Methyl 2-amino-3-cyano-4-methoxyazulene-1-carboxylate | 171363-10-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: Methyl 2-amino-3-cyano-4-methoxyazulene-1-carboxylate
• CAS: 171363-10-3
• 化学式: C₁₄H₁₂N₂O₃
• 分子量: 256.261
• InChiKey: ALFKURGUPVPDHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  85.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl 2-amino-3-cyano-4-methoxyazulene-1-carboxylate 在 硫酸 、 sodium nitrite 作用下， 以 1,4-二氧六环 为溶剂， 反应 2.0h， 以99%的产率得到3-Cyano-2-diazo-4-oxo-2,4-dihydro-azulene-1-carboxylic acid methyl ester
  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：

  3-(甲氧羰基)-2H-环庚[b]呋喃-2-酮 在 盐酸 、 sodium hydroxide 、 sodium methylate 、 silver nitrate 作用下， 以 甲醇 为溶剂， 反应 10.0h， 生成 Methyl 2-amino-3-cyano-4-methoxyazulene-1-carboxylate
  参考文献：
  名称：

  Formation and structure of 2-diazo-2,4-azulenequinone derivatives

  摘要：

  The diazotization of methyl (and ethyl) 2-amino-3-cyano-4-methoxy(and ethoxy)azulene-1-carboxylate (1-4) was examined to determine whether the products are 2-diazo-2,4-azulenequinone derivatives (B) or azulene-2-diazonium-1-carboxylate derivatives (C). Since diazotization of 1 and 2 gave the same diazo compound 5 and diazotization of both 3 and 4-gave diazo compound 6, the diazo compounds are deduced to not be azulene-2-diazonium-1-carboxylate derivatives (7 and 8), but rather to be 2-diazo-2,4-azulenequinone derivatives (5 and 6). The diazo carbons of both 5 and 6 show C-13 NMR signals at delta 66.3, and their carbonyl carbons resonate at 6 181.1, in good agreement with a 2-diazo-2,4-azulenequinone structure. The structures of diazo compounds 24 and 25, which we have previously reported,(1) are reexamined on the basis of the analysis of their C-13 NMR spectra. The contribution of a quinoid structure and a diazoazulenolate structure to 5, 6, 24, and 25 is discussed by comparison of their C-13 NMR spectral data with those of 4-diazo-2,5-cyclohexadien-1-one derivatives. It is concluded that the contribution of the quinoid structure is larger than that of the diazoazulenolate structure.

  DOI：

  10.1021/jo00123a031

文献信息

• Formation and structure of 2-diazo-2,4-azulenequinone derivatives
  作者：Tetsuo Nozoe、Toyonobu Asao、Masafumi Yasunami、Hisamitu Wakui、Toshio Suzuki、Masayoshi Ando

  DOI：10.1021/jo00123a031

  日期：1995.9

  The diazotization of methyl (and ethyl) 2-amino-3-cyano-4-methoxy(and ethoxy)azulene-1-carboxylate (1-4) was examined to determine whether the products are 2-diazo-2,4-azulenequinone derivatives (B) or azulene-2-diazonium-1-carboxylate derivatives (C). Since diazotization of 1 and 2 gave the same diazo compound 5 and diazotization of both 3 and 4-gave diazo compound 6, the diazo compounds are deduced to not be azulene-2-diazonium-1-carboxylate derivatives (7 and 8), but rather to be 2-diazo-2,4-azulenequinone derivatives (5 and 6). The diazo carbons of both 5 and 6 show C-13 NMR signals at delta 66.3, and their carbonyl carbons resonate at 6 181.1, in good agreement with a 2-diazo-2,4-azulenequinone structure. The structures of diazo compounds 24 and 25, which we have previously reported,(1) are reexamined on the basis of the analysis of their C-13 NMR spectra. The contribution of a quinoid structure and a diazoazulenolate structure to 5, 6, 24, and 25 is discussed by comparison of their C-13 NMR spectral data with those of 4-diazo-2,5-cyclohexadien-1-one derivatives. It is concluded that the contribution of the quinoid structure is larger than that of the diazoazulenolate structure.
• 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.

表征谱图