4-(2-chloroethyl)bis[1,2]dithiolo[3,4-b:4',3'-e][1,4]thiazine-3,5-dione | 204758-33-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-(2-chloroethyl)bis[1,2]dithiolo[3,4-b:4',3'-e][1,4]thiazine-3,5-dione
• 英文别名: 8-(2-Chloroethyl)-2,4,5,11,12-pentathia-8-azatricyclo[7.3.0.03,7]dodeca-1(9),3(7)-diene-6,10-dione
• CAS: 204758-33-8
• 化学式: C₈H₄ClNO₂S₅
• 分子量: 341.908
• InChiKey: PEIGOSLZBJMISX-UHFFFAOYSA-N

物化性质

• 熔点：
  175-177 °C
• 沸点：
  468.426±55.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.973±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  17
• 可旋转键数：
  2
• 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-(2-chloroethyl)bis[1,2]dithiolo[3,4-b:4',3'-e][1,4]thiazine-3,5-dione 以 氯苯 为溶剂， 反应 168.0h， 以99%的产率得到4-(2-chloroethyl)bis[1,2]dithiolo[4,3-b:3',4'-d]pyrrole-3,5-dione
  参考文献：
  名称：

  Synthesis of Bis[1,2]dithiolo[1,4]thiazines and a [1,2]Dithiolo[1,4]thiazine from Tertiary Diisopropylamines

  摘要：

  The reaction of N-(2-chloroethyl)diisopropylamine 1a with S2Cl2 allows the selective one-pot preparation of the tricyclic 4-(2-chloroethyl) bisdithiolothiazines 2-4 or, by addition of phosphorus pentasulfide at a rate stage in the reaction, of the dithiolothiazine 5. The chloroethyl derivative 2 is also obtained from (2-diisopropylamino)ethanethiol 1b, or its disulfide 1c, with S2Cl2, in a rare conversion of a thiol or disulfide into the corresponding chloro compound. Compounds 2 and 5 are also obtained from N-(2-hydroxyethyl)diisopropylamine 1d, though in much lower yields. The reaction of N-(2-phenylthioethyl) (1e) or N-(2-phthalimidoethyl)diisopropylamines 1f,g affords bisdithiolothiazines 7, 8, 9, and 11 and the dithiolopyrrole 10, A coherent set of reaction pathways for the formation of these products is proposed. X-ray crystallography shows that the bisdithiolothiazine ring system of 2 is folded out of planarity about the thiazine N-S vector, with the N-chloroethyl group folded back over the thiazine ring with the chlorine atom lying above the thiazine sulfur atom; the dithiolothiazine ring system of 5 has the thiazine ring in a "sofa" conformation.

  DOI：

  10.1021/jo9902345
• 作为产物：
  描述：

  N,N-二异丙基乙醇胺 在 三乙烯二胺 、 二氯化二硫 、 甲酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 1.0h， 以13%的产率得到4-(2-chloroethyl)bis[1,2]dithiolo[3,4-b:4',3'-e][1,4]thiazine-3,5-dione
  参考文献：
  名称：

  Synthesis of Bis[1,2]dithiolo[1,4]thiazines and a [1,2]Dithiolo[1,4]thiazine from Tertiary Diisopropylamines

  摘要：

  The reaction of N-(2-chloroethyl)diisopropylamine 1a with S2Cl2 allows the selective one-pot preparation of the tricyclic 4-(2-chloroethyl) bisdithiolothiazines 2-4 or, by addition of phosphorus pentasulfide at a rate stage in the reaction, of the dithiolothiazine 5. The chloroethyl derivative 2 is also obtained from (2-diisopropylamino)ethanethiol 1b, or its disulfide 1c, with S2Cl2, in a rare conversion of a thiol or disulfide into the corresponding chloro compound. Compounds 2 and 5 are also obtained from N-(2-hydroxyethyl)diisopropylamine 1d, though in much lower yields. The reaction of N-(2-phenylthioethyl) (1e) or N-(2-phthalimidoethyl)diisopropylamines 1f,g affords bisdithiolothiazines 7, 8, 9, and 11 and the dithiolopyrrole 10, A coherent set of reaction pathways for the formation of these products is proposed. X-ray crystallography shows that the bisdithiolothiazine ring system of 2 is folded out of planarity about the thiazine N-S vector, with the N-chloroethyl group folded back over the thiazine ring with the chlorine atom lying above the thiazine sulfur atom; the dithiolothiazine ring system of 5 has the thiazine ring in a "sofa" conformation.

