Study of Organic Reaction Processes by the Use of Low-Temperature Matrix-Isolation Technique
利用低温基质分离技术研究有机反应过程
基本信息
- 批准号:09440214
- 负责人:
- 金额:$ 3.9万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (B)
- 财政年份:1997
- 资助国家:日本
- 起止时间:1997 至 1999
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
The object of this research is to establish the low-temperature matrix-isolation method as a general technique for the study of an organic reaction mechanism by the expansion of the application range of this technique. In order to make possible to apply this technique to less volatile substrates and to reactive intermediates generated by a large apparatus such as laser and flash vacuum pyrolysis, an inner-rotation mechanism was employed in the low-temperature matrix-isolation apparatus which was designed and set up with the aid of this grant. The ability of this new apparatus to make a low-temperature matrix satisfactory for spectroscopic observations was confirmed by the isolation of p-nitorophenyl azide in an argon matrix and comparison of its IR spectrum with that recorded previously using the other apparatus. The direct observation of the processes of the reaction of p-nitrophenylcarbene (1) with acetonitrile was examined next. Irradiation of (p-nitrophenyl)diazomethane matrix-isolated in argon doped with acetonitrile at 10K gave the carbene 1, which reacted with acetonitrile photochemically or thermally. The reactions were nicely monitored by IR and UV-Vis spectroscopy to find that the product formed by the further photolysis of 1 in an acetonitrile-doped matrix was different from that obtained thermally in the matrix. The structure of these products was estimated on the basis of the isotope experiment and DFT calculations. These preliminary results were suggested that the low-temperature matrix-isolation technique would be a powerful method for studying the reaction mechanism of organic reactive intermediates.
本研究的目的是通过扩大低温基质分离法的应用范围,使其成为研究有机反应机理的通用技术。为了使这一技术能够应用于不太挥发性的基板和反应性中间体产生的大型设备,如激光和闪速真空热解,内旋转机构采用的低温基质隔离装置,这是设计和建立的援助,该授权。这种新装置的能力,使低温矩阵满意的光谱观测证实了对硝基苯基叠氮在氩气矩阵中的分离和比较其红外光谱与以前记录的使用其他设备。接下来检查对硝基苯基卡宾(1)与乙腈反应过程的直接观察。对硝基苯基重氮甲烷在掺有乙腈的氩气中于10 K辐照得到卡宾1,卡宾1与乙腈发生光化学或热反应。通过IR和UV-Vis光谱很好地监测了反应,发现在乙腈掺杂的基质中通过1的进一步光解形成的产物不同于在基质中热获得的产物。根据同位素实验和密度泛函理论计算,对产物的结构进行了估算。这些初步结果表明,低温基质分离技术将是研究有机反应中间体反应机理的一种有力手段。
项目成果
期刊论文数量(19)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Shigeru Murata: "Photochemistry of 2,4-Bis(diazo)-1,2,3,4-tetrahydronaphthalene-1, 3-dione : Selective Photodecomposition of One of the Two Inequivalent Diazo Goups"Journal of the American Chemical Society. Vol.120 No.35. 9088-9089 (1998)
Shigeru Murata:“2,4-双(重氮)-1,2,3,4-四氢萘-1,3-二酮的光化学:两个不等重氮基团之一的选择性光分解”美国化学会杂志。
- DOI:
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- 影响因子:0
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- 通讯作者:
Shigeru Murata: "Photochemical Reactions of Mesity1 Azide with Tetracyanoethylene : Competitive Trapping of Singlet Nitrene and Didehydroazepine"Journal of Organic Chemistry. Vol.62 No.5. 3055-3061 (1997)
Shigeru Murata:“Mesity1 叠氮化物与四氰乙烯的光化学反应:单线态氮烯和二脱氢吖庚因的竞争捕获”有机化学杂志。
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- 影响因子:0
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Sigeharu Wakabayashi: "Self-Assembly of 3-[4'-(Diethylboryl)phenyl]pyridine and 3-[3 '-(Diethylboryl)phenyl]-pyridine : Synthesis, Structural Features, and Stability in Solution"Journal of Organic Chemistry. Vol.64 No.19. 6999-7008 (1999)
Sigeharu Wakabayashi:“3-[4-(二乙基硼基)苯基]吡啶和3-[3-(二乙基硼基)苯基]-吡啶的自组装:合成、结构特征和溶液稳定性”有机化学杂志。
- DOI:
- 发表时间:
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- 影响因子:0
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- 通讯作者:
Shigeru Murata: "Photochemistry of 2, 4-Bis(diazo)-1, 2, 3, 4-tetrahydronaphthalene-1, 3-dione : Selective Photodecomposition of One of the Two Inequivalent Diazo Groups"J. Am. Chem. Soc.. Vol. 120, No. 35. 9088-9089 (1998)
Shigeru Murata:“2, 4-双(重氮)-1, 2, 3, 4-四氢萘-1, 3-二酮的光化学:两个不等重氮基团之一的选择性光分解”J。
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- 发表时间:
- 期刊:
- 影响因子:0
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- 通讯作者:
A. Nicolaides: "Direct Observation and Characterization of p-Phenylenebisnitrene. A Labile Quinoidal Diradical"J. Am. Chem. Soc.. Vol. 120, No. 44. 11530-11531 (1998)
A. Nicolaides:“对亚苯基双硝基的直接观察和表征。不稳定的醌型双自由基”J。
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MURATA Shigeru其他文献
MURATA Shigeru的其他文献
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{{ truncateString('MURATA Shigeru', 18)}}的其他基金
Development of multi-wavelength digital holography for highly accurate particle measurement
开发用于高精度粒子测量的多波长数字全息术
- 批准号:
17K06156 - 财政年份:2017
- 资助金额:
$ 3.9万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
photochemical water splitting using a mixed vesicular system
使用混合囊泡系统的光化学分解水
- 批准号:
16K05881 - 财政年份:2016
- 资助金额:
$ 3.9万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Study of High Performance Method for Particle Measurement in 3D-space Based on Digital Holography
基于数字全息术的高性能3D空间粒子测量方法研究
- 批准号:
26420110 - 财政年份:2014
- 资助金额:
$ 3.9万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Introduction of flow system to vesicular reaction systems capable of converting light energy to chemical potential
将流动系统引入能够将光能转化为化学势的囊泡反应系统
- 批准号:
25620147 - 财政年份:2013
- 资助金额:
$ 3.9万 - 项目类别:
Grant-in-Aid for Challenging Exploratory Research
Study in the development of light energy conversion system using lipid bilayer membranes
利用脂质双层膜的光能转换系统的开发研究
- 批准号:
20550119 - 财政年份:2008
- 资助金额:
$ 3.9万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Feasibility study of high performance monocular 3D-PIV using phase-shifting digital holography
使用相移数字全息术的高性能单目 3D-PIV 的可行性研究
- 批准号:
19560172 - 财政年份:2007
- 资助金额:
$ 3.9万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Development of highly accurate dynamic 3D-PIV based on digital holography and its applications
基于数字全息的高精度动态3D-PIV研制及其应用
- 批准号:
17560148 - 财政年份:2005
- 资助金额:
$ 3.9万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Mechanistic Studies of Photoinduced Electron Transport across Vesicle Bilayers
光诱导电子跨囊泡双层传输的机理研究
- 批准号:
16550030 - 财政年份:2004
- 资助金额:
$ 3.9万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Study of 3D-flow-field velocimetry for turbomachine
涡轮机三维流场测速研究
- 批准号:
12650166 - 财政年份:2000
- 资助金额:
$ 3.9万 - 项目类别:
Grant-in-Aid for Scientific Research (C)