dimesityldioxirane | 161807-01-8

• 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: dimesityldioxirane
• 英文别名: Dimesityldioxirane；3,3-bis(2,4,6-trimethylphenyl)dioxirane
• CAS: 161807-01-8
• 化学式: C₁₉H₂₂O₂
• 分子量: 282.382
• InChiKey: CIQXXABRSWBHGW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  25.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  dimesityldioxirane 生成 苯甲酸,2,4,6-三甲基-,2,4,6-三甲苯基酯
  参考文献：
  名称：

  Kirschfeld, Andreas; Muthusamy, Sengodagounder; Sander, Wolfram, Angewandte Chemie, 1994, vol. 106, # 21, p. 2261 - 2263

  摘要：

  DOI：
• 作为产物：
  描述：

  dimesityldiazomethane 在 氧气 作用下， 以 一氟三氯甲烷 为溶剂， 反应 3.0h， 以32%的产率得到2,2’,4,4’,6,6’-六甲基二苯甲酮
  参考文献：
  名称：

  Oxidative Decomplexation of Chromium Fischer Carbene Complexes Induced by Dioxiranes

  摘要：

  The reaction course of the oxidative decomplexation of Fischer carbene complexes with dioxiranes was examined. The portionwise addition of 2.2 equiv of dimethyldioxirane (DMD) to Fischer carbene complex 1 afforded ethyl phenylpropiolate in 90% yield. When the reaction was carried out using a CO2-free DMD solution in a N-2 atmosphere ester 2 was formed in 40% yield, whereas in the presence of an O-2 atmosphere the yield increased to 70%. This same assay performed in the presence of O-18(2) atmosphere afforded the ester 2 partially labeled at the C=O moiety (approximately 50%, CC-MS) with O-18. On the other hand, treatment of Fischer carbene complex 1 with st [O-18(2)]dimesityldioxirane solution led to the formation of O-18-labeled CO2 (trapped as BaCO3 and detected by IRMS). From these results it can be suggested that the oxidative decomplexation of Fischer carbene complexes by dioxiranes involves an initial attack of the dioxirane to the metal coordination sphere. In this step a CO ligand is oxidized to CO2 thus leaving an unstable chromium tetracarbonyl intermediate which would react with O-2 to give the final ester product and chromium(III) oxide.

  DOI：

  10.1021/jo982065e

文献信息

• Kirschfeld, Andreas; Muthusamy, Sengodagounder; Sander, Wolfram, Angewandte Chemie, 1994, vol. 106, # 21, p. 2261 - 2263
  作者：Kirschfeld, Andreas、Muthusamy, Sengodagounder、Sander, Wolfram

  DOI：——

  日期：——
• Dimesityldioxirane
  作者：Wolfram Sander、Kerstin Schroeder、Sengodagounder Muthusamy、Andreas Kirschfeld、Wilhelm Kappert、Roland Boese、Elfi Kraka、Carlos Sosa、Dieter Cremer

  DOI：10.1021/ja964280n

  日期：1997.8.1

  The preparative scale synthesis of dimesityldioxirane (5) via oxidation of dimesitylcarbene (6) is described. The dioxirane was obtained as colorless crystalline material, completely stable at -20 degrees C and characterized by spectroscopic methods, X-ray crystallography, and DFT calculations (B3LYP/6-31G(d)). The molecule shows approximately local C-2 symmetry with the mesityl rings twisted by ca. 60 degrees. The experimental structural parameters, e.g., the O-O distance of 1.503 Angstrom, are in good agreement with the theoretical values. The relief of steric strain caused by the mesityl groups is discussed in terms of the geometric distortion of the three-membered ring and the mesityl groups. Conformational features of 5 in solution are nicely reflected by measured and calculated (SOS-DFPT) NMR chemical shifts.
• Oxidative Decomplexation of Chromium Fischer Carbene Complexes Induced by Dioxiranes
  作者：Mariona Gibert、Marta Ferrer、Anna-Maria Lluch、Francisco Sánchez-Baeza、Angel Messeguer

  DOI：10.1021/jo982065e

  日期：1999.3.1

  The reaction course of the oxidative decomplexation of Fischer carbene complexes with dioxiranes was examined. The portionwise addition of 2.2 equiv of dimethyldioxirane (DMD) to Fischer carbene complex 1 afforded ethyl phenylpropiolate in 90% yield. When the reaction was carried out using a CO2-free DMD solution in a N-2 atmosphere ester 2 was formed in 40% yield, whereas in the presence of an O-2 atmosphere the yield increased to 70%. This same assay performed in the presence of O-18(2) atmosphere afforded the ester 2 partially labeled at the C=O moiety (approximately 50%, CC-MS) with O-18. On the other hand, treatment of Fischer carbene complex 1 with st [O-18(2)]dimesityldioxirane solution led to the formation of O-18-labeled CO2 (trapped as BaCO3 and detected by IRMS). From these results it can be suggested that the oxidative decomplexation of Fischer carbene complexes by dioxiranes involves an initial attack of the dioxirane to the metal coordination sphere. In this step a CO ligand is oxidized to CO2 thus leaving an unstable chromium tetracarbonyl intermediate which would react with O-2 to give the final ester product and chromium(III) oxide.