tetramethyl 2,3,4,5-thiophenetetracarboxylate | 6579-15-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tetramethyl 2,3,4,5-thiophenetetracarboxylate
• 英文别名: Thiophentetracarbonsaeure-tetramethylester；tetramethyl thiophenetetracarboxylate；2,3,4,5-tetra(methoxycarbonyl)thiophene；Tetramethylthiophentetracarboxylat；tetramethyl thiophene-2,3,4,5-tetracarboxylate
• CAS: 6579-15-3
• 化学式: C₁₂H₁₂O₈S
• 分子量: 316.288
• InChiKey: GUXHNAHZCAOGDO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  133
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  tetramethyl 2,3,4,5-thiophenetetracarboxylate 生成 噻吩-2,3,4,5-四羧酸
  参考文献：
  名称：

  Michael, Chemische Berichte, 1895, vol. 28, p. 1632

  摘要：

  DOI：
• 作为产物：
  描述：

  3,4-bis(methoxycarbonyl)-1,2-dithiete 以 对二甲苯 为溶剂， 反应 8.0h， 以31%的产率得到tetramethyl 2,3,4,5-thiophenetetracarboxylate
  参考文献：
  名称：

  Reaction of 1,2-Dithiete with Alkenes and Alkynes:  Experimental and Theoretical Study

  摘要：

  Reactions of 3,4-bis(methoxycarbonyl)-1,2-dithiete (1) with various alkenes or alkynes formed 2,3-dihydro-1,4-dithiins or thiophenes, respectively. The reactions with alkenes were stereospecific, which indicates the concerted reaction between 1,2-bis(methoxycarbonyl)ethane-1,2-dithione (13), the valence isomer of the 1,2-dithiete, and the dienophiles. Theoretical study confirmed the reactions of 13 with alkenes and alkynes are of reverse electron demand hetero Diels-Alder type. The MO calculations showed the 1,2-dithiete 1 was 5.8 kcal mol(-1) more stable than the corresponding ethane-1,2-dithione 13, and the tautomerization energy between the 1,2-dithiete and the ethane-1,2-dithione was also calculated to be 28.5 kcal mol(-1)from the 1,2-dithiete, which suggests the tautomerization from 1,2-dithiete 1 to ethane-1,2-dithione 13 is possible at least at high temperature. Reaction of 3,4,7,8-tetrakis(methoxycarbonyl)-1,2,5, (2) or (Z,Z,Z,Z)-3,4,7,8,1 1,12,15,16-octakis-(methoxycarbonyl)-1,2,5,6,9,10,13,14-octathiacyclohexadeca-3,7,11,12-tetraene (3) with ethyl vinyl ether also formed the 2,3-dihydro-1,4-dithiin derivative, which is the same compound obtained by the reaction of 1,2-dithiete 1 with the ether. 1,2,5,6-Tetrathiocin 2 and 16-membered cyclic compound 3 also reacted with diphenylacetylene to give the thiophene derivative.

  DOI：

  10.1021/jo9908086

文献信息

• The conductive sulfur/carbon mixture cathode. An efficient synthesis of thiophenes and related compounds from acetylenes
  作者：Georges Le Guillanton、Quang Tho Do、Jacques Simonet

  DOI：10.1016/s0040-4039(00)84502-5

  日期：——

  The electroreduction of Michael acceptors such as acetylenic derivatives at a compact sulfur- carbon electrode in aprotic media affords thioorganic compounds, mainly thiophenes, in fairly high yields. Their formation is discussed as a function of the electronic effect of the substituents on the acetylenic triple bond.

  在质子惰性介质中的紧凑型硫碳电极上，迈克尔基受体（例如炔属衍生物）的电还原可提供相当高的收率的硫代有机化合物（主要是噻吩）。根据炔基三键上取代基的电子效应来讨论它们的形成。
• Synthesis of Polysubstituted Thiophenes<i>via</i>Base-Induced [2+2+1] Cycloaddition Reaction of Alkynes and Elemental Sulfur
  作者：Weibing Liu、Cui Chen、Hailing Liu

  DOI：10.1002/adsc.201500422

  日期：2015.12.14

  A simple approach to polysubstituted thiophene derivatives is demonstrated. The synthesis is highlighted by the direct [2+2+1] cycloaddition reaction to construct carbon-sulfur and carbon-carbon bonds, without adding oxidizing, reducing and noble metal agents. All tested substrates provided their corresponding thiophene products in high isolated yields under the optimized conditions.

