6-methyl-1,4-ethano-1,4-dihydronaphthalene | 141319-46-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 6-methyl-1,4-ethano-1,4-dihydronaphthalene
• 英文别名: 6-Methyl-1,4-dihydro-1,4-ethanonaphthalene；4-methyltricyclo[6.2.2.02,7]dodeca-2(7),3,5,9-tetraene
• CAS: 141319-46-2
• 化学式: C₁₃H₁₄
• 分子量: 170.254
• InChiKey: UWQSDBQBAMOEEE-UHFFFAOYSA-N

物化性质

• 沸点：
  268.6±30.0 °C(Predicted)
• 密度：
  1.048±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  6-methyl-1,4-ethano-1,4-dihydronaphthalene 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以76%的产率得到6-methyl-1,2,3,4-tetrahydro-1,4-ethanonaphthalene
  参考文献：
  名称：

  The relationship between partial bond fixation induced by through-bond and/or through-space perturbations in nonplanar benzene derivatives and proton spin-spin coupling constants

  摘要：

  4J(Me - C-C - II) = 4J(OB), the spin-spin coupling constant over four formal bonds between methyl protons and a proton bonded to an sp2 carbon, previously established 9-17 as a probe for bond order, was determined for 6-methyl-1,4-dihydro-1,4-methanonaphthalene (1) and for a number of reference compounds 2-5. Self-consistent field (SCF) calculations at the 3-21G level for 1-4 predict partial bond fixation in the benzene ring for all molecules in the sense predicted by interpretation of previously-reported photoelectron spectra of closely-related molecules. 31,32 The benzene moiety pi-bond orders were calculated from pseudominimal basis sets obtained by contraction of the double-zeta basis. Two types of bond order, one obtained with a nonorthogonal and the other with a Lowdin-orthogonalized pseudominimal basis, are reported. It is found that, as for planar compounds, there is a linear relationship between either type of bond order and 4J(OB) However, the correlation coefficients are considerably smaller, owing partly to the small size of the sample and partly to the fact that the range of values is much smaller than in comparisons for planar molecules, 9-11 so that the importance of contributions of terms other than the Fermi contact term and deviations from the McConnell ''average energy'' approximation 44 may be significant. The partial bond fixation is attributed to the effects of sigma-through-bond coupling to the attached framework, and, in the case of 1 and 2, additional coupling to the sigma-linked pi-bonding orbital of the ethylenic group. This constitutes independent NMR evidence for orbital interaction between sigma-linked pi-orbitals.

  DOI：

  10.1021/j100193a019
• 作为产物：
  描述：

  2-氨基-5-甲基苯甲酸 、 1,3-环己二烯 在 亚硝酸异戊酯 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 1.0h， 以8%的产率得到6-methyl-1,4-ethano-1,4-dihydronaphthalene
  参考文献：
  名称：

  The relationship between partial bond fixation induced by through-bond and/or through-space perturbations in nonplanar benzene derivatives and proton spin-spin coupling constants

  摘要：

  4J(Me - C-C - II) = 4J(OB), the spin-spin coupling constant over four formal bonds between methyl protons and a proton bonded to an sp2 carbon, previously established 9-17 as a probe for bond order, was determined for 6-methyl-1,4-dihydro-1,4-methanonaphthalene (1) and for a number of reference compounds 2-5. Self-consistent field (SCF) calculations at the 3-21G level for 1-4 predict partial bond fixation in the benzene ring for all molecules in the sense predicted by interpretation of previously-reported photoelectron spectra of closely-related molecules. 31,32 The benzene moiety pi-bond orders were calculated from pseudominimal basis sets obtained by contraction of the double-zeta basis. Two types of bond order, one obtained with a nonorthogonal and the other with a Lowdin-orthogonalized pseudominimal basis, are reported. It is found that, as for planar compounds, there is a linear relationship between either type of bond order and 4J(OB) However, the correlation coefficients are considerably smaller, owing partly to the small size of the sample and partly to the fact that the range of values is much smaller than in comparisons for planar molecules, 9-11 so that the importance of contributions of terms other than the Fermi contact term and deviations from the McConnell ''average energy'' approximation 44 may be significant. The partial bond fixation is attributed to the effects of sigma-through-bond coupling to the attached framework, and, in the case of 1 and 2, additional coupling to the sigma-linked pi-bonding orbital of the ethylenic group. This constitutes independent NMR evidence for orbital interaction between sigma-linked pi-orbitals.

  DOI：

  10.1021/j100193a019

文献信息

• The relationship between partial bond fixation induced by through-bond and/or through-space perturbations in nonplanar benzene derivatives and proton spin-spin coupling constants
  作者：J. Simon Craw、Noel S. Hush、Sever Sternhell、Charles W. Tansey

  DOI：10.1021/j100193a019

  日期：1992.7

  4J(Me - C-C - II) = 4J(OB), the spin-spin coupling constant over four formal bonds between methyl protons and a proton bonded to an sp2 carbon, previously established 9-17 as a probe for bond order, was determined for 6-methyl-1,4-dihydro-1,4-methanonaphthalene (1) and for a number of reference compounds 2-5. Self-consistent field (SCF) calculations at the 3-21G level for 1-4 predict partial bond fixation in the benzene ring for all molecules in the sense predicted by interpretation of previously-reported photoelectron spectra of closely-related molecules. 31,32 The benzene moiety pi-bond orders were calculated from pseudominimal basis sets obtained by contraction of the double-zeta basis. Two types of bond order, one obtained with a nonorthogonal and the other with a Lowdin-orthogonalized pseudominimal basis, are reported. It is found that, as for planar compounds, there is a linear relationship between either type of bond order and 4J(OB) However, the correlation coefficients are considerably smaller, owing partly to the small size of the sample and partly to the fact that the range of values is much smaller than in comparisons for planar molecules, 9-11 so that the importance of contributions of terms other than the Fermi contact term and deviations from the McConnell ''average energy'' approximation 44 may be significant. The partial bond fixation is attributed to the effects of sigma-through-bond coupling to the attached framework, and, in the case of 1 and 2, additional coupling to the sigma-linked pi-bonding orbital of the ethylenic group. This constitutes independent NMR evidence for orbital interaction between sigma-linked pi-orbitals.