(3,5-Dichloro-4H-1,2,6-thiadiazin-4-ylidene)propanedinitrile | 278600-22-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (3,5-Dichloro-4H-1,2,6-thiadiazin-4-ylidene)propanedinitrile
• 英文别名: 3,5-Dichloro-4-dicyanomethylene-4H-1,2,6-thiadiazine；2-(3,5-dichloro-4H-1,2,6-thiadiazin-4-ylidene)malononitrile；2-(3,5-Dichloro-1,2,6-thiadiazin-4-ylidene)propanedinitrile
• CAS: 278600-22-9
• 化学式: C₆Cl₂N₄S
• 分子量: 231.065
• InChiKey: TXXFURKLIWESNI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  97.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3,5-Dichloro-4H-1,2,6-thiadiazin-4-ylidene)propanedinitrile 在 二氯化硫 、 苄基三乙基氯化铵 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以20%的产率得到5-Cyano-4,5-dichloropyrrolo[2,3-c][1,2,6]thiadiazine
  参考文献：
  名称：

  四氰基乙烯与SCl 2的反应; 新的分子重排

  摘要：

  氯离子催化将SCl 2加到TCNE中，得到4-二氰基亚甲基-1,2,6-噻二嗪2（60％），具有两个较小的副产物（5％），它们具有广泛的分子重排，嘧啶 4和吡咯并咪唑硫二嗪5。提出的所有三种产物形成的机制都涉及SCl 2与一种氰基双子座和邻位的氰基参加邻近的群体。二氰基亚甲基噻二嗪2与SCl 2进一步反应，得到吡咯并1，2，6-噻二嗪19。吡咯并咪唑并噻二嗪5的两个氯原子被依次取代吡咯烷得到高产率的取代产物20和21。1 H和13 C NMR谱 结果表明，噻二嗪上吡咯烷环的旋转比吡咯环上的旋转慢得多，并且在新的14π三环杂芳族体系中存在电子离域。

  DOI：

  10.1039/b000209g
• 作为产物：
  描述：

  四氰基乙烯 在 二氯化硫 、 苄基三乙基氯化铵 作用下， 以60%的产率得到(3,5-Dichloro-4H-1,2,6-thiadiazin-4-ylidene)propanedinitrile
  参考文献：
  名称：

  Palladium Catalyzed C–C Coupling Reactions of 3,5-Dichloro-4H-1,2,6-thiadiazin-4-one

  摘要：

  Palladium catalyzed Suzuki-Miyaura, Stille, and Sonogashira coupling reactions are reported for the electron-deficient heterocyclic scaffold 3,5-dichloro-4H-1,2,6-thiadiazin-4-one (1). Furthermore, 3,5-di(thien-2-yl)-4H-1,2,6-thiadiazin4-one (7m) is further elaborated to afford the tetrathienyl 3,5-bis[(2,2'-bithien)-5-yl]-4H-1,2,6-thiadiazin-4-one (9). All compounds are fully characterized.

  DOI：

  10.1021/ol201212b

文献信息

• Cyclisation chemistry of 4H-1,2,6-thiadiazines
  作者：Panayiotis A. Koutentis、Charles W. Rees

  DOI：10.1039/b004113k

  日期：——

  3,5-Dichloro-4H-1,2,6-thiadiazin-4-one 1 condenses rapidly at room temperature with 1,2-diaminobenzene, 2-aminothiophenol and sodium 2-aminophenoxide to give, respectively, the purple thiadiazinoquinoxaline 4a, red thiadiazinobenzothiazine 4b and orange thiadiazinobenzoxazine 4c in almost quantitative yield. The 10H tautomer 4a is spectroscopically almost identical with the purple 10-methyl derivative 11 formed by condensation of 1 with N-methyl-1,2-diaminobenzene and by the methylation of 4a. The chlorine substituent in these tricyclic thiadiazino compounds is readily displaced by nucleophiles, to give the 4-ethoxy 13 and 4-piperidino derivative 21. The dicyanomethylene compound 2, analogous to 1, reacts in the same way as 1 with 2-aminothiophenol to give 4b (87%), but its reaction with 1,2-diaminobenzene is more complex since, in addition to the analogous formation of 4a, there is now the possibility of another cyclisation in the intermediate 16 which leads to the tetracyclic compound 14 and its substitution product 15. This difference in reaction pathway between 1 and 2 is further illustrated by their condensation with 1,8-diaminonaphthalene: 1 is converted into 19 by simple displacement of chlorine, whilst 2 gives, almost quantitatively, the product 20 of cyclisation onto the neighbouring cyano group.