  证明了一种简单的多取代噻吩衍生物的方法。直接的[2 + 2 + 1]环加成反应可构建碳-硫和碳-碳键，而无需添加氧化，还原和贵金属试剂，从而突出了合成过程。在优化的条件下，所有测试的底物均以高分离产率提供了其相应的噻吩产物。
• An Efficient Synthesis of Tetraalkyl 2,3,4,5-Thiophenetetracarboxylate Derivatives
  作者：Abdolali Alizadeh、Reza Hosseinpour

  DOI：10.1055/s-0029-1216808

  日期：2009.6

  A facile and direct synthetic entry to tetraalkyl 2,3,4,5-thiophenetetracarboxylate derivatives is described. This involves the reaction of dialkyl acetylenedicarboxylates with elemental sulfur in the presence of triethyl phosphite or an N-heteroaromatic compound such as isoquinoline, 1-methyl-1H-imidazole, or pyridine as catalyst.

  本文介绍了一种简便直接的 2,3,4,5-噻吩四羧酸四烷基衍生物合成方法。这涉及到乙炔二羧酸二烷基酯与元素硫在亚磷酸三乙酯或 N-杂芳香族化合物（如异喹啉、1-甲基-1H-咪唑或吡啶）作为催化剂存在下的反应。
• Rhodium-Catalyzed Isomerization and Alkyne Exchange Reactions of 1,4-Dithiins via the 1,2-Ethenedithiolato Rhodium Complex
  作者：Mieko Arisawa、Kyosuke Sawahata、Takuya Ichikawa、Masahiko Yamaguchi

  DOI：10.1021/acs.organomet.8b00498

  日期：2018.9.24

  Rhodium-catalyzed isomerization and alkyne exchange reactions of 1,4-dithiines occurred by cleavage of two C–S bonds. The 2,5- and 2,6-disubstituted 1,4-dithiins underwent isomerization reactions in toluene at 110 °C, providing equilibrium mixtures of isomers. At 150 °C, the reaction of 1,4-dithiins and dimethyl acetylenedicarboxylate gave unsymmetric 2,3-di(methoxycarbonyl)-1,4-dithiins and 2,3-d

  铑催化的1，4-二乙酮的异构化和炔烃交换反应是通过两个C-S键的断裂而发生的。2，5-和2，6-二取代的1，4-二硫辛在甲苯中于110°C进行异构化反应，提供了异构体的平衡混合物。在150°C下，1,4-二硫辛和乙炔二羧酸二甲酯反应生成不对称的2,3-二（甲氧羰基）-1,4-二硫辛和2,3-二（甲氧羰基）噻吩，后者是由1,4-二硫精脱硫。炔烃和1，2-二硫杂环丁烷的相关反应得到2，3-二（甲氧基羰基）噻吩。这些反应被认为涉及1，2-乙二硫醇基铑中间体。
• The First Synthesis and Properties of 2,3-Di-<i>t</i>-butylthiophene. Reaction of 3,4-Di-<i>t</i>-butyl-1,2-dithiete with Dimethyl Acetylenedicarboxylate
  作者：Juzo Nakayama、Keun Soo Choi、Akihiko Ishii、Masamatsu Hoshino

  DOI：10.1246/bcsj.63.1026

  日期：1990.4

  Heating 3,4-di-t-butyl-1,2-dithiete (5) with dimethyl acetylenedicarboxylate (5 equiv) in refluxing o-dichlorobenzene affords dimethyl 2,5-di-t-butyl-3,4-thiophenedicarboxylate (6) (44%), dimethyl 2,3-di-t-butyl-4,5-thiophenedicarboxylate (7) (5%), tetramethyl 1,4-dithiin-2,3,5,6-tetracarboxylate (8) (4%), and tetramethyl 2,3,4,5-thiophenetetracarboxylate (9) (43%). Mechanism of the formation of these

  在回流的邻二氯苯中加热 3,4-二叔丁基-1,2-二硫醚 (5) 和乙炔二甲酸二甲酯 (5 当量)，得到 2,5-二叔丁基-3,4-噻吩二甲酸二甲酯 (6 ) (44%), 2,3-二叔丁基-4,5-噻吩二甲酸二甲酯 (7) (5%), 1,4-二噻英-2,3,5,6-四甲酸四甲酯 (8) ( 4%) 和 2,3,4,5-噻吩四羧酸四甲酯 (9) (43%)。讨论了这些产物的形成机制。用 1-丙硫醇锂处理受阻酯 7 以 59% 的产率得到 2,3-二叔丁基-4,5-噻吩二甲酸 (13)，它可以通过用铜粉处理脱羧得到 2,3 -二叔丁基噻吩 (4)，产率为 88%。在用氯化铝处理后，噻吩 4 重排为 2,4-二叔丁基噻吩 (1)。用 m-CPBA 氧化得到相应的砜 (23)。