methyl orthoformate of cis-cyclohexa-3,5-diene-1,2-diol | 191406-63-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl orthoformate of cis-cyclohexa-3,5-diene-1,2-diol
• 英文别名: cis-Cyclohexe-3,5-diene-1,2-diol methyl orthoformate；(3aS,7aR)-2-methoxy-3a,7a-dihydro-1,3-benzodioxole
• CAS: 191406-63-0
• 化学式: C₈H₁₀O₃
• 分子量: 154.166
• InChiKey: PJYWSYOUGQJTTB-DHBOJHSNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl orthoformate of cis-cyclohexa-3,5-diene-1,2-diol 在 盐酸 、 占吨酮 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 为溶剂， 反应 28.0h， 生成 (2s,3aR,3bS,3b1S,3b1R,3cS,5aR,5bR,5b1R,5b1S,5cS)-2-phenyl-3a,3b,3b1,3c,3c1,5a,5b1,5a1,5b,5c-decahydrodicyclobuta[4,5:8,1]biphenyleno[2,3-d][1,3]dioxole
  参考文献：
  名称：

  Chemistry of syn-o,o‘-Dibenzene

  摘要：

  Anew and improved synthesis cis, syn-o,o'-dibenzene 1 was developed to obtain 1 in larger amounts with improved purity, syn-Dibenzene 1 undergoes thermolysis to two molecules of benzene at a rate slower than that of the thermodynamically more stable anti-dibenzene 2. Kinetic analysis revealed that the higher thermal stability of 1 is due to the higher heat of activation in thermolysis. Photoelectron spectroscopy of 1 showed that the through-bond interaction between the two cyclohexadiene units in o,o'-dibenzenes is more important than their through-space interaction. A comparative study on the thermolyses of related syn-o,o'arene:benzene dimers suggests that thermolyses of syn-o,o'-arene:benzene dimers proceed via their anti-isomers as an intermediate. syn-Dibenzene 1 also undergoes adiabatic photolysis to one molecule of excited benzene and one molecule of ground-state benzene in goad efficiency. The mechanisms of these reactions an discussed.

  DOI：

  10.1021/ja0023579
• 作为产物：
  描述：

  (3aS,5S,6S,7aR)-5,6-dibromo-2-methoxy-3a,4,5,6,7,7a-hexahydro-1,3-benzodioxole 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 苯 为溶剂， 反应 6.0h， 以49%的产率得到methyl orthoformate of cis-cyclohexa-3,5-diene-1,2-diol
  参考文献：
  名称：

  Chemistry of syn-o,o‘-Dibenzene

  摘要：

  Anew and improved synthesis cis, syn-o,o'-dibenzene 1 was developed to obtain 1 in larger amounts with improved purity, syn-Dibenzene 1 undergoes thermolysis to two molecules of benzene at a rate slower than that of the thermodynamically more stable anti-dibenzene 2. Kinetic analysis revealed that the higher thermal stability of 1 is due to the higher heat of activation in thermolysis. Photoelectron spectroscopy of 1 showed that the through-bond interaction between the two cyclohexadiene units in o,o'-dibenzenes is more important than their through-space interaction. A comparative study on the thermolyses of related syn-o,o'arene:benzene dimers suggests that thermolyses of syn-o,o'-arene:benzene dimers proceed via their anti-isomers as an intermediate. syn-Dibenzene 1 also undergoes adiabatic photolysis to one molecule of excited benzene and one molecule of ground-state benzene in goad efficiency. The mechanisms of these reactions an discussed.

  DOI：

  10.1021/ja0023579

文献信息

• [2+2] Heterodimers of methyl phenanthrene-9-carboxylate and benzene
  作者：Taehee Noh、Hyun Yu、Youngmee Jeong、Kyungmoon Jeon、Sukjin Kang

  DOI：10.1039/b009846i

  日期：——

  Both syn- and anti-[2+2] heterodimers (1 and 2) of methyl phenanthrene-9-carboxylate (9-MP) and benzene were synthesized from 9-MP and cyclohexa-1,4-diene. Upon irradiation of 9-MP and excess methyl orthoformate of cis-cyclohexa-3,5-diene-1,2-diol followed by hydrolysis, the syn-[2+2] cycloadduct and also four cyclodimers of 9-MP were produced. Triplet-sensitized photocycloaddition followed by hydrolysis provided the anti-[2+2] cycloadduct. Dehydroxylation of the cycloadducts under mild conditions gave 1 and 2. In contrast to the previous reports on [2+2] dibenzenes and [2+2] heterodimers of acenaphthylenes and benzene, kinetic analysis of the thermolyses of 1 and 2 indicated that 1 was kinetically less stable than 2. Photodissociation of 1 and 2 were found to be adiabatic with efficiencies of 0.33 and 0.39. An explanation is provided for their thermoreversion and photoreversion.

  由 9-MP 和环己烯-1,4-二烯合成了菲-9-羧酸甲酯（9-MP）和苯的合[2+2]异二聚体（1 和 2）。将 9-MP 和过量的顺式-环己-3,5-二烯-1,2-二醇的原甲酸甲酯进行辐照，然后进行水解，生成了 9-MP 的合成[2+2]环加载物和四个环二聚体。三重敏化光环加成后再水解，可得到反[2+2]环加合物。与之前有关[2+2] 二苯以及苊烯和苯的[2+2] 异二聚体的报道不同，对 1 和 2 的热解动力学分析表明，1 在动力学上不如 2 稳定。研究发现，1 和 2 的光解是绝热的，效率分别为 0.33 和 0.39。这为它们的热转化和光转化提供了解释。
• Noh, Taehee; Jeon, Kyungmoon; Jeong, Youngmee, Journal of the Chemical Society. Perkin Transactions 2 (2001), 1999, # 7, p. 1299 - 1303
  作者：Noh, Taehee、Jeon, Kyungmoon、Jeong, Youngmee、Jang, Shinho、Min, Kil Sik

  DOI：——

  日期：——
• YANG, NIEN-CHU, C.;HORNER, M. G., TETRAHEDRON LETT., 1986, 27, N 5, 543-546
  作者：YANG, NIEN-CHU, C.、HORNER, M. G.

  DOI：——

  日期：——
• Chemistry of <i>s</i><i>yn</i>-<i>o</i>,<i>o</i>‘-Dibenzene
  作者：Hong Gan、M. Glenn Horner、Bruce J. Hrnjez、Thomas A. McCormack、John L. King、Zbigniew Gasyna、Grace Chen、Rolf Gleiter、Nien-chu C. Yang

  DOI：10.1021/ja0023579

  日期：2000.12.1

  Anew and improved synthesis cis, syn-o,o'-dibenzene 1 was developed to obtain 1 in larger amounts with improved purity, syn-Dibenzene 1 undergoes thermolysis to two molecules of benzene at a rate slower than that of the thermodynamically more stable anti-dibenzene 2. Kinetic analysis revealed that the higher thermal stability of 1 is due to the higher heat of activation in thermolysis. Photoelectron spectroscopy of 1 showed that the through-bond interaction between the two cyclohexadiene units in o,o'-dibenzenes is more important than their through-space interaction. A comparative study on the thermolyses of related syn-o,o'arene:benzene dimers suggests that thermolyses of syn-o,o'-arene:benzene dimers proceed via their anti-isomers as an intermediate. syn-Dibenzene 1 also undergoes adiabatic photolysis to one molecule of excited benzene and one molecule of ground-state benzene in goad efficiency. The mechanisms of these reactions an discussed.