methyl 3-(dimethylamino)-3-thioxopropanoate | 1354724-51-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代酰胺
• 英文名称: methyl 3-(dimethylamino)-3-thioxopropanoate
• 英文别名: Methyl 3-(dimethylamino)-3-sulfanylidenepropanoate
• CAS: 1354724-51-8
• 化学式: C₆H₁₁NO₂S
• 分子量: 161.225
• InChiKey: MVDUQGAKHZIXBM-UHFFFAOYSA-N

物化性质

• 沸点：
  203.1±42.0 °C(Predicted)
• 密度：
  1.125±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 3-(dimethylamino)-3-thioxopropanoate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 以 乙酸乙酯 为溶剂， 以95%的产率得到methyl 4,5-dicyano-2-(dimethylamino)thiophene-3-carboxylate
  参考文献：
  名称：

  DDQ-Mediated Oxidative Coupling: An Approach to 2,3-Dicyanofuran (Thiophene)

  摘要：

  A facile oxidative coupling of alpha-carbonyl radicals to 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) for the synthesis of 2,3-dicyanofurans and thiophenes starting from readily available beta-diketones, simple ketones, and beta-keto thioamides in up to 95% yield in one step was developed. Mechanistic investigations revealed that a radical process could be involved in this transformation, and a water promoted C-C bond cleavage pathway is proposed for the formation of 2,3-dicyanofurans and thiophenes.

  DOI：

  10.1021/jo4026034
• 作为产物：
  描述：

  methyl N,N-dimethyl-malonamate 在 劳森试剂 作用下， 以 四氢呋喃 为溶剂， 生成 methyl 3-(dimethylamino)-3-thioxopropanoate
  参考文献：
  名称：

  Direct synthesis of polysubstituted 2-aminothiophenes by Cu(ii)-catalyzed addition/oxidative cyclization of alkynoates with thioamides

  摘要：

  开发了一种简便直接的合成方法，通过在空气氛围下铜(II)催化的硫脲与炔酸酯的加成/氧化环化反应，以中等至优异的产率（高达91%）构建结构重要的2-氨基噻吩。

  DOI：

  10.1039/c4ob01534g

文献信息

• Regioselective Metal-Free One-Pot Synthesis of Functionalized 2-Aminothiophene Derivatives
  作者：Xiaoyan Luo、Li-Shi Ge、Xing-Lan An、Jing-Hai Jin、Yu Wang、Pei-Pei Sun、Wei-Ping Deng

  DOI：10.1021/acs.joc.5b00488

  日期：2015.5.1

  A facile metal-free synthesis of 2-aminothiophene derivatives by the reaction of 2-ynals with thioamides in alcohols has been developed. This transformation allows the assembly of 2-aminothienyl ether derivatives via a well-designed aldol condensation/regioselective intramolecular cyclization/conjugate addition cascade reaction and provides a straightforward synthetic protocol for constructing 2,3

  通过2-炔类与硫代酰胺在醇中的反应，已经开发了一种简便的无金属的2-氨基噻吩衍生物的合成方法。这种转化允许通过精心设计的羟醛缩合/区域选择性分子内环化/缀合物加成级联反应组装2-氨基噻吩醚衍生物，并为构建2,3,5-三取代的2-氨基噻吩提供了直接的合成方案。
• Cu(II)-catalyzed one-pot synthesis of fully substituted dihydrothiophenes and thiophenes from thioamides and enynones
  作者：Min Wen、Pei-Pei Sun、Xiaoyan Luo、Wei-Ping Deng

  DOI：10.1016/j.tet.2018.02.035

  日期：2018.8

  developed for the construction of fully substituted dihydrothiophenes, which via a copper-catalyzed Michael addition/intramolecular cyclization/protonation cascade reaction of readily available thioamides with enynones under air atmosphere. This approach provides 2,3-dihydrothiophenes with up to 92% yield in a one-pot process. In addition, several fully substituted thiophenes could also be synthesized

  开发了一种简单直接的合成方法，用于构建完全取代的二氢噻吩，该方法通过铜催化的迈克尔加成反应/分子内环化/质子化在空气气氛下容易实现的乙酰胺与烯酮的级联反应。这种方法在一锅法中可提供高达92％的收率的2,3-二氢噻吩。另外，还可以通过改变硫酰胺的取代基来合成几种完全取代的噻吩。
• Synthesis of Polysubstituted 3-Aminothiophenes from Thioamides and Allenes via Tandem Thio-Michael Addition/Oxidative Annulation and 1,2-Sulfur Migration
  作者：Teng Han、Yu Wang、Hong-Liang Li、Xiaoyan Luo、Wei-Ping Deng

  DOI：10.1021/acs.joc.7b02616

  日期：2018.2.2

  A facile synthetic method for the construction of 3-aminothiophenes from readily available thioamides and alllenes in the presence of a TBAI/TBHP catalyst system was developed. This protocol represents an efficient and straightforward way to access highly functionalized thiophenes in moderate to excellent yields under mild conditions, via a tandem thio-Michael addition, oxidative annulation, and 1

  开发了一种在TBAI / TBHP催化剂体系存在下，由容易获得的硫代酰胺和烯丙基构建3-氨基噻吩的简便合成方法。该协议代表了在串联条件下，通过串联硫代-迈克尔加成反应，氧化环化反应和1,2-硫迁移途径，以中等至极好的收率获得高官能度噻吩的有效而直接的方法。
• Optically Active Thiophenes via an Organocatalytic One-Pot Methodology
  作者：Lars Krogager Ransborg、Łukasz Albrecht、Christian F. Weise、Jesper R. Bak、Karl Anker Jørgensen

  DOI：10.1021/ol203237r

  日期：2012.2.3

  A general methodology for the synthesis of trisubstituted, optically active thiophenes by an organocatalytic one-pot reaction cascade is presented. The target products are synthesized in good yields (up to 92%) and with excellent enantioselectivities (up to 98% ee). Importantly, based on practical and easily available starting materials, the presented methodology can be conducted under mild reaction conditions. To further elucidate the generality, the synthesis of optically active thienoindoles, as well as selenophenes, is also demonstrated.
• DDQ-Mediated Oxidative Coupling: An Approach to 2,3-Dicyanofuran (Thiophene)
  作者：Zheng-Lin Wang、Hong-Liang Li、Li-Shi Ge、Xing-Lan An、Zi-Gang Zhang、Xiaoyan Luo、John S. Fossey、Wei-Ping Deng

  DOI：10.1021/jo4026034

  日期：2014.2.7

  A facile oxidative coupling of alpha-carbonyl radicals to 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) for the synthesis of 2,3-dicyanofurans and thiophenes starting from readily available beta-diketones, simple ketones, and beta-keto thioamides in up to 95% yield in one step was developed. Mechanistic investigations revealed that a radical process could be involved in this transformation, and a water promoted C-C bond cleavage pathway is proposed for the formation of 2,3-dicyanofurans and thiophenes.