hydrogen methylphosphonate | 39863-50-8

• 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: hydrogen methylphosphonate
• 英文别名: methylphosphonate；Methylphosphonate(1-)；hydroxy(methyl)phosphinate
• CAS: 39863-50-8
• 化学式: CH₄O₃P
• 分子量: 95.0147
• InChiKey: YACKEPLHDIMKIO-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.7
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  60.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  钷 、 hydrogen methylphosphonate 生成
  参考文献：
  名称：

  Borisov, M. S.; Elesin, A. A.; Lebedev, I. A., Radiokhimiya, 1967, vol. 9, p. 164 - 168

  摘要：

  DOI：
• 作为产物：
  描述：

  (2S)-2-hydroxy(2-²H)ethylphosphonate 在 ferrous ammonium sulphate 、 2-hydroxyethylphosphonate dioxygenase E₁₇₆H mutant 、 氧气 作用下， 以 aq. buffer 为溶剂， 反应 2.0h， 生成 hydroxymethylphosphonate 、 hydrogen methylphosphonate
  参考文献：
  名称：

  A Common Late-Stage Intermediate in Catalysis by 2-Hydroxyethyl-phosphonate Dioxygenase and Methylphosphonate Synthase

  摘要：

  2-Hydroxyethylphosphonate dioxygenase (HEPD) and methylphosphonate synthase (MPnS) are nonheme iron oxygenases that-both catalyze the carbon carbon bond cleavage of 2-hydroxyethylphosphonate but generate different products. Substrate labeling experiments led to a mechanistic hypothesis in which the fate of a common intetmediate determined product identity. We report here the generation of a bifunctional mutant of HEPD (E176H) that exhibits the activity of both HEPD and MPnS. The product distribution of the mutant is sensitive to a substrate isotope effect, consistent with an isotope-sensitive branching mechanism involving a common intermediate: The X-ray structure of the mutant was determined and suggested that the introduced histidine does not coordinate the active site metal, unlike the iron-binding glutamate it replaced.

  DOI：

  10.1021/jacs.5b00282

文献信息

• Intermediates in the transformation of phosphonates to phosphate by bacteria
  作者：Siddhesh S. Kamat、Howard J. Williams、Frank M. Raushel

  DOI：10.1038/nature10622

  日期：2011.12

  of PRPn is subsequently cleaved in a radical-based reaction producing α-d-ribose-1,2-cyclic-phosphate-5-phosphate and methane in the presence of S-adenosyl-l-methionine. Substantial quantities of phosphonates are produced worldwide for industrial processes, detergents, herbicides and pharmaceuticals. Our elucidation of the chemical steps for the biodegradation of alkylphosphonates shows how these compounds

  磷是所有已知生命形式的基本元素。在生命系统中，磷是核酸、碳水化合物和磷脂的一个组成部分，它作为磷酸盐的衍生物被掺入。然而，大多数革兰氏阴性细菌能够在磷酸盐饥饿条件下使用膦酸盐作为磷的营养来源。在这些生物体中，甲基膦酸盐被转化为磷酸盐和甲烷。从形式上讲，这种转化是碳-磷 (C-P) 键的水解裂解，但尽管付出了很多努力，但尚未阐明将烷基膦酸盐活化和转化为磷酸盐和烷烃的一般酶促机制。二十年。C-P 键断裂的实际机制可能是基于自由基的转变。在大肠杆菌中，C-P 裂解酶反应的催化机制已定位于 phn 基因簇。该操纵子由 14 个基因 phnC、phnD、...、phnP 组成。遗传和生化实验表明，基因 phnG、phnH、……、phnM 编码的蛋白质对膦酸盐转化为磷酸盐至关重要，而操纵子中其他基因编码的蛋白质具有辅助功能。被认为对 C-P 键裂解至关重要的七种蛋白质中的任何一种都没有功能注释。在这里，我们展示了甲基膦酸与
• Synthesis of Methylphosphonic Acid by Marine Microbes: A Source for Methane in the Aerobic Ocean
  作者：William W. Metcalf、Benjamin M. Griffin、Robert M. Cicchillo、Jiangtao Gao、Sarath Chandra Janga、Heather A. Cooke、Benjamin T. Circello、Bradley S. Evans、Willm Martens-Habbena、David A. Stahl、Wilfred A. van der Donk

  DOI：10.1126/science.1219875

  日期：2012.8.31

  Is methylphosphonate a natural product? If it is, then its catabolism by microrganisms seeking phosphorus might explain the ubiquity of methane in the oceans. Anaerobic Archaea, so far, are the only significant source of methane known. Thus, Metcalf et al. (p. 1104 ) looked for evidence of methylphosphonate biochemistry in the widespread archaeon Nitrosopumilus maritimus. The organism can synthesize C-P bonds using phosphoenolpyruvate mutase. By using its gene, ppm , as a marker, a possible phosphonate biosynthesis gene cluster was identified, and adjacent to this a gene for a cupin was found. Together with Fe(II) and O ₂ the cupin catalyzed the production of methylphosphonate and formate. Homologs of the cupin gene are found in a wide range of common marine microbes, including Pelagibacter ubique and Prochlorococcus.

