3,4-bis(methoxycarbonyl)-1,2-dithiete | 217084-64-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 3,4-bis(methoxycarbonyl)-1,2-dithiete
• 英文别名: bis(methoxycarbonyl)-1,2-dithiete；Dimethyl dithiete-3,4-dicarboxylate
• CAS: 217084-64-5
• 化学式: C₆H₆O₄S₂
• 分子量: 206.243
• InChiKey: VSYCDCJFVBIKGQ-UHFFFAOYSA-N

物化性质

• 熔点：
  83.5-84.0 °C(Solv: chloroform (67-66-3); hexane (110-54-3))
• 沸点：
  220.8±43.0 °C(Predicted)
• 密度：
  1.430±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  109
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,4-bis(methoxycarbonyl)-1,2-dithiete 以 氯仿 为溶剂， 生成 (Z,Z,Z,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
  参考文献：
  名称：

  1,2-二硫醚及相关化合物的合成与反应

  摘要：

  双(甲氧基羰基)-1,2-二硫醚1、环状二聚体2和四聚体3是由二茂钛二硫烯配合物与磺酰氯氧化得到的，1和2的晶体结构由X射线晶体分析确定。在各种条件下，如在非极性溶剂、极性溶剂和硅胶存在下，发现了化合物之间新的环转化反应。

  DOI：

  10.1080/10426509908546506
• 作为产物：
  描述：

  3,4,7,8-tetrakis(methoxycarbonyl)-1,2,5,6-tetrathiocin 以 乙醇 、 氯仿 为溶剂， 反应 2.0h， 以74%的产率得到(Z,Z,Z,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
  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

• Reaction of 1,2-Dithiete with Alkenes and Alkynes:  Experimental and Theoretical Study
  作者：Toshio Shimizu、Hideyuki Murakami、Nobumasa Kamigata

  DOI：10.1021/jo9908086

  日期：1999.11.1

  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.