呋喃-2-硫代羧酸S-苯基酯 | 17357-38-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃
• 中文名称: 呋喃-2-硫代羧酸S-苯基酯
• 英文名称: S-phenyl furan-2-carbothioate
• CAS: 17357-38-9
• 化学式: C₁₁H₈O₂S
• 分子量: 204.249
• InChiKey: XCQROCMQSAUOTM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  55.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2932190090

反应信息

• 作为反应物：
  描述：

  呋喃-2-硫代羧酸S-苯基酯 在 劳森试剂 作用下， 以 甲苯 为溶剂， 生成 phenyl dithio-2-furoate
  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：

  呋喃甲酰氯 在 4-二甲氨基吡啶 、 锰 、 1,3-双(二苯基膦)丙烷 、 三乙胺 、 nickel dibromide 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 18.0h， 生成 呋喃-2-硫代羧酸S-苯基酯
  参考文献：
  名称：

  镍催化酰胺和二硫化物合成硫酯

  摘要：

  开发了一种新型的镍催化的、实用且简单的由酰胺和二硫化物合成硫酯的方法。多种取代的芳香酰胺能够通过 CN/S-S 裂解与二芳基或二烷基二硫化物偶联，以中等至良好的产率产生所需的硫酯。该方法具有廉价的金属、新颖且易于制备的底物的特点，提供了一种简单实用的方法来获得各种硫酯，而无需有毒的硫醇或CO气体。

  DOI：

  10.1002/ejoc.202400026

文献信息

• Thioesterification and Selenoesterification of Amides via Selective N–C Cleavage at Room Temperature: N–C(O) to S/Se–C(O) Interconversion
  作者：Md. Mahbubur Rahman、Guangchen Li、Michal Szostak

  DOI：10.1055/s-0039-1690055

  日期：2020.4

  The direct nucleophilic addition to amides represents an attractive methodology in organic synthesis that tackles amidic resonance by ground-state destabilization. This approach has been recently accomplished with carbon, nitrogen and oxygen nucleophiles. Herein, we report an exceedingly mild method for the direct thioesterification and selenoesterification of amides by selective N–C(O) bond cleavage in the absence of transition metals. Acyclic amides undergo N–C(O) to S/Se–C(O) interconversion to give the corresponding thioesters and selenoesters in excellent yields at room temperature via a tetrahedral intermediate pathway (cf. an acyl metal).

  对酰胺的直接亲核加成代表了有机合成中一种吸引人的方法论，通过基态不稳定化来解决酰胺的共振问题。最近，已经成功地利用碳、氮和氧亲核试剂实现了这种方法。在这里，我们报告了一种极其温和的方法，通过选择性N-C(O)键裂解，在没有过渡金属的情况下直接对酰胺进行硫酯化和硒酯化。无环酰胺经历N-C(O)到S/Se-C(O)的相互转化，在室温下通过四面体中间体途径（与酰基金属相比）以极高的产率给出相应的硫酯和硒酯。
• Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters
  作者：Han Cao、Xuejing Liu、Fusheng Bie、Yijun Shi、Ying Han、Peng Yan、Michal Szostak、Chengwei Liu

  DOI：10.1021/acs.joc.1c01117

  日期：2021.8.6

  valuable thioethers. Notable features include the absence of phosphine ligands, inorganic bases, and other additives and excellent group tolerance to aryl chlorides and bromides that are problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C–S/C–Br cleavage are reported.

  在催化量的 [Rh(cod)Cl] 2 (2 mol%)存在下，从硫酯脱羰合成硫醚。该协议代表了第一个 Rh 催化的硫酯脱羰硫醚化，以产生有价值的硫醚。显着的特点包括没有膦配体、无机碱和其他添加剂，以及对芳基氯和芳基溴的优异基团耐受性，这些都是使用其他金属促进脱羰的问题。报告了克级合成、后期药物衍生化和通过 C-S/C-Br 裂解进行的正交位点选择性交叉偶联。
• 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。
• FACILE REDUCTION OF BENZENETHIOL ESTER UNDER MILD CONDITIONS WITH ZINC BOROHYDRIDE
  作者：Hiyoshizo Kotsuki、Naka Yoshimura、Yasuyuki Ushio、Tatsuya Ohtsuka、Masamitsu Ochi

  DOI：10.1246/cl.1986.1003

  日期：1986.6.5

  Benzenethiol esters are efficiently reduced to alcohols under mild conditions by treatment with zinc borohydride prepared from zinc chloride and sodium borohydride.

  通过用由氯化锌和硼氢化钠制备的硼氢化锌处理，苯硫醇酯在温和条件下可有效还原为醇。
• Rapid and Regiospecific Phenylthiolation of Some Organic Acids Catalyzed by AlCl₃ in the Presence of Excess Anhydrous ZnCl₂
  作者：H. N. Roy、Ashis K. Sarker、A. H. Al Mamun

  DOI：10.1080/00397910903219567

  日期：2010.6.25

  Phenylthiolation of some carboxylic acids catalyzed by AlCl3 in the presence of excess dehydrating agent (ZnCl2) has been achieved. Moreover, regiospecificity was tested of some dioic acids and found to be specific at the aliphatic part of carboxylic functionality.

  在过量脱水剂 (ZnCl2) 存在下，AlCl3 催化某些羧酸的苯硫基化已经实现。此外，对一些二酸进行了区域特异性测试，发现在羧基官能团的脂肪族部分具有特异性。