1-羟基-2,2,2-三氟乙基膦酸 | 1192622-42-6

• 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
• 中文名称: 1-羟基-2,2,2-三氟乙基膦酸
• 英文名称: (2,2,2-trifluoro-1-hydroxyethyl)phosphonic acid
• 英文别名: 1-hydroxy-2,2,2-trifluoroethylphosphonic acid
• CAS: 1192622-42-6
• 化学式: C₂H₄F₃O₄P
• 分子量: 180.02
• InChiKey: KFBJKZIFRSOGGP-UHFFFAOYSA-N

物化性质

• 沸点：
  340.8±52.0 °C(Predicted)
• 密度：
  1.895±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 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：
  77.8
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-羟基-2,2,2-三氟乙基膦酸 在 氧气 作用下， 生成 三氟乙酸
  参考文献：
  名称：

  Hydroperoxylation by Hydroxyethylphosphonate Dioxygenase

  摘要：

  Hydroxyethylphosphonate dioxygenase (HEPD) catalyzes the O-2-dependent cleavage of the carbon-carbon bond of 2-hydroxyethylphosphonate (2-HEP) to afford hydroxymethylphosphonate (HMP) and formate without input of electrons or use of any organic cofactors. Two mechanisms have been proposed to account for this reaction. One involves initial hydroxylation of substrate to an acetal intermediate and its subsequent attack onto an Fe(IV)-oxo species. The second mechanism features initial hydroperoxylation of substrate followed by a Criegee rearrangement. To distinguish between the two mechanisms, substrate analogues were synthesized and presented to the enzyme. Hydroxymethylphosphonate was converted into phosphate and formate, and 1 -hydroxyethylphosphonate was converted to acetylphosphate, which is an inhibitor of the enzyme. These results provide strong support for a Criegee rearrangement with a phosphorus-based migrating group and require that the O-O bond of molecular oxygen is not cleaved prior to substrate activation. (2R)-Hydroxypropylphosphonate partitioned between conversion to 2-oxopropylphosphonate and hydroxymethylphosphonate, with the latter in turn converted to phosphate and formate. Collectively, these results support a mechanism that proceeds by hydroperoxylation followed by a Criegee rearrangement.

  DOI：

  10.1021/ja906238r
• 作为产物：
  描述：

  (2,2,2-三氟-1-羟乙基)膦酸二乙酯 在 盐酸 作用下， 以 水 为溶剂， 反应 12.0h， 以94.5%的产率得到1-羟基-2,2,2-三氟乙基膦酸
  参考文献：
  名称：

  在顺磁氟探针的设计中利用镧系元素配合物的流动性

  摘要：

  Fluorine-19 MRI 越来越多地被视为生物分子成像的工具，但这种技术的灵敏度非常低，限制了大多数应用。以前的研究早已确定，提高19的敏感性F 分子探针需要增加每个探针的氟原子核数量并减少它们的纵向弛豫时间。后者很容易通过将氟原子放置在靠近顺磁性金属离子（例如镧系元素（III））的位置来实现。然而，增加每个分子的氟原子数仅在所有氟原子核化学等效时才有用。以前实现这种等效性的尝试主要集中在设计高度对称和刚性的氟化大环配体。一种更简单的方法包括利用具有开放配位点的高度流动的镧系元素配合物，这些配位点对磷酸化和膦酸化物质具有高亲和力。计算研究表明，Ln III-TREN-MAM 具有高度流动性，可在至少六种不同的异构体之间快速相互转化。在室温下的中性水中，Ln III -TREN-MAM 结合两个或三个当量的氟化膦酸盐。19 F 原子核与三元复合物中 Ln III中心的紧密接近将氟原子核的弛豫时间减少了多达

  DOI：

  10.1021/acs.inorgchem.1c03908

文献信息

• Hydroperoxylation by Hydroxyethylphosphonate Dioxygenase
  作者：John T. Whitteck、Robert M. Cicchillo、Wilfred A. van der Donk

  DOI：10.1021/ja906238r

  日期：2009.11.11

  Hydroxyethylphosphonate dioxygenase (HEPD) catalyzes the O-2-dependent cleavage of the carbon-carbon bond of 2-hydroxyethylphosphonate (2-HEP) to afford hydroxymethylphosphonate (HMP) and formate without input of electrons or use of any organic cofactors. Two mechanisms have been proposed to account for this reaction. One involves initial hydroxylation of substrate to an acetal intermediate and its subsequent attack onto an Fe(IV)-oxo species. The second mechanism features initial hydroperoxylation of substrate followed by a Criegee rearrangement. To distinguish between the two mechanisms, substrate analogues were synthesized and presented to the enzyme. Hydroxymethylphosphonate was converted into phosphate and formate, and 1 -hydroxyethylphosphonate was converted to acetylphosphate, which is an inhibitor of the enzyme. These results provide strong support for a Criegee rearrangement with a phosphorus-based migrating group and require that the O-O bond of molecular oxygen is not cleaved prior to substrate activation. (2R)-Hydroxypropylphosphonate partitioned between conversion to 2-oxopropylphosphonate and hydroxymethylphosphonate, with the latter in turn converted to phosphate and formate. Collectively, these results support a mechanism that proceeds by hydroperoxylation followed by a Criegee rearrangement.
• Exploiting the Fluxionality of Lanthanide Complexes in the Design of Paramagnetic Fluorine Probes
  作者：Randall K. Wilharm、Mandapati V. Ramakrishnam Raju、John C. Hoefler、Carlos Platas-Iglesias、Valérie C. Pierre

  DOI：10.1021/acs.inorgchem.1c03908

  日期：2022.3.7

  increasing the number of fluorine nuclei per probe as well as decreasing their longitudinal relaxation time. The latter is easily achieved by positioning the fluorine atoms in close proximity to a paramagnetic metal ion such as a lanthanide(III). Increasing the number of fluorine atoms per molecule, however, is only useful inasmuch as all of the fluorine nuclei are chemically equivalent. Previous attempts

  Fluorine-19 MRI 越来越多地被视为生物分子成像的工具，但这种技术的灵敏度非常低，限制了大多数应用。以前的研究早已确定，提高19的敏感性F 分子探针需要增加每个探针的氟原子核数量并减少它们的纵向弛豫时间。后者很容易通过将氟原子放置在靠近顺磁性金属离子（例如镧系元素（III））的位置来实现。然而，增加每个分子的氟原子数仅在所有氟原子核化学等效时才有用。以前实现这种等效性的尝试主要集中在设计高度对称和刚性的氟化大环配体。一种更简单的方法包括利用具有开放配位点的高度流动的镧系元素配合物，这些配位点对磷酸化和膦酸化物质具有高亲和力。计算研究表明，Ln III-TREN-MAM 具有高度流动性，可在至少六种不同的异构体之间快速相互转化。在室温下的中性水中，Ln III -TREN-MAM 结合两个或三个当量的氟化膦酸盐。19 F 原子核与三元复合物中 Ln III中心的紧密接近将氟原子核的弛豫时间减少了多达