1,2,4λ⁴δ²,3,5-benzotrithiadiazepine | 395641-83-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1,2,4λ⁴δ²,3,5-benzotrithiadiazepine
• 英文别名: 2,3,5lambda4-Trithia-4,6-diazabicyclo[5.4.0]undeca-1(11),4,5,7,9-pentaene；2,3,5λ4-trithia-4,6-diazabicyclo[5.4.0]undeca-1(11),4,5,7,9-pentaene
• CAS: 395641-83-5
• 化学式: C₆H₄N₂S₃
• 分子量: 200.309
• InChiKey: IAHZNAQMNACZQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  76.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,2,4λ⁴δ²,3,5-benzotrithiadiazepine 在 三甲基氯硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 504.0h， 以10%的产率得到1,2,3-benzodithiazolium chloride
  参考文献：
  名称：

  1,2,4,3,5-Benzotrithiadiazepine and its unexpected hydrolysis to unusual 7H,14H-dibenzo[d,i][1,2,6,7,3,8]tetrathiadiazecine

  摘要：

  以前未知的 1,2,4,3,5-苯并三硫二氮杂卓 1 是 由1:1缩合而成 Ph-NSN-SiMe3 与 S2Cl2 然后进行分子内邻位环化 [Ph-NSN-S-S-Cl]中间体，在吡啶中水解成 异常大环 7H,14H-二苯并[d,i][1,2,6,7,3,8]四硫二氮嗪2。

  DOI：

  10.1039/b105001j
• 作为产物：
  描述：

  N¹-Phenyl-N²-(trimethylsilyl)schwefeldiimid 在 二氯化二硫 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以10%的产率得到1,2,4λ⁴δ²,3,5-benzotrithiadiazepine
  参考文献：
  名称：

  1,2,4,3,5-Benzotrithiadiazepine and its unexpected hydrolysis to unusual 7H,14H-dibenzo[d,i][1,2,6,7,3,8]tetrathiadiazecine

  摘要：

  以前未知的 1,2,4,3,5-苯并三硫二氮杂卓 1 是 由1:1缩合而成 Ph-NSN-SiMe3 与 S2Cl2 然后进行分子内邻位环化 [Ph-NSN-S-S-Cl]中间体，在吡啶中水解成 异常大环 7H,14H-二苯并[d,i][1,2,6,7,3,8]四硫二氮嗪2。

  DOI：

  10.1039/b105001j

文献信息

• New 3,1,2,4-benzothiaselenadiazines, related π-heterocycles including Herz cations, radicals and molecular complexes, and Bunte salts
  作者：Alexander Yu. Makarov、Yulia M. Volkova、Samat B. Zikirin、Irina G. Irtegova、Irina Yu. Bagryanskaya、Yuri V. Gatilov、Andrey A. Nefedov、Andrey V. Zibarev

  DOI：10.1039/d1nj05979c

  日期：——

  carbocycle-chlorinated and non-chlorinated 3,3-dioxides of the starting material, which is a rare example of a molecular complex involving a Herz cation. Formation of the dioxides can be explained through intermediate participation of the benzodithiadiazine radical cation. Hydrolysis of 3,1,2,4-benzothiaselenadiazine or 1,3,2,4-benzodithiadiazine led to Se-(2-aminophenyl)selenosulfate (Se-Bunte salt) or

  通过化合物 Ar-N 的亲电环化合成了新的硫属元素-氮 π-杂环化合物，包括 3,1,2,4-苯并噻吩二嗪、1,3,2,4-苯并二噻二嗪和 1,2,4,3,5-苯并三噻二氮杂S N-SiMe 3在 SeCl 2、 SeCl 4 /FeCp 2、SCl 2和 S 2 Cl 2的作用下。获得的杂环被热解成持久的 2,1,3-苯并噻吩唑基和 1,2,3-苯并二噻唑基（Herz 自由基），使用 EPR 光谱和 DFT 计算对其进行了表征。原型 3,1,2,4-苯并噻吩二嗪与 SCl 2的反应得到 2,1,3-苯并噻吩唑氯化物（Herz 盐），而空间位阻 1,3,2,4-苯并二噻二嗪则导致相应的 Herz 盐与意想不到的碳环氯化和非氯化 3,3-起始材料的二氧化硫，这是涉及 Herz 阳离子的分子复合物的罕见例子。可以通过苯并二噻二嗪自由基阳离子的中间参与来解释二氧化物的形成。3,1,2,4-苯并噻吩二嗪或
• Interaction of 1,3λ4δ2,2,4-benzodithiadiazines with neutral and charged S-electrophiles: SCl2, C6F5SCl, and NS2+
  作者：Alexander Yu. Makarov、Irina Yu. Bagryanskaya、Vladimir V. Zhivonitko

  DOI：10.1007/s10593-020-02760-y

  日期：2020.7

  Reactions of 1,3λ4δ2,2,4-benzothiadiazines with SCl2, C6F5SCl, and [NS2][SbF6] leading to 1,2,3-benzodithiazolium salts (Herz salts) were investigated. The relative rate of reaction with SCl2 significantly depends on the nature of the substituent and its position in the carbocycle. Halogen substituents Cl, Br, and I slow down the reaction, especially if located closely to the heterocycle (positions

