• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Formation of 6-Methyl-1,4-dihydronaphthalene in the Reaction of the p-Toly Radical with 1,3-Butadiene under Single-Collision Conditions
【24h】

Formation of 6-Methyl-1,4-dihydronaphthalene in the Reaction of the p-Toly Radical with 1,3-Butadiene under Single-Collision Conditions

机译：在单碰撞条件下对甲苯基自由基与1,3-丁二烯的反应中形成6-甲基-1,4-二氢萘

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Crossed molecular beam reactions of p-tolyl (C7H7) plus 1,3-butadiene (C4H6), p-tolyl (C7H7) plus 1,3-butadiene-d(6) (C4D6), and p-tolyl-d(7) (C7D7) plus 1,3-butadiene (C4H6) were carried out under single-collision conditions at collision energies of about 55 kJ mol(-1). 6-Methyl-1,4-dihydronaphthalene was identified as the major reaction product formed at fractions of about 94% with the monocyclic isomer (trans-1-p-tolyl-1,3-butadiene) contributing only about 6%. The reaction is initiated by barrierless addition of the p-tolyl radical to the terminal carbon atom of the 1,3-butadiene via a van der Waals complex. The collision complex isomerizes via cyclization to a bicyclic intermediate, which then ejects a hydrogen atom from the bridging carbon to form 6-methyl-1,4-dihydronaphthalene through a tight exit transition state located about 27 kJ mol(-1) above the separated products. This is the dominant channel under the present experimental conditions. Alternatively, the collision complex can also undergo hydrogen ejection to form trans-1-p-tolyl-1,3-butadiene; this is a minor contributor to the present experiment. The de facto barrierless formation of a methyl-substituted aromatic hydrocarbons by dehydrogenation via a single event represents an important step in the formation of polycyclic aromatic hydrocarbons (PAHs) and their partially hydrogenated analogues in combustion flames and the interstellar medium.
机译：对甲苯基（C7H7）加1,3-丁二烯（C4H6），对甲苯基（C7H7）加1,3-丁二烯-d（6）（C4D6）和对甲苯基-d（7）的交叉分子束反应）（C7D7）加1,3-丁二烯（C4H6）在单碰撞条件下以约55 kJ mol（-1）的碰撞能量进行。 6-甲基-1,4-二氢萘被确定为主要反应产物，其形成的比例约为94％，而单环异构体（反式-1-对甲苯基-1,3-丁二烯）仅贡献约6％。通过经由范德华配合物将对甲苯基自由基无障碍地加到1，3-丁二烯的末端碳原子上来引发反应。碰撞复合物通过环化异构化成双环中间体，然后从桥连的碳中喷射出氢原子，通过位于分离物上方约27 kJ mol（-1）的紧密出口过渡态形成6-甲基-1,4-二氢萘。产品。这是目前实验条件下的主要通道。另外，碰撞复合物也可以进行氢喷射形成反式-1-对甲苯基-1,3-丁二烯。这是本实验的次要贡献者。通过单次事件脱氢实际上无障碍地形成了甲基取代的芳烃，代表了在燃烧火焰和星际介质中形成多环芳烃（PAH）及其部分氢化的类似物的重要步骤。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号