4-Ethyl-3H-bis[1,2]dithiolo[4,3-b:3,4-d]pyrrole-3,5-dione | 191615-60-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 4-Ethyl-3H-bis[1,2]dithiolo[4,3-b:3,4-d]pyrrole-3,5-dione
• 英文别名: 7-Ethyl-3,4,10,11-tetrathia-7-azatricyclo[6.3.0.02,6]undeca-1(8),2(6)-diene-5,9-dione
• CAS: 191615-60-8
• 化学式: C₈H₅NO₂S₄
• 分子量: 275.397
• InChiKey: JTBDBOZERRBZAY-UHFFFAOYSA-N

物化性质

• 熔点：
  199-200 °C
• 沸点：
  544.0±60.0 °C(Predicted)
• 密度：
  1.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  140
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-Ethyl-3H-bis[1,2]dithiolo[4,3-b:3,4-d]pyrrole-3,5-dione 在 tetraphosphorus decasulfide 作用下， 以 xylene 为溶剂， 反应 1.0h， 生成 4-ethyl-3H-bis[1,2]dithiolo[4,3-b:3',4'-d]pyrrole-3,5(4H)-dithione
  参考文献：
  名称：

  One-pot synthesis and chemistry of bis[1,2]dithiolopyrroles

  摘要：

  Hünig 的底座和 S 2 氯 2 给融合的 1,4-噻嗪1和（在甲酸存在下）2和3，各自 它很容易选择性地和定量地挤出硫，从而得到 分别为稠合吡咯4、5和6；在较高温度下 Hünig 的底座和 S 2 氯 2 可以转换 一锅中转化为吡咯，环加合物 8 和 10 如下 只需两步即可轻松获得。

  DOI：

  10.1039/a701340j
• 作为产物：
  描述：

  4-ethyl-5-thioxo-3H,5H-bis[1,2]dithiolo[3,4-d][4,3-b]pyrrol-3-one 在 carbethoxyformonitrile oxide 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 生成 4-Ethyl-3H-bis[1,2]dithiolo[4,3-b:3,4-d]pyrrole-3,5-dione
  参考文献：
  名称：

  One-pot synthesis and chemistry of bis[1,2]dithiolopyrroles

  摘要：

  Hünig 的底座和 S 2 氯 2 给融合的 1,4-噻嗪1和（在甲酸存在下）2和3，各自 它很容易选择性地和定量地挤出硫，从而得到 分别为稠合吡咯4、5和6；在较高温度下 Hünig 的底座和 S 2 氯 2 可以转换 一锅中转化为吡咯，环加合物 8 和 10 如下 只需两步即可轻松获得。

  DOI：

  10.1039/a701340j

文献信息

• Synthesis of N-unsubstituted bis[1,2]dithiolo[1,4]thiazines and bis[1,2]dithiolopyrroles
  作者：Lidia S. Konstantinova、Natalia V. Obruchnikova、Oleg A. Rakitin、Charles W. Rees、Tomás Torroba

  DOI：10.1039/b005068g

  日期：——

  The parent bis[1,2]dithiolo[1,4]thiazine-3,5-dione 8, -3,5-dithione 11, the unsymmetrical 3-oxo-5-thione 10 and the bis[1,2]dithiolopyrrole-3,5-dione 9 are synthesised by acid catalysed cleavage of their various N-benzyl, ethyl, ethoxycarbonylethyl and propanoic acid derivatives. These N-alkyl compounds are prepared in the usual way from the appropriate N-alkyldiisopropylamine and S2Cl2. N-Benzyl derivatives 2 and 5 of the thiazine and pyrrole diones give 8 (100%) and 9 (58%) respectively with conc. H2SO4 in dilute DCM solution, and the N-ethyl thiazine derivatives of the dione 12 and the keto-thione 13 give 8 (89%) and 10 (75%) respectively in conc. H2SO4 at 120 °C. Ethyl 3-(diisopropylamino)propanoate 16 with S2Cl2 gives the three thiazines 17 (30%), 18 (15%) and 19 (13%), and 17 and 19 are converted into the pyrroles 20 (95%) and 21 (90%) respectively by thermal extrusion of sulfur in refluxing xylene. All five ethyl esters, 17–21, are hydrolysed with aqueous acid to 22–26 respectively in 92–100% yield, and the N-propanoic acids 22–25 with hot conc. hydrochloric or hot 80–90% sulfuric acid are dealkylated to the corresponding parent products 8–11. It is also shown that the hydrolysis and dealkylation steps 17→22→8 can be combined in one operation (75%).

  母体双[1,2]二硫并[1,4]噻嗪-3,5-二酮8、-3,5-二硫酮11、不对称3-氧代-5-硫酮10和双[1,2]二硫代吡咯-3,5-二酮 9 通过酸催化裂解各种 N-苄基、乙基、乙氧基羰基乙基和丙酸衍生物来合成。这些N-烷基化合物以常规方式由合适的N-烷基二异丙胺和S 2 Cl 2 制备。噻嗪和吡咯二酮的N-苄基衍生物2和5分别得到浓的8(100％)和9(58％)。稀DCM溶液中的H 2 SO 4 以及二酮12和酮硫酮13的N-乙基噻嗪衍生物分别得到浓的8(89％)和10(75％)。 H2SO4，120°C。 3-(二异丙氨基)丙酸乙酯 16 与 S2Cl2 反应生成三种噻嗪 17 (30%)、18 (15%) 和 19 (13%)，17 和 19 转化为吡咯 20 (95%) 和 21 (90 %)分别通过在回流二甲苯中热挤出硫来实现。所有五种乙酯（17-21）均用酸水溶液分别水解为 22-26，产率 92-100%，而 N-丙酸 22-25 则用热浓溶液水解为 22-25。盐酸或热80-90%硫酸脱烷基化得到相应的母体产物8-11。还表明，水解和脱烷基化步骤17→22→8可以合并在一次操作中（75%）。
• Selective Syntheses of Bis[1,2]dithiolo[1,4]thiazines and Bis[1,2]dithiolopyrroles from Hünig's Base
  作者：Charles W. Rees、Andrew J. P. White、David J. Williams、Oleg A. Rakitin、Carlos F. Marcos、Cecilia Polo、Tomás Torroba

  DOI：10.1021/jo971864e

  日期：1998.4.1

  The reaction of N,N-diisopropylethylamine (Hunig's base) and disulfur dichloride in 1,2-dichloroethane, in the presence of DABCO, gives 4-ethylbis[1,2]dithiolo[5,4-b][4',5'-e][1,4]thiazinine-3,5-dithione (1), or, by addition of oxygen donors, the 3-oxo-5-thione 2 or 3,5-dione 3 derivatives are selectively obtained. When the first reaction is performed in boiling chlorobenzene, 4-ethylbis[1,2]dithiolo[4,5-b][5',4'-d]pyrrole-3,5-dithione (4) is obtained by sulfur extrusion from 1, and in the presence of oxygen donors, the 3-oxo-5-thione 5 or 3,5-dione 6 derivatives are selectively obtained. Some interconversions of compounds 1-6 are described, and a coherent set of reaction pathways for the formation of all six products is proposed. X-ray diffraction shows that the new bis-dithiolothiazine ring system of 1-3 is folded out-of planarity about the thiazine N-S vector, with the N-ethyl group folded back over the thiazine ring in a scorpion-like conformation. The new bis-dithiolopyrrole ring system of 4-6 is planar and extensively delocalized.