1-(3,4-dimethylphenyl)-2-phenyl-1-propanone | 135584-30-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1-(3,4-dimethylphenyl)-2-phenyl-1-propanone
• 英文别名: 1-(3,4-Dimethylphenyl)-2-phenylpropan-1-one
• CAS: 135584-30-4
• 化学式: C₁₇H₁₈O
• 分子量: 238.329
• InChiKey: DHPJSEYSWRVSRA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(3,4-dimethylphenyl)-2-phenyl-1-propanone 在 1,3-二溴-5,5-二甲基海因 、 硫酸 、 双氧水 、 magnesium 作用下， 以 四氢呋喃 、 溶剂黄146 为溶剂， 反应 42.92h， 生成 2-bromo-2-(3,4-dimethylphenyl)-3-phenyl-3-hydroperoxybutane
  参考文献：
  名称：

  Excited state selectivity in the thermolysis of a 3,4-diaryl-3,4-dimethyl-1,2-dioxetane

  摘要：

  Total efficiencies for the production of triplet ketones from cis- and trans-3-(3,4-dimethylphenyl)-4-phenyl-1,2-dioxetane (11) are 14.1 +/- 0.2% and 21.3 +/- 0.5%, respectively. The specific efficiency for the production of triplet acetophenone from trans-11 was determined to be 19 +/- 4% by trapping the triplet with 2-methyl-2-butene to give the oxetane. These results show that the production of triplets from the dioxetane is state selective, since the n,pi* acetophenone triplet is higher in energy than the alternative pi,pi* triplet of 3,4-dimethylacetophenone. This state-selective production of triplet ketone is most reasonably dictated by orbital symmetry control in the thermolysis of the dioxetane. With this assumption, implications on the mechanism of dioxetane decomposition in terms of biradical intermediates or a concerted biradicaloid process are considered. Activation parameters for thermolysis of cis- and trans-11 are consistent with a biradical or biradicaloid mechanism. From these activation parameters and molecular mechanics calculations, it was concluded that the transition state was not quite half-way between the dioxetane reactant and a biradical intermediate, if the reaction proceeded through a biradical intermediate. In conjunction with earlier reported triplet efficiencies of 3,4-diaryl-3,4-dimethyl-1,2-dioxetanes and the efficiencies of cis- and trans-11, the participation of a triplet exciplex was suggested.

  DOI：

  10.1021/jo00021a033
• 作为产物：
  描述：

  邻二甲苯 、 2-苯基丙酰氯 在 三氯化铝 作用下， 以 二硫化碳 为溶剂， 反应 14.0h， 以99%的产率得到1-(3,4-dimethylphenyl)-2-phenyl-1-propanone
  参考文献：
  名称：

  Excited state selectivity in the thermolysis of a 3,4-diaryl-3,4-dimethyl-1,2-dioxetane

  摘要：

  Total efficiencies for the production of triplet ketones from cis- and trans-3-(3,4-dimethylphenyl)-4-phenyl-1,2-dioxetane (11) are 14.1 +/- 0.2% and 21.3 +/- 0.5%, respectively. The specific efficiency for the production of triplet acetophenone from trans-11 was determined to be 19 +/- 4% by trapping the triplet with 2-methyl-2-butene to give the oxetane. These results show that the production of triplets from the dioxetane is state selective, since the n,pi* acetophenone triplet is higher in energy than the alternative pi,pi* triplet of 3,4-dimethylacetophenone. This state-selective production of triplet ketone is most reasonably dictated by orbital symmetry control in the thermolysis of the dioxetane. With this assumption, implications on the mechanism of dioxetane decomposition in terms of biradical intermediates or a concerted biradicaloid process are considered. Activation parameters for thermolysis of cis- and trans-11 are consistent with a biradical or biradicaloid mechanism. From these activation parameters and molecular mechanics calculations, it was concluded that the transition state was not quite half-way between the dioxetane reactant and a biradical intermediate, if the reaction proceeded through a biradical intermediate. In conjunction with earlier reported triplet efficiencies of 3,4-diaryl-3,4-dimethyl-1,2-dioxetanes and the efficiencies of cis- and trans-11, the participation of a triplet exciplex was suggested.

  DOI：

  10.1021/jo00021a033

文献信息

• Excited state selectivity in the thermolysis of a 3,4-diaryl-3,4-dimethyl-1,2-dioxetane
  作者：William H. Richardson、Greg Batinica、Kasia Janota-Perret、Todd Miller、Dongming Shen

  DOI：10.1021/jo00021a033

  日期：1991.10

  Total efficiencies for the production of triplet ketones from cis- and trans-3-(3,4-dimethylphenyl)-4-phenyl-1,2-dioxetane (11) are 14.1 +/- 0.2% and 21.3 +/- 0.5%, respectively. The specific efficiency for the production of triplet acetophenone from trans-11 was determined to be 19 +/- 4% by trapping the triplet with 2-methyl-2-butene to give the oxetane. These results show that the production of triplets from the dioxetane is state selective, since the n,pi* acetophenone triplet is higher in energy than the alternative pi,pi* triplet of 3,4-dimethylacetophenone. This state-selective production of triplet ketone is most reasonably dictated by orbital symmetry control in the thermolysis of the dioxetane. With this assumption, implications on the mechanism of dioxetane decomposition in terms of biradical intermediates or a concerted biradicaloid process are considered. Activation parameters for thermolysis of cis- and trans-11 are consistent with a biradical or biradicaloid mechanism. From these activation parameters and molecular mechanics calculations, it was concluded that the transition state was not quite half-way between the dioxetane reactant and a biradical intermediate, if the reaction proceeded through a biradical intermediate. In conjunction with earlier reported triplet efficiencies of 3,4-diaryl-3,4-dimethyl-1,2-dioxetanes and the efficiencies of cis- and trans-11, the participation of a triplet exciplex was suggested.