(1aR,1'aS,7bR,7'bS)-1,1,1',1'-tetrachloro-6,6'-dimethyl-1,1a,1',1'a,2,2',3,3'-octahydro-7b,7'b-bi(cyclopropa[a]naphthalene) | 1263098-93-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: (1aR,1'aS,7bR,7'bS)-1,1,1',1'-tetrachloro-6,6'-dimethyl-1,1a,1',1'a,2,2',3,3'-octahydro-7b,7'b-bi(cyclopropa[a]naphthalene)
• CAS: 1263098-93-6
• 化学式: C₂₄H₂₂Cl₄
• 分子量: 452.251
• InChiKey: HZMSOKSRLJAZPH-ZDNVTZCJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.98
• 重原子数：
  28.0
• 可旋转键数：
  1.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  甲醇 、 (1aR,1'aS,7bR,7'bS)-1,1,1',1'-tetrachloro-6,6'-dimethyl-1,1a,1',1'a,2,2',3,3'-octahydro-7b,7'b-bi(cyclopropa[a]naphthalene) 反应 12.0h， 生成 (1aR*/S*,7bR*/S*)-1,1-dichloro-7b-((R*/S*,Z)-8-chloro-6,7-dihydro-7-methoxy-2-methyl-5H-benzo[7]annulen-9-yl)-1a,2,3,7b-tetrahydro-6-methyl-1H-cyclopropa[a]naphthalene 、 (1aS*/R*,7bS*/R*)-1,1-dichloro-7b-((R*/S*,Z)-8-chloro-6,7-dihydro-7-methoxy-2-methyl-5H-benzo[7]annulen-9-yl)-1a,2,3,7b-tetrahydro-6-methyl-1H-cyclopropa[a]naphthalene
  参考文献：
  名称：

  The marked difference in conformational behavior of the two diastereomers of 7-substituted-1,1-dichloro-7b-((Z)-8-chloro-6,7-dihydro-5H-benzo[7]annulen-9-yl)-1a,2,3,7b-tetrahydro-1H-cyclopropa[a]naphthalene, single crystal X-ray, 1H NMR and AM1 studies

  摘要：

  The 7-substituted of 1 and 2 were synthesized and conformational analysis carried out. While 7-substituted of 2 show two conformers in solution, 7-substituted of 1 show only one form in solution. AM1 semi-empirical molecular orbital calculations show that the conformation of cycloheptadiene ring in 1 and 2 is a twist boat form. In this conformation, the C-7 substituents can be oriented in pseudo equatorial (exo) and pseudo axial (endo) positions. The (3)J calculation with Haasnoot equation on optimized structure of 2 reproduces the observed 3J coupling constants in exo and endo forms. Ring inversion of cycloheptadiene moiety in substituted 2 interconvert the e'-a' (exo-endo) positions. The (3)J calculation on optimized structure of 1 shows that 7-substitution is in pseudo equatorial (exo) direction, as found in the crystal structure of la by single crystal X-ray crystallography. The barrier to ring inversion in 2a is determined by dynamic H-1 NMR spectroscopy to be Delta(not equal)G((335K)) = 68.0 +/- 0.5 kj/mol. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2010.06.037
• 作为产物：
  描述：

  氯仿 、 6-甲基-4-(7-甲基-3,4-二氢萘-1-基)-1,2-二氢萘 在 sodium hydroxide 作用下， 反应 12.0h， 生成 1,1-dichloro-6-methyl-7b-(7-methyl-3,4-dihydronaphthalen-1-yl)-1a,2,3,7b-tetrahydro-1H-cyclopropa[a]naphthalene 、 (1aR,1'aS,7bR,7'bS)-1,1,1',1'-tetrachloro-6,6'-dimethyl-1,1a,1',1'a,2,2',3,3'-octahydro-7b,7'b-bi(cyclopropa[a]naphthalene) 、
  参考文献：
  名称：

  The marked difference in conformational behavior of the two diastereomers of 7-substituted-1,1-dichloro-7b-((Z)-8-chloro-6,7-dihydro-5H-benzo[7]annulen-9-yl)-1a,2,3,7b-tetrahydro-1H-cyclopropa[a]naphthalene, single crystal X-ray, 1H NMR and AM1 studies

  摘要：

  The 7-substituted of 1 and 2 were synthesized and conformational analysis carried out. While 7-substituted of 2 show two conformers in solution, 7-substituted of 1 show only one form in solution. AM1 semi-empirical molecular orbital calculations show that the conformation of cycloheptadiene ring in 1 and 2 is a twist boat form. In this conformation, the C-7 substituents can be oriented in pseudo equatorial (exo) and pseudo axial (endo) positions. The (3)J calculation with Haasnoot equation on optimized structure of 2 reproduces the observed 3J coupling constants in exo and endo forms. Ring inversion of cycloheptadiene moiety in substituted 2 interconvert the e'-a' (exo-endo) positions. The (3)J calculation on optimized structure of 1 shows that 7-substitution is in pseudo equatorial (exo) direction, as found in the crystal structure of la by single crystal X-ray crystallography. The barrier to ring inversion in 2a is determined by dynamic H-1 NMR spectroscopy to be Delta(not equal)G((335K)) = 68.0 +/- 0.5 kj/mol. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2010.06.037

文献信息

• The conformational diastereomers of 7-substituted-(8Z)-8-chloro-6,7-dihydro-9-(1,2-dihydro-6-R-naphthalen-4-yl)-2-R-5H-benzo[7]annulene, the question of atropisomerism versus ring inversion
  作者：Parviz Rashidi Ranjbar、Hamid Roshan

  DOI：10.3998/ark.5550190.0011.905

  日期：——

  Conformational diastereomers of 7-substituted-(8Z)-8-chloro-6,7-dihydro-9-(1,2-dihydro-naphthalen-4-yl)-5H-benzo[7]annulene 1 are observed at room temperature in solution. Two conformational processes are possible in 1, i.e. atropisomerism around the sp(2)-sp(2) pivot bond and ring inversion of cycloheptadiene moiety which together provide four minima structures. The (3)J calculation by Haasnoot equation on optimized structures is accordance with the 7-substituents in pseudo equatorial (exo) position in both forms. The barrier to conformational process is determined by dynamic H-1-NMR spectroscopy to be Delta G(not equal) ((365K))=74.5+/-0.5 kJ/mol. Solvent dependent populations of the two forms are studied in DMSO-d(6) and CDCl3, the population ratio is not sensitive to solvent polarity.