(+/-)-2-phenylbicyclo<3.1.0>hexan-2-ol | 126110-28-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+/-)-2-phenylbicyclo<3.1.0>hexan-2-ol
• 英文别名: Bicyclo[3.1.0]hexan-2-ol, 2-phenyl-；2-phenylbicyclo[3.1.0]hexan-2-ol
• CAS: 126110-28-9
• 化学式: C₁₂H₁₄O
• 分子量: 174.243
• InChiKey: MGJXZLRYSZHEPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-2-phenylbicyclo<3.1.0>hexan-2-ol 在 sodium hydroxide 、 sodium tetrahydroborate 、 三氟化硼乙醚 、 双氧水 作用下， 生成 1-Phenylbicyclo[3.1.0]hexane
  参考文献：
  名称：

  Benzylic Stabilization as a Mechanistic Tool for Studying Radical Rearrangements

  摘要：

  The kinetic parameters for the rearrangement of, and the relative energies of radicals involved in the equilibria of, a bicyclic cyclopropylmethyl/homoallyl system were determined. Benzylic stabilization of the cyclopropylmethyl radical facilitates characterization of all four ring opening and closing processes. Kinetically disfavored endocyclic ring opening produces the thermodynamically favored homoallyl radical(10). Cyclohexenyl radical 10 is approximately 1.7 kcal/mol lower in energy than 9. The regioselectivity of ring opening of 8 is independent of any assumptions involving trapping rate constants of radicals. The regioselectivity for ring opening of 8 (k(1)/k(2) = 30.2 at 298 K) is similar to that of bicyclo[3.1.0]hexan-1-yl (1). These experiments suggest that benzylic stabilization does not significantly perturb the position of the transition state for ring opening. Therefore, phenyl substitution of a bicyclic cyclopropylmethyl radical should be a useful tool for analyzing the effects of substituents elsewhere in the system.

  DOI：

  10.1021/jo00109a043
• 作为产物：
  描述：

  2-环戊烯酮 在 sodium hydride 、 magnesium 作用下， 反应 2.17h， 生成 (+/-)-2-phenylbicyclo<3.1.0>hexan-2-ol
  参考文献：
  名称：

  苯环利定和σ结合位点处的异构体2-苯基-2-（N-哌啶基）双环[3.1.0]己烷的合成，构型和活性。

  摘要：

  新型半刚性衍生物（+）-顺-1- [2-苯基-2-双环[3.1.0]己基]哌啶[（+）-8]，其对映异构体（-）-8和（+-）-合成反式-1- [2-苯基-2-双环[3.1.0]己基]哌啶[（+/-）-9]作为探针，研究苯环利定（PCP）与其结合位点的相互作用方式。 N-甲基-D-天冬氨酸受体复合物。从环戊-2-烯酮开始，通过五个步骤获得每种目标化合物。（+）-和（-）-8通过乙醇从中间体（+-）的（S）-（+）-和（R）-（-）-扁桃酸盐的三重结晶获得，光学纯度高于98％。 ）-顺-2-苯基-2-双环[3.1.0]己胺（[（+/-）-16]。（R）-（-）-扁桃酸盐的结晶，得到（1R，2R，5S）- （-）-16，而（S）-（+）-扁桃酸盐得到（1S，2S，5R）-（+）-16; 通过（-）-16.（R）-（-）-扁桃酸盐的单晶X射线分析确定绝对构型。（+/-）-9-苦味酸盐的单晶X射线

  DOI：

  10.1021/jm00103a008

文献信息

• The influence of intramolecular dynamics on branching ratios in thermal rearrangements
  作者：Richard H. Newman-Evans、Reyna J. Simon、Barry K. Carpenter

  DOI：10.1021/jo00289a053

  日期：1990.1
• NEWMAN-EVANS, RICHARD H.;SIMON, REYNA J.;CARPENTER, BARRY K., J. ORG. CHEM., 55,(1990) N, C. 695-711
  作者：NEWMAN-EVANS, RICHARD H.、SIMON, REYNA J.、CARPENTER, BARRY K.

  DOI：——

  日期：——
• Benzylic Stabilization as a Mechanistic Tool for Studying Radical Rearrangements
  作者：Hariharan Venkatesan、Marc M. Greenberg

  DOI：10.1021/jo00109a043

  日期：1995.2

  The kinetic parameters for the rearrangement of, and the relative energies of radicals involved in the equilibria of, a bicyclic cyclopropylmethyl/homoallyl system were determined. Benzylic stabilization of the cyclopropylmethyl radical facilitates characterization of all four ring opening and closing processes. Kinetically disfavored endocyclic ring opening produces the thermodynamically favored homoallyl radical(10). Cyclohexenyl radical 10 is approximately 1.7 kcal/mol lower in energy than 9. The regioselectivity of ring opening of 8 is independent of any assumptions involving trapping rate constants of radicals. The regioselectivity for ring opening of 8 (k(1)/k(2) = 30.2 at 298 K) is similar to that of bicyclo[3.1.0]hexan-1-yl (1). These experiments suggest that benzylic stabilization does not significantly perturb the position of the transition state for ring opening. Therefore, phenyl substitution of a bicyclic cyclopropylmethyl radical should be a useful tool for analyzing the effects of substituents elsewhere in the system.
• Synthesis, configuration, and activity of isomeric 2-phenyl-2-(N-piperidinyl)bicyclo[3.1.0]hexanes at phencyclidine and .sigma. binding sites
  作者：Brian R. De Costa、Mariena V. Mattson、Clifford George、Joannes T. M. Linders

  DOI：10.1021/jm00103a008

  日期：1992.12

  at sigma sites. Qualitative correlation between the sigma and PCP binding data suggests some similarities between these binding sites. An axial phenyl and equatorial piperidine ring with the nitrogen lone pair of electrons antiperiplanar to the phenyl ring has been postulated as the receptor-active conformation of PCP-like ligands at the PCP binding site. Comparison of the binding data of 7-9 with

  新型半刚性衍生物（+）-顺-1- [2-苯基-2-双环[3.1.0]己基]哌啶[（+）-8]，其对映异构体（-）-8和（+-）-合成反式-1- [2-苯基-2-双环[3.1.0]己基]哌啶[（+/-）-9]作为探针，研究苯环利定（PCP）与其结合位点的相互作用方式。 N-甲基-D-天冬氨酸受体复合物。从环戊-2-烯酮开始，通过五个步骤获得每种目标化合物。（+）-和（-）-8通过乙醇从中间体（+-）的（S）-（+）-和（R）-（-）-扁桃酸盐的三重结晶获得，光学纯度高于98％。 ）-顺-2-苯基-2-双环[3.1.0]己胺（[（+/-）-16]。（R）-（-）-扁桃酸盐的结晶，得到（1R，2R，5S）- （-）-16，而（S）-（+）-扁桃酸盐得到（1S，2S，5R）-（+）-16; 通过（-）-16.（R）-（-）-扁桃酸盐的单晶X射线分析确定绝对构型。（+/-）-9-苦味酸盐的单晶X射线