(1-amino-2,2,2-trifluoroethyl)phosphonic acid | 211571-54-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: (1-amino-2,2,2-trifluoroethyl)phosphonic acid
• CAS: 211571-54-9
• 化学式: C₂H₅F₃NO₃P
• mdl: MFCD02692621
• 分子量: 179.036
• InChiKey: BPFQMPHPVHHLHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.5
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  83.6
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1-amino-2,2,2-trifluoroethyl)phosphonic acid 、 苯乙酰氯 在 碳酸氢钠 作用下， 以 丙酮 为溶剂， 反应 24.0h， 以79%的产率得到(2,2,2-Trifluoro-1-phenylacetylamino-ethyl)-phosphonic acid
  参考文献：
  名称：

  RESOLUTION OF FLUORINATED AMINOMETHANPHOSPHONIC ACIDS CATALYSED BY PENICILLIN G ACYLASE - III

  摘要：

  In this work, we have used penicillin G acylase (EC 3.5.1.11) from E. coli to resolve kinetically four fluorinated aminomethanphosphonic acids: 1: 1-trifluoromethyl-, 2:1-p-fluorophenyl-, 3:1-m-fluorophenyl-, 4: 1-p-trifluoromethylphenyl-1-aminomethanphosphonic acids. This enzyme catalyses enantioselectively the hydrolysis of the N-phenylacetylated derivatives of 1-4, The enantiomeric excesses determined via P-31 NMR spectra of the diastereomeric Pd(II) complexes of 1-4 were high for each compound studied.

  DOI：

  10.1080/10426509708043557
• 作为产物：
  描述：

  diethyl {1-[(benzyloxycarbonyl)amino]-2,2,2-trifluoroethyl}phosphonate 在 氢溴酸 、 溶剂黄146 作用下， 反应 24.0h， 以100%的产率得到(1-amino-2,2,2-trifluoroethyl)phosphonic acid
  参考文献：
  名称：

  第一稳定的膦酰胺过渡态类似物的合成。

  摘要：

  选择了三种方法，使用容易获得的N保护的β-氟代氨基缩醛一锅合成完全保护的β-氟代氨基膦酸。这些通过酰化作用被活化，通过β-消除作用导致瞬时的N-酰亚胺基立即被反应性形式的亚磷酸二烷基酯捕获。避免碱性条件，这些N-保护的β-氟氨基膦酸酯的全部或部分脱保护使得可以合成游离氨基酸，其酯和外消旋的β-三氟膦酰胺酸。后者代表由细菌转肽酶形成的过渡态类似物，与非氟化化合物相反，它在pH 4.7时是完全稳定的。

  DOI：

  10.1021/jo034229j

文献信息

• α-Iminotrifluoroethylphosphonates: The First Representatives of N-H Imidoyl Phosphonates
  作者：Petro Onys’ko、Yuliya Rassukana、Mykola Kolotylo、Oleksii Sinitsa、Volodymir Pirozhenko

  DOI：10.1055/s-2007-983838

  日期：2007.9

  A convenient synthetic approach to previously unknown N-H imidoyl phosphonates, based on addition of dialkyl phosphites to trifluoroacetonitrile, has been developed. The synthetic potential of such imines, which exist as equilibrium mixtures of E/Z-isomers, was demonstrated by their easy reduction and functionalization with O- and P-centered nucleophiles, to afford derivatives of α-aminophosphonic acids containing a trifluoromethyl group. Furthermore, interaction with mercaptoacetic acid proceeds with intramolecular cyclization of the intermediate adduct to produce a novel 2-phosphorylated N-H thiazolidone. Interaction between the N-H imines and trichloroacetylisocyanate leads to novel, reactive, phosphorylated N-acylated imines.

  我们开发了一种基于二烷基亚磷酸酯与三氟乙腈加成的，合成先前未知的N-H亚胺基膦酸酯的便捷方法。这类亚胺存在E/Z异构体平衡混合物，通过它们的易还原性和O/P中心亲核试剂的官能化，展示了其合成潜力，制备了含有三氟甲基的α-氨基膦酸衍生物。此外，与巯基乙酸的反应通过中间加成物的分子内环化，生成了一种新型2-膦酸化的N-H噻唑烷酮。N-H亚胺与三氯乙酰异氰酸酯的反应产生新型、活性高的磷酸化N-酰基亚胺。
• Sigmatropic isomerizations in azaallyl systems: XXI. Alkanimidoylphosphonates and their prototropic and phosphorotropic isomers
  作者：P. P. Onys’ko、T. V. Kim、E. I. Kiseleva、A. D. Sinitsa

