methyl 3-hydroxy-3-(p-methylphenyl)prop-2-enedithioate | 37510-36-4

• 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: methyl 3-hydroxy-3-(p-methylphenyl)prop-2-enedithioate
• 英文别名: (Z)-Methyl 3-hydroxy-3-(p-tolyl)prop-2-enedithioate；methyl 3-hydroxy-3-(4-methylphenyl)prop-2-enedithioate
• CAS: 37510-36-4
• 化学式: C₁₁H₁₂OS₂
• 分子量: 224.348
• InChiKey: VNMOFLGRAVMQKM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  77.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 3-hydroxy-3-(p-methylphenyl)prop-2-enedithioate 在 N-氯代丁二酰亚胺 作用下， 以 二甲基亚砜 为溶剂， 反应 0.17h， 以92%的产率得到dimethyl 2,3-bis(4-methylbenzoyl)butanebis(dithioate)
  参考文献：
  名称：

  室温下α-烯丙基二硫酯的无金属试剂依赖性SS和CC均偶联：通过化学选择性Paal-Knorr方法直接获得完全取代的对称噻吩

  摘要：

  AbstractAn unprecedented metal‐free oxidative homodimerization of α‐enolic dithioesters has been achieved for the first time at room temperature within 5–10 min. Molecular iodine promotes the SS coupling leading to S,S′‐bis(dithioacetals), while N‐chlorosuccinimide facilitates CC coupling to give α,α′‐bis(β‐oxo dithioesters) in good to excellent yields. Furthermore, the newly generated α,α′‐bis(β‐oxo dithioesters) have been directly employed in the synthesis of fully substituted thiophenes with a unique symmetrical substitution pattern in a one‐pot, two‐step reaction sequence.magnified image

  DOI：

  10.1002/adsc.201400828
• 作为产物：
  描述：

  三硫代碳酸二甲酯 、 对甲基苯乙酮 在 sodium hydride 作用下， 以 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 3-hydroxy-3-(p-methylphenyl)prop-2-enedithioate
  参考文献：
  名称：

  Et 3 N介导的α-氧代乙烯酮二硫缩醛合成多取代噻吩

  摘要：

  在这封信中，通过Et 3 N介导的α-氧代S-甲基-S-炔丙基烯酮的Et 3 N介导的（克莱森）重排反应，获得了制备多取代噻吩衍生物的有效合成路线，该反应是通过将β-氧代二硫代酯与炔丙基溴化物，然后进行区域选择性分子内环化。

  DOI：

  10.1016/j.tetlet.2015.09.089

文献信息

• An expedient route to highly functionalized 2H-chromene-2-thiones via ring annulation of β-oxodithioesters catalyzed by InCl3 under solvent-free conditions
  作者：Rajiv Kumar Verma、Girijesh K. Verma、Keshav Raghuvanshi、Maya Shankar Singh

  DOI：10.1016/j.tet.2010.11.055

  日期：2011.1

  A convenient and one-pot synthesis of 3-aroyl/heteroaroyl-2H-chromene-2-thiones and benzo[f]2H-chromene-2-thiones has been developed by the condensation of β-oxodithioesters and salicylaldehydes/α-hydroxynaphthaldehydes in the presence of indium trichloride under solvent-free conditions. The reaction is operationally facile, readily scalable, and offers rapid entry into differentially substituted chromene-2-thione

  通过β-氧代二硫代酯与水杨醛/α-的缩合反应，开发出了一种方便的一锅合成3-芳酰基/杂芳酰基-2 H-亚甲基-2-硫酮和苯并[ f ] 2 H-亚甲基-2-硫酮的方法。在无溶剂条件下在三氯化铟存在下生成羟基萘醛。该反应操作简便，易于扩展，可快速进入差异取代的亚甲基-2-硫酮骨架。
• Site‐Specific S‐Allylation of α‐Enolic Dithioesters with Morita‐Baylis‐Hillman Acetates at Room Temperature: Precursor for Thiopyrans
  作者：Sonam Soni、Suvajit Koley、Monish A. Ansari、Maya Shankar Singh

  DOI：10.1002/adsc.201900580

  日期：2019.9.3

  An efficient one‐pot allylic alkylation of α‐enolic dithioesters (DTEs) with Morita‐Baylis‐Hillman (MBH) acetates has been devised in ethanol at room temperature. The reaction being site‐selective provided S‐allylated product exclusively with trace amount of C‐allylated one. Remarkably, some of the S‐allylated product undergoes [3,3]‐sigmatropic rearrangement to C‐allylated one under ethanol reflux

