S-(4-甲基苯基)硫代乙酸酯 | 10436-83-6

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚酯
• 中文名称: S-(4-甲基苯基)硫代乙酸酯
• 英文名称: S-(4-methylphenyl) ethanethioate
• 英文别名: S-(4-methylphenyl) thioacetate；S-(p-tolyl) ethanethioate；S-p-tolyl thioacetate
• CAS: 10436-83-6
• 化学式: C₉H₁₀OS
• 分子量: 166.244
• InChiKey: XSQUNQSLEIFIHF-UHFFFAOYSA-N

物化性质

• 沸点：
  121 °C(Press: 14 Torr)
• 密度：
  1.10±0.1 g/cm3(Predicted)
• 保留指数：
  1374.5

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2930909090

反应信息

• 作为反应物：
  描述：

  S-(4-甲基苯基)硫代乙酸酯 在 劳森试剂 作用下， 生成 4-methylphenyl dithioacetate
  参考文献：
  名称：

  Kinetics and Mechanism of the Aminolysis of Phenyl Dithioacetates in Acetonitrile

  摘要：

  The aminolysis reactions of phenyl dithioacetates with anilines (AN), N,N-dimethylanilines (DMA), and benzylamines (BA) in acetonitrile are investigated. The mechanism is relatively simple, involving a zwitterionic tetrahedral intermediate, T+/-, and is uncomplicated by the fast proton transfer step which may become rate limiting in the aminolysis of thiono and dithio esters and carbonates with poor leaving groups in water. The mechanism changes from rate-limiting expulsion of the leaving group with beta(X) = 0.80-0.86 and beta(Z) = -0.71 to -0.84 for ANs and DMAs to rate-limiting attack by the nucleophile with much smaller magnitudes of beta(X) and beta(Z) for BAs. The relatively large beta(XZ) values for the former series and a smaller beta(XZ) for the latter series support the proposed mechanistic change.

  DOI：

  10.1021/jo970413r
• 作为产物：
  描述：

  1-(1,2-Dimethyl-propenylsulfanyl)-4-methyl-benzene 在 氧气 、 tetraphenylporphyrin 作用下， 以 氘代氯仿 为溶剂， 反应 0.5h， 生成 S-(4-甲基苯基)硫代乙酸酯
  参考文献：
  名称：

  乙烯基硫化物的光氧化：[2 + 2]环加成反应与申克烯反应模式的取代基效应

  摘要：

  芳基乙烯基硫醚1对位的电子接受取代基与通常的[2 + 2]环加成反应促进单线态氧与烯的反应，而给电子取代基仅提供二氧杂环丁烷产物，该产物通过其热不稳定的特性分解为CC裂解成相应的羰基片段。

  DOI：

  10.1016/0040-4039(95)01669-9

文献信息

• Air-Tolerant Direct Thiol Esterification with Carboxylic Acids Using Hydrosilane via Simple Inorganic Base Catalysis
  作者：Maojie Xuan、Chunlei Lu、Meina Liu、Bo-Lin Lin

  DOI：10.1021/acs.joc.9b00500

  日期：2019.6.21

  thioesterification of carboxylic acids with thiols using nontoxic activation agents is highly desirable. Herein, an efficient and practical protocol using safe and inexpensive industrial waste polymethylhydrosiloxane as the activation agent and K3PO4 with 18-crown-6 as a catalyst is described. Various functional groups on carboxylic acid and thiol substituents can be tolerated by the present system to afford thioesters

  非常需要使用无毒的活化剂将羧酸与硫醇直接硫酯化。在此，描述了一种有效且实用的方案，该方案使用安全且廉价的工业废聚甲基氢硅氧烷作为活化剂，并以18-crown-6作为催化剂的K 3 PO 4。本系统可以耐受羧酸和硫醇取代基上的各种官能团，从而以19-100％的收率提供硫酯。
• A New Method for Oxidation of Various Alcohols to the Corresponding Carbonyl Compounds by Using<i>N</i>-<i>t</i>-Butylbenzenesulfinimidoyl Chloride
  作者：Jun-ichi Matsuo、Daisuke Iida、Kazuya Tatani、Teruaki Mukaiyama

  DOI：10.1246/bcsj.75.223

  日期：2002.2

  Various primary and secondary alcohols were smoothly oxidized to the corresponding aldehydes and ketones by using a new oxidizing agent, N-t-butylbenzenesulfinimidoyl chloride (4a), in the coexistence of DBU or zinc oxide. The present oxidation proceeded under mild conditions via five-membered intramolecular proton-transfer of an alkyl arenesulfinimidate intermediate.

