4,4-dimethyl-1-(4-trichloromethyl-4-methylcyclohexa-2,5-dienylidene)cyclohexane-2,6-dione | 117780-33-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,4-dimethyl-1-(4-trichloromethyl-4-methylcyclohexa-2,5-dienylidene)cyclohexane-2,6-dione
• 英文别名: 4-methyl-4-trichloromethyl-1-(4,4-dimethyl-2,6-dioxocyclohexylidene)-2,5-cyclohexadiene；5,5-dimethyl-2-[4-methyl-4-(trichloromethyl)cyclohexa-2,5-dien-1-ylidene]cyclohexane-1,3-dione
• CAS: 117780-33-3
• 化学式: C₁₆H₁₇Cl₃O₂
• 分子量: 347.669
• InChiKey: JHBYWCGKGLHCFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(ethylene)rhodium(I) chloride dimer 、 4,4-dimethyl-1-(4-trichloromethyl-4-methylcyclohexa-2,5-dienylidene)cyclohexane-2,6-dione 以 二氯甲烷 为溶剂， 以93%的产率得到
  参考文献：
  名称：

  An unusual example ofendo-stereoselectivity in the ligand exchange reactions of rhodium(i)diethylene derivatives withpara-semiquinoid ligands

  摘要：

  The ligand exchange reactions of [(C2H4)(2)Rh(acac)] in benzene and [(C2H4)(2)RhCl](2) in CH2Cl2 with 4-methyl-4-trichloromethyl-2,5-cyclohexadiene-1-one occur with 100% exo-stereoselectivity. The similar process with 4-methyl-4-trichloromethyl-1-(4,4-dimethyl-2,6-dioxocyclohexylidene)-2,5-cyclohexadiene (trienedione) is strictly exo-stereospecific only if [(C2H4)(2)Rh(acac)] in benzene is used, while in the case of [(C2H4)(2)RhCl](2) in CH2Cl2, it proceeds with an endo-stereoselectivity of 43%. An explanation for these facts has been suggested that assumes that the metal atom initially attacks the central double bond in the trienedione, which is removed from the area of main steric hindrance. The subsequent metallotropic rearrangement of the resulting ethylene-triene intermediate gives rise to the final eta(4)-coordinated pi-diene structures.

  DOI：

  10.1007/bf01430741
• 作为产物：
  描述：

  4-甲基-4-(三氯甲基)环己-2,5-二烯-1-酮 、 5,5-二甲基-1,3-环己二酮 在 哌啶 作用下， 以 乙醇 为溶剂， 反应 24.0h， 以7%的产率得到4,4-dimethyl-1-(4-trichloromethyl-4-methylcyclohexa-2,5-dienylidene)cyclohexane-2,6-dione
  参考文献：
  名称：

  Knoevenagel reaction of semiquinoid compounds

  摘要：

  DOI：

  10.1007/bf01455513

文献信息

• NIKANOROV, V. A.;SERGEEV, S. V.;ROZENBERG, V. I.;REUTOV, O. A., IZV. AN CCCP. CEP. XIM.,(1988) N 4, 925-928
  作者：NIKANOROV, V. A.、SERGEEV, S. V.、ROZENBERG, V. I.、REUTOV, O. A.

  DOI：——

  日期：——
• Thermal aromatizational rearrangements of 4,4-dimethyl-l-(4-trichloromethyl-4-methylcyclohexa2,5-dienylidene cyclohexane-2,6-dione
  作者：V. A. Nikanorov、S. V. Sergeev、P. V. Petrovskii、D. V. Zverev、N. A. Klyuev、A. L Gamzazade、G. E. Vainer、F. M. Dolgushin、A. I. Yanovskii、Yu. T. Struchkovt

  DOI：10.1007/bf01431347

  日期：1996.4
• Kharitonov, V. G.; Nikanorov, V. A.; Sergeev, S. V., Doklady Chemistry, 1991, vol. 319, # 1-3, p. 168 - 171
  作者：Kharitonov, V. G.、Nikanorov, V. A.、Sergeev, S. V.、Galakhov, M. V.、Yakushin, S.O.、et al.

  DOI：——

  日期：——
• An unusual example ofendo-stereoselectivity in the ligand exchange reactions of rhodium(i)diethylene derivatives withpara-semiquinoid ligands
  作者：S. V. Sergeev、V. A. Nikanorov、S. G. Novikov、P. V. Petrovskii、D. V. Zverev

  DOI：10.1007/bf01430741

  日期：1996.9

  The ligand exchange reactions of [(C2H4)(2)Rh(acac)] in benzene and [(C2H4)(2)RhCl](2) in CH2Cl2 with 4-methyl-4-trichloromethyl-2,5-cyclohexadiene-1-one occur with 100% exo-stereoselectivity. The similar process with 4-methyl-4-trichloromethyl-1-(4,4-dimethyl-2,6-dioxocyclohexylidene)-2,5-cyclohexadiene (trienedione) is strictly exo-stereospecific only if [(C2H4)(2)Rh(acac)] in benzene is used, while in the case of [(C2H4)(2)RhCl](2) in CH2Cl2, it proceeds with an endo-stereoselectivity of 43%. An explanation for these facts has been suggested that assumes that the metal atom initially attacks the central double bond in the trienedione, which is removed from the area of main steric hindrance. The subsequent metallotropic rearrangement of the resulting ethylene-triene intermediate gives rise to the final eta(4)-coordinated pi-diene structures.
• Knoevenagel reaction of semiquinoid compounds
  作者：V. A. Nikanorov、S. V. Sergeev、V. I. Rozenberg、O. A. Reutov

  DOI：10.1007/bf01455513

  日期：1988.4