期刊文献+
任意字段
题名或关键词
题名
关键词
文摘
作者
第一作者
机构
刊名
分类号
参考文献
作者简介
基金资助
栏目信息

(Me)3CO·自由基和异-3-己烯反应机理的理论研究

原文传递
导出
摘要 对(Me)3CO·自由基和异-3-己烯在苯溶液中的反应机理进行了理论研究,在B3LYP/6-311++G(d,p)//B3LYP/6-31G(d)+ZPVE水平下,得到了两条可能的反应通道:(1)夺氢-加成;(2)加成-加成-消除.势能面分析表明,该反应以夺氢-加成(1)为主,加成-加成-消除(2)为辅.计算结果能很好地解释近期Coseri等人实验测得的产物分布,而Coseri等人建议的加成-夺氢通道在动力学上是不可行的.
作者 石国升 丁益宏
机构地区 吉林大学理论化学研究所
出处 《科学通报》 EI CAS CSCD 北大核心 2008年第10期1185-1188,共4页 Chinese Science Bulletin
基金 国家自然科学基金(批准号:20103003,20573046) 吉林省杰出青年基金(批准号:20050103) 新世纪优秀人才支持计划资助项目
关键词 (Me)3CO· 异-3-己烯 势能面 反应机理
分类号 O643.12 [理学—物理化学] O621.146 [理学—有机化学]
  • 相关文献

参考文献16

  • 1Coseri S, Mendenhall G D, Ingold K U. Mechanisms of reaction of aminoxyl (nitroxide), iminoxyl, and imidoxyl radicals with alkenes and evidence that in the presence of lead tetraacetate, N-hydroxyphthalimide reacts with alkenes by both radical and nonradical mechanisms. J Org Chem, 2005, 70(12): 4629-4636.
  • 2Adam W, Saha-Moller C R, Ganeshpure P A. Synthetic applications of nonmetal catalysts for homogeneous oxidations. Chem Rev, 2001, 101(11): 3499-3548.
  • 3董锋,孔繁敖.丙烯自由基与O_2的基元化学反应[J].科学通报,2003,48(8):793-796. 被引量：1
  • 4Fokin A A, Schreiner P R. Selective alkane transformations via radicals and radical cations: Insights into the activation step from experiment and theory, Chem Rev, 2002, 102(5): 1551-1593.
  • 5Walling C, McGuiness J A. Positive halogen compounds. ⅩⅥ. Comparison of alkoxy radicals from different sources and the role of halogen atoms in hypohalite reactions. J Am Chem Soc, 1969, 91(8): 2053-2058.
  • 6Carter W P L, Darnall, K R, Lioyd A C, et al. Evidence for alkoxy radical isomerization in photooxidations of C4-C6 alkanes under simulated atmospheric conditions. Chem Phys Lett, 1976, 42(1): 22-27.
  • 7Walling C, Clark R T. Reactions of primary and secondary alkoxy radicals derived from hypochlorites. J Am Chem Soc, 1974, 96(14): 4530-4534.
  • 8Hartung J, Schneiders N, Gottwald T. On the synthesis of β-bromohydrine ethers via intermolecular alkoxyl radical addition to bicyclo[2.2.1]heptene. Tetrahedron Lett, 2007, 48:6027-6030.
  • 9Paul H, Small R D Jr, Scaiano J C. Hydrogen abstraction by tert-butoxy radicals: A laser photolysis and electron spin resonance study. J Am Chem Soc, 1978, 100(14): 4520-4527.
  • 10Encinas M V, Scaiano J C. Reaction of benzophenone triplets with allylic hydrogens: Laser flash photolysis study. J Am Chem Soc, 1981, 103(21): 6393-6397.

二级参考文献23

  • 1朱起鹤,黄寿龄,王学斌,郝振,张其菲,曹建如,武小军,吕宁,姚思迅,孔繁敖.激光光解时间分辩红外发射谱仪[J].Chinese Journal of Chemical Physics,1993,6(1):87-94. 被引量：5
  • 2Morton M L, Butler L J, Stephenson T A, et al. C-Cl bond fission,HCl elimination, and secondary radical decomposition in the 193 nm Photodissociation of allyl chloricle. J Chem Phys, 2002,116(7): 2763-2775.
  • 3Krueger H, Weitz E. Diode laser probes of vinyl radical kinetics:The reaction of C2H3 with HCl and DCl. J Chem Phys, 1988,88(3): 1608-1616.
  • 4Westbook C K, Pitz W J. A comprehensive chemical kinetic reaction mechanism for oxidation and pyrolysis of propane and propene. Combust Sci Technol, 1984, 37:117-152.
  • 5Edelson D, Allara D L. A computational analysis of the alkane pyrolysis mechanism: sensitivity analysis of individual reaction steps. Int J Chem Kinet, 1980, 12:605-608.
  • 6Smith R D. A direct mass spectrometric study of the mechanism of toluene pyrolysis at high temperatures. J Phys Chem, 1979, 83(12):1553-1563.
  • 7Slagle I R, Park J Y, Heaven M C, et al. Kinetics of polyatomic free radicals produced by laser photolysis. 3. Reaction of vinyl radicals with molecular oxygen. J Am Chem Soc, 1984, 106(16):4356--4361.
  • 8Fahr A, Laufer A H, Ultraviolet absorption of the vinyl radical and reaction with oxygen. J Phys Chem, 1998, 92(26): 7229-7232.
  • 9Knyazev V D, Slagle I R. Kinetics of the reaction of vinyl radical with molecular oxygen. J Phys Chem, 1995; 99(8): 2247-2249.
  • 10Park J Y, Heaven M C, Gutman D. Kinetics and mechanism of the vinyl radicals with molecular oxygen. Chem Phys Lett, 1984,104(5): 469--474.
科学通报
2008年 第10期

相关作者

内容加载中请稍等...

相关机构

内容加载中请稍等...

相关主题

内容加载中请稍等...

浏览历史

内容加载中请稍等...
;
使用帮助 返回顶部