NUCLEOPHILIC SUBSTITUTION REACTION OF ARYL TRIFLATES VIA ARYL CATIONS
芳基三氟甲磺酸酯通过芳基阳离子的亲核取代反应
基本信息
- 批准号:60550614
- 负责人:
- 金额:$ 1.41万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for General Scientific Research (C)
- 财政年份:1985
- 资助国家:日本
- 起止时间:1985 至 1986
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
The solvolytic generation of aryl cations from aryl triflates with trimethylsilyl group(s) and/or tert-butyl group(s) on the both ortho positions in the aromatic rings was demonstrated as a new type of nucleophilic aromatic substitution reactions.The trimethylsilyl groups on the both ortho positions of the aryl cations play important roles not only in stabilizing the cations, whose hyperconjugative stabilization energy was calculated to be more than 30 kcal <mol^(-1)> , but also in controlling sterically the attack of the nucleophilee on the cationic center.The selectivity values of the aryl cations toward several nucleophiles are obtained from the ration of the products from the reactions of the cations with the nucleophiles and the products from that with the solvent TFE in the solvolysis of the triflate in TFE in the presence of the nucleophiles; <k_(Nu)> / <k_(TFE)> = 7.7( <I^-> ), 6.5(PhCN), 5.8(MeCN), 4.3( <Br^-> ), 3.5 (EtSH), and 1.7(MeOH).The solvolysis of the triflate in HFIP, on the other hand, gave the products from the reactions with the external nucleophiles exclusively and no hexafluoroisopropyl ether from that with HFIP was formed due to the steric hindrance among the both trimethylsilyl groups of the distorted aryl cation and the bulky HFIP.A first example of the generation of the aryl cations was also shown in the photochemical solvolysis of the aryl triflates and halides, where the initially formed radical pairs by homolytic cleavage of the C-X bond undego subsequent electron transfer to afford an ion pair and cationic products. The carbene-cation character of the aryl cations was indicated in the formation of indane by the intramolecular C-H insertion reaction of 2-propylphenyl cation generated in the photolysis of 2-propylphenyl triflate.
芳基三氟酸酯与芳环上两个邻位上的三甲基硅基(S)和/或叔丁基(S)反应生成的芳基阳离子是一种新型的亲核芳香取代反应。芳基阳离子的两个邻位上的三甲基硅基不仅对阳离子的稳定起着重要的作用,其超共轭稳定能大于30kcal;芳基阳离子对几种亲核试剂的选择性是由阳离子与亲核剂反应的产物与TFE在亲核剂存在下与TFE在TFE中的溶解反应产物的比例得到的;<;k_(Nu)>;/<;k_(TFE)>;=7.7(<;i^->;)、6.5(PHCN)、5.8(MeCN)、4.3(<;BR^->;),3.5(EtSH)和1.7(MeOH)。另一方面,三氟酸盐在HFIP中的溶解只得到与外部亲核试剂反应的产物,由于扭曲的芳基阳离子的三甲基硅基和大体积HFIP之间的空间位阻,与HFIP反应没有生成六氟异丙基醚。第一个例子也显示在芳基三氟酸盐和卤化物的光化学分解中,最初通过C-X键的均质裂解形成的自由基对随后进行电子转移得到离子对和阳离子产物。3-丙基苯基三氟酸异丙酯光解生成的2-丙基苯基阳离子在分子内的C-H插入反应生成了吲哚,说明了芳基阳离子的卡宾阳离子性质。
项目成果
期刊论文数量(10)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Yitzhak APEROIG, Dorit ARAD, Yoshio HIMESHIMA, Junji ICHIKAWA, Hiroshi KOBAYASHI, Takaaki SONODA: "The Reactivity of Aryl Cations Generated in the Solvolysis of Aryl Triflates" Journal of the American Chemical Society. 109. (1987)
Yitzhak APEROIG、Dorit ARAD、Yoshio HIMESHIMA、Junji ICHIKAWA、Hiroshi KOBAYASHI、Takaaki SONODA:“芳基三氟甲磺酸酯溶剂分解中产生的芳基阳离子的反应性”美国化学会杂志。
