Methyl 1-methyl-6-phenylpyrrolo[2,1-e]tetrazole-7-carboxylate | 155699-45-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: Methyl 1-methyl-6-phenylpyrrolo[2,1-e]tetrazole-7-carboxylate
• CAS: 155699-45-9
• 化学式: C₁₃H₁₂N₄O₂
• 分子量: 256.264
• InChiKey: IIZDZEVGNGIAJN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  61.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 1-methyl-6-phenylpyrrolo[2,1-e]tetrazole-7-carboxylate 在 盐酸 、 溶剂黄146 、 sodium nitrite 、 亚磷酸三乙酯 作用下， 生成 (Z)-3-(1-Methyl-1H-tetrazol-5-yl)-2-phenyl-acrylonitrile
  参考文献：
  名称：

  Pyrrole Ring Opening in 5-Nitroso- and 5-Phenylazo-1H-pyrrolotetrazoles --- An Unexpected Valence Isomerism

  摘要：

  1,6-Disubstituted 5-nitroso-1H-pyrrolotetrazoles ring open below 20-degrees-C to give the isomeric acrylonitrile oxides. The 5-phenylazo analogs as well as 5-nitroso derivatives having in addition an acceptor group at C-7 are stable at 20-degrees-C, but heating with the dipolarophile DMAD leads to pyrazoles and isoxazoles.

  DOI：

  10.3987/com-93-s68
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 sodium acetate 、 溶剂黄146 作用下， 反应 1.0h， 以82%的产率得到Methyl 1-methyl-6-phenylpyrrolo[2,1-e]tetrazole-7-carboxylate
  参考文献：
  名称：

  Pyrrole Ring Opening in 5-Nitroso- and 5-Phenylazo-1H-pyrrolotetrazoles --- An Unexpected Valence Isomerism

  摘要：

  1,6-Disubstituted 5-nitroso-1H-pyrrolotetrazoles ring open below 20-degrees-C to give the isomeric acrylonitrile oxides. The 5-phenylazo analogs as well as 5-nitroso derivatives having in addition an acceptor group at C-7 are stable at 20-degrees-C, but heating with the dipolarophile DMAD leads to pyrazoles and isoxazoles.

  DOI：

  10.3987/com-93-s68

文献信息

• Aromatic azapentalenes: 1H- and (mesoionic) 2H-pyrrolotetrazoles. Part 1. Synthesis and spectral characteristics
  作者：Dietrich Moderhack、Dirk Decker、Bernhard Holtmann

  DOI：10.1039/b007873p

  日期：——

  Two separate series of the title systems have been prepared by cyclisation of tetrazolium salts having acylmethyl functions attached to both the ring carbon and the adjacent nitrogen atom (3, 4): (i) working in an acetate buffer led to 7-acyl derivatives (5, 6; Scheme 3), and (ii) treatment with anhydride–base gave 5,7-diacyl compounds by a deviating ring closure mechanism (11, 12; Scheme 4). These materials could be defunctionalised to afford pyrrolotetrazoles (7, 8) which were earlier approached in vain from the respective 5-methyltetrazolium salts (Tschitschibabin reaction). Regarding characterisation data, attention is drawn to the conspicuous spectroscopic differences between the 1H- and the 2H-system. 2H-Pyrrolotetrazoles (6, 8, 12) represent a novel class of Ramsden’s ‘type C’ heteropentalene mesoions.

  两系列独立的标题系统是通过环化含有酰基甲基功能团的叠氮盐制备的，这些功能团附着在环碳和相邻氮原子上（3，4）：(i) 在醋酸盐缓冲液中反应得到了7-酰基衍生物（5，6；方案3），(ii) 与酸酐-碱的处理通过偏差的环闭合机制得到了5,7-二酰基化合物（11，12；方案4）。这些材料可以去功能化，最终得到吡咯并叠氮唑（7，8），而早期尝试通过相应的5-甲基叠氮盐（Tschitschibabin反应）得到这些化合物则未能成功。关于表征数据，特别需要注意的是1H系统和2H系统之间显著的光谱差异。2H-吡咯并叠氮唑（6，8，12）代表了一类新型的Ramsden“C型”杂五苯的中间离子。
• Aromatic azapentalenes: 1H- and (mesoionic) 2H-pyrrolotetrazoles. Part 2. Reaction with electrophiles
  作者：Dietrich Moderhack、Dirk Decker、Bernhard Holtmann

  DOI：10.1039/b007874n

  日期：——

  AM1 calculations. 1,3-Dipolar cycloaddition behaviour of 2 towards DMAD, a conceivable process, could not be detected; only linear addition was observed. Nitroso derivatives of the series 3, 4 and 8 were not isolated as such but as the ring-opened nitrile oxides 11 and 12; at elevated temperature analogous valence isomers arise also from the nitroso derivative 7e and the azo compounds 3e and 4e.

  质子化 乙酰化， 苯甲酰化， 氨基甲酰化，甲酰化， 溴化， 偶氮偶合，亚硝化和添加到DMAD中进行了研究。通常发生单取代（溴化除外），如果5个和7个位置都没有空位，则首选攻击地点为C（5）。许多观察结果表明，介电异构体2的反应性略高；反之亦然。这与AM1的计算是一致的。1,3-偶极环加成无法检测到2对DMAD的行为（一个可能的过程）；仅观察到线性加法。该系列的亚硝基衍生物3，4和8分别不分离为例如但作为开环一氧化氮 11和12 ; 在高温下，类似的化合价异构体也来自亚硝基衍生物7e和偶氮化合物 3e和4e。