磷酸二乙酯铵盐 | 24856-80-2

• 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
• 中文名称: 磷酸二乙酯铵盐
• 中文别名: 2-苯甲酰-N-(2-羟基乙基)-N-甲基苯酰胺
• 英文名称: ammonium diethyl hydrogen phosphate
• 英文别名: Azane;diethyl hydrogen phosphate；azane;diethyl hydrogen phosphate
• CAS: 24856-80-2
• 化学式: C₄H₁₁O₄P*H₃N
• 分子量: 171.133
• InChiKey: FOBUVCHEKOTWKT-UHFFFAOYSA-N

物化性质

• 熔点：
  102 °C

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  59.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  O,O-diethyl O-[4-(N-methyl)amino]butyl phosphotriester 在 ammonium hydroxide 作用下， 生成 1-甲基吡咯烷 、 磷酸二乙酯铵盐
  参考文献：
  名称：

  The 4-[N-Methyl-N-(2,2,2-trifluoroacetyl)amino]butyl Group as an Alternative to the 2-Cyanoethyl Group for Phosphate Protection in the Synthesis of Oligodeoxyribonucleotides

  摘要：

  The 4-[N-methyl-N-(2,2,2-trifluoroacetyl)amino]butyl group for phosphate protection in the synthesis of oligodeoxyribonucleotides has been developed to completely prevent nucleobase alkylation by acrylonitrile that could potentially occur upon deprotection of the traditional 2-cyanoethyl phosphate protecting group. The properties of this new phosphate protecting group were evaluated using the model phosphotriester 9. The mechanism of phosphate deprotection was studied by treating 9 with concentrated NH4OH. NMR analysis,of the deprotection reaction demonstrated that cleavage of the N-trifluoroacetyl group is rate-limiting. The resulting phosphotriester intermediate 13 was also shown to undergo rapid cyclodeesterification to produce O,O-diethyl phosphate 15 and N-methylpyrrolidine -16 (Scheme 2). Given the facile removal of the 4-[N-methyl-N-(2,2,2-trifluoroacetyl)amino]butyl phosphate protecting group under mild basic conditions, its utilization in oligonucleotide synthesis began with the preparation of the deoxyribonucleoside phosphoramidites 4a-d (Scheme 3). The coupling efficiency of 4a-d and conventional a-cyanoethyl deoxyribonucleoside phosphoramidites 24a-d was then compared in the solid-phase synthesis of the 20-mer d(ATCCGTAGCTAAGGTCATGC). As previously observed in the deprotection of 9, the 4-[N-methyl,N-(2,2,2-trifluoroacetyl)amino]butyl phosphate protecting groups were easily and completely removed from the oligonucleotide by using either concentrated NH4OH or pressurized ammonia gas. Analysis of the deprotected oligomer by polyacrylamide gel electrophoresis (Figure 3) indicated that the phosphoramidites 4a-d are as efficient as the 2-cyanoethyl phosphoramidites 24a-d in the synthesis of the 20-mer. Furthermore, following digestion of the crude 20-mer by snake venom phosphodiesterase and bacterial alkaline phosphatase, HPLC analysis showed complete hydrolysis to individual nucleosides and no detectable nucleobase modification.

  DOI：

  10.1021/jo990835w

文献信息

• One-step transformation of ammonium dialkyl phosphoroselenoates into dialkyl phosphoramidates
  作者：Gra?yna Mielniczak、Andrzej ?opusi?ski

  DOI：10.1002/hc.10110

  日期：——

  Ammonium dialkyl phosphoroselenoates are directly converted into the dialkyl phosphoramidates by iodosobenzene and iodoxybenzene. The inversion of configuration at the phosphorus atom, using model diastereoisomeric ammonium cis- and trans-2-oxo-2-seleno-4-methyl-1,3,2-dioxaphosphinan system, was observed. The mechanistic scheme of this transformation is discussed. © 2003 Wiley Periodicals, Inc. Heteroatom

