Reactions of N-(vinylimonophosphoranes) : Synthesis and properties of new aromatic compounds

N-(乙烯基单正膦)的反应：新型芳香族化合物的合成和性能

• 批准号: 03640466
• 负责人: NITTA Mokoto
• 金额: $ 1.34万
• 依托单位: School of Science and Engineering
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03640466/
• 关键词: vinyliminophosphorane; [n] (2,4) pyridinophane; aminoazulene; azuleno [1,2-a] azulene; azuleno [2,1-b] pyridine; メタノウンデカピロール; N-ビニルイミノホスホラン; 2-アミノアズレン; アズレノ[1,2‐a]アズレン; アザアリルアニオン; [n][2,4]ピリジノファン; アザアズレン; [n](2,4)ピリジノファン; アザヴィッティッヒ反応; アザフルオレ

Preparation and thermal reactions of [(azulen-2-yl) imino] phosphorane and [(1-azaazulenyl) imino] phosphorane with 2-bromotropone afforded 6-aza-and 6,7-diazaazuleno [1,2-a] azulenes. The NMR and electronic spectral studies including PPP-type MO calculations of the compounds revealed that there are litle contribbution of peropheral 18-pi conjugation, but there are rather composed of two azulene-type pi-systems. The both compounds existing as cationic and dicationic species in acidic media were also studied. In relation to the studies, azuleno-[1,2-a] azulene was also prepared through the thermal reaction of 2H-cyclohepta [b]-furan-2-one with 2-(1-pyrrolidinyl)-3(2,4,6-cycloheptatrienlylpropene and subsequent hydride abstraction-deprotonation processes. The spectral data revealed also that the compound are composed of two azulene-type pi-systems, are agreeable with the theoretical predictions.Furthermore, diphenylphosphinyltroponeimine reacted with enolates to give 1-azaazalene derivatives. Furthear studies are underway in our laboratory to explore the scompe and generality of the methodology.

[(2-氮杂-2-基)亚氨基]磷烷和[(1-氮杂唑基)亚氨基]磷烷与2-溴代丁酮反应合成了6-氮杂-和6，7-二氮杂[1，2-a]氮烯。核磁共振和电子光谱研究，包括PPP型分子轨道计算表明，化合物有少量的18-pi共轭分布，但有两个天青型的pi-体系。研究了这两种化合物在酸性介质中分别以阳离子和阳离子形式存在的情况。在研究过程中，还通过2H-环七[b]-呋喃-2-酮与2-(1-pyrrolidinyl)-3(2，4，6-cycloheptatrienlylpropene的热反应以及随后的氢化物提取-去质子化反应合成了偶氮基-[1，2-a]蔚蓝烯。光谱数据还表明，该化合物是由两个天青烯型的pi-体系组成的，与理论预测相一致。此外，二苯基膦基托酮亚胺与烯醇酸酯反应得到了1-氮杂氮烯衍生物。我们的实验室正在进行进一步的研究，以探索该方法的复杂性和普遍性。

项目成果

M.Nitta,K.Nishimura,Y.Iino: "Synthesis and structural studies of novel azuleno〔1,2-a〕-azulene and its derivatives" Tetrahedron Lett.34. 2157-2160 (1993)

M. Nitta、K. Nishimura、Y. Iino：“新型甘菊烯〔1,2-a〕-甘菊烯及其衍生物的合成和结构研究”Tetrahedron Lett.34（1993）。

M.Nitta,S.Mori and Y.Iino: "A novel route to 1-azaazulenes by the reaction of β-amino enones with activated tropones" Heterocycles. 32. 23-28 (1991)

M.Nitta、S.Mori 和 Y.Iino：“通过 β-氨基烯酮与活化托酮反应制备 1-azaazulenes 的新途径”Heterocycles 32. 23-28 (1991)。

M.Nitta, Y.Iino, and S.Mori: "A short new synthesis of 5-azaazulene derivatives" Tetrahedron Lett.32. 6727-6730 (1991)

M.Nitta、Y.Iino 和 S.Mori：“5-azaazulene 衍生物的简短新合成”Tetrahedron Lett.32。

M.Nitta,Y.Iino and S.Mori: "On the reaction of(vinylimino)phosphoranes and related compounds. 20. Synthesis and properties of 5-aza-azulene derivatives" Tetrahedron Lett.32. 6727-6730 (1991)

M.Nitta、Y.Iino 和 S.Mori：“关于（乙烯基亚氨基）正膦及相关化合物的反应。20。5-氮杂-甘菊环衍生物的合成和性质”Tetrahedron Lett.32。

N.Kanomata, H.Kawaji, and M.Nitta: "Synthesis and properties of methanocyclodeca [b] pyridine ring system" J.Org.Chem.57. 618-625

N.Kanomata、H.Kawaji 和 M.Nitta：“methanocyclodeca [b] 吡啶环系统的合成和特性”J.Org.Chem.57。