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Abe Noritaka

Affiliate Master Yamaguchi University

Cycloaddition reactions of 2-acetylamino-, 2-alkylamino-, 8-ethylamino-, and 8-acetylamino-1-azaazulenes with dimethyl acetylenedicarboxylate

Bulletin of the Chemical Society of Japan Volume 65 Issue 7 Page 1784-1793
published_at 1992
Title
Cycloaddition reactions of 2-acetylamino-, 2-alkylamino-, 8-ethylamino-, and 8-acetylamino-1-azaazulenes with dimethyl acetylenedicarboxylate
Creators Abe Noritaka
Creators Fukazawa Yoshimasa
Creators Hirai Yoshimasa
Creators Sakurai Tosio
Creators Urushido Kunio
Creators Kakehi Akikazu
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-3,4,5-tricarboxylate, tetramethyl 6-ethyl-1-phenyl-4a,5-dihydro-6H-2a,6-diazapentaleno[1,6-cd]azulene-3,4,4a,5-tetracarboxylate, tetramethyl 3-phenyl-9b-azaindeno[1,6,7-bcd]azulene-1,2,8,9-tetracarboxylate, and dimethyl [8-phenyl-1,2,3-tris(methoxycarbonyl)-8H-3a-azacyclopent[1,2-a]inden-8-yl]maleate. However, the reaction of 8-acetylamino-3-phenyl-1-azaazulene with DMAD gave dimethyl-1-phenyl-2a,5-diazabenz[cd]azulene-3,4-dicarboxylate, trimethyl 3-phenyl-8,9b-diazaindeno[1,6,7-bcd]azulene-1,2,9-tricarboxylate, dimethyl 3-phenyl-8,9b-diazaindeno[1,6,7-bcd]azulene-1,2-dicarboxylate, tetramethyl 6-acetyl-1-phenyl-4a,5-dihydro-6H-2a,6-diazapentaleno[1,6,7-cd]azulene-3,4,4a,5-tetracarboxylate. The structures of the obtained compounds were determined by inspections of their physical and spectral data, and by single-crystal X-ray analyses of some of these compounds. The reaction mechanisms of these reactions are discussed.
Languages eng
Resource Type journal article
Publishers 日本化学会
Date Issued 1992
File Version Not Applicable (or Unknown)
Access Rights metadata only access
Relations
[ISSN]0009-2673
[NCID]AA00580132
info:doi/10.1246/bcsj.65.1784
[isVersionOf] [URI]http://www.jstage.jst.go.jp/browse/bcsj/-char/en
Schools 大学院医学系研究科(理学)