Cycloaddition Reactions of 2-Acetylamino-, 2-Alkylamino-, 8-Ethylamino-, and 8-Acetylamino-1-azaazulenes with Dimethyl Acetylenedicarboxylate
Cycloaddition Reactions of 2-Acetylamino-, 2-Alkylamino-, 8-Ethylamino-, and 8-Acetylamino-1-azaazulenes with Dimethyl Acetylenedicarboxylate
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2-乙酰氨基-、2-烷基氨基-、8-乙氨基-和8-乙酰氨基-1-氮杂薁烯与乙炔二甲酸二甲酯的环加成反应
DOI：
10.1246/bcsj.65.1784
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发表时间：
1992
期刊：
影响因子：
--
通讯作者：
A. Kakehi,
中科院分区：
文献类型：
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作者：
N. Abe;Y. Fukazawa;Y. Hirai;T. Sakurai;K. Urushido;A. Kakehi,
研究了2-和8-（取代氨基）-1-氮杂奥与乙炔二甲酸二甲酯（DMAD）的反应。2-乙酰氨基-1-氮杂甘菊环-3-甲酸乙酯与DMAD在乙腈中反应，得到1，2，3-三甲基-3a-氮杂环戊二烯并[a]甘菊环-1，2，3，9-四甲酸9-乙酯、1，2，2a，3-四甲基-4-乙酰基-2a，3-二氢-4H-4，10b-二氮杂并环戊二烯并[1，6-aj]甘菊环-1，2，2a，3，5-五甲酸5-乙酯（3a）、和（10-乙氧羰基-4-甲氧羰基-2，4a-二氢-2-氧代-2H-1，4a-二氮杂苯并[a]甘菊环-3-基）马来酸二甲酯。化合物3a热重排为1-乙酰基-2，3，4，4a-四氢-1H-1，4-二氮杂-3，4a-亚乙基芴-2，3，9，10，11-五甲酸9-乙酯。2-烷氨基-1-氮杂甘菊环-3-羧酸乙酯与DMAD反应，得到相应的4-烷基-2a，3-二氢-4H-4，10b-二氮杂并环戊二烯并[1，6-aj]甘菊环衍生物和乙烯桥连的1-氮杂庚烯衍生物。以8-乙氨基-3-苯基-1-氮杂甘菊环为原料，与DMAD反应，合成了1-苯基-2a-氮杂苯并[cd]甘菊环三甲酯.
The reactions of 2- and 8-(substituted amino)-1-azaazulenes with dimethyl acetylenedicarboxylate (DMAD) were investigated. Treatment of ethyl 2-acetylamino-1-azaazulene-3-carboxylate with DMAD in refluxing acetonitrile gave 9-ethyl 1,2,3-trimethyl 3a-azacyclopent[a]azulene-1,2,3,9-tetracarboxylate, 5-ethyl 1,2,2a,3-tetramethyl 4-acetyl-2a,3-dihydro-4H-4, 10b-diazapentaleno[1,6-aj]azulene-1,2,2a,3,5-pentacarboxylate (3a), and dimethyl (10-ethoxycarbonyl-4-methoxycarbonyl-2,4a-dihydro-2-oxo-2H-1,4a-diazabenz[a]azulen-3-yl)maleate. Compound 3a thermally rearranged to 9-ethyl 2,3,10,11-tetramethyl 1-acetyl-2,3,4,4a-tetrahydro-1H-1,4-diaza-3,4a-ethenofluorene-2,3,9,10,11-pentacarboxylate. The reaction of ethyl 2-alkylamino-1-azaazulene-3-carboxylate with DMAD gave the corresponding 4-alkyl-2a,3-dihydro-4H-4,10b-diazapentaleno[1,6-aj]azulene derivatives, and the etheno-bridged 1-azaheptalene derivative. The reaction of 8-ethylamino-3-phenyl-1-azaazulene with DMAD gave trimethyl 1-phenyl-2a-azabenz[cd]azulene-3,...