3,5-dimethyl-4-thiocyanatophenol | 6074-30-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 3,5-dimethyl-4-thiocyanatophenol
• 英文别名: 4-Hydroxy-2,6-dimethylphenyl thiocyanate；(4-hydroxy-2,6-dimethylphenyl) thiocyanate
• CAS: 6074-30-2
• 化学式: C₉H₉NOS
• 分子量: 179.243
• InChiKey: QRELYANLFSVTPU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  69.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,5-dimethyl-4-thiocyanatophenol 在 四丁基氟化铵 、 碳酸氢钠 、 间氯过氧苯甲酸 、 三氟乙酸酐 、 烯丙基三甲基硅烷 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 9.75h， 生成 2,6-二甲基-2,5-环己二烯-1,4-二酮
  参考文献：
  名称：

  Novel ipso-Substitution of p-Sulfinylphenols through the Pummerer-Type Reaction:  A Selective and Efficient Synthesis of p-Quinones and Protected p-Dihydroquinones

  摘要：

  The treatment of p-sulfinylphenols 3a-q with trifluoroacetic anhydride caused a Pummerer-type reaction on aromatic rings and concomitant desulfurization to give mixtures of the corresponding p-dihydroquinones 9 and p-quinones 10, which were subsequently oxidized under mild conditions to provide high yields of p-quinones 10. On the other hand, the treatment of p-(phenylsulfinyl)-phenyl ethers 6 with trifluoroacetic anhydride in the presence of styrene caused the direct ipso-substitution of the sulfinyl groups into trifluoroacetoxy groups, giving the protected dihydroquinones 14 in high yields. Both types of reactions were generally completed below room temperature within 1 h and compatible with various functional groups such as the allyl, carbonyl, ester, amide, and silyloxy groups. The preparation of the p-sulfinylphenols 3 and the silyl ethers 6 is also described through p-specific thiocyanation of phenols followed by the Grignard reaction and oxidation.

  DOI：

  10.1021/jo970418o
• 作为产物：
  描述：

  异硫氢酸三甲基硅酯 、 3,5-二甲基苯酚 在 1-氯-1Λ3,2-苯碘酰-3-酮 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以94%的产率得到3,5-dimethyl-4-thiocyanatophenol
  参考文献：
  名称：

  用1-氯-1,2-苯并恶恶酚-3-（1H）-一和（三甲基甲硅烷基）异硫氰酸酯对芳香族和杂芳香族化合物进行硫氰化。

  摘要：

  已使用1-氯-1,2-苯并恶唑3-（1H）-一（1）和（三甲基甲硅烷基）异硫氰酸酯（TMSNCS）的组合研究了芳族化合物的硫氰酸化。与富电子芳族化合物的反应进行得很顺利，以高收率提供了硫氰酸化产物，而缺电子的杂芳族化合物不适合该反应。在这些反应中，区域选择性通常很高。还研究了产物的转化以证明反应的效用。基于NMR实验，我们建议原位生成氯化硫氰作为活性物质。

  DOI：

  10.1248/cpb.c19-00352

文献信息

• Transition-metal-free regioselective thiocyanation of phenols, anilines and heterocycles
  作者：Trimbak B. Mete、Tushar M. Khopade、Ramakrishna G. Bhat

  DOI：10.1016/j.tetlet.2016.12.043

  日期：2017.2

  An expedient direct and regioselective thiocyanation of phenols, anilines and heterocycles is described. Transformation is realized via the direct CH functionalization under transition metal free conditions at ambient temperature in excellent yields. Method proved to be monoselective and variety of functional groups tolerated the reaction conditions. The practicality of the protocol is demonstrated

  描述了酚，苯胺和杂环的方便的直接和区域选择性的硫氰化。通过在无过渡金属条件下于环境温度下直接C H官能化以优异的收率实现转化。方法被证明是单选择性的，并且各种官能团都能耐受反应条件。该协议的实用性在PPARδ激动剂前体的克级合成中得到了很好的证明。
• Compounds that modulate PPAR activity and methods of preparation
  申请人：——

  公开号：US20030207924A1

  公开（公告）日：2003-11-06

  This invention discloses compounds that alter PPAR activity. The invention also discloses pharmaceutically acceptable salts of the compounds, pharmaceutically acceptable compositions comprising the compounds or their salts, and methods of using them as therapeutic agents for treating or preventing hyperlipidemia and hypercholesteremia in a mammal. The present invention also discloses methods for making the disclosed compounds.

