O-ethyl N-mesitylphosphoramidic acid | 132434-70-9

• 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: O-ethyl N-mesitylphosphoramidic acid
• 英文别名: O-ethyl N-mesitylphosphoramidate；ethoxy-N-(2,4,6-trimethylphenyl)phosphonamidic acid
• CAS: 132434-70-9
• 化学式: C₁₁H₁₈NO₃P
• 分子量: 243.243
• InChiKey: NAKLMEBQJPXVKY-UHFFFAOYSA-N

物化性质

• 沸点：
  345.7±52.0 °C(Predicted)
• 密度：
  1.202±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  O-ethyl N-mesitylphosphoramidic acid 以 乙醇 为溶剂， 反应 1.0h， 生成 2,4,6-Trimethyl-phenylamine; compound with phosphoric acid diethyl ester
  参考文献：
  名称：

  O-Ethyl Phosphoramidic Acids with Sterically Demanding N-Substituents: Useful Precursors of Ethyl Metaphosphate on Thermolysis

  摘要：

  Kinetics of the thermal fragmentation of four N-substituted derivatives of O-ethyl phosphoramidic acids, (EtO-P(O)(NRR')(OH), were examined. When N contained either of the sterically demanding mesityl or 1-adamantyl groups, the reaction followed first-order kinetics, both in the absence and presence of an alcohol trapping reagent. In the former case, the product was a pyrophosphate (RR'N(EtO)(O)P-O-P(O)(OEt)OH). In the latter case, phosphorus was trapped as a dialkyl phosphate. Both reactions are therefore indicated to follow an elimination-addition mechanism, with ethyl metaphosphate as transient intermediate. The pyrophosphate is derived from reaction of the metaphosphate with unreacted phosphoramidic acid. With less bulky substituents (N-phenyl or N,N-diethyl), mixed first- and second-order kinetics were followed in the absence of a trapping agent; some bimolecular interaction of the substrate to form the pyrophosphate product is indicated by the second-order kinetics. Product analyses and quantitative measurements were made with P-31 NMR spectroscopy. From all phosphoramidic acids, the intermediate metaphosphate was effectively trapped by reaction with the OH group on the surface of solid silica gel. The presence of covalently bonded phosphate on the surface was shown by P-31 and Si-29 CP/MAS NMR spectroscopy.

  DOI：

  10.1021/jo00095a013
• 作为产物：
  描述：

  ethyl mesitylphosphoramidochloridate 在 sodium hydroxide 、 Amberlyst*H⁽¹⁺⁾ 作用下， 生成 O-ethyl N-mesitylphosphoramidic acid
  参考文献：
  名称：

  O-Ethyl Phosphoramidic Acids with Sterically Demanding N-Substituents: Useful Precursors of Ethyl Metaphosphate on Thermolysis

  摘要：

  Kinetics of the thermal fragmentation of four N-substituted derivatives of O-ethyl phosphoramidic acids, (EtO-P(O)(NRR')(OH), were examined. When N contained either of the sterically demanding mesityl or 1-adamantyl groups, the reaction followed first-order kinetics, both in the absence and presence of an alcohol trapping reagent. In the former case, the product was a pyrophosphate (RR'N(EtO)(O)P-O-P(O)(OEt)OH). In the latter case, phosphorus was trapped as a dialkyl phosphate. Both reactions are therefore indicated to follow an elimination-addition mechanism, with ethyl metaphosphate as transient intermediate. The pyrophosphate is derived from reaction of the metaphosphate with unreacted phosphoramidic acid. With less bulky substituents (N-phenyl or N,N-diethyl), mixed first- and second-order kinetics were followed in the absence of a trapping agent; some bimolecular interaction of the substrate to form the pyrophosphate product is indicated by the second-order kinetics. Product analyses and quantitative measurements were made with P-31 NMR spectroscopy. From all phosphoramidic acids, the intermediate metaphosphate was effectively trapped by reaction with the OH group on the surface of solid silica gel. The presence of covalently bonded phosphate on the surface was shown by P-31 and Si-29 CP/MAS NMR spectroscopy.

  DOI：

  10.1021/jo00095a013

文献信息

• Kinetic Isotope Effects on Ethyl Metaphosphate Transfer from a Phosphoramidate to Ethanol
  作者：Stefan Jankowski、Louis D. Quin、Piotr Paneth、Marion H. O'Leary

  DOI：10.1021/ja00105a008

  日期：1994.12

  Kinetic isotope effects of nitrogen and hydrogen on thermolysis of O-ethyl N-mesityl- (1) and O-ethyl N-phenylphosphoramidates (2) in anhydrous ethanol at 80 degrees C are reported. The solvent hydrogen effect k(EtOH)/k(EtOD) is equal to 0.62 +/- 0.03 for 1 and 0.67 +/- 0.05 for 2. The kinetic nitrogen isotope effect k(14)/k(15) was found to be equal to 1.0056 +/- 0.0011 for 1 and 0.9925 +/- 0.0024 for 2. These results are consistent with a mechanism which involves proton transfer from the OH group to the nitrogen moiety. The recalculated nitrogen kinetic effect for the second step (amine departure) is equal to 1.021 for 1 and 1.008 for 2. On this basis a metaphosphate-like transition state or ''exploded'' S(N)2(P) transition state is proposed for solvolysis of 1. With its less bulky substituent, an earlier transition state in the unimolecular process or a change into the addition-elimination mechanism is considered for phosphoramidate 2.
• Jankowski, Stefan; Quin, Louis D.; Flubacher, Dietmar, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 77, # 1-4, p. 236
  作者：Jankowski, Stefan、Quin, Louis D.、Flubacher, Dietmar

  DOI：——

  日期：——
• Direct detection of two metaphosphoramidates in −75° the solutions by 31P NMR spectroscopy
  作者：Louis D. Quin、Catherine Bourdieu、Gyöngyi S. Quin

  DOI：10.1016/s0040-4039(00)97094-1

  日期：1990.1