysis and molecular weight determination to be 5-ketopyrrolo [l, 2-a] indole (III). This compound would arise from dimetalation of 1-phenylpyrrole in the 2-and2'-positions followed by intramolecular ketone formation with carbon dioxide. Ketones are commonly formed as by-products from the action of re-active organometallic compounds on carbon dioxide, but in this case the cyclic ketone is the only product isolated from dimetalation. This is undoubtedly due to the favorable steric arrangement of functional groups after one molecule of carbon dioxide has reacted. A similar situation was encountered in the dimetala-tion of 1-phenylindóle (1), although here it was possible also to isolate some of the dicarboxylic acid.