7,7-diphenyl-2-methyl-6-heptenoic acid 2-thioxo-2H-pyridin-1-yl ester | 220976-34-1

• 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: 7,7-diphenyl-2-methyl-6-heptenoic acid 2-thioxo-2H-pyridin-1-yl ester
• 英文别名: (2-Sulfanylidenepyridin-1-yl) 2-methyl-7,7-diphenylhept-6-enoate
• CAS: 220976-34-1
• 化学式: C₂₅H₂₅NO₂S
• 分子量: 403.545
• InChiKey: SUQOPUURSFXMSF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  7,7-diphenyl-2-methyl-6-heptenoic acid 2-thioxo-2H-pyridin-1-yl ester 在 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 3.0h， 以58%的产率得到2-(diphenylmethyl)-1-methylcyclohexane
  参考文献：
  名称：

  Adjusting the Top End of the Alkyl Radical Kinetic Scale. Laser Flash Photolysis Calibrations of Fast Radical Clocks and Rate Constants for Reactions of Benzeneselenol

  摘要：

  Rate constants for 5-exo cyclizations of the 6,6-diphenyl-5-hexenyl radical (la), the 1-methyl-6,6-diphenyl-5-hexenyl radical (Ib), and the 1,1-dimethyl-6,6-diphenyl-5-hexenyl radical (Ic) were measured by laser flash photolysis methods, and Arrhenius parameters for these cyclizations were determined. Relative rate constants for cyclizations of radicals 1 and reactions with benzeneselenol were determined by indirect kinetic methods, and the relative Arrhenius parameters for the competing reactions were combined with the parameters for the cyclization reactions to give absolute Arrhenius parameters for the PhSeH reactions. At 20 degrees C, PhSeH reacts with the 1 degrees, 2 degrees, and 3 degrees radicals 1 with nearly the same rate constants, (1.2 +/- 0.1) x 10(9) M-1 s(-1). Absolute Arrhenius parameters for reactions of PhSH and t-BuSH with the primary alkyl radical la were calculated using literature values for the competition between cyclization of la and reactions with the appropriate thiol and the absolute values for cyclization of la determined in this work. The results suggest that rate constants for reactions of primary alkyl radicals with t-BuSH are about 20% smaller than those previously reported. In the case of PhSH, the results are in good agreement with one previously reported set of rate constants but about 35% smaller than another set of rate constants that was subsequently incorporated into fast alkyl radical kinetics. The rate constants for alkyl radical reactions calibrated by competition against reaction with PhSeH and PhSH apparently are 30-40% smaller than those previously reported, and the derived rate constants for the fast radical reactions should be adjusted. An especially noteworthy example is ring opening of the cyclopropylcarbinyl radical, the Arrhenius function for which was determined in part from PI ISH trapping results. Using the adjusted rate constants for PhSH and recalculating the Arrhenius parameters for the cyclopropylcarbinyl radical ring opening gives log(k/s(-1)) = (13.04(5) +/- 0.10) - (6.99 +/- 0.09)/theta (kcal/mol, errors at 2 sigma); the rate constant at 20 degrees C of 6.7 x 10(7) s(-1) is about 13% smaller than that previously calculated.

  DOI：

  10.1021/jo981930s
• 作为产物：
  描述：

  7,7-diphenyl-2-methyl-6-heptenoic acid 在 4-二甲氨基吡啶 、 草酰氯 、 N,N-二甲基甲酰胺 作用下， 以 苯 为溶剂， 反应 3.0h， 生成 7,7-diphenyl-2-methyl-6-heptenoic acid 2-thioxo-2H-pyridin-1-yl ester
  参考文献：
  名称：

  Adjusting the Top End of the Alkyl Radical Kinetic Scale. Laser Flash Photolysis Calibrations of Fast Radical Clocks and Rate Constants for Reactions of Benzeneselenol

