2,4,6,2',4',6'-hexaethylbenzil | 165897-48-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,4,6,2',4',6'-hexaethylbenzil
• 英文别名: 2,4,6,2',4',6'-Hexaaethyl-benzil；1,2-Bis(2,4,6-triethylphenyl)ethane-1,2-dione；1,2-bis(2,4,6-triethylphenyl)ethane-1,2-dione
• CAS: 165897-48-3
• 化学式: C₂₆H₃₄O₂
• 分子量: 378.555
• InChiKey: OSKXMNSVDOPCDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  2,4,6,2',4',6'-hexaethylbenzil 在 四氯化碳 、 溴 、 铁粉 作用下， 生成 2,4,6,2',4',6'-hexaethyl-3,3'-dibromo-benzil
  参考文献：
  名称：

  Enediols. VII.¹ Bromostilbenediols

  摘要：

  DOI：

  10.1021/ja01851a049
• 作为产物：
  描述：

  2,4,6-三乙基苯甲酸 在 氯化亚砜 、 乙醚 、 magnesium 、 magnesium iodide 作用下， 生成 2,4,6,2',4',6'-hexaethylbenzil
  参考文献：
  名称：

  1,2-Diarylacetylene Glycols. II. An Enediol from Hexaethylbenzil

  摘要：

  DOI：

  10.1021/ja01877a018

文献信息

• Enediols. IV. cis—trans Isomerism
  作者：Reynold C. Fuson、S. L. Scott、E. C. Horning、C. H. McKeever

  DOI：10.1021/ja01865a050

  日期：1940.8
• New Compounds. Some Polysubstituted Benzene Derivatives
  作者：Reynold Fuson、Joseph Corse

  DOI：10.1021/ja01227a054

  日期：1945.11
• The Coupling Action of the Grignard Reagent. VI. A New Synthesis of Hexaalkylbenzils
  作者：Reynold C. Fuson、Joseph Corse

  DOI：10.1021/ja01276a015

  日期：1938.9
• Photocyclization of 2,4,6,2',4',6'-Hexaalkylbenzils
  作者：Peter J. Wagner、Bong-Ser Park、Martin Sobczak、Joseph Frey、Zvi Rappoport

  DOI：10.1021/ja00134a006

  日期：1995.7

  Three of the title compounds-the hexamethyl-, hexaethyl-, and hexaisopropylbenzils-all photocyclize both in solution and as solids to 5,7-dialkyl-2-(2',4',6'-trialkylphenyl)-2-hyudroxy-1-indanones. At wavelengths <370 nm these primary photoproducts undergo secondary photocleavage to ketoaldehydes. The hexaethylbenzil produces only the (Z)-hydroxyindanone in the solid but a 2/1 Z/E ratio at low conversion in solution. The solid-state reactivity and the preference for formation of the (Z)-hydroxyindanone from the hexaethylbenzil suggest that much of the reaction involves delta-hydrogen abstraction followed by coupling of the 1,5-biradical. The formation of (E)-hydroxyindanones from o-ethylphenyl diketones had been attributed to stereospecific rearrangement of a photodienol formed by gamma-hydrogen abstraction. However, none of the H/D exchange of benzylic hydrogens expected of a photodienol occurs in methanol-d(4). Moreover, AM1-level semiempirical calculations suggest that a simple exothermic hydrogen transfer can convert the 1,4-biradical tripler dienol to the same 1,5-biradical formed by delta-hydrogen abstraction. The 1,5-biradical has two major conformations, one leading to Z product and an internally OH-O=C hydrogen bonded one leading to E product. The AM1 computations suggest that the two conformations are of comparable energy and thus implicate 1,5-biradicals as the major precursors to hydroxyindanone products. Stem-Volmer quenching studies indicate a triplet decay rate of 5 x 10(6) s(-1) for the hexaisopropylbenzil. The known behavior of structurally similar monoketones predicts such a rate for delta-hydrogen abstraction but a much slower rate for gamma-hydrogen abstraction. However, relative quantum efficiencies parallel those for benzocyclobutenol formation from 2,4,6-trialkylbenzophenones (iPr and Et similar to 0.3, Me similar to 0.03). The hexa-tert-butylbenzil undergoes very low quantum yield formation of 3,3-dimethyl-5,7-di-tert-butyl-1-indanone and 2,4,6-tri-tert-butylbenzaldehyde, presumably by delta-hydrogen abstraction and highly efficient radical cleavage of the resulting 1-aroyl-1-indanol.
• Enediols. VII.¹ Bromostilbenediols
  作者：Reynold C. Fuson、S. L. Scott、R. V. Lindsey

  DOI：10.1021/ja01851a049

  日期：1941.6