  在 DBU 或氧化锌的共存下，通过使用新的氧化剂 N-叔丁基苯亚磺酰亚胺酰氯 (4a)，将各种伯醇和仲醇顺利氧化成相应的醛和酮。本氧化反应在温和条件下通过烷基芳烃亚砜中间体的五元分子内质子转移进行。
• Harnessing the catalytic behaviour of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP): An expeditious synthesis of thioesters
  作者：Pallavi Singh、Rama Krishna Peddinti

  DOI：10.1016/j.tetlet.2017.04.004

  日期：2017.5

  promoting the thiocarbonylation of acyl halides and thiols is disclosed. HFIP was recovered with ease and reused for further reactions without any loss of reactivity. Both aryl and alkyl thiols bearing electron-donating and electron-withdrawing groups as well as aryl- and alkyl acyl halides worked well in this reaction. Inexpensive precursors, short reaction time, obviating workup, high atom economy, and

  已经开发出一种新颖，有效，无金属，无碱和无酸的简单方法来构建有用的硫酯。公开了HFIP促进酰基卤和硫醇的硫羰基化的巨大催化潜力。可以轻松回收HFIP，并重新用于进一步反应，而不会损失任何反应性。带有给电子基团和吸电子基团的芳基和烷基硫醇以及芳基和烷基酰基卤在该反应中均表现良好。廉价的前体，短的反应时间，避免后处理，高原子经济性和克级制备是发达的硫醇S-羰基化生态友好路线的重要特征。
• Bismuth Oxide Perchlorate as a Highly Efficient Catalyst for Heteroatom Acylation Under Solvent-Free Conditions
  作者：Asit K. Chakraborti、Rajesh Gulhane、Shivani

  DOI：10.1055/s-2003-41442

  日期：——

  Bismuth oxide perchlorate efficiently catalyzes the acetylation of structurally diverse phenols, alcohols, thiols, and amines under solvent free conditions. Sterically hindered and electron deficient phenols are acetylated in excellent yields with stoichiometric amounts of Ac 2 O at room temperature. Acylation of acid-sensitive alcohols is carried out efficiently without competitive side reactions

  高氯酸铋在无溶剂条件下有效催化结构不同的酚、醇、硫醇和胺的乙酰化。空间位阻和缺电子酚在室温下用化学计量的 Ac 2 O 以极好的收率乙酰化。酸敏感醇的酰化可以有效地进行，没有竞争性副反应。光学活性底物被乙酰化，对光学纯度没有任何不利影响。
• Zirconium(IV) Chloride as a New, Highly Efficient, and Reusable Catalyst for Acetylation of Phenols, Thiols, Amines, and Alcohols under Solvent-Free Conditions
  作者：Asit K. Chakraborti、Rajesh Gulhane

  DOI：10.1055/s-2004-815442

  日期：——

  chloride has been found to be a new. highly efficient, and reusable catalyst for acetylation of structurally diverse phenols, thiols, amines and alcohols under solvent-free condtions. Acetylation of sterically hindered and electron deficient phenols is achieved in excellent yields with stoichiometric amounts of Ac 2 O at room temperature. Acid-sensitive alcohols undergo acetylation with excellent chemoselectivity

  已发现氯化锆 (IV) 是一种新的。一种高效、可重复使用的催化剂，用于在无溶剂条件下对结构不同的酚、硫醇、胺和醇进行乙酰化。在室温下使用化学计量量的 Ac 2 O 以极好的收率实现空间位阻和缺电子酚的乙酰化。酸敏感醇以优异的化学选择性进行乙酰化，而不会发生脱水或重排等竞争性副反应。催化剂的温和路易斯酸性质使乙酰化能够与光学活性底物一起进行，而不会对光学纯度产生任何不利影响。