首页> 外文学位 >Part I. The radical chemistry of geminal bis-azoalkanes. Part II. The radical chemistry of vicinal bis-azoalkanes. Part III. Homolysis of a weak carbon-carbon bond.

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Part I. The radical chemistry of geminal bis-azoalkanes. Part II. The radical chemistry of vicinal bis-azoalkanes. Part III. Homolysis of a weak carbon-carbon bond.

机译：第一部分。双双偶氮烷的自由基化学。第二部分邻位双偶氮烷的自由基化学。第三部分弱碳-碳键的均解。

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Part I. The radical chemistry of geminal bis-azoalkanes. Two geminal bis-azoalkanes have been employed to generate carbon centered radicals adjacent to azo substituents. The activation free energies for C-N bond homolysis of 2,2-bis-(phenylazo)propane (1) and 2-methylazo-2-phenylazopropane (2) were 8 kcal/mol lower than for the corresponding model compounds 3-methyl-3-phenylazo-1-butene (4) and 3-methyl-3-methylazo-1-butene (5). This large rate enhancing effect of an ;Part II. The radical chemistry of vicinal bis-azoalkanes. Three vicinal bis-azoalkanes have been synthesized by oxidation of hydrazones. In thermolysis, substituents on the azo group dramatically influence the bond homolysis pattern, which varies from pure C-C homolysis when the substituent is phenyl to pure C-N homolysis in the case of a t-butyl substituent. Phenylazo accelerates ;Part III. Homolysis of a weak C-C bond. The formal para-recombination product of 2-methoxycarbonylpropyl and trityl radicals (53) was readily air oxidized to hydroperoxide through a radical chain mechanism. The weak C-C bond in 53 was cleaved homolytically in thermolysis, photolysis, and triplet sensitized photolysis generating methyl isobutyrate radical and triphenylmethyl radical. This result rules out McElvain's concerted thermolysis mechanism. Triphenylmethyl radical underwent intramolecular cyclization under the photolysis conditions. The facile aromatization of 53 through a radical mechanism was observed.

机译：第一部分。双双偶氮烷的自由基化学。已使用两种双键双偶氮烷烃来产生与偶氮取代基相邻的碳中心自由基。 2,2-双-（苯基偶氮）丙烷（1）和2-甲基偶氮-2-苯基偶氮丙烷（2）的CN键均质分解的活化自由能比相应的模型化合物3-methyl-3低8 kcal / mol -苯基偶氮-1-丁烯（4）和3-甲基-3-甲基偶氮-1-丁烯（5）。第二部分。邻位双偶氮烷的自由基化学。通过的氧化合成了三种邻位的双偶氮烷。在热分解中，偶氮基上的取代基会显着影响键的均化模式，该模式从取代基为苯基时的纯C-C均质到叔丁基取代基的纯C-N均质而变化。苯偶氮加速；第三部分。弱C-C键的均解。 2-甲氧基羰基丙基和三苯甲基自由基的形式对位重组产物（53）容易通过自由基链机理被空气氧化为氢过氧化物。在热解，光解和三重态敏化光解中，53中的弱C-C键被均裂，生成异丁酸甲酯和三苯甲基。该结果排除了麦克尔文一致的热解机理。三苯甲基自由基在光解条件下进行了分子内环化。观察到通过自由基机理的53的容易的芳构化。

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Chen, Yanqiu.;
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Rice University.;

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授予单位 Rice University.;
学科 Organic chemistry.
学位 Ph.D.
年度 1989
页码 176 p.
总页数 176
原文格式 PDF
正文语种 eng
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Part I. The radical chemistry of geminal bis-azoalkanes. Part II. The radical chemistry of vicinal bis-azoalkanes. Part III. Homolysis of a weak carbon-carbon bond.

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