endo-6-Methyl-2,3-benzobicyclo<3.1.0>hex-2-en | 30021-35-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: endo-6-Methyl-2,3-benzobicyclo<3.1.0>hex-2-en
• 英文别名: (1S,1aS,6aR)-1-methyl-1,1a,6,6a-tetrahydrocyclopropa[a]indene
• CAS: 30021-35-3
• 化学式: C₁₁H₁₂
• 分子量: 144.216
• InChiKey: MDBNGEUOVCKBLP-WHGOUJPWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1,1-二碘乙烷 、 茚 生成 endo-6-Methyl-2,3-benzobicyclo<3.1.0>hex-2-en
  参考文献：
  名称：

  锌的甲基卡宾在与苯乙烯、茚和萘反应中的立体选择性

  摘要：

  在与苯乙烯、茚和萘的反应中研究了由二乙基锌和亚乙基碘生成的甲基卡宾的立体选择性。1-甲基-2-苯基环丙烷（顺式/反式=4.1）以13%的产率从苯乙烯中获得。茚仅以 28% 的产率得到 6-甲基-2,3-苯并双环[3.1.0]己-2-烯的内异构体。从萘中，5,8-二甲基-2,3-苯并三环[5.1.0.04,6]辛-2-烯的三种异构体以顺式形式有利地获得，如在苯乙烯和茚的情况下，但两种异构体7-甲基-2,3-苯并双环[4.1.0]-庚-2,4-二烯的形成优于反形式。这种反选择性可以通过逐步加成机制来解释，该机制先前已提出用于烷基苯通过甲基卡宾的扩环反应。

  DOI：

  10.1246/bcsj.43.2195

文献信息

• Picosecond Radical Kinetics. Fast Ring Openings of Constrained, Aryl-Substituted Cyclopropylcarbinyl Radicals
  作者：Amanda A. Martin-Esker、Cathy C. Johnson、John H. Horner、Martin Newcomb

  DOI：10.1021/ja00099a036

  日期：1994.10

  The kinetics of ring openings of the exo- and endo-(2,3-benzobicyclo [3.1.0]hex-2-en-6-yl)methyl radicals (4a and 5a), the trans-(spiro[cyclopropane-1,1'-indan]-2-yl)methyl radical (6a), and the (spiro[cyclopropane-1,9'-fluorene]-2-yl)methyl radical (7a) have been studied by competition kinetics employing benzeneselenol trapping. Arrhenius functions for ring openings were determined for reactions conducted between -80 and 50 degrees C. Each radical rearranges rapidly, with rate constants at 25 degrees C of 3 x 10(11) (4a), 2 x 10(11) (5a), 6 x 10(11) (6a), and 6 x 10(12) s(-1) (7a). Precursors to these radicals represent hypersensitive mechanistic probes with unambiguous rate constants for rearrangement. The results confirm the utility of a previously employed semiquantitative method for estimating rate constants for aryl-substituted cyclopropylcarbinyl rearrangements based on Marcus theory. However, they also show that severe dihedral angles between the aromatic pi-systems and the breaking cyclopropyl C-C bonds in the energy-minimized structures cannot be used to predict kinetic effects in the rearrangement reactions. The ramifications of the kinetic results for mechanistic studies of enzyme-catalyzed oxidations of hydrocarbons that employed hypersensitive probes are discussed.
• Rapid intramolecular addition reactions of triplet arylcarbenes
  作者：Guenter Hoemberger、Andrea E. Dorigo、Wolfgang Kirmse、K. N. Houk

  DOI：10.1021/ja00184a011

  日期：1989.1