S-(p-tolyl) thiophene-2-carbothioate | 72899-24-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: S-(p-tolyl) thiophene-2-carbothioate
• 英文别名: S-4-tolyl thiophene-2-carbothioate；S-p-methylphenyl thio-2-thophenate；S-p-tolyl thiophene-2-carbothioate；S-(p-tolyl)thiophene-2-thioate；thiophene-2-carbothioic acid S-p-tolyl ester；Thiophen-2-thiocarbonsaeure-S-p-tolylester；S-(4-methylphenyl) thiophene-2-carbothioate
• CAS: 72899-24-2
• 化学式: C₁₂H₁₀OS₂
• 分子量: 234.343
• InChiKey: UCGRSIBRLZCEGR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  70.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

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

  Aminolysis of aryl dithio-2-thiophenates and dithio-2-furoates in acetonitrile

  摘要：

  The aminolyses of the title substrates with anilines and benzylamines are investigated in acetonitrile. A clean second-order kinetics is obtained with a first-order rate law in the amine concentration, which is uncomplicated by the fast proton transfer step. The large magnitude of rho(z) (rho(1g)) as well as rho(x) (rho(nuc)) together with relatively large positive p(xz) values is consistent with a stepwise mechanism in which thiophenolate ion expulsion from the intermediate is rate limiting. For the reactions of aryl dithio-2-thiophenates with benzylamines the magnitude of rho(x) and rho(z) values is relatively smaller suggesting that both the addition and expulsion of thiophenolate are partially rate determining. Relatively large secondary kinetic isotope effects, k(H)/k(D) greater than or equal to 1.7, with deuterated nucleophiles, support involvement a concurrent proton transfer to the departing thiophenolate ion in the transition state. (C) 1998 John Wiley & Sons, Inc.

  DOI：

  10.1002/(sici)1097-4601(1998)30:11<849::aid-kin7>3.0.co;2-v
• 作为产物：
  描述：

  4-甲苯硫酚 在 1,1'-双(二苯基膦)二茂铁 、 bis(acetylacetonate)nickel(II) 作用下， 以 甲苯 为溶剂， 反应 17.0h， 生成 S-(p-tolyl) thiophene-2-carbothioate
  参考文献：
  名称：

  镍催化的羧酸和硫酯之间的复分解：直接获得硫酯

  摘要：

  我们描述了一种从羧酸和硫酯生成硫酯的独特策略。该转化具有操作简单和步骤经济性高的特点，其中硫代酯的-SR部分顺利地从硫代乙酸酯作为起始原料转移到羧酸。具有不同电子性质水平的各种底物都适用于该反应，以中等至出色的产率提供硫酯。根据初步的机理研究，酸酐中间体可能参与了本反应。

  DOI：

  10.1021/acs.orglett.3c02664

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。
• Nickel-Catalyzed C−S Bond Formation via Decarbonylative Thioetherification of Esters, Amides and Intramolecular Recombination Fragment Coupling of Thioesters
  作者：Shao-Chi Lee、Hsuan-Hung Liao、Adisak Chatupheeraphat、Magnus Rueping

  DOI：10.1002/chem.201705842

  日期：2018.3.7

  A nickel catalyzed cross‐coupling protocol for the straightforward C−S bond formation has been developed. Various mercaptans and a wide range of ester and amide substrates bearing various substituents were tolerated in this process which afforded products in good to excellent yields. Furthermore, an intramolecular protocol for the synthesis of thioethers starting from thioesters has been developed

  已经开发出一种镍催化的交叉偶联方案，用于直接形成C-S键。在该方法中可以耐受各种硫醇以及带有各种取代基的各种酯和酰胺底物，从而以良好或极好的收率提供产物。此外，已经开发了用于从硫代酯开始合成硫醚的分子内方案。该方案的效用已在苯并噻吩的新合成方案中得到证明。
• Synthesis of thioesters through copper-catalyzed coupling of aldehydes with thiols in water
  作者：Chih-Lun Yi、Yu-Ting Huang、Chin-Fa Lee

  DOI：10.1039/c3gc40946e

  日期：——

  Copper-catalyzed C–S bond formation between aldehydes and thiols in the presence of TBHP as an oxidant is described. Functional groups including chloro, trifluoromethyl, bromo, iodo, nitrile, ester and thiophene are all tolerated by the reaction conditions employed. This reaction is performed in water without the use of a surfactant. Both aryl and alkyl aldehydes couple suitably with aryl- and alkyl thiols, affording the corresponding thioesters in moderate to good yields.

  介绍了在氧化剂TBHP存在下，铜催化的醛与硫醇之间的C-S键形成反应。所采用的反应条件能够容忍包括氯、三氟甲基、溴、碘、腈、酯和噻吩在内的多种官能团。该反应在水相中进行，无需使用表面活性剂。芳基和烷基醛均能与芳基和烷基硫醇适当地耦合，以中等至良好的产率得到相应的硫酯。
• Visible-Light-Promoted Thiyl Radical Generation from Sodium Sulfinates: A Radical–Radical Coupling to Thioesters
  作者：Ganganna Bogonda、Dilip V. Patil、Hun Young Kim、Kyungsoo Oh

  DOI：10.1021/acs.orglett.9b01218

  日期：2019.5.17

  available starting materials: acid chlorides and sodium sulfinates. The facile generation of acyl radical species under the visible light photoredox conditions allows the formation of thiyl radical species from sodium sulfinates via multiple single electron transfer reactions, where the final acyl radical-thiyl radical coupling has been accomplished. The direct radical–radical coupling strategy offers a mild

  已经开发了一种方便的可见光光氧化还原催化剂，用于从两种容易获得的起始原料：酰氯和亚磺酸钠合成硫酯。在可见光光氧化还原条件下容易地产生酰基基团物种使得可以通过多个单电子转移反应由亚磺酸钠形成硫基基团物种，其中已经完成了最终的酰基基团-噻吩基基团偶联。自由基-自由基直接偶联策略为重要的合成构件（例如硫酯）提供了温和且受控的光化学方法。
• Sulfonyl Chlorides as Thiol Surrogates for Carbon–Sulfur Bond Formation: One-Pot Synthesis of Thioethers and Thioesters
  作者：Torsten Cellnik、Alan R. Healy

  DOI：10.1021/acs.joc.2c00330

  日期：2022.5.6

  A method to synthesize thioethers and thioesters directly from readily available sulfonyl chlorides is reported. We demonstrate that a transient intermediate formed during phosphine-mediated deoxygenation of sulfonyl chlorides can be trapped in situ by activated alcohols or carboxylic acids to effect carbon–sulfur bond formation. The method is operationally simple and tolerates a broad range of functional

  报道了一种直接从容易获得的磺酰氯合成硫醚和硫酯的方法。我们证明了在膦介导的磺酰氯脱氧过程中形成的瞬态中间体可以被活化的醇或羧酸原位捕获，从而影响碳硫键的形成。该方法操作简单并且可以容忍广泛的官能团。特别关注的是密集功能化天然产物和药物的后期多样化。