O-ethyl N-1-adamantyl phosphoramidate | 155051-57-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: O-ethyl N-1-adamantyl phosphoramidate
• 英文别名: O-ethyl N-1-adamantylphosphoramidic acid；O-ethyl-N-1-adamantyl amidophosphoric acid；N-(1-adamantyl)-ethoxyphosphonamidic acid
• CAS: 155051-57-3
• 化学式: C₁₂H₂₂NO₃P
• 分子量: 259.285
• InChiKey: YIMAFLFDIUXWHZ-UHFFFAOYSA-N

物化性质

• 沸点：
  370.8±25.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 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-1-adamantyl phosphoramidate 以 甲苯 为溶剂， 生成
  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：

  O-Ethyl-N-1-adamantyl amidochlorophosphate 在 sodium hydroxide 、 Amberlyst*H⁽¹⁺⁾ 作用下， 生成 O-ethyl N-1-adamantyl phosphoramidate
  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

• Generation of Ethyl Metathiophosphate by Thermal Fragmentation of <i>O</i>-Ethyl <i>N</i>-Substituted Phosphoramidothioates
  作者：Louis D. Quin、Petr Hermann、Stefan Jankowski

  DOI：10.1021/jo952270j

  日期：1996.1.1

  and found to fragment on heating in inert solvents to form the pyrophosphate AdNHP(S)(OEt)OP(S)(OEt)OH. The proposed mechanism involves an elimination of the amine portion with release of ethyl metathiophosphate (EtOP(S)O), as was confirmed in previous work for the comparable structure with oxygen. This transient compound then phosphorylates the starting phosphoramidothioate. O-Ethyl N,N-diethylphosphoramidothioate

  合成了N-1-金刚烷基磷酰胺基硫代O-乙基，发现在惰性溶剂中加热裂解后形成焦磷酸盐AdNHP（S）（OEt）OP（S）（OEt）OH。所提出的机理涉及消除胺部分，同时释放出乙基硫代磷酸酯（EtOP（S）O），这在先前的工作中已经证实了与氧气相当的结构。然后，该瞬态化合物使起始的氨基硫代磷酸酯磷酸化。还合成了N，N-二乙基磷酰胺基硫代O-乙基，虽然加热时得到类似的吡咯化合物，但反应混合物更复杂。然而，两种氨基磷酸硫代酰胺都有效地用作针对醇，硅烷醇和硅胶表面上的硅烷醇基团的硫代磷酸化剂。
• Phosphorylation with monomeric metaphosphates
  申请人：Research Corporation Technologies, Inc.

  公开号：US05334741A1

  公开（公告）日：1994-08-02

  Solid substrates with free hydroxyl groups are phosphorylated by thermolysing a solution of phosphoramidate of the formula ##STR1## in the presence of the substrate, whereby metaphosphate is generated which phosphorylates the substrate.

  具有自由羟基固体基质在存在基质的情况下，通过热解式磷酰胺盐溶液（式子如下）的磷酸化作用，生成亚磷酸酯，从而磷酸化基质。
• Kinetic and isotope effect studies on the intermediacy of ethyl metathiophosphate in ethanolysis of O-ethyl N-1-adamantyl phosphoramidothioate
  作者：Stefan Jankowski、Louis D. Quin、Piotr Paneth、Marion H. O'Leary

  DOI：10.1016/s0022-328x(96)06484-4

  日期：1997.2

  The fragmentation of O-ethyl N-1-adamantylphosphoramidothioate (in) and its oxygen counterpart 1b was examined in ethanol at 65-100 degrees C. The solvent hydrogen effect k(EtOH)/k(EtOD) and kinetic nitrogen effect k(14)/k(15) were determined at 80 degrees C. The rates and parameters of activation of ethanolysis of 1a and 1b are slightly different. The solvent effect k(EtOH)/k(EtOD) was found to be equal to 0.84 +/- 0.05 for 1a and 0.83 +/- 0.04 for 1b. The nitrogen effect k(14)/k(15) was found to be sensitive to replacement of sulfur by oxygen, and equal to 1.0083 +/- 0.0004 for 1a and 1.0065 +/- 0.0006 for 1b. The data indicate that proton transfer from the OH group to the amine moiety precedes the P-N bond breakage. The kinetic nitrogen isotope effect for the amine elimination recalculated for the pre-equilibrium step is equal to 1.0232 for 1a and 1.0215 for 1b. These results are consistent with the intermediacy of ethyl metathiophosphate in the solvolysis of 1a.
• US5334741A
  申请人：——

  公开号：US5334741A

  公开（公告）日：1994-08-02
• [EN] PHOSPHORYLATION WITH MONOMERIC METAPHOSPHATES<br/>[FR] PHOSPHORYLATION A L'AIDE DE METAPHOSPHATES MONOMERES
  申请人：——

  公开号：WO1994002226A1

  公开（公告）日：1994-02-03

  [EN] Solid substrates with free hydroxyl groups as phosphorylated by thermolysing a solution of phosphoramidate of formula (I), in the presence of the substrate, whereby metaphosphate is generated which phosphorylates the substrate.
  [FR] Des substrats solides à groupes hydroxyles libres sont phosphorylés par la thermolyse d'une solution de phosphoramidate de la formule (I) en présence du substrat, ce qui produit du métaphosphate qui phosphoryle le substrat.