REACTIONS OF ACYLAMINOQUINONE TOSYLHYDRAZONES .4. NEW SYNTHESIS OF PYRROLO[1,2-A]INDOLOQUINONE AND RELATED COMPOUNDS VIA BENZOXAZOLINE BY THERMOLYSIS AND PHOTOLYSIS
REACTIONS OF ACYLAMINOQUINONE TOSYLHYDRAZONES .4. NEW SYNTHESIS OF PYRROLO[1,2-A]INDOLOQUINONE AND RELATED COMPOUNDS VIA BENZOXAZOLINE BY THERMOLYSIS AND PHOTOLYSIS
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DOI：
10.1021/jo00417a017
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发表时间：
1978-01-01
影响因子：
3.6
通讯作者：
TAKADA, T
中科院分区：
文献类型：
--
作者：
AKIBA, M;KOSUGI, Y;TAKADA, T
在丝裂霉素类抗生素的合成研究中，最近报道了乙酰氨基醌对甲苯肼(1)的热分解一步合成了吡咯并[1，2-α]吲哚醌及其相关化合物(8)。这些结果初步表明卡宾作为反应中间体的存在。现在描述了通过严格控制1的热分解和光解来分离不稳定的苯并恶唑啉中间体(5)，并且产率很高。然后，化合物5通过二氢化合物变成8。考察了1的热分解和光解过程中的溶剂效应。在合成吡咯并[1，2-α]吲哚醌及相关化合物方面，通过苯并恶唑啉进行的这一分步反应明显比原来的方法更加通用，原来的方法也提供了吲哚并[1，2-α]吲哚和吲唑类化合物作为次要产物。
In synthetic studies on mitomycin antibiotics, it was recently reported that the thermolysis of acetylaminoquinone tosylhydrazones (1) gave the pyrrolo[1,2-.alpha.]indoloquinones and related compounds (8) in a 1-step synthesis. These results suggested tentatively the existence of carbenes as the reaction intermediates. The isolation of the unstable benzoxazoline intermediates (5) by the carefully controlled thermolysis and photolysis of 1 in good yields is now described. Compounds 5 then turned into 8 via the dihydro compounds. The solvent effects in the thermolysis and photolysis of 1 was also examined. This stepwise procedure via the benzoxazoline appears to be distinctly more versatile than the original procedure, which also afforded indazoloquinones and indazoles as the minor products, for the synthesis of pyrrolo[1,2-.alpha.]indoloquinones and related compounds.