S-methyl S-<1-(1-phenylprop-2-enyl)> dithiocarbonate | 56504-14-4

• 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: S-methyl S-<1-(1-phenylprop-2-enyl)> dithiocarbonate
• 英文别名: S-(1-phenylallyl) S-methyl dithiocarbonate；1-Phenylallyl-methyl-dithiolcarbonat；Methylsulfanyl(1-phenylprop-2-enylsulfanyl)methanone
• CAS: 56504-14-4；142109-00-0
• 化学式: C₁₁H₁₂OS₂
• 分子量: 224.348
• InChiKey: XNTVPSJZXVBEQP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 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：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-methyl S-<1-(1-phenylprop-2-enyl)> dithiocarbonate 在 三氯化铝 作用下， 以 氯仿 为溶剂， 以100%的产率得到E-(3-phenylallyl) methyl sulfide
  参考文献：
  名称：

  烯丙基二硫代碳酸酯的反烯型断裂

  摘要：

  发现通过挤出COS由S-（2-链烯基）S-烷基二硫代碳酸酯形成2-链烯基烷基硫化物可有效地被路易斯酸催化。该从头计算强烈建议反应属于“复古硫基烯”反应的范畴。

  DOI：

  10.1016/0040-4039(96)00314-0
• 作为产物：
  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

• A convenient and stereoselective synthesis of allylic sulfides
  作者：Kazunobu Harano、Norihide Ohizumi、Takuzo Hisano

  DOI：10.1016/s0040-4039(00)98992-5

  日期：1985.1

  The fractional distillation of 0-(2-alkenyl or 2-cycloalkenyl) S-alkyl dithiocarbonates (xanthates) affords 2-alkenyl or 2-cycloalkenyl alkyl sulfides. The reaction involves the [3,3]-sigmatropic rearrangement of the xanthates to produce S-(2-alkenyl or 2-cycloalkenyl) S-alkyl dithiocarbonates followed by extrusion of carbon oxysulfide to give 2-alkenyl or 2-cycloalkenyl alkyl sulfides.

  0-（2-烯基或2-环烯基）S-烷基二硫代碳酸酯（黄原酸酯）的分馏得到2-烯基或2-环烯基烷基硫化物。该反应涉及黄原酸酯的[3，3]-σ重排，以产生S-（2-烯基或2-环烯基）S-烷基二硫代碳酸酯，随后挤出氧硫化碳，得到2-烯基或2-环烯基烷基硫化物。
• Catalytic behavior of phenols in pyrolytic conversion of allylic dithiolcarbonates to allylic sulfides.
  作者：Kazunobu HARANO、Shigeru YAMASHIRO、Keisuke MISAKA、Takuzo HISANO

  DOI：10.1248/cpb.38.2956

  日期：——

  Pyrolytic conversion of S-(2-alkenyl) S-alkyl dithiocarbonates (allylic dithiolcarbonates) to 2-alkenyl alkyl sulfides (allylic sulfides) was catalyzed by phenols bearing electron-attracting substituents. The reaction is pseudo-first-order and the apparent first-order rate constants are proportional not only to the concentration of phenols but also to the hydrogen-bonding capability of phenols. The entropy of activation for the phenol-catalyzed reaction is ca. 8 e.u. smaller than that for the uncatalyzed reaction. The reactivity of S-(1-phenylallyl) S-alkyl dithiocarbonates did not obey Hammett's or Taft's equation. Based on these findings together with the MNDO (modified neglect of diatomic overlap) calculation data, a possible role of phenols in the pyrolytic conversion of allylic dithiolcarbonates to allylic sulfides is discussed.

  在具有电子吸引取代基的酚类催化下，S-(2-烯基)S-烷基二硫代碳酸盐（烯丙基二硫代碳酸盐）发生热解转化，生成2-烯基烷基硫化物（烯丙基硫化物）。反应呈现伪一级动力学特征，表观一级速率常数不仅与酚类浓度成正比，还与酚类的氢键形成能力成正比。与非催化反应相比，酚类催化反应的活化熵减少了约8熵单位。S-(1-苯基烯丙基)S-烷基二硫代碳酸盐的反应活性不遵循Hammett或Taft方程。结合MNDO（修正的双原子重叠忽略）计算数据，基于这些发现，讨论了酚类在烯丙基二硫代碳酸盐热解转化为烯丙基硫化物过程中的可能作用。
• Palladium-Catalyzed Synthesis of Allylic and Benzylic Sulfides from the Corresponding Dithiocarbonates
  作者：Xiyan Lu、Zhijie Ni

  DOI：10.1055/s-1987-27849

  日期：——

  Allylic and benzylic sulfides are prepared from O-(2-alkenyl) or S-(2-alkenyl) S-alkyl and O-benzyl S-alkyl dithiocarbonates in the presence of palladium(0)-phosphine complex as a catalyst.

  烯丙基和苄基硫化物是在存在钯(0)-膦配合物催化剂的条件下，由O-(2-烯烃基)或S-(2-烯烃基) S-烷基和O-苄基 S-烷基二硫氨基碳酸酯制备的。
• Correlation of thione-to-thiol rearrangement rates of xanthates with solvent scales. Analysis of the reaction behavior by the Kamlet-Taft parameters, , α and β
  作者：Masashi Eto、Okiyasu Tajiri、Hidetoshi Nakagawa、Kazunobu Harano

  DOI：10.1016/s0040-4020(98)00438-4

  日期：1998.7

  O-(2-methylthioethyl) (1e) S-methyl xanthates were analyzed by the Kamlet-Taft equation. The results indicate that solvent polarity and solvent hydrogen-bond donation ability (acidity) are operative in the thione-to-thiol rearrangement reactions. In the case of 1e, the reaction is found to be influenced by solvent acidity and retarded by the increase of the solvent polarity.

  通过分析O-（2-烯基）（1a-c），O-（1-环丙基乙基）（1d）和O-（2-甲基硫乙基）（1e）S-甲基黄药的硫酮到硫醇重排速率。Kamlet-Taft方程。结果表明，溶剂极性和溶剂氢键给定能力（酸度）在硫酮到硫醇的重排反应中起作用。在1e的情况下，发现该反应受溶剂酸度影响并且受溶剂极性增加的阻碍。
• Rearrangement and trans-elimination contrary to the chugaev reaction rule. XIII. Solvent effect on rearrangement reaction of allylic xanthates and a correction of the former report.
  作者：KAZUNOBU HARANO、TANEZO TAGUCHI

  DOI：10.1248/cpb.23.467

  日期：——

  To provide an additional evidence which confirms the concerted mechanism postulated for the thermal rearrangement reaction of allylic xanthates, the kinetic study on the rearrangement of them was conducted in a variety of solvent. The rearrangement showed a first order process with relatively low sensitivity to the ionizing power of the medium indicating that it proceeds by a mechanism which involves very little change in charge separation between the ground state and the transition state. In addition, this paper includes the correction of the former report referring to the product formation in the thermolysis of cinnamyl S-methyl xanthate.

  为了进一步证实烯丙基黄原酸盐热重排反应的协同机制，我们在多种溶剂中对其重排进行了动力学研究。重排显示了一个一阶过程，对介质电离力的敏感性相对较低，这表明重排是在基态和过渡态之间电荷分离变化很小的机制下进行的。此外，本文还更正了之前关于 S-甲基黄原酸肉桂酯热解产物形成的报告。