2-phenyl-2,2-d2-ethyl 4-methylbenzenesulfonate | 53907-39-4

• 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: 2-phenyl-2,2-d2-ethyl 4-methylbenzenesulfonate
• 英文别名: toluene-4-sulfonic acid-(β,β-dideuterio-phenethyl ester)；Toluol-4-sulfonsaeure-(β,β-dideuterio-phenaethylester)；p-Toluolsulfonsaeure-<2-phenyl-ethyl-(2,2-d2)-ester>；2-Phenylethyl-2,2-d(2)-p-toluolsulfonat；2-Phenyl-(2-d2)ethyl-p-toluolsulfonat；2-Phenylethyl-p-toluolsulfonat-2,2-d2；(2,2-dideuterio-2-phenylethyl) 4-methylbenzenesulfonate
• CAS: 53907-39-4
• 化学式: C₁₅H₁₆O₃S
• 分子量: 278.34
• InChiKey: CVPPUZPZPFOFPK-ZWGOZCLVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2-phenyl-2,2-d2-ethyl 4-methylbenzenesulfonate 在 正丁基锂 、 sodium iodide 作用下， 以 四氢呋喃 、 正己烷 、 丙酮 为溶剂， 反应 0.5h， 生成 1-ethynyl-2-(4-phenyl-4,4-d2-but-1-yn-1-yl)benzene
  参考文献：
  名称：

  金亚乙烯基的实验和计算证据：通过分叉途径和简单的 C-H 插入从末端炔烃生成

  摘要：

  提议通过两个分子的 BrettPhosAuNTf(2) 协同促进（2-乙炔基苯基）炔烃的简便环异构化，从而以良好的收率提供三环茚。基于机理研究和理论计算，金亚乙烯基最有可能作为反应中间体之一产生。与众所周知的 Rh、Ru 和 W 对应物不同，这种新型金物种具有高度的反应性，并且易于进行分子内 C(sp(3))-H 插入以及 OH 和 NH 插入。理论上预测亚乙烯基金的形成步骤与分叉的反应途径复杂。吡啶N-氧化物充当弱碱以促进炔基金中间体的形成，

  DOI：

  10.1021/ja2091992
• 作为产物：
  描述：

  苯乙酸-Alpha,Alpha-d2 、 对甲苯磺酰氯 、 吡啶 、 氢化铝锂 生成 2-phenyl-2,2-d2-ethyl 4-methylbenzenesulfonate
  参考文献：
  名称：

  ETTINGER, MICHAEL D.;MAHASAY, SUMIT R.;STOCK, LEON M.;ZABRANSKY, ROBERT F+, ENERGY AND FUELS, 1,(1987) N 3, 274-279

  摘要：

  DOI：

文献信息

• Thermolysis of Phenethyl Phenyl Ether: A Model for Ether Linkages in Lignin and Low Rank Coal
  作者：Phillip F. Britt、A. C. III Buchanan、Elizabeth A. Malcolm

  DOI：10.1021/jo00125a044

  日期：1995.10

  The thermolysis of phenethyl phenyl ether (PPE) was studied at 330-425 degrees C to resolve the discrepancies in the reported mechanisms of this important model of the beta-ether linkage found in lignin and low rank coal. Cracking of PPE proceeded by two competitive pathways that produced styrene plus phenol and two previously undetected products, benzaldehyde plus toluene. The ratio of these pathways, defined as the alpha/beta selectivity, was 3.1 +/- 0.3 at 375 degrees C and independent of the PPE concentration. The kinetic order over ca. 10(3) variation in the initial concentration from the neat liquid, in solutions with biphenyl, and in the gas phase was 1.29 +/- 0.02. The rate expression for the decomposition in the liquid phase was log (k/M(-0.29) s(-1)) = (11.4 +/- 0.1) - (46.4 +/- 1.0)/2.303RT. The reaction could be accelerated by the addition of a free-radical initiator or a hydrogen bonding solvent, such as p-phenylphenol, but the product composition was altered with the latter. Thermolysis of PPE in tetralin, a model hydrogen donor solvent, increased the alpha/beta selectivity to 7 and accelerated the formation of secondary products. All the data was consistent with a free-radical chain mechanism for the decomposition of PPE. Styrene and phenol are produced by hydrogen abstraction at the alpha-carbon, beta-scission to form styrene and the phenoxy radical, followed by hydrogen abstraction. Benzaldehyde and toluene are formed by hydrogen abstraction at the beta-carbon, 1,2-phenyl migration from oxygen to carbon, beta-scission to form benzaldehyde, and the benzyl radical, followed by hydrogen abstraction. Thermochemical kinetic estimates indicate that product formation is controlled by the relative rate of hydrogen abstraction at the alpha- and beta-carbons by the phenoxy radical (dominant) and benzyl radical (minor) since beta-scission and 1,2-phenyl migration are fast relative to hydrogen abstraction. The electrophilic phenoxy radical has an inherently lower alpha/beta selectivity than the nonpolar benzyl radical because it benefits from the polar effects of the alpha-oxygen at the beta-carbon. The rate of the 1,2-phenyl migration was much faster than interconversion of 1-phenoxy-2-phenyl-1-ethyl radical and 1-phenoxy-2-phenyl-2-ethyl radical, and an activation barrier of <18 kcal mol(-1) was estimated for the 1,2-phenyl migration. Thermolysis of PhCD(2)CH(2)OPh and PhCH(2)CD(2)OPh was consistent with the previous results, indicating that there was no significant contribution of a concerted retro-ene pathway to the thermolysis of PPE.