methyl 3-[(3,6-dioxocyclohexa-1,4-dienyl)sulfanyl]propanoate | 441764-32-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-[(3,6-dioxocyclohexa-1,4-dienyl)sulfanyl]propanoate
• 英文别名: methyl 3-((3,6-dioxocyclohexa-1,4-dien-1-yl)thio)propanoate；Methyl 3-[(3,6-dioxo-1,4-cyclohexadien-1-yl)sulfanyl]propanoate；Methyl 3-(3,6-dioxocyclohexa-1,4-dien-1-yl)sulfanylpropanoate
• CAS: 441764-32-5
• 化学式: C₁₀H₁₀O₄S
• 分子量: 226.253
• InChiKey: BICGBDFLRCVMBJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  85.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 3-[(3,6-dioxocyclohexa-1,4-dienyl)sulfanyl]propanoate 在 甲醇 、 锌 作用下， 以55%的产率得到methyl 3-[(2,5-dihydroxyphenyl)sulfanyl]propanoate
  参考文献：
  名称：

  对苯醌与硫亲核试剂的反应

  摘要：

  讨论了对称对苯醌与亲核试剂反应的取向。对苯醌与烷基硫醇的一锅反应生成了2-、2,6-和2,5-连接加成产物。通过顺序加成/原位氧化法获得了新颖的2,6-和2,5-双(烷基硫基)-、2,3,5-三(烷基硫基)-和2,3,5,6-四(烷基硫基)-对苯醌及其相应的氢醌，收率良好，进一步用于测试作为橡胶和石油产品的聚合抑制剂。通过X射线晶体学确定了五种2,5-和2,6-二取代异构体的结构。

  DOI：

  10.1055/s-2008-1032186
• 作为产物：
  描述：

  3-巯基丙酸甲酯 、 对苯二酚 在 chromium(VI) oxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.67h， 以78%的产率得到methyl 3-[(3,6-dioxocyclohexa-1,4-dienyl)sulfanyl]propanoate
  参考文献：
  名称：

  使用铬酸的氢醌和硫醇的氧化自由基偶联：醌基烷基/芳基硫醚的一锅法合成

  摘要：

  开发了一种高效、简单且实用的方案，用于硫醇与氢醌 (HQ) 的一锅顺序氧化自由基 C–H/S–H 交叉偶联和氧化，从而使用 H 2 CrO 4形成醌基烷基/芳基硫醚。硫基和芳基的这种交叉偶联以良好至中等的产率提供单硫醚，并且与多种硫醇配合良好。同样，该方法适用于 2-氨基苯硫酚和 HQ 的偶联形成吩噻嗪-3-酮5a–c 。首次使用铬试剂观察到通过硫醚合成形成 C-S 键。对化合物5a–c药代动力学特性的理论研究表明，由于具有药物样特性，化合物5b与阿尔茨海默病 (AD) 相关的 AChE 靶位点强烈结合。

  DOI：

  10.1039/d0ra01519a

文献信息

• 2-Thio-5-amino substituted benzoquinones, their manufacture and their use in rubber
  申请人：——

  公开号：US20020128499A1

  公开（公告）日：2002-09-12

  The invention comprises a process for preparing a compound having the formula comprising: 1 where Z and W are the same or different, and selected from the group consisting of O, NH and NR, where R is H, alkyl, cycloalkyl or aryl, R′ is alkyl, cycloalkyl, alkylene, alkyl 3-propionate, aryl or arylene. A is H if either or both of Z and W are not O, but if both Z and W are O, A is: 2 or a carbon based heterocyclic component having an amine constituent, or RR″N-, where R″ is the same or different than R and is selected from the same group as R. The process comprises preparing an alkylthio-substituted benzoquinone intermediate by reacting in a first reaction mixture a thio-substituted aromatic having the formula: 3 where X is OH, NH 2 or NHR when Z is O, NH or NR, respectively, and where Y is OH, NH 2 or NHR when W is O, NH or NR, respectively, with an alkali metal periodate in the presence of a phase transfer catalyst, followed, if A is not H, by reacting the intermediate in a second reaction mixture containing an amine included in the group of amines comprising A, and in the presence of oxygen to obtain the compound. If A is H no second reaction mixture is employed and the intermediate comprises the compound. The invention includes a process for making the composition and the use of the composition in natural and synthetic rubber, and with monomers, gasoline and lubricating oil to inhibit polymerization.

