cis-5,6-Dimethylbicyclo<3.2.1.0>hept-1(5)-en | 87116-60-7

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: cis-5,6-Dimethylbicyclo<3.2.1.0>hept-1(5)-en
• 英文别名: cis-6,7-dimethylbicyclo<3.2.0>hept-1-(5)-ene；cis-6,7-dimethylbicyclo[3.2.0]hept-1(5)-ene；cis-6,7-dimethylbicycloheptene；(6R,7S)-6,7-Dimethylbicyclo[3.2.0]hept-1(5)-ene
• CAS: 87116-60-7
• 化学式: C₉H₁₄
• 分子量: 122.21
• InChiKey: PEVJKSXXDGFJKM-KNVOCYPGSA-N

物化性质

• 沸点：
  159.6±7.0 °C(Predicted)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  cis-5,6-Dimethylbicyclo<3.2.1.0>hept-1(5)-en 生成 (E,Z)-1,2-bis(ethylidene)cyclopentane
  参考文献：
  名称：

  Roth, Wolfgang R.; Rekowski, Volker; Boerner, Sabine, Liebigs Annalen, 1996, # 3, p. 409 - 430

  摘要：

  DOI：
• 作为产物：
  描述：

  2-重氮基环戊酮 在 sodium methylate 、 对甲苯磺酰肼 作用下， 生成 cis-5,6-Dimethylbicyclo<3.2.1.0>hept-1(5)-en
  参考文献：
  名称：

  Stereochemical course of thermal cycloreversion of [3.2.1]propellanes to 1,3-dialkenylcyclohexanes

  摘要：

  DOI：

  10.1021/ja00358a038

文献信息

• Altering the Allowed/Forbidden Gap in Cyclobutene Electrocyclic Reactions:  Experimental and Theoretical Evaluations of the Effect of Planarity Constraints
  作者：Patrick S. Lee、Shogo Sakai、Peter Hörstermann、Wolfgang R. Roth、E. Adam Kallel、K. N. Houk

  DOI：10.1021/ja028963g

  日期：2003.5.1

  the forbidden disrotatory pathways decreases. For the ring-opening of a cyclobutene fused to norbornene, the energy gap between the forbidden and the allowed transition state is only 4.1 kcal/mol by CASSCF and 8.0 kcal/mol by CAS-MP2 as compared to 13.4 and 19.2 kcal/mol, respectively, for the parent cyclobutene. Experimental studies of 3,4-dimethylcyclobutenes fused to various ring systems are reported

  允许的旋转环丁烯开环具有明显的非平面碳骨架。Brauman 和 Archie 以及 Freedman 等人的经典实验将允许/禁止的间隙设置为大于 15 kcal/mol。Wolfgang Roth 提出，与不受约束的系统相比，被迫平面化的系统对旋转模式的偏好可能更小。现在已经在理论上和实验上研究了这样的系统，这里提供了证实 Roth 假设的结果。实验在波鸿进行，计算在大阪和洛杉矶进行。随着环丁烯开环过渡结构接近平面，允许旋转和禁止旋转路径之间的能隙减小。对于稠合到降冰片烯的环丁烯的开环，与母体环丁烯的分别为 13.4 和 19.2 kcal/mol 相比，CASSCF 的禁止和允许过渡态之间的能隙仅为 4.1 kcal/mol，CAS-MP2 为 8.0 kcal/mol。3,4-二甲基环丁烯稠合到各种环系统的实验研究被报道，并且发现随着环丁烯的平面性的加强，允许/禁止间隙减小的趋势。
• Cyclobutene photochemistry. Adiabatic photochemical ring opening of alkylcyclobutenes
  作者：William J. Leigh、J. Alberto Postigo、K.C. Zheng

  DOI：10.1139/v96-105

  日期：1996.6.1

  The photochemistry of the cis and trans isomers of a series of dimethylbicyclo(n.2.O)alk-(n+2)-enes (n = 2-5) (bicyclic cyclobutene derivatives in which the C=C bond is shared by the two rings) in pentane solution is described. Irradiation of these compounds using monochromatic 193- or 214-nm light sources results in ring opening to yield the corresponding 1,2-bis(l-ethylidene)cycloalkanes (C,-C,)

  一系列二甲基双环 (n.2.O)alk-(n+2)-enes (n = 2-5)（双环环丁烯衍生物，其中 C=C 键被共享）的顺式和反式异构体的光化学描述了戊烷溶液中的两个环）。使用单色 193 或 214 nm 光源照射这些化合物会导致开环，以高化学和量子产率产生相应的 1,2-双（1-亚乙基）环烷烃 (C,-C,)。在所有情况下，反应都以高 (70-90%) 程度的反旋立体选择性进行。还测定了异构 E,E-和 E,Z-1,2-双(1-亚乙基)环烷烃的直接顺、反光异构化的量子产率。环丁烯辐照的产物分布与波长有关，但是对于 214 nm 激发，从环丁烯开环获得的异构二烯分布与根据异构二烯的顺式、反式光异构化的量子产率计算的分布非常一致，前提是该过程涉及纯粹的旋转开环以产生单个二烯处于最低激发单线态的异构体。结果与轨道对称控制的开环绝热机制一致。
• The effect of central bond torsional mobility on the Rydberg state ring opening of alkylcyclobutenes
  作者：Bruce H Cook、William J Leigh