  这项发明揭示了能够改变PPAR活性的化合物。该发明还揭示了这些化合物的药用盐、包含这些化合物或其盐的药用组合物，以及将它们用作治疗或预防哺乳动物高脂血症和高胆固醇血症的治疗剂的方法。本发明还揭示了制备所述化合物的方法。
• Straightforward Access to Thiocyanates via Dealkylative Cyanation of Sulfoxides
  作者：Uroš Todorović、Immo Klose、Nuno Maulide

  DOI：10.1021/acs.orglett.1c00460

  日期：2021.4.2

  Thiocyanates, versatile building blocks in organic synthesis, are shown to be easily accessible via an interrupted Pummerer reaction of sulfoxides. This facile dealkylative functionalization proceeds under mild conditions through electrophilic activation of the sulfoxide partner. The resulting thiocyanate itself can serve as a handle for diversification in a straightforward one-pot procedure.

  硫氰酸盐是有机合成中的通用结构单元，可以通过亚砜的间断 Pummerer 反应轻松获得。这种容易的脱烷基官能化在温和条件下通过亚砜伴侣的亲电活化进行。由此产生的硫氰酸盐本身可以作为一个简单的一锅法多样化的处理。
• An Efficient p-Thiocyanation of Phenols and Naphthols Using a Reagent Combination of Phenyliodine Dichloride and Lead(II) Thiocyanate.
  作者：Yasuyuki KITA、Yoshifumi TAKEDA、Takayuki OKUNO、Masahiro EGI、Kiyosei IIO、Ken-ichi KAWAGUCHI、Shuji AKAI

  DOI：10.1248/cpb.45.1887

  日期：——

  A combination of PhICl2 and Pb(SCN)2 is effective for the p-selective thiocyanation of various types of p-unsubstituted phenols and naphthols 1 to give p-thiocyanatophenols and naphthols 3. The reaction proceeded at 0°C to room temperature in good to quantitative yields. Twenty-five examples are given, in which various functional groups, such as chloro, allyl, carbonyl, ester, amide, and primary hydroxyl groups, are shown to be compatible with this reaction.

  PhICl2 和 Pb(SCN)2 的组合可有效地对各种类型的对未取代苯酚和萘酚 1 进行对选择性硫氰酸化，从而得到对硫氰酸苯酚和萘酚 3。反应在 0°C 至室温下进行，产率高至定量。文中给出了 25 个例子，表明氯基、烯丙基、羰基、酯基、酰胺基和伯羟基等各种官能团与该反应相容。
• Regioselective C–H Thiocyanation of Arenes by Iron(III) Chloride Catalysis
  作者：Lachlan J. N. Waddell、Maisie R. Senkans、Andrew Sutherland

  DOI：10.1021/acs.joc.3c00454

  日期：2023.6.2

  preparation of a diverse range of arene building blocks for medicinal chemistry. Here, we report a fast and efficient Lewis acid-catalyzed method for the regioselective thiocyanation of arenes. Iron(III) chloride was found to be an effective Lewis acid for the activation of N-thiocyanatosaccharin and the subsequent thiocyanation of a wide range of activated arenes. The procedure was applicable for

  芳基硫氰酸酯是灵活的合成中间体，可用于制备用于药物化学的各种芳烃结构单元。在这里，我们报告了一种快速有效的路易斯酸催化方法，用于芳烃的区域选择性硫氰化。氯化铁 (III) 被发现是一种有效的路易斯酸，可用于活化N-硫氰酸糖精和随后对各种活化芳烃进行硫氰化。该程序适用于生物活性化合物（如美他沙酮和雌二醇衍生物）的硫氰化，并用作单锅串联铁催化过程的一部分，用于芳烃结构单元的区域选择性双功能化。