  3,5-二氯-4H-1,2,6-噻二嗪-4-酮1在室温下与1,2-二氨基苯、2-氨基噻吩酚和钠盐2-氨基苯氧化物迅速缩合，分别生成紫色的噻二嗪喹啉4a、红色的噻二嗪苯并噻嗪4b和橙色的噻二嗪苯并噁嗪4c，产率几乎是定量的。10H互变异构体4a在光谱上与通过与N-甲基-1,2-二氨基苯的缩合反应和对4a的甲基化反应生成的紫色10-甲基衍生物11几乎相同。这些三环噻二嗪化合物中的氯取代基可以被亲核试剂轻易取代，生成4-乙氧基衍生物13和4-哌啶基衍生物21。与1类似的二氰甲烯化合物2与2-氨基噻吩酚的反应与1相似，生成4b（87%），但与1,2-二氨基苯的反应更为复杂，除了类似于4a的反应，现在还可能在中间体16中发生另一个环化，导致四环化合物14及其取代产物15。1和2在反应路径上的差异通过它们与1,8-二氨基萘的缩合进一步说明：1通过简单的氯取代反应转化为19，而2则几乎定量生成与相邻氰基反应的环化产物20。
• A Qualitative Comparison of the Reactivities of 3,4,4,5-Tetrachloro-4H-1,2,6-thiadiazine and 4,5-Dichloro-1,2,3-dithiazolium Chloride
  作者：Andreas Kalogirou、Panayiotis Koutentis

  DOI：10.3390/molecules200814576

  日期：——

  The high yielding transformations of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine into 3,5-dichloro-4H-1,2,6-thiadiazin-4-one (up to 85%) and 2-(3,5-dichloro-4H-1,2,6-thiadiazin-4-ylidene)malononitrile (up to 83%) have been investigated and compared to the analogous transformations of the closely-related 4,5-dichloro-1,2,3-dithiazolium chloride (Appel’s salt) into 4-chloro-5H-1,2,3-dithiazol-5-one and 2-(4-chloro-5H-1,2,3-dithiazol-5-ylidene)malononitrile. Furthermore, cyclocondensation of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine with 2-aminophenol and 1,2-benzenediamines gave fused 4H-1,2,6-thiadiazines in 68%–85% yields.

  研究了 3,4,4,5-四氯-4H-1,2,6-噻二嗪向 3,5-二氯-4H-1,2,6-噻二嗪-4-酮（高达 85%）和 2-(3,5-二氯-4H-1,2,6-噻二嗪-4-亚基)丙二腈（高达 83%）的高产率转化、噻二嗪-4-酮（高达 85%）和 2-(3,5-二氯-4H-1,2,6-噻二嗪-4-亚基)丙二腈（高达 83%）的类似转化进行了研究，并与密切相关的 4,5-二氯-1,2,3-二噻唑氯化物（阿贝尔盐）转化为 4-氯-5H-1,2,3-二噻唑-5-酮和 2-(4-氯-5H-1,2,3-二噻唑-5-亚基)丙二腈的类似转化进行了比较。此外，3,4,4,5-四氯-4H-1,2,6-噻二嗪与 2-氨基苯酚和 1,2-苯二胺进行环缩合，可得到产率为 68%-85% 的融合 4H-1,2,6-噻二嗪。
• Chemistry of 4-dicyanomethylene-1,2,6-thiadiazines
  作者：Panayiotis A. Koutentis、Charles W. Rees