  摘要：

  Rate constants for 5-exo cyclizations of the 6,6-diphenyl-5-hexenyl radical (la), the 1-methyl-6,6-diphenyl-5-hexenyl radical (Ib), and the 1,1-dimethyl-6,6-diphenyl-5-hexenyl radical (Ic) were measured by laser flash photolysis methods, and Arrhenius parameters for these cyclizations were determined. Relative rate constants for cyclizations of radicals 1 and reactions with benzeneselenol were determined by indirect kinetic methods, and the relative Arrhenius parameters for the competing reactions were combined with the parameters for the cyclization reactions to give absolute Arrhenius parameters for the PhSeH reactions. At 20 degrees C, PhSeH reacts with the 1 degrees, 2 degrees, and 3 degrees radicals 1 with nearly the same rate constants, (1.2 +/- 0.1) x 10(9) M-1 s(-1). Absolute Arrhenius parameters for reactions of PhSH and t-BuSH with the primary alkyl radical la were calculated using literature values for the competition between cyclization of la and reactions with the appropriate thiol and the absolute values for cyclization of la determined in this work. The results suggest that rate constants for reactions of primary alkyl radicals with t-BuSH are about 20% smaller than those previously reported. In the case of PhSH, the results are in good agreement with one previously reported set of rate constants but about 35% smaller than another set of rate constants that was subsequently incorporated into fast alkyl radical kinetics. The rate constants for alkyl radical reactions calibrated by competition against reaction with PhSeH and PhSH apparently are 30-40% smaller than those previously reported, and the derived rate constants for the fast radical reactions should be adjusted. An especially noteworthy example is ring opening of the cyclopropylcarbinyl radical, the Arrhenius function for which was determined in part from PI ISH trapping results. Using the adjusted rate constants for PhSH and recalculating the Arrhenius parameters for the cyclopropylcarbinyl radical ring opening gives log(k/s(-1)) = (13.04(5) +/- 0.10) - (6.99 +/- 0.09)/theta (kcal/mol, errors at 2 sigma); the rate constant at 20 degrees C of 6.7 x 10(7) s(-1) is about 13% smaller than that previously calculated.

  DOI：

  10.1021/jo981930s

文献信息

• Adjusting the Top End of the Alkyl Radical Kinetic Scale. Laser Flash Photolysis Calibrations of Fast Radical Clocks and Rate Constants for Reactions of Benzeneselenol
  作者：Martin Newcomb、Seung-Yong Choi、John H. Horner

  DOI：10.1021/jo981930s

  日期：1999.2.1

  Rate constants for 5-exo cyclizations of the 6,6-diphenyl-5-hexenyl radical (la), the 1-methyl-6,6-diphenyl-5-hexenyl radical (Ib), and the 1,1-dimethyl-6,6-diphenyl-5-hexenyl radical (Ic) were measured by laser flash photolysis methods, and Arrhenius parameters for these cyclizations were determined. Relative rate constants for cyclizations of radicals 1 and reactions with benzeneselenol were determined by indirect kinetic methods, and the relative Arrhenius parameters for the competing reactions were combined with the parameters for the cyclization reactions to give absolute Arrhenius parameters for the PhSeH reactions. At 20 degrees C, PhSeH reacts with the 1 degrees, 2 degrees, and 3 degrees radicals 1 with nearly the same rate constants, (1.2 +/- 0.1) x 10(9) M-1 s(-1). Absolute Arrhenius parameters for reactions of PhSH and t-BuSH with the primary alkyl radical la were calculated using literature values for the competition between cyclization of la and reactions with the appropriate thiol and the absolute values for cyclization of la determined in this work. The results suggest that rate constants for reactions of primary alkyl radicals with t-BuSH are about 20% smaller than those previously reported. In the case of PhSH, the results are in good agreement with one previously reported set of rate constants but about 35% smaller than another set of rate constants that was subsequently incorporated into fast alkyl radical kinetics. The rate constants for alkyl radical reactions calibrated by competition against reaction with PhSeH and PhSH apparently are 30-40% smaller than those previously reported, and the derived rate constants for the fast radical reactions should be adjusted. An especially noteworthy example is ring opening of the cyclopropylcarbinyl radical, the Arrhenius function for which was determined in part from PI ISH trapping results. Using the adjusted rate constants for PhSH and recalculating the Arrhenius parameters for the cyclopropylcarbinyl radical ring opening gives log(k/s(-1)) = (13.04(5) +/- 0.10) - (6.99 +/- 0.09)/theta (kcal/mol, errors at 2 sigma); the rate constant at 20 degrees C of 6.7 x 10(7) s(-1) is about 13% smaller than that previously calculated.