4-acetylphenyl N-(phenylsulfonyl)carbamate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-acetylphenyl N-(phenylsulfonyl)carbamate
• 英文别名: (4-acetylphenyl) N-(benzenesulfonyl)carbamate
• 化学式: C₁₅H₁₃NO₅S
• 分子量: 319.338
• InChiKey: LIQMOAZFDMRRCD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  97.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  异氰酸苯磺酰酯 、 对羟基苯乙酮 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 4-acetylphenyl N-(phenylsulfonyl)carbamate
  参考文献：
  名称：

  A General Acid-Catalyzed Anion Breakdown Associated with an E1cB Reaction in the Hydrolysis of Aryl N-(Substituted Phenylsulfonyl)carbamates

  摘要：

  The hydrolysis of aryl N-(substituted phenylsulfonyl)carbamates at 50 degrees C in the pH range 0-13.5 leading to substituted benzenesulfonamides and phenols involves acyl group transfer. Reaction rates were measured spectrophotometrically and are independent of the concentration of the catalyst for buffers of pK(BH) > 8. With more acidic buffers, a general acid catalysis is observed for the hydrolysis of phenyl N-(phenylsulfonyl)carbamate la (pK, = 2.85) leading to a Bronsted relation (alpha = 0.46) including hydronium ion while it does not occur for 4-cyanophenyl N-(phenylsulfonyl)carbamate 1d. In alkaline media, the values of the entropies of activation are positive and lie between 0.20 and 15.0 cal mol(-1) K-1. The Hammett rho(-) value for the expulsion rate k(p) of phenolate ion from aryl N-(phenylsulfonyl)carbamates is positive (rho(-) = +2.93) while, for phenyl N-(substituted phenylsulfonyl)carbamates it is negative (rho = -0.66). An electrophilic intermediate, phenylsulfonyl isocyanate, was trapped with piperidine to give N-(piperidinocarbonyl)benzenesulfonamide. These results are consistent with an elimination-addition mechanism A(rh)D(H) + D-N (E1cB). In HCl solutions, solvent isotope effects k(obsd)(H2O)/k(obsd)(D2O) equal to 1.68 for 1a and 2.46 for Id have been measured. For molar concentrations of water lying between 40 and 55.5 M(-1), the rate of hydrolysis of la in 0.5 M HCl solutions increases in the presence of dioxan while it decreases with chloral. The Hammett rho values for the reactivity k,in acidic media of aryl N-(phenylsulfonyl)carbamates (rho = +0.87) and for phenyl N-(substituted phenylsulfonyl)carbamates (rho = +0.22) agree with the protonation of the oxygen atom of the leaving group. Trapping experiment for the hydrolysis of 1a and 1d in a chloroacetate buffer in the presence of 4-chloroaniline gave in both cases N-(((4-chlorophenyl)amino)carbonyl)sulfo. Reaction carried out in (H2O)-O-18 with O-16- containing substrate indicates that there is no exchange from water to the carbonyl group of the sulfonylcarbamate. These data support a general acid catalysis of the breakdown of the anion which cuts in depending on the leaving group ability.

  DOI：

  10.1021/ja00105a020

文献信息

• A General Acid-Catalyzed Anion Breakdown Associated with an E1cB Reaction in the Hydrolysis of Aryl N-(Substituted Phenylsulfonyl)carbamates
  作者：Alain Vigroux、Michel Bergon、Catherine Bergonzi、Pierre Tisnes

  DOI：10.1021/ja00105a020

  日期：1994.12

  The hydrolysis of aryl N-(substituted phenylsulfonyl)carbamates at 50 degrees C in the pH range 0-13.5 leading to substituted benzenesulfonamides and phenols involves acyl group transfer. Reaction rates were measured spectrophotometrically and are independent of the concentration of the catalyst for buffers of pK(BH) > 8. With more acidic buffers, a general acid catalysis is observed for the hydrolysis of phenyl N-(phenylsulfonyl)carbamate la (pK, = 2.85) leading to a Bronsted relation (alpha = 0.46) including hydronium ion while it does not occur for 4-cyanophenyl N-(phenylsulfonyl)carbamate 1d. In alkaline media, the values of the entropies of activation are positive and lie between 0.20 and 15.0 cal mol(-1) K-1. The Hammett rho(-) value for the expulsion rate k(p) of phenolate ion from aryl N-(phenylsulfonyl)carbamates is positive (rho(-) = +2.93) while, for phenyl N-(substituted phenylsulfonyl)carbamates it is negative (rho = -0.66). An electrophilic intermediate, phenylsulfonyl isocyanate, was trapped with piperidine to give N-(piperidinocarbonyl)benzenesulfonamide. These results are consistent with an elimination-addition mechanism A(rh)D(H) + D-N (E1cB). In HCl solutions, solvent isotope effects k(obsd)(H2O)/k(obsd)(D2O) equal to 1.68 for 1a and 2.46 for Id have been measured. For molar concentrations of water lying between 40 and 55.5 M(-1), the rate of hydrolysis of la in 0.5 M HCl solutions increases in the presence of dioxan while it decreases with chloral. The Hammett rho values for the reactivity k,in acidic media of aryl N-(phenylsulfonyl)carbamates (rho = +0.87) and for phenyl N-(substituted phenylsulfonyl)carbamates (rho = +0.22) agree with the protonation of the oxygen atom of the leaving group. Trapping experiment for the hydrolysis of 1a and 1d in a chloroacetate buffer in the presence of 4-chloroaniline gave in both cases N-(((4-chlorophenyl)amino)carbonyl)sulfo. Reaction carried out in (H2O)-O-18 with O-16- containing substrate indicates that there is no exchange from water to the carbonyl group of the sulfonylcarbamate. These data support a general acid catalysis of the breakdown of the anion which cuts in depending on the leaving group ability.