  DOI：10.1039/b000964o

  日期：——

  The chlorine atoms in 3,5-dichloro-4-dicyanomethylene-1,2,6-thiadiazine 1 are readily displaced by thiophenols in the presence of Hünig’s base, the first at −78 °C and the second at 20 °C to give the orange mono- and bis-arylthio derivatives in high yield (Table 1). Similarly secondary amines give the red mono- and blue bis-amino compounds in high yield (Table 2); piperidine, for example, gives the former at −78 °C and the latter at −30 °C. A low limit of reactivity is reached with diisopropylamine which gives the mono derivative only, in low yield (30%). Reactions with ammonia and with primary amines are complex since the amines formed can cyclise onto the adjacent cyano group, aniline giving only a low yield of the pyrrolo[2,3-c][1,2,6]thiadiazine 8. The 4-dicyanomethylene compound 1 is more reactive than the known 4-oxo analogue 2, but can suffer the added complications of cyano group cyclisation and hydrolysis of dicyanomethylene to the keto group. 3,5-Dimorpholino-4-dicyanomethylene-1,2,6-thiadiazine 7c is oxidized to the sulfoxide 9 with MCPBA or N2O4, and 9 reverts to 7c with triphenylphosphine–tetrachloromethane, all in high yield. Thiadiazine 1 undergoes a complex reaction with DMSO at 20 °C to give the three furo[2,3-c][1,2,6]thiadiazines 10, 11 and (tentatively) 12 which could all arise from the initial product 13 of displacement of chlorine by DMSO, by cyclisation and sulfoxide type rearrangements. Mechanisms are proposed for all new reactions.

  3,5-二氯-4-二氰基亚甲基-1,2,6-噻二嗪 1 中的氯原子很容易在 Hünig 碱存在下被噻吩酚置换，前者在 -78 °C 时，后者在 20 °C 时，高产率地得到橙色的单芳基巯基和双芳基巯基衍生物（表 1）。同样，仲胺也能以高产率生成红色的单氨基化合物和蓝色的双氨基化合物（表 2）；例如，哌啶能在 -78 °C 时生成前者，在 -30 °C 时生成后者。与二异丙基胺的反应活性较低，只能得到单衍生物，产率较低（30%）。与氨和伯胺的反应比较复杂，因为形成的胺可以与邻近的氰基发生环化反应，苯胺只能得到低产率的吡咯并[2,3-c][1,2,6]噻二嗪 8。与已知的 4-氧代类似物 2 相比，4-二氰基亚甲基化合物 1 的反应性更强，但会出现氰基环化和二氰基亚甲基水解为酮基的复杂情况。3,5-二吗啉基-4-二氰亚甲基-1,2,6-噻二嗪 7c 在 MCPBA 或 N2O4 的作用下被氧化成亚砜 9，9 在三苯基膦-四氯甲烷的作用下还原成 7c，所有这些反应的产率都很高。噻二嗪 1 在 20 ℃ 下与二甲基亚砜发生复杂反应，生成三种呋喃并[2,3-c][1,2,6]噻二嗪 10、11 和（暂定）12，它们都可能是由二甲基亚砜置换氯的初始产物 13 通过环化和亚砜型重排生成的。本文提出了所有新反应的机理。
• Reaction of tetracyanoethylene with SCl2: new molecular rearrangements
  作者：Panayiotis A. Koutentis、Charles W. Rees、Andrew J. P. White、David J. Williams

  DOI：10.1039/a909307i

  日期：——

  The chloride ion catalysed addition of SCl2 to TCNE gives the dicyanomethylene-1,2,6-thiadiazine 3 as major product together with two unexpected minor products, pyrimidine 4 and pyrroloimidazothiadiazine 5, whose X-ray crystal structures are described; the products are derived from interaction of SCl2 with one cyano group with neighbouring group participation by two others.

  氯离子催化 SCl2 与 TCNE 的加成得到二氰亚甲基-1,2,6-噻二嗪 3 作为主要产物以及两个意想不到的次要产物嘧啶 4 和吡咯并咪唑噻二嗪 5，其 X 射线晶体结构已被描述；这些产物来自 SCl2 与一个氰基的相互作用，相邻的两个基团参与其中。
• Palladium Catalyzed C–C Coupling Reactions of 3,5-Dichloro-4<i>H</i>-1,2,6-thiadiazin-4-one
  作者：Heraklidia A. Ioannidou、Christos Kizas、Panayiotis A. Koutentis

  DOI：10.1021/ol201212b

  日期：2011.7.1

  Palladium catalyzed Suzuki-Miyaura, Stille, and Sonogashira coupling reactions are reported for the electron-deficient heterocyclic scaffold 3,5-dichloro-4H-1,2,6-thiadiazin-4-one (1). Furthermore, 3,5-di(thien-2-yl)-4H-1,2,6-thiadiazin4-one (7m) is further elaborated to afford the tetrathienyl 3,5-bis[(2,2'-bithien)-5-yl]-4H-1,2,6-thiadiazin-4-one (9). All compounds are fully characterized.