  室温下在乙醇中设计了一种有效的一锅法烯醇二硫代酯（DTE）与Morita-Baylis-Hillman（MBH）乙酸酯的烯丙基烷基化反应。现场选择性反应只为S-烯丙基化产物提供痕量的C-烯丙基化产物。值得注意的是，一些S-烯丙基化的产物在乙醇回流下经历了[3,3]-σ重排，变成C-烯丙基化的产物。该方案的典型特征是分离出S-烯丙基化的α-氧杂环丁烯二硫缩醛（一种三取代的烯烃），该化合物已被进一步用于合成硫吡喃。
• Synthesis of 1,3,4-Thiadiazoles and 1,4,2-Oxathiazoles from α-Enolic Dithioesters and Active 1,3-Dipoles
  作者：Bin Cheng、Hui Li、Jianguo Sun、Xinping Zhang、Yixuan He、Haiyan Sun、Wei Xu、Taimin Wang、Hongbin Zhai

  DOI：10.1021/acs.joc.1c00156

  日期：2021.4.2

  synthesis of two kinds of five-membered organosulfur heterocycles (i.e., 1,4,2-oxathiazoles and 1,3,4-thiadiazoles) from α-enolic dithioesters with active 1,3-dipoles (nitrile oxides and nitrilimines) generated in situ was achieved under mild reaction conditions. This transformation further expands the synthetic application of α-enolic dithioesters as the sulfur-containing building blocks.

  由具有活性的1,3-偶极（腈氧化物和腈）的α-烯醇二硫代酯合成两种五元有机硫杂环（即1,4,2-氧杂噻唑和1,3,4-噻二唑）。原位反应是在温和的反应条件下完成的。这种转变进一步扩大了α-烯醇二硫酯作为含硫结构单元的合成应用。
• Indium(0)-Mediated C sp 3-S/O Cross-Coupling Approach Towards the Regioselective Alkylation of α-Enolic Esters/Dithioesters: A Mechanistic Insight
  作者：Sushobhan Chowdhury、Tanmoy Chanda、Ashutosh Gupta、Suvajit Koley、B. Janaki Ramulu、Raymond C. F. Jones、Maya Shankar Singh

  DOI：10.1002/ejoc.201301788

  日期：2014.5

  We have reported an indium(0)-mediated C sp 3–S/O cross-coupling approach that leads to the highly regioselective alkylation of α-enolic acetate/dithioacetate systems. This hetero cross-coupling reaction does not require additional co-catalyst or promoter, and the in situ generated organoindium species promotes the reaction by acting as the coupling partner of the α-enolic acetate/dithioacetate substrates

  我们已经报道了一种铟（0）介导的 C sp 3-S/O 交叉偶联方法，该方法导致 α-烯醇乙酸酯/二硫代乙酸酯系统的高度区域选择性烷基化。这种杂交叉偶联反应不需要额外的助催化剂或促进剂，原位生成的有机铟物质通过充当 α-烯醇乙酸酯/二硫代乙酸酯底物的偶联伙伴来促进反应。C-、S- 或 O-烷基化的出色选择性完全取决于 α-烯醇乙酸酯/二硫代乙酸酯体系的亲核行为。这些结果得到了底物和产物的相对电子能量的 DFT 计算以及相应转换的激活势垒的进一步支持。
• Acid-Controlled Chemodivergent Synthesis of Three Differently Substituted Quinolines<i>via</i>Site Selective Coupling of<i>ortho</i>- Aminoaryl Ketones with α-Enolic Dithioesters
  作者：Suvajit Koley、Tanmoy Chanda、B. Janaki Ramulu、Sushobhan Chowdhury、Maya Shankar Singh

  DOI：10.1002/adsc.201500962

  日期：2016.4.14

  straightforward approach for the chemodivergent synthesis of quinolines is described through site‐selective coupling of ortho‐aminoaryl ketones with α‐enolic dithioesters (DTEs) under solvent‐free conditions. The operationally and user‐simple one‐pot methodology is based on the trifunctional nature of DTEs. Both the carbonyl and the thiocarbonyl moiety in α‐enolic dithioesters were employed for the efficient

  通过在无溶剂条件下将邻氨基芳基酮与α-烯丙基二硫代酯（DTE）进行位点选择性偶联，描述了一种喹啉化学发散合成的简单方法。操作简便，用户简单的一站式方法基于DTE的三功能性质。仅通过改变易于处理的酸催化剂，即可将α-烯丙基二硫代酸酯中的羰基和硫代羰基部分用于以化学选择性方式高效构建三种不同取代的喹啉。