methyl 1-cyano-trans-2(e),6(a)-diphenyl-4,4-(ethylenedioxy)cyclohexane-1(e)-carboxylate | 111904-74-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 1-cyano-trans-2(e),6(a)-diphenyl-4,4-(ethylenedioxy)cyclohexane-1(e)-carboxylate
• 英文别名: methyl (7R,9R)-8-cyano-7,9-diphenyl-1,4-dioxaspiro[4.5]decane-8-carboxylate
• CAS: 111904-74-6
• 化学式: C₂₃H₂₃NO₄
• 分子量: 377.44
• InChiKey: ZVCADECOIBCGRN-WOJBJXKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  68.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 1-cyano-trans-2(e),6(a)-diphenyl-4,4-(ethylenedioxy)cyclohexane-1(e)-carboxylate 在 盐酸 、 氢氧化钾 作用下， 以 二甲基亚砜 、 丙酮 为溶剂， 反应 5.0h， 生成 2(e),6(e)-diphenyl-4-oxocyclohexane-1(e)-carboxamide
  参考文献：
  名称：

  On the Stereochemistry of Diaryl-Substituted Cyclohexanones Formed by Michael Reactions. Trans to Cis Isomerization of Their Ketals under Basic Conditions

  摘要：

  The stereochemistry of C-1-substituted 2,6-diphenylcyclohexan-4-ones 1-3 prepared by Michael reactions has been investigated. While preparations of these compounds have been reported over the past 70 years, in many instances the correct stereochemistry at C-2 (6) and, in some instances at C-1, was uncertain. We show here that in one case in which two identical substituents (CN) are present at C-1, it is possible to isomerize the initially formed trans isomer Id to the cis isomer 3f. When a cyano group and a dissimilar substituent are present at C-1, the initially formed trans isomer may be isomerized to the cis compound. The stereochemistry is vertified by NMR spectroscopy and by X-ray analysis. Reaction of the ethylene ketals (4 and 5) of these ketones with KOH in DMSO at elevated temperatures gives rise to cis products, and deuterium-labeling studies demonstrated the acidity of the benzylic hydrogen at C-2 (6). Isomerization was evident since the trans ketal 4a and the cis ketal 4b gave the same amide 6a. H-1 and C-13 NMR spectra provided conclusive evidence for the cis - trans rearrangement.

  DOI：

  10.1021/jo9801059
• 作为产物：
  描述：

  1-cyano-trans-2,6-diphenyl-4-oxocyclohexane-1-carboxylate 、 乙二醇 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 3.3h， 以69%的产率得到methyl 1-cyano-trans-2(e),6(a)-diphenyl-4,4-(ethylenedioxy)cyclohexane-1(e)-carboxylate
  参考文献：
  名称：

  Structures of Marvel's .delta.-lactone and polymer

  摘要：

  DOI：

  10.1021/jo00237a042

文献信息

• ROWLAND, ALEX T.;GILL, BENJAMIN C., J. ORG. CHEM., 53,(1988) N 2, 434-437
  作者：ROWLAND, ALEX T.、GILL, BENJAMIN C.

  DOI：——

  日期：——
• Structures of Marvel's .delta.-lactone and polymer
  作者：Alex T. Rowland、Benjamin C. Gill

  DOI：10.1021/jo00237a042

  日期：1988.1
• On the Stereochemistry of Diaryl-Substituted Cyclohexanones Formed by Michael Reactions. Trans to Cis Isomerization of Their Ketals under Basic Conditions
  作者：Alex T. Rowland、Sandra A. Filla、Marilyn L. Coutlangus、Mark D. Winemiller、Mark J. Chamberlin、Gary Czulada、Steven D. Johnson、Michal Sabat

  DOI：10.1021/jo9801059

  日期：1998.6.1

  The stereochemistry of C-1-substituted 2,6-diphenylcyclohexan-4-ones 1-3 prepared by Michael reactions has been investigated. While preparations of these compounds have been reported over the past 70 years, in many instances the correct stereochemistry at C-2 (6) and, in some instances at C-1, was uncertain. We show here that in one case in which two identical substituents (CN) are present at C-1, it is possible to isomerize the initially formed trans isomer Id to the cis isomer 3f. When a cyano group and a dissimilar substituent are present at C-1, the initially formed trans isomer may be isomerized to the cis compound. The stereochemistry is vertified by NMR spectroscopy and by X-ray analysis. Reaction of the ethylene ketals (4 and 5) of these ketones with KOH in DMSO at elevated temperatures gives rise to cis products, and deuterium-labeling studies demonstrated the acidity of the benzylic hydrogen at C-2 (6). Isomerization was evident since the trans ketal 4a and the cis ketal 4b gave the same amide 6a. H-1 and C-13 NMR spectra provided conclusive evidence for the cis - trans rearrangement.