2-Acetoxy-1,1-dimesityl-3,3-dimethyl-1-butene | 146819-84-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-Acetoxy-1,1-dimesityl-3,3-dimethyl-1-butene
• 英文别名: 1-tert-butyl-2,2-dimesitylvinyl acetate；[3,3-Dimethyl-1,1-bis(2,4,6-trimethylphenyl)but-1-en-2-yl] acetate
• CAS: 146819-84-3
• 化学式: C₂₆H₃₄O₂
• 分子量: 378.555
• InChiKey: WEPHCYNBVZWTHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-Acetoxy-1,1-dimesityl-3,3-dimethyl-1-butene 在 tris(1,10-phenanthroline)iron(III) hexafluorophosphate 作用下， 以 乙腈 为溶剂， 生成 2-tert-butyl-3-mesityl-4,6,7-trimethylbenzofuran
  参考文献：
  名称：

  Electroactive Protecting Groups and Reaction Units. Part 1. Mesolytic Cleavage of the O-CO Bond in Enol Acetate Cation Radicals with Direct Formation of .alpha.-Carbonyl Cations. Mechanistic and Synthetic Aspects

  摘要：

  For the first time, enol ester cation radicals are reversibly monitored in a cyclic voltammetry experiment. Preparative one-electron oxidation of enol acetates A1-A4 leads to the formation of benzofurans B1-B4 through mesolytic O-CO bond fragmentation to alpha-carbonyl cations and the acetyl radical. With A3(.+), the kinetics of the O-CO bond cleavage was investigated by cyclic voltammetry, providing Delta H double dagger = 17.0 kcal mol(-1) and Delta S double dagger = 11 cal mol(-1) K-1 in dichloromethane. The slightly increased rate of bond dissociation upon addition of acetonitrile is explained with charge localization in the transition state rather than with a solvent-assisted bond cleavage mechanism. The occurrence of curve crossings and isopotential points in the cyclic voltammograms of the model compounds A1-A4 at low scan rates can be rationalized by a multiparameter reaction scheme based on an ECCE(DISP) mechanism, digital simulation of which confirmed the cleavage selectivity and allowed for the determination of the involved rate constants of the homogeneous chemical reaction steps.

  DOI：

  10.1021/jo00114a020
• 作为产物：
  描述：

  bis(mesityl)ketene 、 叔丁基锂 、 乙酰氯 生成 2-Acetoxy-1,1-dimesityl-3,3-dimethyl-1-butene
  参考文献：
  名称：

  Electroactive Protecting Groups and Reaction Units. Part 1. Mesolytic Cleavage of the O-CO Bond in Enol Acetate Cation Radicals with Direct Formation of .alpha.-Carbonyl Cations. Mechanistic and Synthetic Aspects

  摘要：

  For the first time, enol ester cation radicals are reversibly monitored in a cyclic voltammetry experiment. Preparative one-electron oxidation of enol acetates A1-A4 leads to the formation of benzofurans B1-B4 through mesolytic O-CO bond fragmentation to alpha-carbonyl cations and the acetyl radical. With A3(.+), the kinetics of the O-CO bond cleavage was investigated by cyclic voltammetry, providing Delta H double dagger = 17.0 kcal mol(-1) and Delta S double dagger = 11 cal mol(-1) K-1 in dichloromethane. The slightly increased rate of bond dissociation upon addition of acetonitrile is explained with charge localization in the transition state rather than with a solvent-assisted bond cleavage mechanism. The occurrence of curve crossings and isopotential points in the cyclic voltammograms of the model compounds A1-A4 at low scan rates can be rationalized by a multiparameter reaction scheme based on an ECCE(DISP) mechanism, digital simulation of which confirmed the cleavage selectivity and allowed for the determination of the involved rate constants of the homogeneous chemical reaction steps.

  DOI：

  10.1021/jo00114a020

文献信息

• Eventova, Irina; Nadler, Ella B.; Rochlin, Elimelech, Journal of the American Chemical Society, 1993, vol. 115, # 4, p. 1290 - 1302
  作者：Eventova, Irina、Nadler, Ella B.、Rochlin, Elimelech、Frey, Joseph、Rappoport, Zvi

  DOI：——

  日期：——
• Electroactive Protecting Groups and Reaction Units. Part 1. Mesolytic Cleavage of the O-CO Bond in Enol Acetate Cation Radicals with Direct Formation of .alpha.-Carbonyl Cations. Mechanistic and Synthetic Aspects
  作者：Michael Schmittel、Juergen Heinze、Holger Trenkle

  DOI：10.1021/jo00114a020

  日期：1995.5

  For the first time, enol ester cation radicals are reversibly monitored in a cyclic voltammetry experiment. Preparative one-electron oxidation of enol acetates A1-A4 leads to the formation of benzofurans B1-B4 through mesolytic O-CO bond fragmentation to alpha-carbonyl cations and the acetyl radical. With A3(.+), the kinetics of the O-CO bond cleavage was investigated by cyclic voltammetry, providing Delta H double dagger = 17.0 kcal mol(-1) and Delta S double dagger = 11 cal mol(-1) K-1 in dichloromethane. The slightly increased rate of bond dissociation upon addition of acetonitrile is explained with charge localization in the transition state rather than with a solvent-assisted bond cleavage mechanism. The occurrence of curve crossings and isopotential points in the cyclic voltammograms of the model compounds A1-A4 at low scan rates can be rationalized by a multiparameter reaction scheme based on an ECCE(DISP) mechanism, digital simulation of which confirmed the cleavage selectivity and allowed for the determination of the involved rate constants of the homogeneous chemical reaction steps.