4'-Methoxy-2.2-dimethylpropiophenonhydrazon | 54953-03-6

• 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: 4'-Methoxy-2.2-dimethylpropiophenonhydrazon
• 英文别名: 1-(4-methoxy-phenyl)-2,2-dimethyl-propan-1-one hydrazone；[1-(4-Methoxyphenyl)-2,2-dimethylpropylidene]hydrazine
• CAS: 54953-03-6
• 化学式: C₁₂H₁₈N₂O
• 分子量: 206.288
• InChiKey: SAOJIYINYDNITO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4'-Methoxy-2.2-dimethylpropiophenonhydrazon 在 三乙胺 、 间氯过氧苯甲酸 、 溴化硒 作用下， 以 二氯甲烷 为溶剂， 生成 1-(4-甲氧基苯基)-2,2-二甲基丙烷-1-酮
  参考文献：
  名称：

  First Isolation of cis- and trans-1,3,4-Selenadiazolines from Pivarophenone Hydrazones

  摘要：

  Sterically congested cis- and trans-1,3,4-selenadiazolines were isolated by one-pot reaction of pivalophenone hydrazones with diselenium dibromide, which suggested in situ formation of selenoketone and diazoalkane intermediates. Thermolysis of these compounds gave symmetrical olefins, whereas oxidation afforded the corresponding azines.

  DOI：

  10.3987/com-02-9672
• 作为产物：
  描述：

  1-(4-甲氧基苯基)-2,2-二甲基丙烷-1-酮 在 一水合肼 作用下， 以 乙醇 为溶剂， 反应 8.0h， 生成 4'-Methoxy-2.2-dimethylpropiophenonhydrazon
  参考文献：
  名称：

  Formation and reactivity of .sigma.-radical cation intermediates in the carbon-carbon coupling reaction of phenyldiazomethanes by one-electron oxidation

  摘要：

  One-electron oxidation of phenyldiazomethanes afforded cis-stilbene predominantly. The reaction was independent of the oxidation methods, e.g., electrolysis, copper(II), triarylaminium salts, or photosensitized one-electron oxidations. The C-C coupling reaction was retarded by introducing alpha-substituents on phenyldiazomethane. The ESR spectra of diazoalkane radical cations could be obtained during the electrolysis at low temperature and the resulting spectra revealed their unique electronic structure as sigma-radicals for most cases. When a bulky tert-butyl group was substituted, the corresponding pi-radical cation was observed, but the C-C coupling reaction did not occur. The novel HOMO-LUMO switching by one-electron removal from the HOMO pi-orbital of diazomethane is explained by the interaction of phenyl group with the C-N-N sigma-radical moiety. The C-C coupling reaction proceeds via facile [4 + 2] cycloaddition between the diazomethane and sigma-radical cation, and the preferential formation of cis-olefins is based on the secondary orbital interaction between the two phenyl groups. The structure and the stability of radical cation intermediates are rationalized on the basis of ab initio calculations.

  DOI：

  10.1021/jo00037a021

文献信息

• Preparation and N.M.R. spectra of 2,5-Diaryl-2,5-di-t-butyl-Δ3-1,3,4-thiadiazoline 1,1-Dioxides
  作者：GC Brophy、DJ Collins、JJ Hobbs、S Sternhell

  DOI：10.1071/ch9750151

  日期：——

  The reaction of 1-(4-methoxyphenyl)-2,2-dimethyldiazopropane with sulphur dioxide in benzene at 5? gave a 54% yield of 2,5-di-t-butyl- 2,5-bis(4-methoxyphenyl)-Δ3-1,3,4-thiadiazoline 1,1-dioxide (4a). The n.m.r, spectra of this and the analogous compounds from 1-(4- chlorophenyl)-, and 1-(3,4,5-trimethoxyphenyl)-diazopropane, showed temperature dependence due to restricted rotation of the aryl groups. The energy barriers associated with this process were determined.��� Structural factors profoundly influence the course of the reaction of 1-aryldiazoalkanes with sulphur dioxide. For example, 1-adamantyl-1- (4-methoxyphenyl)diazomethane gave no detectable amount of the thiadiazoline derivative, but an almost quantitative yield of 1-(4- methoxybenzoyl)-adamantane.

  反应 1-(4-甲氧基苯基)-2,2-二甲基二氮丙烷与二氧化硫在苯中于 5? 的条件下与二氧化硫在苯中反应，得到了产率为 54%的 2,5-二叔丁基-2,5-双（4-甲氧基苯基）-Δ3-1,3,4-噻二唑啉（4a）。 1,1-二氧化物 (4a)。该化合物和以下类似化合物的 n.m.r.光谱 1-（4-氯苯基）- 和 1-（3,4,5-三甲氧基苯基）- 二氮丙烷的类似化合物、 由于芳基旋转受限，该化合物显示出温度依赖性。 结构因素对 1-芳基-3,4,5-三甲氧基苯基-二氮丙烷的反应过程影响深远。 结构因素深刻影响着 1-芳基重氮烷烃与二氧化硫的反应过程。例如 例如，1-金刚烷基-1-(4-甲氧基苯基)重氮甲烷在与二氧化硫的反应中不会产生可检测到的 噻二唑啉衍生物，但几乎可以定量生成 1-（4-甲氧基苯甲酰基）-金刚烷。
• Synthesis and properties of 3-oxo-1,2-diazetidinium ylides
  作者：Edward C. Taylor、Neil F. Haley、Robert J. Clemens

  DOI：10.1021/ja00416a009

  日期：1981.12
• Formation and reactivity of .sigma.-radical cation intermediates in the carbon-carbon coupling reaction of phenyldiazomethanes by one-electron oxidation
  作者：Katsuya Ishiguro、Masatoshi Ikeda、Yasuhiko Sawaki

  DOI：10.1021/jo00037a021

  日期：1992.5

  One-electron oxidation of phenyldiazomethanes afforded cis-stilbene predominantly. The reaction was independent of the oxidation methods, e.g., electrolysis, copper(II), triarylaminium salts, or photosensitized one-electron oxidations. The C-C coupling reaction was retarded by introducing alpha-substituents on phenyldiazomethane. The ESR spectra of diazoalkane radical cations could be obtained during the electrolysis at low temperature and the resulting spectra revealed their unique electronic structure as sigma-radicals for most cases. When a bulky tert-butyl group was substituted, the corresponding pi-radical cation was observed, but the C-C coupling reaction did not occur. The novel HOMO-LUMO switching by one-electron removal from the HOMO pi-orbital of diazomethane is explained by the interaction of phenyl group with the C-N-N sigma-radical moiety. The C-C coupling reaction proceeds via facile [4 + 2] cycloaddition between the diazomethane and sigma-radical cation, and the preferential formation of cis-olefins is based on the secondary orbital interaction between the two phenyl groups. The structure and the stability of radical cation intermediates are rationalized on the basis of ab initio calculations.
• First Isolation of cis- and trans-1,3,4-Selenadiazolines from Pivarophenone Hydrazones
  作者：Kentaro Okuma、Kento Kubo、Yoshinobu Yokomori

  DOI：10.3987/com-02-9672

  日期：——

  Sterically congested cis- and trans-1,3,4-selenadiazolines were isolated by one-pot reaction of pivalophenone hydrazones with diselenium dibromide, which suggested in situ formation of selenoketone and diazoalkane intermediates. Thermolysis of these compounds gave symmetrical olefins, whereas oxidation afforded the corresponding azines.