2-Amino-4-methoxy-azulene-1,3-dicarbonitrile | 205595-23-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2-Amino-4-methoxy-azulene-1,3-dicarbonitrile
• 英文别名: 2-Amino-4-methoxyazulene-1,3-dicarbonitrile
• CAS: 205595-23-9
• 化学式: C₁₃H₉N₃O
• 分子量: 223.234
• InChiKey: BBJXIZCAUAITRI-UHFFFAOYSA-N

物化性质

• 沸点：
  458.6±45.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  82.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-Amino-4-methoxy-azulene-1,3-dicarbonitrile 在 三氟乙酸 、 sodium nitrite 作用下， 反应 8.0h， 生成 7,10,13,16,19-pentaoxatricyclo[18.2.1.06,22]tricosa-1,3,5,20(23),21-pentaene-21,23-dicarbonitrile
  参考文献：
  名称：

  New Method for the Synthesis of Polyether-Bridged Azulenes:  Reactions of Conjugated Ketocarbenes Generated from the Corresponding Azulenoquinone Diazides

  摘要：

  The diazide of 2,4-azulenoquinone carrying 1,3-cyano and carbomethoxy substituents was synthesized and photolyzed in cyclic ethers (THF, dioxane, and tetrahydropyran) to give good yields of 2,4-polyether-bridged azulenes. The shapes of some azulene polyethers were examined by X-ray structural determination to show the cavity size ranging from 6.4 to 4.1 Angstrom (long-short diameters) to 7.36-6.6 Angstrom encircled by an azulene and polyether are. In analogy to 2,5-cyclohexadien-4-onylidenes, photogenerated conjugated azulenone carbenes were assumed to have energetically closely spaced triplet and singlet ground states that can interconvert readily and react from one of these states under ambient conditions. The spanning of a polyether bridge is initiated by the electrophilic attack of a singlet state on the oxygen of solvent ethers, followed by one or two propagation steps and a ring closure by phenolate attack. The 1,3-dicarbomethoxy group could exert steric effects to hinder the approach of the ether oxygen and control the polyether spanning processes and ring size; this caused a triplet state reaction to supersede the overall reaction. While radical and insertion reactions are common for ketocarbene reactions, the present description adduces a well manifested electrophilic reaction of the allied transients.

  DOI：

  10.1021/jo971494u
• 作为产物：
  描述：

  环庚三烯酚酮 在 硝酸铵 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 丙酮 为溶剂， 反应 7.0h， 生成 2-Amino-4-methoxy-azulene-1,3-dicarbonitrile
  参考文献：
  名称：

  Electrochemical Methoxylation of 1,2,3-Trisubstituted Azulenes

  摘要：

  Abstract1,2,3‐Trisubstituted azulene analogs 6a and 6b easily underwent methoxylation in position 4 or 6 of an azulene ring via an electrochemical oxidation. It is a simple, convenient and selective method for introducing a methoxy group into a 7‐membered ring of azulene analogs when compared with traditional chemical methods. It could be useful in preparing 2,4‐ and 2,6‐azuloquinone analogs.

  DOI：

  10.1002/jccs.199900004

文献信息

• Electromethoxylation of diethyl 2-hydroxyazulene 1,3-dicarboxylate and 2-amino-1,3-dicyanoazulene
  作者：Arh-Hwang Chen、(the Late) Tetsuo Nozoe

  DOI：10.1016/s0040-4039(98)01632-3

  日期：1998.10

  A simple new method for methoxylation of 7-membered ring of 1,2,3-trisubstituted azulenes via electrooxidation is reported. It could be useful in preparing 2,4- and 2,6-azuloquinone analogs.

  报道了一种通过电氧化对1,2,3-三取代的天青烯的7元环进行甲氧基化的简单新方法。在制备2，4-和2，6-azuloquinone类似物时可能很有用。
• New Method for the Synthesis of Polyether-Bridged Azulenes:  Reactions of Conjugated Ketocarbenes Generated from the Corresponding Azulenoquinone Diazides
  作者：Yun-Shan Lin、Shuan-Ya Jiang、Tian-Chyuan Huang、Shih-Jue Lin、Yuan L. Chow

  DOI：10.1021/jo971494u

  日期：1998.5.1

  The diazide of 2,4-azulenoquinone carrying 1,3-cyano and carbomethoxy substituents was synthesized and photolyzed in cyclic ethers (THF, dioxane, and tetrahydropyran) to give good yields of 2,4-polyether-bridged azulenes. The shapes of some azulene polyethers were examined by X-ray structural determination to show the cavity size ranging from 6.4 to 4.1 Angstrom (long-short diameters) to 7.36-6.6 Angstrom encircled by an azulene and polyether are. In analogy to 2,5-cyclohexadien-4-onylidenes, photogenerated conjugated azulenone carbenes were assumed to have energetically closely spaced triplet and singlet ground states that can interconvert readily and react from one of these states under ambient conditions. The spanning of a polyether bridge is initiated by the electrophilic attack of a singlet state on the oxygen of solvent ethers, followed by one or two propagation steps and a ring closure by phenolate attack. The 1,3-dicarbomethoxy group could exert steric effects to hinder the approach of the ether oxygen and control the polyether spanning processes and ring size; this caused a triplet state reaction to supersede the overall reaction. While radical and insertion reactions are common for ketocarbene reactions, the present description adduces a well manifested electrophilic reaction of the allied transients.
• Electrochemical Methoxylation of 1,2,3-Trisubstituted Azulenes
  作者：Arh-Hwang Chen

  DOI：10.1002/jccs.199900004

  日期：1999.2

  Abstract1,2,3‐Trisubstituted azulene analogs 6a and 6b easily underwent methoxylation in position 4 or 6 of an azulene ring via an electrochemical oxidation. It is a simple, convenient and selective method for introducing a methoxy group into a 7‐membered ring of azulene analogs when compared with traditional chemical methods. It could be useful in preparing 2,4‐ and 2,6‐azuloquinone analogs.