p-methylphenyl phenyldithioacetate | 378791-48-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: p-methylphenyl phenyldithioacetate
• 英文别名: p-tolyl 2-phenylethanedithioate；(4-Methylphenyl) 2-phenylethanedithioate；(4-methylphenyl) 2-phenylethanedithioate
• CAS: 378791-48-1
• 化学式: C₁₅H₁₄S₂
• 分子量: 258.408
• InChiKey: GCTXVIBALMFNJA-UHFFFAOYSA-N

物化性质

• 沸点：
  400.6±48.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  57.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(三氟甲基)苄胺 、 p-methylphenyl phenyldithioacetate 以 乙腈 为溶剂， 生成 2-phenyl-N-[[4-(trifluoromethyl)phenyl]methyl]ethanethioamide
  参考文献：
  名称：

  Oh, Hyuck Keun; Kim, Sun Kyung; Cho, In Ho, Journal of the Chemical Society. Perkin Transactions 2 (2001), 2000, # 11, p. 2306 - 2310

  摘要：

  DOI：
• 作为产物：
  描述：

  S-(p-tolyl) 2-phenylethanethioate 在 劳森试剂 作用下， 以 甲苯 为溶剂， 生成 p-methylphenyl phenyldithioacetate
  参考文献：
  名称：

  Oh, Hyuck Keun; Kim, Sun Kyung; Cho, In Ho, Journal of the Chemical Society. Perkin Transactions 2 (2001), 2000, # 11, p. 2306 - 2310

  摘要：

  DOI：

文献信息

• Structure–reactivity correlations in the aminolysis of aryl dithiomethyl- and dithiophenylacetates with anilines in acetonitrile
  作者：Hyuck Keun Oh、Sun Kyung Kim、Hai Whang Lee、Ikchoon Lee

  DOI：10.1039/b104295p

  日期：——

  The kinetics and mechanism of the anilinolysis (XC6H4NH2) of dithio esters, RC(S)SC6H4Z with R = C2H5 and C6H5CH2 are investigated in acetonitrile at 45.0 °C. By application of various structure–reactivity correlations, selectivity parameters ρX, βX, ρZ, βZ and ρXZ are determined. The reactions are predicted to proceed stepwise with rate-limiting expulsion of the ArS− group. The dithio ester with R = C2H5 exhibits the fastest rate and the largest positive ρXZ value; this is interpreted to result from the strongest electron donating ability of the ethyl group in the intermediate and a crowded tetrahedral intermediate and transition state in which the nucleophile (X) and leaving group (Z) are in close proximity due to the bulky C2H5 group. Much faster rates are observed for the thiocarbonyl (CS) rather than carbonyl (CO) esters in the stepwise nucleophilic substitution reactions, which may be ascribed to the lower π*CS and σ*C–LG levels than those of the corresponding antibonding levels in the carbonyl esters. The normal kinetic isotope effects, kH/kD > 1.0, involving deuterated anilines suggest concurrent proton transfer with the expulsion of the ArS− leaving group in a four-center hydrogen bonded transition state.

  在 45.0°C 乙腈中研究了二硫酯、RC(S)SC6H4Z（其中 R = C2H5 和 C6H5CH2）苯胺分解 (XC6H4NH2) 的动力学和机理。通过应用各种结构-反应性相关性，可以确定选择性参数δX、δX、δZ、δZ 和δXZ。预计反应将逐步进行，并限速排出 ArS 基团。 R= 的二硫酯表现出最快的速率和最大的正δXZ值；这被解释为中间体中乙基最强的给电子能力和拥挤的四面体中间体的结果 以及过渡态，其中亲核试剂 (X) 和离去基团 (Z) 由于庞大的 基团而非常接近。在逐步亲核取代反应中，观察到硫代羰基 (CS) 酯的速率比羰基 (CO) 酯快得多，这可能是由于 α*CS 和 α*C-LG 水平低于相应的反应水平。羰基酯中的反键水平。涉及氘代苯胺的正常动力学同位素效应 kH/kD > 1.0 表明质子转移与四中心氢键过渡态的 ArS- 离去基团的排出同时进行。
• Ynamide-Mediated Thionoester and Dithioester Syntheses
  作者：Chaochao Yao、Jinhua Yang、Xiaobiao Lu、Shuyu Zhang、Junfeng Zhao

  DOI：10.1021/acs.orglett.0c02402

  日期：2020.8.21

  A novel ynamide-mediated synthesis of thionoesters and dithioesters is described. The selective addition reactions of various monothiocarboxylic acids with ynamide furnish alpha-thioacyloxyenamides, which undergo transesterification with nucleophilic -OH or -SH species to afford thionoesters and dithioesters, respectively. The broad substrate scope, mild reaction conditions, and excellent yields make this method an attractive synthetic approach to thionoesters and dithioesters.