  二烷基磷酸硒酸铵被碘代苯和碘氧基苯直接转化为氨基磷酸二烷基酯。使用模型非对映异构铵顺式和反式 2-oxo-2-seleno-4-methyl-1,3,2-dioxaphosphinan 系统观察到磷原子的构型反转。讨论了这种转换的机制方案。© 2003 Wiley Periodicals, Inc. 杂原子化学 14:121–127, 2003; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.10110
• A novel phosphate protection for oligonucleotide synthesis: the 2-[(1-naphthyl)carbamoyloxy]ethyl (NCE) group
  作者：Andrei P Guzaev、Muthiah Manoharan

  DOI：10.1016/s0040-4039(00)00911-4

  日期：2000.7

  The utility of the 2-(arylcarbamoyloxy)ethyl group for protection of internucleosidic phosphate linkages in oligonucleotide synthesis was studied. Of the three protecting groups tested, the 2-[(1-naphthyl)carbamoyloxy]ethyl demonstrated high coupling yields, favorable deprotection kinetics and the highest hydrolytic stability of the thymidine phosphoramidite building block. The mechanism of deprotection

  研究了2-（芳基氨基甲酰氧基）乙基在寡核苷酸合成中用于保护核苷间磷酸酯键的实用性。在测试的三个保护基中，2-[（（1-萘基）氨基甲酰氧基]乙基]显示出较高的偶联收率，有利的脱保护动力学和胸苷亚磷酰胺结构单元的最高水解稳定性。脱保护的机理是通过脱保护模型磷酸三酯和合成的十二烷基甲酸酯来证实的。
• The 4-[<i>N</i>-Methyl-<i>N</i>-(2,2,2-trifluoroacetyl)amino]butyl Group as an Alternative to the 2-Cyanoethyl Group for Phosphate Protection in the Synthesis of Oligodeoxyribonucleotides
  作者：Andrzej Wilk、Andrzej Grajkowski、Lawrence R. Phillips、Serge L. Beaucage

  DOI：10.1021/jo990835w

  日期：1999.10.1

  The 4-[N-methyl-N-(2,2,2-trifluoroacetyl)amino]butyl group for phosphate protection in the synthesis of oligodeoxyribonucleotides has been developed to completely prevent nucleobase alkylation by acrylonitrile that could potentially occur upon deprotection of the traditional 2-cyanoethyl phosphate protecting group. The properties of this new phosphate protecting group were evaluated using the model phosphotriester 9. The mechanism of phosphate deprotection was studied by treating 9 with concentrated NH4OH. NMR analysis,of the deprotection reaction demonstrated that cleavage of the N-trifluoroacetyl group is rate-limiting. The resulting phosphotriester intermediate 13 was also shown to undergo rapid cyclodeesterification to produce O,O-diethyl phosphate 15 and N-methylpyrrolidine -16 (Scheme 2). Given the facile removal of the 4-[N-methyl-N-(2,2,2-trifluoroacetyl)amino]butyl phosphate protecting group under mild basic conditions, its utilization in oligonucleotide synthesis began with the preparation of the deoxyribonucleoside phosphoramidites 4a-d (Scheme 3). The coupling efficiency of 4a-d and conventional a-cyanoethyl deoxyribonucleoside phosphoramidites 24a-d was then compared in the solid-phase synthesis of the 20-mer d(ATCCGTAGCTAAGGTCATGC). As previously observed in the deprotection of 9, the 4-[N-methyl,N-(2,2,2-trifluoroacetyl)amino]butyl phosphate protecting groups were easily and completely removed from the oligonucleotide by using either concentrated NH4OH or pressurized ammonia gas. Analysis of the deprotected oligomer by polyacrylamide gel electrophoresis (Figure 3) indicated that the phosphoramidites 4a-d are as efficient as the 2-cyanoethyl phosphoramidites 24a-d in the synthesis of the 20-mer. Furthermore, following digestion of the crude 20-mer by snake venom phosphodiesterase and bacterial alkaline phosphatase, HPLC analysis showed complete hydrolysis to individual nucleosides and no detectable nucleobase modification.