S-ethyl S-methyl dithiocarbonate | 10596-55-1

• 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-ethyl S-methyl dithiocarbonate
• 英文别名: Ethylsulfanyl(methylsulfanyl)methanone
• CAS: 10596-55-1
• 化学式: C₄H₈OS₂
• 分子量: 136.239
• InChiKey: ZBQVEDZPGKJKDV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  7
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  O-乙基 S-甲基二硫代碳酸酯 在 对硝基苯酚 作用下， 反应 6.0h， 以35%的产率得到S-ethyl S-methyl 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

• Synthesis of mono- and 1,4-dicarbonyl compounds based on the oxygenation of phosphonate carbanions. Synthesis of dihydrojasmone, allethrone and methylenomycin b
  作者：Marian Mikołajczyk、Wanda Midura、Sławomir Grzejszczak

  DOI：10.1016/s0040-4039(01)81212-0

  日期：1984.1

  Oxidation of the α-alkylthio-substituted phosphonate carbanions was found to give the corresponding carbonyl compounds. A new synthesis of 1,4-dicarbonyl systems involving the oxygenation of phosphonate carbanions as a key step is described. Total synthesis of dihydrojasmone and allethrone and formal synthesis of methylenomycin B is reported.

  发现α-烷硫基取代的膦酸酯碳负离子的氧化得到相应的羰基化合物。描述了涉及膦酸碳负离子的氧化作为关键步骤的1,4-二羰基系统的新合成。报道了二氢茉莉酮和烯丙酮的全合成和甲基新霉素B的正式合成。
• 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。
• On the mechanism of deoxygenation of secondary alcohols by tin hydride reduction of methyl xanthates and other thiocarbonyl derivatives
  作者：Derek H.R. Barton、Jang Doo Ok、Joseph Cs. Jaszberenyi

  DOI：10.1016/s0040-4039(00)94480-0

  日期：1990.1

  The room temperature deoxygenation of xanthates and thionocarbonates using (n-Bu) 3Sn-H — Et3B — air has been studied, especially with 119Sn N.M.R. spectroscopy. The original conception of tin radical attack on thiocarbonyl is confirmed.

  使用（n -Bu ）3 Sn-H-Et 3 B-空气对黄原酸酯和硫代碳酸酯的室温脱氧进行了研究，尤其是利用119 Sn NMR光谱。锡自由基攻击硫代羰基的最初概念得到证实。
• A general strategy for elaboration of the dithiocarbonyl functionality, -(C:O)SS-: application to the synthesis of bis(chlorocarbonyl)disulfane and related derivatives of thiocarbonic acids
  作者：George Barany、Alayne L. Schroll、Andrew W. Mott、David A. Halsrud

  DOI：10.1021/jo00172a056

  日期：1983.12
• Trifluoroacetic-acid-catalyzed rearrangement of dialkyl xanthates to dithiocarbonates with inversion of configuration
  作者：Michael W. Fichtner、Neil F. Haley

  DOI：10.1021/jo00328a036

  日期：1981.7