2,2,2-trifluoro-1-(4-methoxy-2,6-dimethylphenyl)ethanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2,2-trifluoro-1-(4-methoxy-2,6-dimethylphenyl)ethanone
• 英文别名: 2,2,2-Trifluoro-1-(4-methoxy-2,6-dimethylphenyl)ethanone
• 化学式: C₁₁H₁₁F₃O₂
• 分子量: 232.202
• InChiKey: PRRKLMNOWBVDKE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  三氟乙酸乙酯 、 2-溴-5-甲氧基-1,3-二甲苯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.5h， 以79%的产率得到2,2,2-trifluoro-1-(4-methoxy-2,6-dimethylphenyl)ethanone
  参考文献：
  名称：

  Quantum chemical calculation of 19F NMR chemical shifts of trifluoromethyl diazirine photoproducts and precursors

  摘要：

  Irradiation of aryl(trifluoromethyl)diazirines may result in a multitude of products, which are difficult to assign in the F-19 NMR spectrum. In this article, it is demonstrated that an average accuracy of 2.9 ppm (standard deviation) can be achieved by quantum chemical calculations at the B3LYP 6-311G++(2d,2p) level of theory, followed by a Boltzmann weighting of the optimized conformers. A set of 30 compounds was investigated both-experimentally and theoretically. F-19 NMR chemical shifts of precursor Z-oximes and Z-tosyloximes ranged from delta(F) -62.9 to -61.8 ppm, whereas their E counterparts showed shifts between delta(F) -67.2 and -66.2 ppm. Stereochemical assignments were confirmed by two X-ray analyses. Quantum chemical calculation also allowed the assignment of the configuration of an (E,E) azine. Trifluoromethyl diazirines exhibited a delta(F) between -66.1 and -65.6, diaziridines between -76.2 and -75.9 ppm. The smallest delta(F) values were observed for alpha-oxygenated trifluoromethyl compounds (delta(F) -78.9 to -77.4 ppm). The average deviation of the calculated from the experimental values corresponds to only about 1% of the standard F-19 NMR chemical shift range. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2014.06.027

文献信息

• Quantum chemical calculation of 19F NMR chemical shifts of trifluoromethyl diazirine photoproducts and precursors
  作者：Björn Raimer、Peter G. Jones、Thomas Lindel

  DOI：10.1016/j.jfluchem.2014.06.027

  日期：2014.10

  Irradiation of aryl(trifluoromethyl)diazirines may result in a multitude of products, which are difficult to assign in the F-19 NMR spectrum. In this article, it is demonstrated that an average accuracy of 2.9 ppm (standard deviation) can be achieved by quantum chemical calculations at the B3LYP 6-311G++(2d,2p) level of theory, followed by a Boltzmann weighting of the optimized conformers. A set of 30 compounds was investigated both-experimentally and theoretically. F-19 NMR chemical shifts of precursor Z-oximes and Z-tosyloximes ranged from delta(F) -62.9 to -61.8 ppm, whereas their E counterparts showed shifts between delta(F) -67.2 and -66.2 ppm. Stereochemical assignments were confirmed by two X-ray analyses. Quantum chemical calculation also allowed the assignment of the configuration of an (E,E) azine. Trifluoromethyl diazirines exhibited a delta(F) between -66.1 and -65.6, diaziridines between -76.2 and -75.9 ppm. The smallest delta(F) values were observed for alpha-oxygenated trifluoromethyl compounds (delta(F) -78.9 to -77.4 ppm). The average deviation of the calculated from the experimental values corresponds to only about 1% of the standard F-19 NMR chemical shift range. (C) 2014 Elsevier B.V. All rights reserved.