  该发明涉及一种制备具有以下式的化合物的过程：1其中Z和W相同或不同，选择自O，NH和NR的组，其中R为H，烷基，环烷基或芳基，R'为烷基，环烷基，烷基3-丙酸酯，芳基或芳烃基。如果Z和W中的任意一个或两个不是O，则A为H，但如果Z和W都是O，则A为：2或具有胺基组分的碳基杂环组分，或RR″N-，其中R″与R相同或不同，并选择自与R相同的组中的烷基，环烷基或芳基。该过程包括通过在第一反应混合物中反应具有以下式的硫代取代芳香族物质制备烷基硫代苯醌中间体：3其中当Z为O，NH或NR时，X为OH，NH2或NHR，而当W为O，NH或NR时，Y为OH，NH2或NHR，并在相转移催化剂的存在下与碱金属碘酸盐反应，如果A不是H，则通过在第二反应混合物中反应中间体以及属于包括A的胺基组的胺的存在下，并在氧气的存在下获得化合物。如果A为H，则不使用第二反应混合物，并且中间体包括化合物。该发明包括制备该组合物的过程以及在天然和合成橡胶中使用该组合物，并与单体，汽油和润滑油一起抑制聚合的用途。
• [EN] 2-THIO-5-AMINO SUBSTITUTED BENZOQUINONES, THEIR MANUFACTURE AND THEIR USE IN RUBBER<br/>[FR] BENZOQUINONES A SUBSTITUTION 2-THIO-5-AMINO, LEUR FABRICATION ET LEUR UTILISATION DANS DU CAOUTCHOUC
  申请人：FLEXSYS AMERICA LP

  公开号：WO2002046149A2

  公开（公告）日：2002-06-13

  The invention comprises a process for preparing a compound having the formula where Z and W are the same or different, and selected from the group consisting of O, NH and NR, where R is H, alkyl, cycloalkyl or aryl, R' is alkyl, cycloalkyl, alkylene, alkyl 3-propionate, aryl or arylene. A is H if either or both of Z and W are not O, but if both Z and W are O, A is (I) or a carbon based heterocyclic component having an amine constituent, or RR''N-, where R'' is the same or different than R and is selected from the same group as R. The process comprises preparing an alkylthio-substituted benzoquinone intermediate by reacting in a first reaction mixture a thiosubstituted aromatic having the formula (II) where X is OH, NH2 or NHR when Z is O, NH or NR, respectively, and where Y is OH, NH2 or NHR when W is O, NH or NR, respectively, with an alkali metal periodate in the presence of a phase transfer catalyst, followed, if A is not H, by reacting the intermediate in a second reaction mixture containing an amine included in the group of amines comprising A, and in the presence of oxygen to obtain the compound. If A is H no second reaction mixture is employed and the intermediate comprises the compound. The invention includes a process for making the composition and the use of the composition in natural and synthetic rubber, and with monomers, gasoline and lubricating oil to inhibit polymerization.
• Oxidative radical coupling of hydroquinones and thiols using chromic acid: one-pot synthesis of quinonyl alkyl/aryl thioethers
  作者：T. P. Adarsh Krishna、Sakthivel Pandaram、Suresh Chinnasamy、Andivelu Ilangovan

  DOI：10.1039/d0ra01519a

  日期：——

  An efficient, simple and practical protocol for one-pot sequential oxidative radical C–H/S–H cross-coupling of thiols with hydroquinones (HQs) and oxidation leading to the formation of quinonyl alkyl/aryl thioethers using H2CrO4 was developed. This cross-coupling of thiyl and aryl radicals offers mono thioethers in good to moderate yield and works well with a wide variety of thiols. Similarly, this

  开发了一种高效、简单且实用的方案，用于硫醇与氢醌 (HQ) 的一锅顺序氧化自由基 C–H/S–H 交叉偶联和氧化，从而使用 H 2 CrO 4形成醌基烷基/芳基硫醚。硫基和芳基的这种交叉偶联以良好至中等的产率提供单硫醚，并且与多种硫醇配合良好。同样，该方法适用于 2-氨基苯硫酚和 HQ 的偶联形成吩噻嗪-3-酮5a–c 。首次使用铬试剂观察到通过硫醚合成形成 C-S 键。对化合物5a–c药代动力学特性的理论研究表明，由于具有药物样特性，化合物5b与阿尔茨海默病 (AD) 相关的 AChE 靶位点强烈结合。
• Reactions of <i>p</i>-Benzoquinone with Sulfur Nucleophiles
  作者：Alan Katritzky、Dmytro Fedoseyenko、Prabhu Mohapatra、Peter Steel

  DOI：10.1055/s-2008-1032186

  日期：2008.3

  The orientations of the reactions of p-benzoquinone with nucleophiles are discussed. The one-pot reaction of p-benzoquinone with alkanethiols gave the 2-, 2,6-, and 2,5-conjugate addition products. Novel 2,6- and 2,5-bis(alkylsulfanyl)-, 2,3,5-tris(alkylsulfanyl)-, and 2,3,5,6-tetrakis(alkylsulfanyl)-p-benzoquinones, and their corresponding hydroquinones, were obtained in good yields through a sequential addition/in situ oxidation protocol for further testing as polymerization inhibitors in rubber and petroleum products. The structures of five 2,5- and 2,6-disubstituted isomers were established by X-ray crystallography.

  讨论了对称对苯醌与亲核试剂反应的取向。对苯醌与烷基硫醇的一锅反应生成了2-、2,6-和2,5-连接加成产物。通过顺序加成/原位氧化法获得了新颖的2,6-和2,5-双(烷基硫基)-、2,3,5-三(烷基硫基)-和2,3,5,6-四(烷基硫基)-对苯醌及其相应的氢醌，收率良好，进一步用于测试作为橡胶和石油产品的聚合抑制剂。通过X射线晶体学确定了五种2,5-和2,6-二取代异构体的结构。