2-Diazo-4-oxo-2,4-dihydro-azulene-1,3-dicarbonitrile | 205595-25-1

• 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-Diazo-4-oxo-2,4-dihydro-azulene-1,3-dicarbonitrile
• 英文别名: 1,3-Dicyano-2-diazonioazulen-4-olate
• CAS: 205595-25-1
• 化学式: C₁₂H₄N₄O
• 分子量: 220.19
• InChiKey: OXPOSZGZVUPFPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 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：
  98.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  四氢吡喃 、 2-Diazo-4-oxo-2,4-dihydro-azulene-1,3-dicarbonitrile 反应 6.0h， 以72%的产率得到7,13,19-Trioxa-tricyclo[18.2.1.0^6,22]tricosa-1(23),2,4,6(22),20-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：

  2-Amino-4-methoxy-azulene-1,3-dicarbonitrile 在 三氟乙酸 、 sodium nitrite 作用下， 以92%的产率得到2-Diazo-4-oxo-2,4-dihydro-azulene-1,3-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

文献信息

• 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.