  DOI：10.1007/s11176-005-0110-8

  日期：2004.12

  Synthetic procedures for alkanimidoylphosphoryl derivatives with α-hydrogen atoms in the N-alkyl radical are developed. Data on the effect of substituents at the carbon and phosphorus atoms on the facility of prototropic transitions in the C=N-C triad are summarized. The most facile proton transfer occurs in the N-benzyl derivatives, and the prototropic isomer is the more stable, the stronger the electron-acceptor power of the substituent at the sp 3-carbon atom of the azaallyl triad. The proton transfer in N-(α-phenethyl)-trifluoroacetimidoylphosphonates proceeds selectively, which allows preparation of enantiomerically enriched derivatives of α-aminotrifluoroethylphosphonic acid. A specific effect of substituents at the phosphorus atom on the prototropism attendant on phosphorylation of imidoyl chlorides is demonstrated.

  开发了含有α-氢原子的N-烷基自由基的烷基脲膦酰基衍生物的合成方法。总结了碳原子和磷原子上的取代基对C=N-C三元组中质子转移便利性的影响数据。在N-苄基衍生物中，质子转移最为容易，随着位于氮杂烯三元组的sp³碳原子上的取代基的电子受体能力增强，质子异构体愈加稳定。在N-(α-苯乙基)-三氟乙酰基脲膦酸酯中，质子转移选择性进行，这使得能够制备富含对映体的α-氨基三氟乙基膦酸的衍生物。证实了磷原子上取代基对氯脲酰化反应中伴随的质子转移的特定影响。
• Resolution of fluorinated aminophosphonic acid enantiomers by precolumn derivatization with following reverse phase liquid chromatography
  作者：Michael Yu. Belik、Oleg Yegorov、Alexander E. Sorochinsky、Valery P. Kukhar

  DOI：10.1080/10426507.2015.1094656

  日期：2016.3.3

  GRAPHICAL ABSTRACT ABSTRACT Precolumn chiral derivatization of fluorinated aminophosphonic acids was successfully accomplished with standard reagent consisting of N-acetyl-L-cysteine and o-phthaldialdehyde. Thus formed diastereomeric isoindole derivatives were characterized by means of ultraviolet- and mass-spectroscopic techniques. The chromatographic behavior of diastereomeric isoindole derivatives

  图形摘要 摘要 氟化氨基膦酸的柱前手性衍生化成功地使用由 N-乙酰基-L-半胱氨酸和邻苯二甲醛组成的标准试剂完成。由此形成的非对映异构异吲哚衍生物通过紫外和质谱技术表征。非对映异构异吲哚衍生物的色谱行为已在不同的反相色谱柱上进行了研究。操作简单的色谱分析能够选择性区分氟化氨基膦酸对映体。
• A new strategy for asymmetric synthesis of aminophosphonic acid derivatives: the first enantioselective catalytic reduction of C-phosphorylated imines
  作者：Yuliya V. Rassukana、Petro P. Onys’ko、Mykola V. Kolotylo、Anatolii D. Sinitsa、Piotr Łyżwa、Marian Mikołajczyk

  DOI：10.1016/j.tetlet.2008.10.152

  日期：2009.1

  The first highly enantioselective catalytic reduction of 1-imino-2,2,2-trifluoroethylphosphonates and the synthesis of enantiomerically enriched biorelevant phosphonotrifluoroalanine is reported.

  报道了1-亚氨基-2,2,2-三氟乙基膦酸酯的首次高对映选择性催化还原和对映异构体富集的生物相关膦酰基三氟丙氨酸的合成。
• Fluorinated NH-iminophosphonates and iminocarboxylates: novel synthons for the preparation of biorelevant α-aminophosphonates and carboxylates
  作者：Yuliya V. Rassukana、Ivanna P. Yelenich、Anatoly D. Synytsya、Petro P. Onys'ko

  DOI：10.1016/j.tet.2014.03.030

  日期：2014.5

  A convenient synthetic approach to previously unknown N-H alpha-iminophosphonates and iminotrifluoropropionates was developed. The synthetic potential of N-H iminophosphonates and iminotrifluoropropionates, existing as an equilibrium mixture of E/Z-isomers, was demonstrated by their easy functionalization to afford biorelevant fluorinated alpha-aminophosphonic and alpha-aminocarboxylic acid derivatives. (C) 2014 Elsevier Ltd. All rights reserved.