  的1,3λ反应4 δ 2，2,4- benzothiadiazines SCL为2，C 6 ˚F 5 SCL，和[NS 2 ] [的SbF 6 ]导致1,2,3- benzodithiazolium盐（赫茨盐）进行了调查。与SCl 2的相对反应速率显着取决于取代基的性质及其在碳环中的位置。卤素取代基Cl，Br和I减慢了反应的速度，尤其是如果其紧邻杂环（位置5和8）。在C的情况下，6 ˚F 5 SCL和R = H，杂环的碳环和开口的氯化也发生与7-氯1,3λ形成4δ 2，2,4-苯并噻二嗪和C 6 ˚F 5 -S-N = S = N-Ar（气体的Ar = 2-CL-6-F 5 C ^ 6 SC 6 ħ 3）表示。与NS反应2 +，具有杂环的收缩沿，也其扩张与1,2,4λ的形成发生4 δ 2，3,5- benzotrithiadiazepine。
• New Polysulfur‐Nitrogen Heterocycles by Thermolysis of 1,3λ ⁴ δ ² ,2,4‐Benzodithiadiazines in the Hydrocarbon and Fluorocarbon Series
  作者：Vladimir V. Zhivonitko、Alexander Yu. Makarov、Irina Yu. Bagryanskaya、Yuri V. Gatilov、Makhmut M. Shakirov、Andrey V. Zibarev

  DOI：10.1002/ejic.200500383

  日期：2005.10

  AbstractIn contrast to thermolysis of 1,3λ4δ2,2,4‐benzodithiadiazine (1) and its 5,6,7,8‐tetrafluoro derivative 2 in dilute (10–3 M) hydrocarbon solutions, which leads to persistent 1,2,3‐benzodithiazolyls in nearly quantitative yields, the thermolysis of 1 and 2 (the 6‐6 bicyclic system) in concentrated (0.5 M) solutions at 150–170 °C results in complex mixtures of various polysulfur‐nitrogen heterocycles, in particular differently fused 5‐5‐6, 5‐6‐7 and 5‐6‐6‐6 polycyclic systems that were previously unknown. The products were isolated by column chromatography, and the structures of the 5‐5‐6 (11, 12), 5‐6‐7 (5, 13), and 5‐6‐6‐6 (6, 14, 15) polycyclic systems, as well as the 6‐7 (4) and 5‐6 (16) bicyclic derivatives, confirmed by X‐ray diffraction. The crystal packing of 6 and 11–16 is discussed with special emphasis on π‐stacking interactions. The fluorescent properties of the 5‐6‐6‐6 systems synthesized are reported. An alternative approach to the linear 5‐6‐6‐6 system 15 based on self‐condensation of an R–N=PPh3 precursor (R = 4,5,6,7‐tetrafluoro‐1,2,3‐benzodithiazol‐2‐yl) is described, and the free‐radical character of this new reaction is proved. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• New polysulfur–nitrogen heterocycles as precursors of thiazyl radicals
  作者：Konstantin V. Shuvaev、Victor A. Bagryansky、Nina P. Gritsan、Alexander Yu. Makarov、Yuri N. Molin、Andrey V. Zibarev

  DOI：10.1070/mc2003v013n04abeh001741

  日期：2003.1

  Both thermolysis and photolysis of 1,2,4lambda(4)delta(2),3,5- and 1,3lambda(4)delta(2),5,2,4-benzotrithiadiazepines in hydrocarbon solvents yielded stable 1,2,3- and 1,3,2-benzodithiazolyls, which can be considered as a particular case of a previously unmentioned trend of neutral polysulfur-nitrogen heterocycles to form thiazyl pi-radicals.
• 1,2,4,3,5-Benzotrithiadiazepine and its unexpected hydrolysis to unusual 7H,14H-dibenzo[d,i][1,2,6,7,3,8]tetrathiadiazecine
  作者：Alexander Yu. Makarov、Makhmut M. Shakirov、Irina Yu. Bagryanskaya、Yuri V. Gatilov、Andrey V. Zibarev、Konstantin V. Shuvaev

  DOI：10.1039/b105001j

  日期：——

  Previously unknown 1,2,4,3,5-benzotrithiadiazepine 1 was prepared by 1∶1 condensation of Ph-NSN-SiMe3 with S2Cl2 followed by intramolecular ortho-cyclization of [Ph-NSN-S-S-Cl] intermediate, and hydrolyzed in pyridine to unusual macrocyclic 7H,14H-dibenzo[d,i][1,2,6,7,3,8]tetrathiadiazecine 2.

  以前未知的 1,2,4,3,5-苯并三硫二氮杂卓 1 是 由1:1缩合而成 Ph-NSN-SiMe3 与 S2Cl2 然后进行分子内邻位环化 [Ph-NSN-S-S-Cl]中间体，在吡啶中水解成 异常大环 7H,14H-二苯并[d,i][1,2,6,7,3,8]四硫二氮嗪2。