1,1-Dicarbethoxy-2,2-dimethyl-3-phenylcyclopropane | 123436-26-0

• 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: 1,1-Dicarbethoxy-2,2-dimethyl-3-phenylcyclopropane
• 英文别名: Diethyl 2,2-dimethyl-3-phenyl-1,1-cyclopropanedicarboxylate；diethyl 2,2-dimethyl-3-phenylcyclopropane-1,1-dicarboxylate
• CAS: 123436-26-0
• 化学式: C₁₇H₂₂O₄
• 分子量: 290.359
• InChiKey: MCIMUUDLSGRBFK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1-Dicarbethoxy-2,2-dimethyl-3-phenylcyclopropane 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以96%的产率得到1,1-Bis(hydroxymethyl)-2,2-dimethyl-3-phenylcyclopropane
  参考文献：
  名称：

  Rearrangement of 1,3-diradicals. Arylcyclopropane photochemistry

  摘要：

  The photochemistry of a series of aryl-substituted cyclopropanes was investigated as part of our continuing investigations of these systems. The literature held a puzzling discrepancy in which several similar reactants exhibited differing photochemistry. A series of 3-aryl-1,1,2,2-tetramethylcyclopropanes was found to rearrange photochemically to give primarily two types of products, the anticipated 4-aryl-2,3,3-trimethyl-1-butenes and, additionally, 1-aryl-2,3,3-trimethyl-1-butenes. The latter arise from regioselective methyl migration of intermediate singlet 1,3-diradicals. Also, the usual Griffin carbene fragmentation was encountered as a minor pathway. Biphenylyl-, p-cyanophenyl-, and p-anisyl-substituted cyclopropanes were studied. Also, the photochemistry of 3-phenyl-1,1,2,2-tetramethylcyclopropane was reinvestigated and found to conform to the general pattern of reactivity. Throughout, it was the singlet excited states responsible for the observed reactivity, and the triplet counterparts were found to be unreactive. In addition, the photochemistry of 3-biphenylyl-2,2-dimethyl-1,1-diphenylcyclopropane was studied. Again, the triplet was unreactive. The singlet gave rise to 4-biphenylyl-2-methyl-3,3-diphenyl-1-butene exclusively. The differing behavior of the various arylcyclopropanes is discussed from a mechanistic viewpoint. In the case of the 3-aryl-1,1,2,2-tetramethylcyclopropanes, the regioselectivity of the 1,3-diradical intermediate favors migration toward the less delocalized odd-electron center. This selectivity is understood on a quantum mechanical basis. Finally, quantum yields are reported.

  DOI：

  10.1021/jo00005a018
• 作为产物：
  描述：

  2-硝基丙烷 、 亚苯甲基丙二酸二乙酯 在 potassium tert-butylate 作用下， 生成 1,1-Dicarbethoxy-2,2-dimethyl-3-phenylcyclopropane
  参考文献：
  名称：

  Rearrangement of 1,3-diradicals. Arylcyclopropane photochemistry

  摘要：

  The photochemistry of a series of aryl-substituted cyclopropanes was investigated as part of our continuing investigations of these systems. The literature held a puzzling discrepancy in which several similar reactants exhibited differing photochemistry. A series of 3-aryl-1,1,2,2-tetramethylcyclopropanes was found to rearrange photochemically to give primarily two types of products, the anticipated 4-aryl-2,3,3-trimethyl-1-butenes and, additionally, 1-aryl-2,3,3-trimethyl-1-butenes. The latter arise from regioselective methyl migration of intermediate singlet 1,3-diradicals. Also, the usual Griffin carbene fragmentation was encountered as a minor pathway. Biphenylyl-, p-cyanophenyl-, and p-anisyl-substituted cyclopropanes were studied. Also, the photochemistry of 3-phenyl-1,1,2,2-tetramethylcyclopropane was reinvestigated and found to conform to the general pattern of reactivity. Throughout, it was the singlet excited states responsible for the observed reactivity, and the triplet counterparts were found to be unreactive. In addition, the photochemistry of 3-biphenylyl-2,2-dimethyl-1,1-diphenylcyclopropane was studied. Again, the triplet was unreactive. The singlet gave rise to 4-biphenylyl-2-methyl-3,3-diphenyl-1-butene exclusively. The differing behavior of the various arylcyclopropanes is discussed from a mechanistic viewpoint. In the case of the 3-aryl-1,1,2,2-tetramethylcyclopropanes, the regioselectivity of the 1,3-diradical intermediate favors migration toward the less delocalized odd-electron center. This selectivity is understood on a quantum mechanical basis. Finally, quantum yields are reported.

  DOI：

  10.1021/jo00005a018

文献信息

• ZIMMERMAN, HOWARD E.;HEYDINGER, JENIFER A., J. ORG. CHEM., 56,(1991) N, C. 1747-1758
  作者：ZIMMERMAN, HOWARD E.、HEYDINGER, JENIFER A.

  DOI：——

  日期：——
• CEKOVIC, ZIVORAD;MATOVIC, RADOMIR, J. SERB. CHEM. SOC., 53,(1988) N 5, C. 257-264
  作者：CEKOVIC, ZIVORAD、MATOVIC, RADOMIR

  DOI：——

  日期：——
• Rearrangement of 1,3-diradicals. Arylcyclopropane photochemistry
  作者：Howard E. Zimmerman、Jenifer A. Heydinger

  DOI：10.1021/jo00005a018

  日期：1991.3

  The photochemistry of a series of aryl-substituted cyclopropanes was investigated as part of our continuing investigations of these systems. The literature held a puzzling discrepancy in which several similar reactants exhibited differing photochemistry. A series of 3-aryl-1,1,2,2-tetramethylcyclopropanes was found to rearrange photochemically to give primarily two types of products, the anticipated 4-aryl-2,3,3-trimethyl-1-butenes and, additionally, 1-aryl-2,3,3-trimethyl-1-butenes. The latter arise from regioselective methyl migration of intermediate singlet 1,3-diradicals. Also, the usual Griffin carbene fragmentation was encountered as a minor pathway. Biphenylyl-, p-cyanophenyl-, and p-anisyl-substituted cyclopropanes were studied. Also, the photochemistry of 3-phenyl-1,1,2,2-tetramethylcyclopropane was reinvestigated and found to conform to the general pattern of reactivity. Throughout, it was the singlet excited states responsible for the observed reactivity, and the triplet counterparts were found to be unreactive. In addition, the photochemistry of 3-biphenylyl-2,2-dimethyl-1,1-diphenylcyclopropane was studied. Again, the triplet was unreactive. The singlet gave rise to 4-biphenylyl-2-methyl-3,3-diphenyl-1-butene exclusively. The differing behavior of the various arylcyclopropanes is discussed from a mechanistic viewpoint. In the case of the 3-aryl-1,1,2,2-tetramethylcyclopropanes, the regioselectivity of the 1,3-diradical intermediate favors migration toward the less delocalized odd-electron center. This selectivity is understood on a quantum mechanical basis. Finally, quantum yields are reported.