N¹-(4-oxo-2,5-cyclohexadien-1-ylidene)-N²-(4-chlorophenyl)-2,2,2-trifluoroethanimidamide | 137927-32-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N¹-(4-oxo-2,5-cyclohexadien-1-ylidene)-N²-(4-chlorophenyl)-2,2,2-trifluoroethanimidamide
• 英文别名: N'-(4-chlorophenyl)-2,2,2-trifluoro-N-(4-oxocyclohexa-2,5-dien-1-ylidene)ethanimidamide
• CAS: 137927-32-3
• 化学式: C₁₄H₈ClF₃N₂O
• 分子量: 312.679
• InChiKey: SKOPISRSVLPBCP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  41.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N¹-(4-oxo-2,5-cyclohexadien-1-ylidene)-N²-(4-chlorophenyl)-2,2,2-trifluoroethanimidamide 以 二甲基亚砜 为溶剂， 反应 2.0h， 以97%的产率得到2'-(trifluoromethyl)-6'-chlorospiro<2,5-cyclohexadiene-1,4'-3'H-quinazolin>-4-one
  参考文献：
  名称：

  Intramolecular Cyclization of N1-(4-Oxo-2,5-cyclohexadien-1-ylidene)-N2-substituted-2,2,2- trifluoroethanimidamides (p-Benzoquinone Imine Derivatives): Syntheses of Trifluoromethylated 6-Hydroxybenzimidazoles and Spiro Dienone Diazacarbocycles

  摘要：

  Lewis acid-catalyzed intramolecular cyclization of N-1-(4-oxo-2,5-cyclohexadien-1-ylidene)-N-2- substituted-2,2,2-trifluoroethanimidamide (p-benzoquinone imine derivatives, 1) prepared by electrooxidation of N-(4-methoxyphenyli-N'-substituted-2,2 2-trifluoroethanimidamides 2 occurred to give 1-substituted-2-(trifluoromethyl)-6-hydroxybenzimidazoles 3. Alternatively, thermal cyclization of 1 gave spiro dienone diazacarbocycles 9 and 10, which were converted into diazepine 12 via a dienone-phenol rearrangement.

  DOI：

  10.1021/jo00125a028
• 作为产物：
  描述：

  2,2,2-三氟-N-(4-甲氧基苯基)-亚氨基氯化物 在 sodium hydride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 0.5h， 生成 N¹-(4-oxo-2,5-cyclohexadien-1-ylidene)-N²-(4-chlorophenyl)-2,2,2-trifluoroethanimidamide
  参考文献：
  名称：

  Electrochemical Oxidation of N,N'-Disubstituted Trifluoroethanimidamides. An Approach to N-Substituted 2-(Trifluoromethyl)benzimidazoles

  摘要：

  Electrochemical oxidation of N,N'-disubstituted trifluoroethanimidamides 11 in dry acetonitrile and in aqueous acetonitrile provided N-substituted 2-(trifluoromethyl)benzimidazoles 15 and N-1-(4-oxo-2,5-cyclohexadien-1-ylidene)-N-2-substituted-2,2,2-trifluoroethanimidamides (p-benzoquinone imine derivatives) 20, respectively. In dry acetonitrile, electron-donating para substituents in the N,N'-diaryl derivatives strongly promoted the formation of benzimidazoles, whereas N-alkyl-N'(4-methoxyphenyl) derivatives provided rather complex mixtures of 11,20, and polymeric compounds. In wet acetonitrile, p-benzoquinone imines 20 were major products regardless of the substituents. An ECEC process via two-electron oxidation is proposed.

  DOI：

  10.1021/jo00090a017

文献信息

• Thermal electrocyclic spirocyclization of p-benzoquinone imines: A novel synthetic route to trifluoromethylated spirodiazacarbocycles
  作者：Masafumi Kobayashi、Kenji Uneyama、Noritaka Hamada、Setsuo Kashino

  DOI：10.1016/s0040-4039(00)77072-9

  日期：1994.7

  2′-trifluoromethyl-spiro[2,5-cyclohexadiene-1,4′-1H(or 3H)-quinazolin]-4-ones (spirodienone derivatives) (3) and (4), which were transformed to 1,3-diazepine derivative (7) by Lewis acid-catalyzed dienone-phenol rearrangement.

  电化学制备的N-（4-氧代-2,5-环己二烯-1-亚基）-2,2,2,3-三氟乙酰胺（对苯醌衍生物）（2）在DMSO中于120°C加热加热环化成2'-三氟甲基-螺[2,5-环己二烯-1,4'-1 H（或3 H）-喹唑啉] -4-酮（螺二烯酮衍生物）（3）和（4），它们被转化为1,3-二氮杂pine衍生物（7）由路易斯酸催化的二烯酮-苯酚重排。
• Syntheses of 1-aryl-2-trifluoromethylbenzimidazoles via electrochemically prepared p-benzoquinone imines
  作者：Kenji Uneyama、Masafumi Kobayashi

  DOI：10.1016/s0040-4039(00)79443-3

  日期：1991.10

  Electrooxidation of N-(4-methoxyphenyl)-N'-aryl-2,2,2-trifluoroethanimidamides 1 in an MeCN-H2O-NaClO4-(C)-(Pt) system affords p-benzoquinone imines 2 which are converted to 1-aryl-2-trifluoromethylbenzimidazoles 3 by acid catalyzed cyclization.
• Electrochemical Oxidation of N,N'-Disubstituted Trifluoroethanimidamides. An Approach to N-Substituted 2-(Trifluoromethyl)benzimidazoles
  作者：Kenji Uneyama、Masafumi Kobayashi

  DOI：10.1021/jo00090a017

  日期：1994.6

  Electrochemical oxidation of N,N'-disubstituted trifluoroethanimidamides 11 in dry acetonitrile and in aqueous acetonitrile provided N-substituted 2-(trifluoromethyl)benzimidazoles 15 and N-1-(4-oxo-2,5-cyclohexadien-1-ylidene)-N-2-substituted-2,2,2-trifluoroethanimidamides (p-benzoquinone imine derivatives) 20, respectively. In dry acetonitrile, electron-donating para substituents in the N,N'-diaryl derivatives strongly promoted the formation of benzimidazoles, whereas N-alkyl-N'(4-methoxyphenyl) derivatives provided rather complex mixtures of 11,20, and polymeric compounds. In wet acetonitrile, p-benzoquinone imines 20 were major products regardless of the substituents. An ECEC process via two-electron oxidation is proposed.
• Intramolecular Cyclization of N1-(4-Oxo-2,5-cyclohexadien-1-ylidene)-N2-substituted-2,2,2- trifluoroethanimidamides (p-Benzoquinone Imine Derivatives): Syntheses of Trifluoromethylated 6-Hydroxybenzimidazoles and Spiro Dienone Diazacarbocycles
  作者：Masafumi Kobayashi、Kenji Uneyama、Noritaka Hamada、Setsuo Kashino

  DOI：10.1021/jo00125a028

  日期：1995.10

  Lewis acid-catalyzed intramolecular cyclization of N-1-(4-oxo-2,5-cyclohexadien-1-ylidene)-N-2- substituted-2,2,2-trifluoroethanimidamide (p-benzoquinone imine derivatives, 1) prepared by electrooxidation of N-(4-methoxyphenyli-N'-substituted-2,2 2-trifluoroethanimidamides 2 occurred to give 1-substituted-2-(trifluoromethyl)-6-hydroxybenzimidazoles 3. Alternatively, thermal cyclization of 1 gave spiro dienone diazacarbocycles 9 and 10, which were converted into diazepine 12 via a dienone-phenol rearrangement.