Properties and Reaction of π-Conjugated Carbonyl Compounds

π-共轭羰基化合物的性质和反应

• 批准号: 12640512
• 负责人: HASEGAWA Toshio
• 金额: $ 1.22万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640512/
• 关键词: monothiotropolone; equilibrium; azulene; troponolid; activated methylene compound; カルボニル; π電子; NMR; IR; 分子軌道法; 共役; トロポン; ベンザイン; Diels-Alder

We have found the following results,1. Novel solid-state propertie :Tropolone exsits as an last equilibrium mixture of a ketone form and an enol form. This equilibrium of tropolone is extremely fast in solution, but is frozened on the NMR time scale in the solid state. Monthiotropolone is the sulfur analogue of tropolone. We have found that this compound exists as extremely fast equilibrium mixture both in solution and in the solid state. This novel behavior in the solid-state is found to be due to packing arrangement of monothiotropolone.2. Azulene synthesis in the reaction of an activated trponoid compound with an activated methylene compound :Reaction of activated troponoid compounds with activated methylene compounds gave azulenes in good yields. These reactions are useful methods to obtain azulene derivatives with polyfunctional groups in five-membered ring moiety. We investigated the reaction mechanism of 2-methoxytropone with malonouilrilc to give an azulene and found the detailed reaction path of many steps containing several equilibrium processes.

我们发现了以下结果，1.新的固态性质：环庚三烯酚酮以酮型和烯醇型的最终平衡混合物形式存在。环酚酮的这种平衡在溶液中非常快，但在固态下在NMR时间尺度上被冻结。Monthiotropolone是托酚酮的硫类似物。我们发现，这种化合物在溶液和固态中都以极快的平衡混合物形式存在。这种新颖的行为在固态被发现是由于堆积排列的monothiotropolone.在活化的类托品化合物与活化的亚甲基化合物的反应中合成甘菊环：活化的类托品化合物与活化的亚甲基化合物的反应以良好的产率得到甘菊环。这些反应是合成五元环上含多官能团的甘菊环衍生物的有效方法。本文研究了2-甲氧基托品酮与丙二酰亚胺反应生成一个甘菊环的反应机理，得到了包含多个平衡过程的多步反应的详细路径。

项目成果

T.Machiguchi: "Innovation of Ketene Chemistry. Big Faults in Ketene History and the Solutions"CACS Form. 20. 29-38 (2001)

T.Machiguchi：“乙烯酮化学的创新。乙烯酮历史上的大错误及其解决方案”CACS 表格。

T.Machiguchi: "Reinvesligation of Tropore-Beucyne Reation To Givp Dids-Alder Type Adduot"Proc.ISNA. 10. 251 (2001)

T.Machiguchi：“Tropore-Beucyne 反应对 Givp Dids-Alder 型加合物的重新研究”Proc.ISNA。

A.Ishiwata: "Norcaradiene Intermediates in Mass Spectral Fragmentations of tropone and tropothione"J. Chem. Soc., Perkin Trans. 2. 2202-2210 (2001)

A.Ishiwata：“去甲二烯中间体在托酮和托硫酮的质谱裂解中的作用”J。

A. Ishiwatai: "Norcaradiene Intermediates in Mass Spectral Fragmenrations of Tropone and Tropothione"J. Chem. Soc., Perkin Trans.. 2. 2202-2210 (2001)

A. Ishiwatai：“托品酮和托吗硫酮的质谱碎片中的去甲二烯中间体”J。