S-Methyl-S-(n-propyl) dithiocarbonate | 10596-54-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫基化合物
• 英文名称: S-Methyl-S-(n-propyl) dithiocarbonate
• 英文别名: S-methyl S-(n-propyl) dithiocarbonate；S-methyl S-n-propyl dithiocarbonate；S-methyl S-propyl dithiocarbonate；S-n-Propyl-S-methyldithiocarbonat；n-Propyl-methyl-dithiocarbonat；Methylsulfanyl(propylsulfanyl)methanone
• CAS: 10596-54-0
• 化学式: C₅H₁₀OS₂
• 分子量: 150.266
• InChiKey: TVYVJLINWJKBCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  8
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  67.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  methyl O-n-propyl dithiocarbonate 在 对硝基苯酚 作用下， 反应 8.0h， 以50%的产率得到S-Methyl-S-(n-propyl) dithiocarbonate
  参考文献：
  名称：

  Phenol-Catalyzed Thione-Thiol Rearrangement of Xanthates and Modified Intermediate Neglect of Differential Overlap(MINDO/3) Analysis of the Reaction Mechanism.

  摘要：

  含有σ键的烷醇的S-烷基二硫代碳酸酯（黄药）在酚类化合物的催化下发生重排，生成S，S-二烷基二硫代碳酸酯。该反应遵循一级动力学，速率受酚类化合物的酸度影响。速率常数与酚类化合物浓度的平方成正比。对忽略差分重叠（MINDO/3）几何优化的修正中间体表明，S，S-二烷基二硫代碳酸酯比O，S-二烷基黄药稳定约9 kcal/mol。硫醇-硫醚重排和硫化物形成反应通过MO模拟进行了分析。实验结果可以通过MINDO/3方法而不是修正的忽略二原子重叠（MNDO）方法很好地再现。基于这些数据，讨论了反应机理。

  DOI：

  10.1248/cpb.40.2654

文献信息

• Catalytic rearrangement of O,S-dialkyl dithiocarbonates to S,S-dialkyl dithiocarbonates. IV. Use of boron trifluoride etherate as catalyst.
  作者：KEIJI KOMAKI、TOSHINOBU KAWATA、KAZUNOBU HARANO、TANEZO TAGUCHI

  DOI：10.1248/cpb.26.3807

  日期：——

  Migration of alkyl group from O to S in the reaction of O, S-dialkyl dithiocarbonates with boron trifluoride etherate was studied to elucidate the reaction mechanism on the basis of results from kinetics, crossover reaction, and products formed. It was worthy of note that dialkyl methyl sulfonium fluoroborates were formed in a fairly good yield in reactions with O-alkyl S-methyl dithiocarbonates (alkyl=benzyl and cholesteryl) with boron trifiuoride etherate. Formation mechanism of these by-products was investigated and discussed.

  研究了 O、S-二烷基二硫代碳酸酯与三氟化硼醚反应中烷基从 O 向 S 的迁移，并根据动力学、交叉反应和生成物的结果阐明了反应机理。值得注意的是，在 O-烷基 S-甲基二硫代碳酸酯（烷基=苄基和胆甾基）与三氟化硼醚酸盐的反应中，生成的二烷基甲基氟硼酸锍的产率相当高。对这些副产品的形成机理进行了研究和讨论。
• Thione-Thiol Rearrangement of Xanthates Catalyzed by Pyridine N-Oxides. Remarkably Enhanced Reactivity of 4-Dialkylaminopyridine N-Oxides.
  作者：Kazunobu HARANO、Hidetoshi NAKAGAWA、Kumiko KAMEI、Hideo KIYONAGA、Takuzo HISANO

  DOI：10.1248/cpb.40.1675

  日期：——

  Pyridine N-oxides bearing electron-donating substituents (III) are efficient catalysts for rearrangement of O-alkyl S-methyl dithiocarbonates (xanthates) (I) to the corresponding S-alkyl S-methyl dithiocarbonates (dithiolcarbonates) (II). Of the catalysts tested, 4-piperidinopyridine N-oxide (IIIh) is the best from the viewpoints of catalytic activity and solubility in I. Heating of I in the presence of catalytic amounts (0.02-0.05 molar eq) of IIIh gave II together with the symmetric S, S-dialkyl and S, S-dimethyl dithiocarbonates in good yields. The catalytic behavior of donor-substituted pyridine N-oxides is discussed on the basis of kinetic and molecular orbital calculation data. The complete calculation of the perturbation equation on the initial stage of the reaction was consistent with the experimentally observed activity of the catalysts.

  带有给电子取代基的吡啶N-氧化物(III)是O-烷基S-甲基二硫代碳酸酯(黄原酸酯)(I)重排成相应S-烷基S-甲基二硫代碳酸酯(二硫醇碳酸酯)(II)的有效催化剂。在所测试的催化剂中，从催化活性和在 I 中的溶解度的角度来看，4-哌啶吡啶 N-氧化物 (IIIh) 是最好的。在催化量（0.02-0.05 摩尔当量）的 IIIh 存在下加热 I，得到 II 以及对称的S，S-二烷基酯和S，S-二甲基二硫代碳酸酯的产率良好。基于动力学和分子轨道计算数据讨论了供体取代的吡啶氮氧化物的催化行为。反应初始阶段微扰方程的完整计算与实验观察到的催化剂活性一致。
• Harano, Kazunobu; Shinohara, Ikuo; Sugimoto, Shin-ichiro, Chemical and pharmaceutical bulletin, 1989, vol. 37, # 3, p. 576 - 581
  作者：Harano, Kazunobu、Shinohara, Ikuo、Sugimoto, Shin-ichiro、Matsuoka, Toshikazu、Hisano, Takuzo

  DOI：——

  日期：——
• 4-Dimethylaminopyridine N-Oxide as an Excellent Catalyst for Thione to Theol Rearrangement of Xathates
  作者：Kazunobu Harano、Hideo Kiyonaga、Shin-ichiro Sugimoto、Toshikazu Matsuoka、Takuzo Hisano

  DOI：10.3987/com-88-4657

  日期：——
• Kawata,T. et al., Chemical and pharmaceutical bulletin, 1973, vol. 21, p. 604 - 608
  作者：Kawata,T. et al.

  DOI：——

  日期：——