5,6,8-trifluoro-1,3λ⁴δ²,2,4-benzodithiadiazine | 530102-82-0

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 5,6,8-trifluoro-1,3λ⁴δ²,2,4-benzodithiadiazine
• 英文别名: 5,6,8-trifluoro-1,3,2,4-benzodithiadiazine；7,8,10-Trifluoro-2,4lambda4-dithia-3,5-diazabicyclo[4.4.0]deca-1(10),3,4,6,8-pentaene；7,8,10-trifluoro-2,4λ4-dithia-3,5-diazabicyclo[4.4.0]deca-1(10),3,4,6,8-pentaene
• CAS: 530102-82-0
• 化学式: C₆HF₃N₂S₂
• 分子量: 222.215
• InChiKey: VFNFAZLXGCFYLJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  13
• 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：
  51
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5,6,8-trifluoro-1,3λ⁴δ²,2,4-benzodithiadiazine 以 角鲨烷 为溶剂， 反应 0.67h， 生成
  参考文献：
  名称：

  Interaction of 1,3,2,4-Benzodithiadiazines and Their 1-Se Congeners with Ph₃P and Some Properties of the Iminophosphorane Products

  摘要：

  Interaction between Ph3P and 1,3,2,4-benzodithiadiazine (I); its 6,7-difluoro (2), 5,6,8-trifluoro (3) and 5,6,7,8-tetrafluoro (4) derivatives; and 5,6,8-trifluoro-3,1,2,4-benzothiaselenadiazine (5) proceeded via a 1:1 condensation to give Ph3P=N-R iminophosphoranes (1a-5a, R = corresponding 1,2,3-benzodichalcogenazol-2-yls), which are inaccessible by general approaches based on the Staudinger and Kirsanov reactions. In contrast, neither Ph3As nor Ph3Sb reacted with 1 and 4. Molecular structures of 1a-5a and 5 were confirmed by X-ray diffraction (XRD). The crystals formed by chiral molecules of 2a-5a were racemic, whereas the crystal of la was formed by a single enantiomer. In all Of the Ph3P=N-R derivatives, one of the Ph rings is oriented face-to-face to the hetero ring, R. Upon heating to similar to 120 degrees C in squalane (1a, 3a, 4a) or dissolving in chloroform at ambient temperatures (1a, 2a, 4a) the Ph3P=N-R derivatives generated the 1,2,3-benzodithiazolyls (1b-4b, respectively) whose identity was confirmed by electron paramagnetic resonance (EPR). 2,1,3-Benzothiaselenazolyls 5b and 6b were detected by EPR as the main paramagnetic products of solution thermolysis of 5 and its 5,6,7,8-tetrafluoro congener (6), respectively. Passing a chloroform solution of 4a through silica column unexpectedly gave 5-6-6-6 tetracyclic (9) and 6-10-6 tricyclic (10) sulfur-nitrogen compounds, which were 'characterized by XRD.

  DOI：

  10.1021/ic102565x
• 作为产物：
  描述：

  1,2,3,5-四氟苯 在 正丁基锂 、 氯 、 cesium fluoride 作用下， 以 四氯化碳 、 乙醚 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 17.5h， 生成 5,6,8-trifluoro-1,3λ⁴δ²,2,4-benzodithiadiazine
  参考文献：
  名称：

  氟化 1,3λ4δ2,2,4-苯并二噻二嗪 - 合成、结构和理论研究

  摘要：

  通过亲电 (C6HnF5−n−N=S=N−SiMe3 + SCl2) 和亲核 (C6HF4−S−N=S=N−SiMe3 + CsF) 分子内正环化反应制备了一系列标题化合物，并且前一种路线似乎更有效。在两种情况下都观察到闭环程序的高区域选择性。化合物通过 X 射线晶体学和多核 (1H、13C、15N 和 19F) NMR 光谱进行表征。根据 GIAO 计算、 15N{1H} 实验和观察到的氢完全被氟取代的影响， 15N NMR 光谱中的高场信号可以分配给 N-4，低场信号分配给 N-2 . 在晶体中，5,6,7-三氟-(5)和5,6,8-三氟-1,3λ4δ2,2,4-苯并二噻嗪(6)是平面的，而6,8-二氟衍生物3是弯曲的沿 S1...N4 线 8.3°。根据 NICS 计算，此类化合物中的杂环部分是反芳香族的，而碳环是芳香族的。氟取代基增加了相应环的芳香性 - 在某些情况下（尤其是当 8

  DOI：

  10.1002/ejic.200390016

文献信息

• Unexpected water addition to fluorinated 1,3λ4δ2,2,4-benzodithiadiazines with the formation of 2-amino-N-sulfinylbenzenesulfenamides
  作者：Alexander Yu. Makarov、Irina Yu. Bagryanskaya、Yuri V. Gatilov、Makhmut M. Shakirov、Andrey V. Zibarev

  DOI：10.1070/mc2003v013n01abeh001700

  日期：2003.1

  Fluoro-containing 1,3λ4δ2,2,4-benzodithiadiazines 2–4 unexpectedly add water to give previously unknown 2-amino-N-sulfinylbenzenesulfenamides 5–7 as the first derivatives of still undescribed 2-aminobenzenesulfenamide 10.

