4-mercapto-3-methyl-1-p-tolylpent-1-yn-3-ol | 1403459-92-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-mercapto-3-methyl-1-p-tolylpent-1-yn-3-ol
• 英文别名: 3-Methyl-1-(4-methylphenyl)-4-sulfanylpent-1-yn-3-ol；3-methyl-1-(4-methylphenyl)-4-sulfanylpent-1-yn-3-ol
• CAS: 1403459-92-6
• 化学式: C₁₃H₁₆OS
• 分子量: 220.335
• InChiKey: UVHBUTSZXPRIHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  21.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-mercapto-3-methyl-1-p-tolylpent-1-yn-3-ol 在 碘 作用下， 反应 24.0h， 以81%的产率得到3-iodo-4,5-dimethyl-2-p-tolylthiophene
  参考文献：
  名称：

  A recyclable and base-free method for the synthesis of 3-iodothiophenes by the iodoheterocyclisation of 1-mercapto-3-alkyn-2-ols in ionic liquids

  摘要：

  本报告首次报道了通过使用离子液体作为反应介质使碘环化反应可循环使用的实例。以 1-ethyl-3-methylimidazolium ethyl sulfate (EmimEtSO4) 等适当的离子液体为溶剂，在温和的反应条件下（25 °C），在没有外部碱的情况下，让 1-巯基-3-炔-2-醇与碘（1-2 等量）反应，可顺利转化为相应的 3-碘噻吩（产率 50-81%，10 个实例）。反应介质可以多次循环使用，而不会对反应结果产生重大影响。此外，还进行了理论计算，以研究离子液体阴离子在反应中的作用。

  DOI：

  10.1039/c3ob41928b
• 作为产物：
  描述：

  3-巯基-2-丁酮 、 4-甲苯基乙炔 在 正丁基锂 、 lithium bromide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 以80%的产率得到4-mercapto-3-methyl-1-p-tolylpent-1-yn-3-ol
  参考文献：
  名称：

  An Iodocyclization Approach to Substituted 3-Iodothiophenes

  摘要：

  A novel approach to 3-iodothiophenes by direct iodocyclization of alkynylthiol derivatives is presented. A variety of 1-mercapto-3-yn-2-ols 5 (readily available from alkynylation of the corresponding alpha-mercapto ketones or alpha-mercapto esters) were smoothly converted into the corresponding 3-iodothiophene derivatives 6 in good yields by reaction with molecular iodine in the presence of NaHCO3 at room temperature in MeCN as the solvent.

  DOI：

  10.1021/jo301001j

文献信息

• A recyclable and base-free method for the synthesis of 3-iodothiophenes by the iodoheterocyclisation of 1-mercapto-3-alkyn-2-ols in ionic liquids
  作者：Raffaella Mancuso、Christian S. Pomelli、Cinzia Chiappe、Richard C. Larock、Bartolo Gabriele

  DOI：10.1039/c3ob41928b

  日期：——

  The first example of an iodocyclisation reaction made recyclable by the use of an ionic liquid as the reaction medium is reported. Readily available 1-mercapto-3-alkyn-2-ols were smoothly converted into the corresponding 3-iodothiophenes (50–81% yields, 10 examples) when allowed to react with iodine (1–2 equiv.) in a proper ionic liquid, such as 1-ethyl-3-methylimidazolium ethyl sulfate (EmimEtSO4), as the solvent under mild reaction conditions (25 °C) and in the absence of an external base. The reaction medium can be recycled several times without significantly affecting the reaction outcome. Theoretical calculations have also been performed to investigate the role of the ionic liquid anion in the reaction.

  本报告首次报道了通过使用离子液体作为反应介质使碘环化反应可循环使用的实例。以 1-ethyl-3-methylimidazolium ethyl sulfate (EmimEtSO4) 等适当的离子液体为溶剂，在温和的反应条件下（25 °C），在没有外部碱的情况下，让 1-巯基-3-炔-2-醇与碘（1-2 等量）反应，可顺利转化为相应的 3-碘噻吩（产率 50-81%，10 个实例）。反应介质可以多次循环使用，而不会对反应结果产生重大影响。此外，还进行了理论计算，以研究离子液体阴离子在反应中的作用。
• An Iodocyclization Approach to Substituted 3-Iodothiophenes
  作者：Bartolo Gabriele、Raffaella Mancuso、Giuseppe Salerno、Richard C. Larock

  DOI：10.1021/jo301001j

  日期：2012.9.7

  A novel approach to 3-iodothiophenes by direct iodocyclization of alkynylthiol derivatives is presented. A variety of 1-mercapto-3-yn-2-ols 5 (readily available from alkynylation of the corresponding alpha-mercapto ketones or alpha-mercapto esters) were smoothly converted into the corresponding 3-iodothiophene derivatives 6 in good yields by reaction with molecular iodine in the presence of NaHCO3 at room temperature in MeCN as the solvent.
• Synthesis of Substituted Thiophenes by Palladium-Catalyzed Heterocyclodehydration of 1-Mercapto-3-yn-2-ols in Conventional and Nonconventional Solvents
  作者：Bartolo Gabriele、Raffaella Mancuso、Lucia Veltri、Vito Maltese、Giuseppe Salerno

  DOI：10.1021/jo301943k

  日期：2012.11.2

  A variety of readily available 1-mercapto-3-yn-2-ols 5 were conveniently converted into the corresponding thiophenes 6 in good to high yields in MeOH as the solvent at 50-100 degrees C in the presence of catalytic amounts (1-2%) of PdI2 in conjunction with KI (KI:PdI2 molar ratio = 10). The catalyst could be made recyclable employing an ionic liquid, such as BmimBF(4), as the solvent under suitable conditions.
• Synthesis of thiophenes in a deep eutectic solvent: heterocyclodehydration and iodocyclization of 1-mercapto-3-yn-2-ols in a choline chloride/glycerol medium
  作者：Raffaella Mancuso、Asif Maner、Luciana Cicco、Filippo M. Perna、Vito Capriati、Bartolo Gabriele

  DOI：10.1016/j.tet.2016.05.062

  日期：2016.7

  The heterocyclodehydration and iodocyclization of readily available 1-mercapto-3-yn-2-ols has been performed in a deep eutectic solvent (DES), that is, ChCl/Gly (1:2 molar ratio; ChCl=choline chloride, Gly=glycerol), as a non-conventional green solvent. The processes, carried out at 50 degrees C for 8 h in the presence of the PdI2/KI catalytic system or at room temperature for 5 h with 1.2 equiv of I-2, led to the formation of the corresponding thiophenes and 3-iodothiophenes in good to high yields. The DES/catalytic system could be easily recycled several times without appreciable loss of activity, after extraction of the thiophene product with hexane or Et2O. The alkynylation reaction of alpha-mercapto ketones, necessary for the preparation of the allcynylthiol substrates, was also successfully accomplished in the above protic eutectic mixture competitively with protonolysis. (C) 2016 Elsevier Ltd. All rights reserved.