Study on the Production and the Reaction Mechanism of Unstable Molecules produced by the Pyrolysis and Photolysis

热解和光解不稳定分子的产生及反应机理研究

• 批准号: 04640477
• 负责人: HAMADA Yoshiaki
• 金额: $ 1.34万
• 依托单位: The University of the Air
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640477/
• 关键词: N-Chloroamine; Pyrolysis; High Resolution FTIR; Amino Inversion; Imines; MOPAC-PM3; Transition State Structure; フーリエ変換赤外分光; N-Cl化物; PM3法; 星間分子; HCN=量体; フーリェ変換赤外分光; シアノエチン系列

Infrared spectra of the N-Cl containing molecules and their pyrolytic products have been observed. The Spectra were analyzed guided by the results of ab initio MO calculations. The pyrolytic mechanism were considered experiment-ally and also theoretically using the information of the structures and energ-ies of the transition states.(1) High resolution spectra of NH_2Cl were measured in the mid-infrared region. The amino scissorring level has the inversion splitting of about 0.2cm^<-1>. This is the first of observation of the inversion splitting except the wagging band. The amino twisting band was observed, and nu_0 was determined to be 1169cm^<-1>.(2) There have been observed two branchings of the pyrolysis reaction of dialkylamines, R_1(R_2)NCl (R_1, R_2 : C_2H_5, C_3H_7), one is the dehydrochlorination, and the other is C-N cession. The branching is temperature-dependent. and at lower temperature proceeds the dehydrochlorination to give imines.(3) MOPAC-PM3 method was applied to calculate the relative stabilities of the molecules and transition states related to the pyrolysis of amines. The results were used to identify and predict the reaction products. The pyrotitic mechanism including the intramolecular hydrogen transfer, ring cession, and dehydrogen has been invesigated in detail.

研究了含N-Cl分子及其热解产物的红外光谱。在从头算MO计算结果的指导下对光谱进行了分析。利用过渡态的结构和能量信息，从实验和理论上考虑了热解机理。(1)测定了NH_2Cl在中红外区域的高分辨光谱。氨基酸剪切能级的反转分裂约为0.2cm^<-1>。这是除摇带外首次观测到逆分裂现象。观察到氨基扭曲带，确定nu_0为1169cm^<-1>。(2)二烷基胺热解反应有两个分支，R_1(R_2)NCl (R_1, R_2: C_2H_5, C_3H_7)，一个是脱氢氯化反应，另一个是C-N反应。分支与温度有关。在较低温度下进行脱氯化氢反应生成亚胺。(3)采用MOPAC-PM3方法计算与胺类热解相关的分子的相对稳定性和过渡态。结果用于反应产物的鉴别和预测。详细研究了分子内氢转移、环切和脱氢的热解机理。

项目成果

Y.Hamada and H.Takeo: "Spectroscopic Study on the Pyrolytic Products of Amines" Applied Spectroscopy Reviews. 27(3). 289-321 (1992)

Y.Hamada 和 H.Takeo：“胺热解产物的光谱研究”应用光谱学评论。

A.Matsuzaki,H.Morita,and Y.Hamada: "Morphological characteristics in Laser-Induced Aerosol Formation from CS_2 Vapor" Chemical Physics Letters. 190. 331-336 (1992)

A.Matsuzaki、H.Morita 和 Y.Hamada：“CS_2 蒸气激光诱导气溶胶形成的形态特征”化学物理快报。

濱田,嘉昭: "振動分光法の基礎-フーリエ変換分光の現状と可能性" 放送大学研究年報. 11. 151-180 (1993)

Hamada, Yoshiaki：“振动光谱学基础 - 傅立叶变换光谱学的现状和可能性”日本开放大学年度报告 11. 151-180 (1993)。

朽津耕三 濱田嘉昭: "量子化学" 放送大学教育振興会, 273 (1993)

Kozo Kutsutsu 和 Yoshiaki Hamada：“量子化学”开放大学教育促进协会，273（1993）

Y.Hamada: "Spectroscopic Study on the Pyrolytic Products of Amines" Applied Spectroscopy Reviews. 27. 289-321 (1992)

Y.Hamada：“胺热解产物的光谱研究”应用光谱学评论。