Ethyl 2-amino-3-cyano-4-methoxyazulene-1-carboxylate | 171363-16-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: Ethyl 2-amino-3-cyano-4-methoxyazulene-1-carboxylate
• CAS: 171363-16-9
• 化学式: C₁₅H₁₄N₂O₃
• 分子量: 270.288
• InChiKey: QIOXMWNFYJBTRG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  Ethyl 2-amino-3-cyano-4-methoxyazulene-1-carboxylate 在 palladium on activated charcoal 硫酸 、 氢气 、 sodium nitrite 作用下， 以 1,4-二氧六环 、 甲醇 、 水 为溶剂， 反应 2.0h， 生成 Ethyl 3-cyano-4-hydroxyazulene-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
• 作为产物：
  描述：

  ethyl 2-oxo-2H-cyclohepta[b]furan-3-carboxylate 在 盐酸 、 sodium hydroxide 、 sodium ethanolate 、 silver nitrate 作用下， 以 乙醇 为溶剂， 反应 10.0h， 生成 Ethyl 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

• Synthesis of 2-Amino-1-cyanoazulenes: Substituent Effect on 2H-Cyclohepta[b]furan-2-ones toward the Reaction with Malononitrile
  作者：Taku Shoji、Shuhei Sugiyama、Kota Miura、Akira Ohta、Ryuta Sekiguchi、Shunji Ito、Shigeki Mori

  DOI：10.3987/com-18-s(t)89

  日期：——

  3-Substituted 2-amino- 1-cyanoazulene derivatives were prepared by the reaction of 2H-cyclohepta[b]furan-2-ones with malononitrile in the presence of triethylamine as a base. The great influence of the substituent at their 3-position on the reactivity to form the 2-aminoazulene derivatives was revealed. The intramolecular charge transfer (ICT) characters of 2-amino- 1-cyano-3-vinylazulenes were investigated by UV/Vis spectroscopy and theoretical calculations. The structure of compounds 13b and 14b was clarified by single crystal X-ray analysis.
• 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.