4-Ethylbis[1,2]dithiolo[3,4-b:4',3'-e][1,4]thiazine-3,5(4H)-dione | 188535-17-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-Ethylbis[1,2]dithiolo[3,4-b:4',3'-e][1,4]thiazine-3,5(4H)-dione
• 英文别名: 8-Ethyl-2,4,5,11,12-pentathia-8-azatricyclo[7.3.0.03,7]dodeca-1(9),3(7)-diene-6,10-dione
• CAS: 188535-17-3
• 化学式: C₈H₅NO₂S₅
• 分子量: 307.463
• InChiKey: OAWCFFKDGCRPDI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 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：
  164
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4-Ethylbis[1,2]dithiolo[3,4-b:4',3'-e][1,4]thiazine-3,5(4H)-dione 在 劳森试剂 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以70%的产率得到4-ethylbis[1,2]dithiolo[3,4-b:4′,3′-e][1,4]thiazin-3,5-dithione
  参考文献：
  名称：

  From Hünig's Base to Bis([1,2]dithiolo)-[1,4]thiazines in One Pot: The Fast Route to Highly Sulfurated Heterocycles

  摘要：

  DOI：

  10.1002/anie.199702811
• 作为产物：
  描述：

  4-ethyl-3-oxobis[1,2]dithiolo[3,4:4',3'-e][1,4]thiazine-5-thione 在 三乙胺 、 氯代肟基乙酸乙酯 作用下， 以 四氢呋喃 为溶剂， 以95%的产率得到4-Ethylbis[1,2]dithiolo[3,4-b:4',3'-e][1,4]thiazine-3,5(4H)-dione
  参考文献：
  名称：

  From Hünig's Base to Bis([1,2]dithiolo)-[1,4]thiazines in One Pot: The Fast Route to Highly Sulfurated Heterocycles

  摘要：

  DOI：

  10.1002/anie.199702811

文献信息

• Conversion of N-alkyldiisopropylamines into N,N-bis(5-chloro-3-oxo[1,2]dithiol-4-yl)amines
  作者：Susana Barriga、Lidia S. Konstantinova、Carlos F. Marcos、Oleg A. Rakitin、Charles W. Rees、Tomás Torroba、Andrew J. P. White、David J. Williams

  DOI：10.1039/a904680a

  日期：——

  Triisopropylamine 1a and S2Cl2, in the presence of DABCO and formic acid, give the bicyclic amine 2a, and its N-dealkylated product 3, rather than the tricyclic bisdithiolothiazine system 7 produced by Hünig’s base 1b. However, when S2Cl2 is in molar excess over DABCO, Hünig’s base and related N-alkyldiisopropylamines 1c–g also give the analogous bicyclic compounds 2b–g together with the tricyclic compounds 7b–g. The N-benzyl compound 2c is debenzylated quantitatively to the secondary amine 3 by sulfuric acid. X-Ray crystallography of N,N-bis(dithiolyl)ethylamine 2b shows the two dithiole rings to be steeply inclined to each other (85°) and the geometry at nitrogen to be slightly pyramidal. The crystal packing is dominated by S· · ·O electrostatic and weak CO· · ·Cl charge-transfer interactions.

  在DABCO和甲酸的存在下，三异丙胺1a与S2Cl2反应生成双环胺2a及其N-去烷基化产物3，而不是由Hünig碱1b产生的三环双二硫氮杂环庚烷体系7。然而，当S2Cl2的摩尔过量于DABCO时，Hünig碱及相关N-烷基二异丙胺1c–g也能生成类似的双环化合物2b–g以及三环化合物7b–g。N-苄基化合物2c可通过硫酸定量去苄基化转化为二级胺3。N,N-双(二硫烷基)乙胺2b的X射线晶体学显示，两个二硫烷环彼此陡峭地倾斜（85°），氮原子周围的几何形状略呈锥形。晶体堆积主要受S··O静电作用和弱的CO··Cl电荷转移相互作用支配。
• Transformations of N-ethylamines into amide derivatives under the action of sulfur monochloride
  作者：L. S. Konstantinova、A. A. Berezin、O. A. Rakitin

  DOI：10.1007/s11172-007-0179-9

  日期：2007.6

  Tertiary N-ethylamines were converted into amide derivatives by reactions with sulfur monochloride and DABCO at 0 °C. Depending on the nature of the substituents in the amine, the reaction can be accompanied by unexpected transformations.

  通过在 0 °C 下与一氯化硫和 DABCO 反应，将叔 N-乙胺转化为酰胺衍生物。根据胺中取代基的性质，该反应可能伴随着意想不到的转变。
• Synthesis of Thiadiazole, Dithietane, and Imine Derivatives of the [1,2]Dithiolo[1,4]thiazine Ring System
  作者：Susana Barriga、Pedro Fuertes、Carlos F. Marcos、Daniel Miguel、Oleg A. Rakitin、Charles W. Rees、Tomás Torroba

  DOI：10.1021/jo010368u

  日期：2001.8.1

  heterocyclics by cycloaddition reactions to the thioketo group of readily available tricyclic 1,2-dithiole-3-thiones. Thus treatment of bis[1,2]dithiolo[1,4]thiazine ketothione 1 with diaryl nitrile imines generated from hydrazonoyl chlorides 2a-g gave [1,3,4]thiadiazolylidenyl[1,2]dithiolo[1,4]thiazines 4a-g in high yield. Compounds 4a-f, bearing the same substituents in both aryl groups, were stable

  我们报告通过环加成反应容易获得的三环1,2-二硫代3-硫酮的硫酮基合成了一些新的多硫-氮杂环。因此用由酰氯酰氯2a-g产生的二芳基腈亚胺处理双[1,2]二硫代[1,4]噻嗪酮噻酮1，得到[1,3,4]噻二唑基[1,2]二硫代[1,4]噻嗪4a-g高产。在两个芳基上均带有相同取代基的化合物4a-f稳定，但在碳上具有对硝基苯基的类似4g，h给出的双[1,2]二硫代[1,4]噻嗪二酮9色谱过程中环还原和水解。用乙氧基羰基叠氮化物11处理1，双[1,2]二硫代吡咯酮酮13和二硫酮12分别得到亚胺12和15和双亚胺16，通过保留1，2-二硫环的初始环加合物的另一种断裂方式。1与TosMIC的反应得到亚氨基-1,3-二硫杂环丁烷17。
• One-pot synthesis and chemistry of bis[1,2]dithiolopyrroles
  作者：Carlos F. Marcos、Cecilia Polo、Oleg A. Rakitin、Charles W. Rees、Tomás Torroba

  DOI：10.1039/a701340j

  日期：——

  Hünig’s base and S 2 Cl 2 give the fused 1,4-thiazines 1 and (in the presence of formic acid) 2 and 3, each of which readily extrudes sulfur, selectively and quantitatively, to give the fused pyrroles 4, 5 and 6 respectively; at higher temperatures Hünig’s base and S 2 Cl 2 can be converted into the pyrroles in one pot, and the cycloadducts 8 and 10 are thus readily available in two steps.

  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。
• 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%）。