N-(2-diisopropylaminoethyl)-3,4,5,6-tetrachlorophthalimide | 239135-26-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: N-(2-diisopropylaminoethyl)-3,4,5,6-tetrachlorophthalimide
• 英文别名: 4,5,6,7-Tetrachloro-2-[2-[di(propan-2-yl)amino]ethyl]isoindole-1,3-dione
• CAS: 239135-26-3
• 化学式: C₁₆H₁₈Cl₄N₂O₂
• 分子量: 412.143
• InChiKey: DWUDWHYAOAFDOU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(2-diisopropylaminoethyl)-3,4,5,6-tetrachlorophthalimide 在 三乙烯二胺 、 二氯化二硫 、 四甲基氯化铵 、 甲酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.75h， 以16%的产率得到4-[2-(tetrachlorophthalimido)ethyl]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
• 作为产物：
  描述：

  4,5,6,7-四氯邻苯二甲酰亚胺 、 2-(N,N-二异丙氨基)氯乙烷 在 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 38.0h， 以35%的产率得到N-(2-diisopropylaminoethyl)-3,4,5,6-tetrachlorophthalimide
  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。
• 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.