2-(3,5-di(thien-2-yl)-4H-1,2,6-thiadiazin-4-ylidene)malononitrile | 1365337-34-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 2-(3,5-di(thien-2-yl)-4H-1,2,6-thiadiazin-4-ylidene)malononitrile
• 英文别名: 2-[3,5-di(thien-2-yl)-4H-1,2,6-thiadiazin-4-ylidene]malononitrile；2-(3,5-Dithiophen-2-yl-1,2,6-thiadiazin-4-ylidene)propanedinitrile；2-(3,5-dithiophen-2-yl-1,2,6-thiadiazin-4-ylidene)propanedinitrile
• CAS: 1365337-34-3
• 化学式: C₁₄H₆N₄S₃
• 分子量: 326.426
• InChiKey: UZCPIQAJWQYASK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  154
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  3,5-di(thien-2-yl)-4H-1,2,6-thiadiazin-4-one 在 tetraphosphorus decasulfide 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 、 甲苯 为溶剂， 反应 5.67h， 生成 2-(3,5-di(thien-2-yl)-4H-1,2,6-thiadiazin-4-ylidene)malononitrile
  参考文献：
  名称：

  Substitution at C-4 in 3,5-disubstituted 4H-1,2,6-thiadiazin-4-ones

  摘要：

  3,5-Diaryl-4H-1,2,6-thiadiazin-4-ones react with NaBH4 to give the 3,5-diaryl-4H-1,2,6-thiadiazin-4-ols and with MeLi to give 4-methyl-3,5-diaryl-4H-1,2,6-thiadiazin-4-ols. The latter dehydrate with p-toluenesulfonic acid to give (3,5-diarylthiadiazin-4-ylidene)methanes. (3,5-Diphenyl-4H-1,2,6-thiadiazin-4-ylidene)methane 15 suffers mono bromination with NBS to give bromo(3,5-diphenyl-4H-1,2,6-thiadiazin-4-ylidene)methane 17. Dichloro- and dibromo(3,5-diphenyl-4H-1,2,6-thiadiazin-4-ylidene) methanes 18 and 19 are formed directly from the 3,5-diphenylthiadiazin-4-one 9 via the Appel reaction using Ph3P and CCl4 or CBr4, respectively. 3,5-Diarylthiadiazin-4-ones treated with P2S5 give 3,5-diarylthiadiazine-4-thiones that react with tetracyanoethylene oxide to give the (thiadiazin-4-ylidene) malononitriles. Finally, the 3,5-diphenylthiadiazine-4-thione 20 reacts with ethyl diazoacetate to give ethyl 2-(3,5-diphenyl-4H-1,2,6-thiadiazin-4-ylidene)acetate 26. The above reactions show that a variety of substitutions at C-4 of 3,5-diaryl substituted 1,2,6-thiadiazin-4-ones can be achieved, which extends the potential applications of this heterocycle. All compounds are fully characterized and a brief comparison of their spectroscopic properties is given. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.01.098

文献信息

• Synthesis of 2-(4H-1,2,6-thiadiazin-4-ylidene)malononitriles
  作者：Andreas S. Kalogirou、Panayiotis A. Koutentis

  DOI：10.1016/j.tet.2014.09.008

  日期：2014.11

  The base-free TiCl4-mediated condensation of 3,5-disubstituted-4H-1,2,6-thiadiazin-4-ones 8 with malononitrile affords 20 difficult to access (3,5-disubstituted-4H-1,2,6-thiadiazin-4-ylidene)malononitriles 7. The reaction tolerates 3,5-diaryl, diphenoxy, dimethoxy and diphenylthio substituted thiadiazinones, but not diamino, monohydroxy or dihalo substituents. Nevertheless, asymmetrically substituted 3-halo-5-phenyl- and 3-chloro-5-methoxy-4H-1,2,6-thiadiazin-4-ones convert into the corresponding ylide-nemalononitriles in good yield. Furthermore, the condensation works well with ethyl cyanoacetate and diethyl malonate, but not with Meldrum's acid, dimedone or nitromethane. Finally, 2-(3-chloro-5-phenyl-4H-1,2,6-thiadiazin-4-ylidene)malononitrile (7q) reacts with aniline to give 4,7-diphenyl-6-(phenylimino)-6,7-dihydropyrrolo[2,3-c][1,2,6]thiadiazine-5-carbonitrile (12) in moderate yield demonstrating the potential use of these ylidenes to prepare novel 6-5 fused 4H-1,2,6-thiadiazines. (C) 2014 Elsevier Ltd. All rights reserved.