methyl O-n-propyl dithiocarbonate | 25954-88-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: methyl O-n-propyl dithiocarbonate
• 英文别名: O-(n-propyl) S-methyl dithiocarbonate；O-propyl S-methyl dithiocarbonate；O-n-propyl S-methyl xanthate；O-Propyl S-methyl xanthate；dithiocarbonic acid S-methyl ester-O-propyl ester；Dithiokohlensaeure-S-methylester-O-propylester；O-propyl methylsulfanylmethanethioate
• CAS: 25954-88-5
• 化学式: C₅H₁₀OS₂
• 分子量: 150.266
• InChiKey: NIOBMCVPNXBNEW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 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：
  66.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl O-n-propyl dithiocarbonate 在 乙醇 、 氨 作用下， 生成 O-propyl thiocarbamate
  参考文献：
  名称：

  Delepine; Schving, Bulletin de la Societe Chimique de France, 1910, vol. <4>7, p. 895,901

  摘要：

  DOI：
• 作为产物：
  描述：

  丙黄原酸钾 、 碘甲烷 以 甲醇 为溶剂， 生成 methyl O-n-propyl dithiocarbonate
  参考文献：
  名称：

  Methanesulfenyl Chloride. IV. The Reaction of Sulfenyl Chlorides with Alkyl Xanthates and Trimethyl Thionophosphate¹

  摘要：

  DOI：

  10.1021/jo01025a041

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。
• Synthesis of α-Oxoketene<i>O</i>-Alkyl/Aryl,<i>S</i>-Alkyl Acetals
  作者：Makhan L. Purkayastha、Malapaka Chandrasekharam、Jai N. Vishwakarma、Hiriyakkanavar Ila、Hiriyakkanavar Junjappa

  DOI：10.1055/s-1993-25841

  日期：——

  The synthesis of acylketene O,S-dialkyl acetals 2a-p and acylketene O-aryl S-alkyl acetals 6a-i is described. The compounds 2a-n are obtained by base-catalyzed alkylation of the respective β-oxo thiono esters 4a-n prepared by alkoxythiocarbonylation of active methylene ketones in the presence of sodium tert-butoxide. The corresponding O-dodecanyl 2o, O-benzyl 2p and O-aryl, S-methyl 6a-i acetals are synthesized via base-catalyzed displacement of the sulfonium salts 5a-b with the corresponding alkanol or phenol.

  描述了酰基烯酮O,S-二烷基缩醛2a-p和酰基烯酮O-芳基S-烷基缩醛6a-i的合成。化合物 2a-n 是通过在叔丁醇钠存在下通过活性亚甲基酮的烷氧基硫代羰基化制备的相应β-氧代硫代酯 4a-n 的碱催化烷基化获得的。相应的O-十二烷基2o、O-苄基2p和O-芳基、S-甲基6a-i缩醛通过用相应的链烷醇或苯酚碱催化置换锍盐5a-b来合成。
• Phenol-Catalyzed Thione-Thiol Rearrangement of Xanthates and Modified Intermediate Neglect of Differential Overlap(MINDO/3) Analysis of the Reaction Mechanism.
  作者：Kazunobu HARANO、Hideo KIYONAGA、Takuzo HISANO

  DOI：10.1248/cpb.40.2654

  日期：——

  S-Alkyl dithiocarbonates (xanthates) of alkanols containing strained σ bonds underwent rearrangement to S, S-dialkyl dithiocarbonates, catalyzed by phenolic compounds. The reaction followed first-order kinetics and the rates were affected by the acidity of the phenols. The rate contants are proportional to the square of the concentration of phenol.The modified intermediate neglect of differential overlap (MINDO/3) geometry optimization indicates that S, S-dialkyl dithiocarbonate is ca. 9 kcal/mol more stable than O, S-dialkyl xanthate. The thione-thiol rearrangement and sulfide formation reactions were analyzed by MO simulations. The experimental results can be well reproduced by the MINDO/3 method rather than the modified neglect of diatomic overlap (MNDO) method. Based on these data, the reaction mechanism is discussed.

  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。
• The Anhydrous Chlorination of Thioesters and Related Compounds^1,2
  作者：Irwin B. Douglass、Charles E. Osborne

  DOI：10.1021/ja01114a506

  日期：1953.9