  DOI：10.1139/v03-058

  日期：2003.6.1

  The stereochemistry of the π,R(3s) excited state ring opening of a series of bicyclic alkylcyclobutenes has been studied in hydrocarbon solution with 228 nm excitation. In these compounds, the C=C bond is shared between the cyclobutene ring and a five-, six-, or seven-membered ancillary ring, which has the effect of restricting the torsional mobility about the central C—C bond in the isomeric diene products. It has previously been shown that monocyclic alkylcyclobutenes undergo stereospecific conrotatory ring opening upon excitation at the long wavelength edge of the π,R(3s) absorption band (228 nm), and nonstereospecific ring opening upon irradiation at shorter wavelengths (within the π,π* absorption band). Different behaviour is observed for the bicyclic systems studied in the present work. The bicyclo[3.2.0]hept-1-ene, bicyclo[4.2.0]oct-1-ene, and one of the bicyclo[5.2.0]non-1-ene derivatives yield nearly the same mixtures of E,E- and E,Z-diene isomers upon irradiation at 214 and 228 nm, with the product mixtures being heavily weighted in favor of the isomer(s) corresponding to disrotatory ring opening. The results may indicate that the stereochemical characteristics of the Rydberg-derived ring opening of alkylcyclobutenes depends on the ability of the molecule to twist about the "central" bond (i.e., the C=C bond in the cyclobutene) as ring opening proceeds. It is proposed that restricting the torsional mobility about the central bond activates internal conversion from the π,R(3s) to the π,π* potential energy surface, from which predominant disrotatory ring opening ensues.Key words: cyclobutene, Rydberg, ring opening, photopericyclic, electrocyclic.

  一系列双环烷基环丁烯的π，R（3s）激发态环开启的立体化学已在烃溶液中通过228纳米激发进行了研究。在这些化合物中，C=C键在环丁烯环和一个五、六或七元辅助环之间共享，这限制了异构双烯产物中心C-C键周围的扭转活性。先前已经表明，单环烷基环丁烯在π，R（3s）吸收带（228纳米）的长波长边激发时发生立体特异的同向环开启，而在较短波长（在π，π*吸收带内）照射时发生非立体特异的环开启。在本研究中研究的双环系统表现出不同的行为。双环[3.2.0]庚-1-烯，双环[4.2.0]辛-1-烯和双环[5.2.0]壬-1-烯衍生物之一在214和228纳米照射时产生几乎相同的E，E-和E，Z-双烯异构体混合物，产物混合物在向有利于相反方向环开启的异构体方向严重倾斜。结果可能表明，烷基环丁烯的Rydberg导出的环开启的立体化学特性取决于分子围绕“中心”键（即环丁烯中的C=C键）扭转的能力，随着环开启的进行，扭转活性受到限制。提出限制中心键周围的扭转活性会激活从π，R（3s）到π，π*势能表面的内部转化，从而导致主要的相反方向环开启。关键词：环丁烯，Rydberg，环开启，光周环，电环。
• The role of central bond torsional motions in the direct cis⇌trans-photoisomerization of conjugated dienes
  作者：William J. Leigh、J. Alberto Postigo

  DOI：10.1039/c39930001836

  日期：——

  The photochemistry of the E,E- and E,Z-geometric isomers of 1,2-bis(ethylidene)-cyclopentane and -cyclobutane, and 2,3-bis(ethylidene)norbornane has been studied in hydrocarbon solution at room temperature; the results are inconsistent with the classical theoretical models for diene cis⇌trans photoisomerization and ring closure, which assume that both processes involve only simple torsional motions about (one or both of) the termini of buta-1,3-diene.

  在室温下的碳氢化合物溶液中，研究了 1,2-双（亚乙基）环戊烷和环丁烷以及 2,3-双（亚乙基）降冰片烷的 E,E- 和 E,Z- 几何异构体的光化学过程；研究结果与二烯顺反光异构化和闭环的经典理论模型不一致，后者假定这两个过程都只涉及丁-1,3-二烯端部（一个或两个）的简单扭转运动。
• Reciprocal Tests of Steric Opposition to Down-Disrotatory ThermalDecyclization of [3.2.1] Propellanes. The Cycloreversion Stereochemistry of the 6,7,8-Trimethyltricyclo[3.2.1.01,5] octanes
  作者：Lauren Lee Stevens、Jerome A. Berson

  DOI：10.1016/s0040-4039(00)80621-8

  日期：1988.1

  isomeric title compounds are described. The cis, endo isomers undergo down-disrotatory cycloreversion to E,E-2-methyl-1,3-bis-(ethylidene)-cyclohexane with high stereospecificity, regardless of the stereochemistry of the C8-methyl group. Both 8-syn - and 8-anti - 6,7-trans -trimethyl isomers decyclize with low stereochemical preference,suggesting that the orbital overlap factors favoring the down-disrotatory

  描述了异构标题化合物的合成和热分解。无论C 8-甲基的立体化学如何，顺式内消旋异构体都经历下旋转环还原成具有高立体特异性的E，E -2-甲基-1,3-双-（亚乙基）-环己烷。8-顺-和8-反-6,7-反式-三甲基异构体都以较低的立体化学偏好性脱环，这表明在顺式情况下，有利于下旋转路径的轨道重叠因子很容易被空间效应克服。