O-cinnamyl S-methyl dithiocarbonate | 3817-87-6

• 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: O-cinnamyl S-methyl dithiocarbonate
• 英文别名: O-cinnamyl S-methyl xanthate；O-(3-phenylprop-2-enyl) methylsulfanylmethanethioate
• CAS: 3817-87-6
• 化学式: C₁₁H₁₂OS₂
• 分子量: 224.348
• InChiKey: ILHZBJHFBAQDHM-UHFFFAOYSA-N

物化性质

• 沸点：
  361.9±31.0 °C(Predicted)
• 密度：
  1.188±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  66.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  O-cinnamyl S-methyl dithiocarbonate 反应 1.0h， 以100%的产率得到S-methyl S-<1-(1-phenylprop-2-enyl)> dithiocarbonate
  参考文献：
  名称：

  Stereoselective formation of allylic sulfides via two sequential (3,3)-sigmatropic rearrangements of allylic xanthates and its mechanistic aspects.

  摘要：

  O-(2-炔基) S-烷基二硫代碳酸酯（烯丙基黄原酸酯）通过相应的烯丙异构S-(2-烯基) S-烷基二硫代碳酸酯，热解生成2-烯基烷基硫醚（烯丙基硫醚）。该反应遵循一级速率定律，对介质的电离能力相对不敏感，并且活化熵显著为负。当含有不同S-(2-烯基)基团和不同S-烷基基团的两种二硫酯混合物进行热解时，未观察到“交叉产物”。发现反应在酚类化合物或路易斯酸的存在下得到促进。基于这些发现以及改进的原子间重叠忽略（MNDO）计算数据，讨论了2-烯基烷基硫醚生成反应的机理。

  DOI：

  10.1248/cpb.38.619

文献信息

• Linear Correlation of the Solvolysis Rates of Xanthates with the Grunwald-Winstein Y Values.
  作者：Kazunobu HARANO、Hideo KIYONAGA、Chiaki YOKOTE、Takuzo HISANO

  DOI：10.1248/cpb.39.1952

  日期：——

  O-Cinnamyl and O-(2-methylthioethyl) S-methyl dithiocarbonates (xanthates) underwent thione-thiol rearrangement to the dithiol esters in various solvents. The reactions followed first-order kinetics and the rates were affected by change of the solvent polarity. Plots of the rate constants against the Y values showed good linear relationships. The rate constants may be used as a new empirical parameter of solvent polarity in place of Y values. Modified intermediate neglect of differential overlap (MINDO/3) calculations indicate that allylic xanthates undergo [3, 3]-sigmatropic rearrangement via a polarizable transition state.

  O-肉桂基和O-(2-甲硫基乙基) S-甲基二硫代碳酸酯（黄原酸盐）在各种溶剂中发生硫醇-硫醚重排反应，生成二硫醇酯。反应遵循一级动力学，速率受溶剂极性变化的影响。速率常数与Y值的曲线图显示出良好的线性关系。速率常数可作为溶剂极性的新经验参数，代替Y值。修改后的中间体忽略差分重叠（MINDO/3）计算表明，烯丙基黄原酸盐通过可极化过渡态发生[3,3]-顺式重排。
• Stereoselective formation of allylic sulfides via two sequential (3,3)-sigmatropic rearrangements of allylic xanthates and its mechanistic aspects.
  作者：Kazunobu HARANO、Norihide OHIZUMI、Keisuke MISAKA、Shigeru YAMASHIRO、Takuzo HISANO

  DOI：10.1248/cpb.38.619

  日期：——

  O-(2-Alkynyl) S-alkyl dithiocarbonates (allylic xanthates) were pyrolyzed to give 2-alkenyl alkyl sulfides (allylic sulfides) via the corresponding allylically isomeric S-(2-alkenyl) S-alkyl dithiocarbonates. The reaction follows the first-order rate law with relatively low sensitivity to the ionizing power of the medium and sizeably negative entropies of activation. When a mixture of two dithiol esters having different S-(2-alkenyl) groups and different S-alkyl groups was pyrolyzed, a "cross product" was not observed. The reaction was found to be facilitated by the presence of phenolic compounds or Lewis acids.Based on these findings together with modified neglect of diatomic overlap (MNDO) calculation data, the mechanism for the formation reaction of 2-alkenyl alkyl sulfides is discussed.

  O-(2-炔基) S-烷基二硫代碳酸酯（烯丙基黄原酸酯）通过相应的烯丙异构S-(2-烯基) S-烷基二硫代碳酸酯，热解生成2-烯基烷基硫醚（烯丙基硫醚）。该反应遵循一级速率定律，对介质的电离能力相对不敏感，并且活化熵显著为负。当含有不同S-(2-烯基)基团和不同S-烷基基团的两种二硫酯混合物进行热解时，未观察到“交叉产物”。发现反应在酚类化合物或路易斯酸的存在下得到促进。基于这些发现以及改进的原子间重叠忽略（MNDO）计算数据，讨论了2-烯基烷基硫醚生成反应的机理。