trifluoroacetophenone O-oxide | 111351-10-1

• 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: trifluoroacetophenone O-oxide
• CAS: 111351-10-1
• 化学式: C₈H₅F₃O₂
• 分子量: 190.122
• InChiKey: YOKVRPZLMPIQIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.49
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  29.13
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  (1-重氮基-2,2,2-三氟乙基)苯 在 氧气 、 亚甲兰 作用下， 以 乙腈 为溶剂， 生成 2,2,2-三氟苯乙酮 、 trifluoroacetophenone O-oxide
  参考文献：
  名称：

  潜在的吸电子三氟甲基使氧化碳反应性发生剧烈变化。

  摘要：

  由（1）O（2）氧化Ph（CF（3））CN（2）生成的α，α，α-三氟苯乙酮氧化物，与亚砜（rho = -0.74 vs sigma; r = 0.95）发生亲电反应，提供硫化物作为主要产品。通过（18）O-示踪剂研究以及在与苄基苯基亚砜的反应中苯甲醛的形成，证明了在新型脱氧反应中通过环状过氧化物硫烷形成的过亚砜的中间体。Ph（CF（3））CN（2）的光氧化过程中，烯烃被氧化成环氧化物。由于环氧化反应几乎是立体定向的，并且取代基对苯乙烯的作用导致-rh值为-1.66 vsσ（r = 0.97），所以建议使用二环氧乙烷作为第二种中间体，这可能是羰基异构化形成的氧化物。用苯乙烯和亚砜的诱捕实验表明，羰基氧化物的环化与亚砜的反应具有竞争性。与已知的羰基氧化物的亲核性质相反，本发明的氧化物显示出具有亲电特性，表明羰基氧化物的反应性可以由取代基控制。

  DOI：

  10.1021/jo961728u

文献信息

• Mechanistic Study on the Reaction of Phenyldiazomethanes with Singlet Oxygen:  Formation and Cycloreversion of 1,2,3,4-Dioxadiazole Intermediates
  作者：Takayuki Nojima、Katsuya Ishiguro、Yasuhiko Sawaki

  DOI：10.1021/jo9711394

  日期：1997.10.1

  The formation of carbonyl oxides in the singlet oxygen (O-1(2)) oxidation of phenyldiazomethanes 1 has been investigated mechanistically. Product ratios of N-2/N2O, which are indicative of the selectivity in the carbonyl oxide/ketone formation, were determined by gas chromatography/mass spectrometry (GC/MS). The yields of carbonyl oxides were not affected by changing solvents but were significantly increased with the increasing electron-donating ability of substituents on diazomethanes. Rate constants for the quenching of O-1(2) by 1 as determined by monitoring the emission of O-1(2) at 1270 nm were also insensitive to solvents. These results suggest the predominant formation of 1,2,3,4-dioxadiazole intermediates by the cycloaddition of O-1(2) to 1 followed by its cycloreversion, the selectivity of which is controlled by the relative stability of resulting carbonyl oxides. The formation of carbonyl oxides, observable from its transient absorption at similar to 400 nm, was in good agreement with the decay of O-1(2) within the experimental error, indicating that the 1,2,3,4-dioxadiazoles are a highly labile intermediate with the lifetime of less than 100 ns.