  甲基膦酸盐是一种自然产物吗？如果是，那么微生物通过分解甲基膦酸盐以寻找磷，可能解释了海洋中甲烷的普遍存在。到目前为止，厌氧古菌是已知的唯一重要甲烷来源。因此，Metcalf等人（第337卷，第1104页）在广泛存在的古菌Nitrosopumilus maritimus中寻找了甲基膦酸盐生物化学的证据。该生物可以使用磷酸烯醇丙酮酸异构酶合成C-P键。通过使用其基因ppm作为标记，可能的膦酸盐生物合成基因簇被鉴定出来，并且在此基因簇旁边发现了一个杯状蛋白基因。与Fe（II）和O2一起，杯状蛋白催化了甲基膦酸盐和甲酸的产生。杯状蛋白基因的同源物在广泛存在的海洋微生物中发现，包括Pelagibacter ubique和Prochlorococcus。

• An Oxidative Pathway for Microbial Utilization of Methylphosphonic Acid as a Phosphate Source
  作者：Simanga R. Gama、Margret Vogt、Thomas Kalina、Kendall Hupp、Friedrich Hammerschmidt、Katharina Pallitsch、David L. Zechel

  DOI：10.1021/acschembio.9b00024

  日期：2019.4.19

  Methylphosphonic acid is synthesized by marine bacteria and is a prominent component of dissolved organic phosphorus. Consequently, methylphosphonic acid also serves as a source of inorganic phosphate (Pi) for marine bacteria that are starved of this nutrient. Conversion of methylphosphonic acid into Pi is currently only known to occur through the carbon-phosphorus lyase pathway, yielding methane as

  甲基膦酸是由海洋细菌合成的，是溶解的有机磷的重要组成部分。因此，甲基膦酸还可以作为缺乏这种营养的海洋细菌的无机磷酸盐（Pi）的来源。目前仅已知通过碳-磷裂解酶途径发生甲基膦酸向Pi的转化，产生副产物甲烷。在这项工作中，我们描述了Gimesia maris DSM8797中甲基膦酸分解代谢的氧化途径。尽管缺乏编码碳-磷裂解酶途径的phn操纵子，但马氏酵母仍可以使用甲基膦酸作为Pi来源。相反，该基因组包含一个编码非血红素依赖Fe（II）的加氧酶HF130PhnY *和HF130PhnZ的同源物的基因座，先前已证明可将2-氨基乙基膦酸转化为甘氨酸和Pi。GmPhnY *和GmPhnZ1在大肠杆菌中生产，并纯化用于体外表征。用一组合成的膦酸酯评估酶的底物特异性。通过31 P NMR光谱证明，GmPhnY *将甲基膦酸转化为羟甲基膦酸，然后被GmPhnZ1氧化生成甲酸和Pi。相反，2-氨基乙基膦酸不是GmPhnY
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Sc: MVol.D4, 3.4.1.1, page 143 - 143
  作者：

  DOI：——

  日期：——
• A Common Late-Stage Intermediate in Catalysis by 2-Hydroxyethyl-phosphonate Dioxygenase and Methylphosphonate Synthase
  作者：Spencer C. Peck、Jonathan R. Chekan、Emily C. Ulrich、Satish K. Nair、Wilfred A. van der Donk

  DOI：10.1021/jacs.5b00282

  日期：2015.3.11

  2-Hydroxyethylphosphonate dioxygenase (HEPD) and methylphosphonate synthase (MPnS) are nonheme iron oxygenases that-both catalyze the carbon carbon bond cleavage of 2-hydroxyethylphosphonate but generate different products. Substrate labeling experiments led to a mechanistic hypothesis in which the fate of a common intetmediate determined product identity. We report here the generation of a bifunctional mutant of HEPD (E176H) that exhibits the activity of both HEPD and MPnS. The product distribution of the mutant is sensitive to a substrate isotope effect, consistent with an isotope-sensitive branching mechanism involving a common intermediate: The X-ray structure of the mutant was determined and suggested that the introduced histidine does not coordinate the active site metal, unlike the iron-binding glutamate it replaced.