phenyl N-(phenylsulfonyl)carbamate | 14437-05-9

• 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: phenyl N-(phenylsulfonyl)carbamate
• 英文别名: benzenesulfonyl-carbamic acid phenyl ester；Benzolsulfonyl-carbamidsaeure-phenylester；Benzolsulfonylcarbaminsaeure-phenylester；phenyl N-(benzenesulfonyl)carbamate
• CAS: 14437-05-9
• 化学式: C₁₃H₁₁NO₄S
• 分子量: 277.301
• InChiKey: VEHJNSOWFJORJJ-UHFFFAOYSA-N

物化性质

• 熔点：
  124 °C
• 密度：
  1.349±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  80.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  异氰酸苯磺酰酯 、 苯酚 以 二氯甲烷 为溶剂， 反应 5.0h， 以95%的产率得到phenyl 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

• Polyolefin resin composition containing diacetal
  申请人：Horie Shouichi

  公开号：US20060100324A1

  公开（公告）日：2006-05-11

  An object of the present invention is to provide a polyolefin resin composition with excellent transparency, which is obtained by a method which is economically advantageous, and easily produces said composition, wherein said composition hardly generates white spots thought to be an insoluble part of a diacetal compound, while retaining the intact transparency imparted by the diacetal. A clarifier for polyolefin resins which comprises a combination of an acetal compound represented by the general formula (1) with a specific amount of a modifier represented by the general formula (2) or (3) is used. Thus, white spots thought to be an insoluble part of the diacetal compound can be significantly diminished.

  本发明的目的是提供一种具有优异透明度的聚烯烃树脂组合物，该组合物通过一种经济上有利的方法获得，并且易于生产所述组合物，其中所述组合物几乎不产生被认为是二缩醛化合物不溶部分的白点，同时保持二缩醛赋予的完整透明度。聚烯烃树脂澄清剂由通式（1）表示的缩醛化合物与一定量的通式（2）或（3）表示的改性剂组合而成。因此，被认为是二缩醛化合物不溶性部分的白点可以显著减少。
• The Chemistry of Benzenesulfonyl Isocyanate. I. Identification of Hindered Phenols and Alcohols¹
  作者：John W. McFarland、James B. Howard

  DOI：10.1021/jo01014a517

  日期：1965.3
• Billeter, Chemische Berichte, 1904, vol. 37, p. 694
  作者：Billeter

  DOI：——

  日期：——
• US3933894A
  申请人：——

  公开号：US3933894A

  公开（公告）日：1976-01-20
• 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.