tetramethyl 1,4-dithiin-2,3,5,6-tetracarboxylate | 6579-12-0

• 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 1,4-dithiin-2,3,5,6-tetracarboxylate
• 英文别名: 2,3,5,6-tetrakis(methoxycarbonyl)-1,4-dithiin；Tetramethyl 1,4-dithiine-2,3,5,6-tetracarboxylate
• CAS: 6579-12-0
• 化学式: C₁₂H₁₂O₈S₂
• 分子量: 348.354
• InChiKey: GEJALPRNRWAASI-UHFFFAOYSA-N

物化性质

• 熔点：
  126-127 °C
• 沸点：
  418.5±45.0 °C(Predicted)
• 密度：
  1.486±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  22
• 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：
  156
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  disodium cis-1,2-bis(methoxycarbonyl)ethene-1,2-dithiolate 在 碘 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 6.0h， 以39%的产率得到tetramethyl 1,4-dithiin-2,3,5,6-tetracarboxylate
  参考文献：
  名称：

  Synthesis, Structure, and Ring Conversion of 1,2-Dithiete and Related Compounds

  摘要：

  3,4-Bis(methoxycarbonyl)-1,2-dithiete (6), 3,4,7,8-tetrakis(methoxycarbonyl)-1,2,5,6-tetrathiocin (8), and (Z,ZZ,Z)-3,4,7,8, 11,12,15,16-octakis(methoxycarbonyl)-1,2,5,6,9, 10, 13,14-octathiacyclohexadeca-3,7,11,15-tetraene (9) were synthesized by oxidation of titanocene dithiolene complex 4 with sulfuryl chloride, and the crystal structures of 6 and 8 were characterized by X-ray crystallographic analysis which revealed planar and twist geometries, respectively. Tetrathiocin 1, 11, and 12, and 16-membered cyclic compound 3 were also obtained by oxidation of the corresponding dithiolate or dithiolene complex. Dithiete 6 underwent tetramerization selectively to give 16-membered cyclic product 9 even at room temperature. Ring conversion reactions also proceeded among the 4-, 8-, and 16-membered unsaturated cyclic compounds possessing disulfide bonds under various conditions, such as in polar solvent or in the presence of silica gel. The ring-size selectivity of these ring conversion reactions was studied using ab initio molecular orbital calculations.

  DOI：

  10.1021/jo9806714

文献信息

• Synthesis of Symmetrical and Unsymmetrical 1,4-Dithiins by Rhodium-Catalyzed Sulfur Addition Reaction to Alkynes
  作者：Mieko Arisawa、Masahiko Yamaguchi、Takuya Ichikawa、Saori Tanii

  DOI：10.1055/s-0035-1561452

  日期：——

  4-dithiins was developed using sulfur and alkynes. A rhodium complex catalyzes the addition reaction of sulfur with cyclic alkynes giving the corresponding symmetrical 1,4-dithiines under reflux conditions in 2-butanone. Unsymmetrical 1,4-dithiins are synthesized by the reaction of sulfur with dialkyl acetylenedicarboxylates in the presence of cyclic alkynes or vinyl ethers. A convenient synthetic method

  摘要 使用硫和炔烃开发了一种简便的1,4-二硫辛合成方法。铑配合物在2-丁酮中在回流条件下催化硫与环状炔烃的加成反应，得到相应的对称1,4-二硫烷。不对称的1，4-二硫辛是在环炔烃或乙烯基醚存在下，通过硫与乙炔二羧酸二烷基酯的反应合成的。 使用硫和炔烃开发了一种简便的1,4-二硫辛合成方法。铑配合物在2-丁酮中在回流条件下催化硫与环状炔烃的加成反应，得到相应的对称1,4-二硫烷。不对称的1，4-二硫辛是在环炔烃或乙烯基醚存在下，通过硫与乙炔二羧酸二烷基酯的反应合成的。
• 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)。
• Zborovskii, Yu. L.; Smirnov-Zamkov, I. V.; Staninets, V. I., Journal of Organic Chemistry USSR (English Translation), 1984, p. 1617 - 1625
  作者：Zborovskii, Yu. L.、Smirnov-Zamkov, I. V.、Staninets, V. I.

  DOI：——

  日期：——
• Daley, Stephen T. A. K.; Rees, Charles W., Journal of the Chemical Society. Perkin transactions I, 1987, p. 207 - 210
  作者：Daley, Stephen T. A. K.、Rees, Charles W.

  DOI：——

  日期：——
• NAKAYAMA, JUZO;CHOI, KEUN SOO;ISHII, AKIHIKO;HOSHINO, MASAMATSU, BULL. CHEM. SOC. JAP., 63,(1990) N, C. 1026-1031
  作者：NAKAYAMA, JUZO、CHOI, KEUN SOO、ISHII, AKIHIKO、HOSHINO, MASAMATSU

  DOI：——

  日期：——