  DOI：

  10.1021/jo9902345

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。
• Tertiary amine–S2Cl2 chemistry: interception of reaction intermediates
  作者：Carlos F. Marcos、Tomás Torroba、Oleg A. Rakitin、Ljudmila I. Souvorova、Charles W. Rees、Andrew J. P. White、David J. Williams

  DOI：10.1039/a708396c

  日期：——

  The reaction of N-(2-chloroethyl)diisopropylamine 1a with S2Cl2 allows the selective one-pot preparation of the tricyclic 4-(2-chloroethyl)bisdithiolothiazines 8 and 9 or, by addition of phosphorus pentasulfide at a late stage of the reaction, of the dithiolothiazine 6b characterised by X-ray crystallography; the chloroethyl derivative 8 is also obtained from (2-diisopropylamino)ethanethiol 1b and its disulfide 1c and S2Cl2, in a rare conversion of a thiol or disulfide into the corresponding chloro compound.

  通过 N-(2-氯乙基)二异丙基胺 1a 与 S2Cl2 的反应，可以选择性地一次性制备出三环 4-(2-氯乙基)双硫代噻嗪 8 和 9，或者在反应后期加入五硫化二磷，制备出 X 射线晶体学表征的二硫代噻嗪 6b；从（2-二异丙基氨基）乙硫醇 1b 及其二硫化物 1c 和 S2Cl2 中也可以得到氯乙基衍生物 8，这是一种罕见的将硫醇或二硫化物转化为相应的氯化合物的方法。
• Selective synthesis of bis[1,2]dithiolo[1,4]thiazines from 4-isopropylamino-5-chloro-1,2-dithiole-3-ones
  作者：Lidia S. Konstantinova、Andrej A. Berezin、Kirill A. Lysov、Oleg A. Rakitin

  DOI：10.1016/j.tetlet.2007.06.071

  日期：2007.8

  Reaction of 4-isopi-opylamiiio-5-chloro-1,2-dithiole-3-oiies 3 and S2Cl2 in acetonitrile gave selectively 3-oxo-bis[1,2]dithiolo[1,4]tliiazine-5-tiliones I by the addition of triethylamine and bis[1,2]dithiolo[1,4]thiazine-3,5-diones 5 under the action of formic acid. 3,5-Diones 5 were also obtained by intramolecular cyclization of N,N-bis(5-chloro-3-oxo[1,2]dithiol-4-yl)amines 6 with S,Cl, in the presence of Et3N. (c) 2007 Elsevier Ltd. All rights reserved.
• Synthesis of Bis[1,2]dithiolo[1,4]thiazines and a [1,2]Dithiolo[1,4]thiazine from Tertiary Diisopropylamines
  作者：Charles W. Rees、Andrew J. P. White、David J. Williams、Oleg A. Rakitin、Lidia S. Konstantinova、Carlos F. Marcos、Tomás Torroba

  DOI：10.1021/jo9902345

  日期：1999.7.1

  The reaction of N-(2-chloroethyl)diisopropylamine 1a with S2Cl2 allows the selective one-pot preparation of the tricyclic 4-(2-chloroethyl) bisdithiolothiazines 2-4 or, by addition of phosphorus pentasulfide at a rate stage in the reaction, of the dithiolothiazine 5. The chloroethyl derivative 2 is also obtained from (2-diisopropylamino)ethanethiol 1b, or its disulfide 1c, with S2Cl2, in a rare conversion of a thiol or disulfide into the corresponding chloro compound. Compounds 2 and 5 are also obtained from N-(2-hydroxyethyl)diisopropylamine 1d, though in much lower yields. The reaction of N-(2-phenylthioethyl) (1e) or N-(2-phthalimidoethyl)diisopropylamines 1f,g affords bisdithiolothiazines 7, 8, 9, and 11 and the dithiolopyrrole 10, A coherent set of reaction pathways for the formation of these products is proposed. X-ray crystallography shows that the bisdithiolothiazine ring system of 2 is folded out of planarity about the thiazine N-S vector, with the N-chloroethyl group folded back over the thiazine ring with the chlorine atom lying above the thiazine sulfur atom; the dithiolothiazine ring system of 5 has the thiazine ring in a "sofa" conformation.