  含氟的1,3λ4δ2,2,4-苯并噻二嗪2–4意外地加水生成先前未知的2-氨基-N-亚磺酰基苯亚磺酰胺5–7，作为尚未描述的2-氨基苯亚磺酰胺10的第一衍生物。
• Fluorinated 1,3λ ⁴ δ ² ,2,4‐Benzodithiadiazines − A Synthetic, Structural and Theoretical Study
  作者：Alexander Yu. Makarov、Irina Yu. Bagryanskaya、Frank Blockhuys、Christian Van Alsenoy、Yuri V. Gatilov、Vladimir V. Knyazev、Alexander M. Maksimov、Tatiana V. Mikhalina、Vyacheslav E. Platonov、Makhmut M. Shakirov、Andrey V. Zibarev

  DOI：10.1002/ejic.200390016

  日期：2003.1

  when a fluorine atom is present in the 8-position) the antiaromaticity − of the corresponding rings. The ortho-fluoro-containing starting material C6HnF5−n−N=S=N−SiMe3 (n = 2: 10) cyclises to the fluorinated 2,1,3-benzothiadiazole 27 upon treatment with CsF instead of SCl2. For starting compound 6-HC6F4−S−N=S=N−SiMe3 (14) the planar (Z,E) configuration features a short intramolecular H···N contact, as

  通过亲电 (C6HnF5−n−N=S=N−SiMe3 + SCl2) 和亲核 (C6HF4−S−N=S=N−SiMe3 + CsF) 分子内正环化反应制备了一系列标题化合物，并且前一种路线似乎更有效。在两种情况下都观察到闭环程序的高区域选择性。化合物通过 X 射线晶体学和多核 (1H、13C、15N 和 19F) NMR 光谱进行表征。根据 GIAO 计算、 15N1H} 实验和观察到的氢完全被氟取代的影响， 15N NMR 光谱中的高场信号可以分配给 N-4，低场信号分配给 N-2 . 在晶体中，5,6,7-三氟-(5)和5,6,8-三氟-1,3λ4δ2,2,4-苯并二噻嗪(6)是平面的，而6,8-二氟衍生物3是弯曲的沿 S1...N4 线 8.3°。根据 NICS 计算，此类化合物中的杂环部分是反芳香族的，而碳环是芳香族的。氟取代基增加了相应环的芳香性 - 在某些情况下（尤其是当 8
• Interaction of 1,3,2,4-Benzodithiadiazines and Their 1-Se Congeners with Ph₃P and Some Properties of the Iminophosphorane Products
  作者：Alexander Yu. Makarov、Vladimir V. Zhivonitko、Arkady G. Makarov、Samat B. Zikirin、Irina Yu. Bagryanskaya、Victor A. Bagryansky、Yuri V. Gatilov、Irina G. Irtegova、Makhmut M. Shakirov、Andrey V. Zibarev

  DOI：10.1021/ic102565x

  日期：2011.4.4

  Interaction between Ph3P and 1,3,2,4-benzodithiadiazine (I); its 6,7-difluoro (2), 5,6,8-trifluoro (3) and 5,6,7,8-tetrafluoro (4) derivatives; and 5,6,8-trifluoro-3,1,2,4-benzothiaselenadiazine (5) proceeded via a 1:1 condensation to give Ph3P=N-R iminophosphoranes (1a-5a, R = corresponding 1,2,3-benzodichalcogenazol-2-yls), which are inaccessible by general approaches based on the Staudinger and Kirsanov reactions. In contrast, neither Ph3As nor Ph3Sb reacted with 1 and 4. Molecular structures of 1a-5a and 5 were confirmed by X-ray diffraction (XRD). The crystals formed by chiral molecules of 2a-5a were racemic, whereas the crystal of la was formed by a single enantiomer. In all Of the Ph3P=N-R derivatives, one of the Ph rings is oriented face-to-face to the hetero ring, R. Upon heating to similar to 120 degrees C in squalane (1a, 3a, 4a) or dissolving in chloroform at ambient temperatures (1a, 2a, 4a) the Ph3P=N-R derivatives generated the 1,2,3-benzodithiazolyls (1b-4b, respectively) whose identity was confirmed by electron paramagnetic resonance (EPR). 2,1,3-Benzothiaselenazolyls 5b and 6b were detected by EPR as the main paramagnetic products of solution thermolysis of 5 and its 5,6,7,8-tetrafluoro congener (6), respectively. Passing a chloroform solution of 4a through silica column unexpectedly gave 5-6-6-6 tetracyclic (9) and 6-10-6 tricyclic (10) sulfur-nitrogen compounds, which were 'characterized by XRD.