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- 影响因子:0
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Junji ICHIKAWA, Hiroshi KOBAYASHI, Takaaki SONODA: "Photochemical Generation of Aryl Cations from Aryl Triflates and Halides" Journal of the American Chemical Society. 109. (1987)
Junji ICHIKAWA、Hiroshi KOBAYASHI、Takaaki SONODA:“从芳基三氟甲磺酸酯和卤化物中光化学生成芳基阳离子”美国化学会杂志。
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ICHIKAWA,Junji;KOBAYASHI,Hiroshi;SONODA,Takaaki: Journal of the American Chemical Society. 109. (1987)
市川顺二;小林浩;SONODA,Takaaki:美国化学会杂志。
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- 影响因子:0
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M.KOBAYASHI,Edt.KOBAYASHI,Hiroshi;SONODA,Takaaki: ""The Reactivity of Aryl Cations in the Solvolysis of Aryl Triflate"in part of"Physycal Organic Chemistry 1986,"" Elsevier,Amsterdam, (1987)
M.KOBAYASHI,Edt.KOBAYASHI,Hiroshi;SONODA,Takaaki:““物理有机化学 1986”部分中的“芳基三氟甲磺酸酯溶剂解中芳基阳离子的反应性”,Elsevier,阿姆斯特丹,(1987)
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Yoshio HIMESHIMA, Hiroshi KOBAYASHI, Takaaki SONODA: "A First Example of Generating Aryl Cations in the Solvolysis of Aryl Triflates in Trifluoroethanol" Journal of the American Chemical Society,. 107. 5286-5288 (1985)
Yoshio HIMESHIMA、Hiroshi KOBAYASHI、Takaaki SONODA:“在三氟乙醇中芳基三氟甲磺酸酯溶剂分解中生成芳基阳离子的第一个例子”美国化学会杂志。
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SONODA Takaaki其他文献
SONODA Takaaki的其他文献
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{{ truncateString('SONODA Takaaki', 18)}}的其他基金
STUDY ON THE ACIDITY OF POLYFLUORINATED CARBON COMPOUNDS
多氟碳化合物酸性的研究
- 批准号:
19550045 - 财政年份:2007
- 资助金额:
$ 1.41万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
DEVELOPMENT OF NEW CATALYSIS REACTIONS WITH METAL SALTS OF FLUORINATED WEAKLY COORDINATED ANIONS
含氟弱配位阴离子金属盐新催化反应的开发
- 批准号:
12640572 - 财政年份:2000
- 资助金额:
$ 1.41万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Reorganization of the citizenship education in Russia under the period of shifting regime
政权更迭时期俄罗斯公民教育的重组
- 批准号:
11610274 - 财政年份:1999
- 资助金额:
$ 1.41万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
The Study of Generating Stabilized Phenyl Cations by Using New Super-Leaving Groups
利用新型超离去基团生成稳定苯基阳离子的研究
- 批准号:
07640726 - 财政年份:1995
- 资助金额:
$ 1.41万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
The Study on the Development of New Types of Lithium Battery Electrolyte Solution with Highly Lipophilic Fluorinated Organic Lithium Salts
高亲油性含氟有机锂盐新型锂电池电解液的开发研究
- 批准号:
05555241 - 财政年份:1993
- 资助金额:
$ 1.41万 - 项目类别:
Grant-in-Aid for Developmental Scientific Research (B)
The Study on the Mechanism of Conjugative Stabilization of Phenyl Cations
苯基阳离子共轭稳定机理的研究
- 批准号:
05804032 - 财政年份:1993
- 资助金额:
$ 1.41万 - 项目类别:
Grant-in-Aid for General Scientific Research (C)
A New Type of Nonbenzenoid Aromatic Carbocation : 1, 6-Methano[10]AnnulenylCation.
一种新型非苯环芳香族碳正离子:1, 6-甲醇[10]环烯基阳离子。
- 批准号:
02804041 - 财政年份:1990
- 资助金额:
$ 1.41万 - 项目类别:
Grant-in-Aid for General Scientific Research (C)