Diamidophosphate

Diamidophosphate

Diamidophosphate

Chemical compound

Diamidophosphate (DAP) is the simplest phosphorodiamidate ion, with formula PO2(NH2)2−. It is a phosphorylating ion and was first used for phosphorylation of sugars in aqueous medium.[1] DAP has attracted interest in the area of primordial chemistry.[2]

Quick Facts Names, Identifiers ...

Salts

Several salts of the formula MPO2(NH2)2(H2O)x are known.[3]

  • The sodium salt can be made by base hydrolysis of phenyl phosphorodiamidate.[4] It crystallises as a hexahydrate. It can be dehydrated.
  • The silver salt AgPO2(NH2)2 can react using double decomposition with bromides forming other salts.
  • The potassium diamidophosphate salt KPO2(NH2)2 is also known.
  • Phosphorodiamidic acid crystallizes as a trihydrate.[4]

Reactions

Heating anhydrous sodium diamidophosphate causes polmerization:[3]

  • At 160 °C, Na2P2O4(NH)(NH2)2, Na3P3O6(NH)2(NH2)2, Na4P4O8(NH)3(NH2)2, Na5P5O10(NH)4(NH2)2 and Na6P6O12(NH)5(NH2)2 are produced. These substances contain P-N-P backbones. These can be separated by paper chromatography.
  • At 200 °C the hexa-phosphate is produced.
  • At 250 °C the typical chain length is 18.

Heating hydrated salts induces loss of ammonia to form oligophosphates and polyphosphates.[3]

Diamidophosphate inhibits urease enzymes by blocking up the active site, binding to two nickel centers. Diamidophosphate mimics the urea hydrolysis intermediate.[5]

Diamidophosphate is tribasic, and the amine groups may also lose hydrogen to form more metallic salts. With silver, further reactions can yield explosive salts: tetrasilver orthodiamidophosphate (AgO)3P(NH2)NHAg, and pentasilver orthodiamidophosphate (AgO)3P(NHAg)2.[6]

Organic esters and amides

Phenyl phosphorodiamidate, an inhibitor of urease, is a controlled release fertilizers.[7]

Numerous organic derivatives are known. One example is phenyl phosphorodiamidate.[8]

Reactions with nucleosides

DAP phosphorylates deoxynucleosides (the building blocks of DNA, and at the same time initiates polymerization to make DNA.[9] DAP facilitates the synthesis of larger RNA sequences (ribozymes) from smaller RNA strands.[10] Other nitrogenous derivatives of phosphorus derivatives have also been proposed in this context in a review article.[11]

See also

References

  1. [1]
    Krishnamurthy, Ramanarayanan; Guntha, Sreenivasulu; Eschenmoser, Albert (4 July 2000). "Regioselective α-Phosphorylation of Aldoses in Aqueous Solution". Angewandte Chemie International Edition. 39 (13): 2281–2285. doi:10.1002/1521-3773(20000703)39:13<2281::AID-ANIE2281>3.0.CO;2-2. ISSN 1521-3773. PMID 10941064.
  2. [2]
    Gibard, Clémentine; Bhowmik, Subhendu; Karki, Megha; Kim, Eun-Kyong; Krishnamurthy, Ramanarayanan (2018). "Phosphorylation, oligomerization and self-assembly in water under potential prebiotic conditions". Nature Chemistry. 10 (2): 212–217. doi:10.1038/nchem.2878. PMC 6295206. PMID 29359747.
  3. [3]
    Klement, R.; Biberacher, G. (May 1956). "Das thermische Verhalten von Natriumdiamidophosphat, Darstellung von kondensierten Imidophosphaten". Zeitschrift für Anorganische und Allgemeine Chemie. 285 (1–2): 74–85. doi:10.1002/zaac.19562850109.
  4. [4]
    Coggins, Adam J.; Powner, Matthew W. (10 October 2016). "Prebiotic synthesis of phosphoenol pyruvate by α-phosphorylation-controlled triose glycolysis Supplementary Information Compound 8" (PDF). Nature Chemistry. 9 (4): 310–317. Bibcode:2017NatCh...9..310C. doi:10.1038/nchem.2624. ISSN 1755-4349. PMID 28338685. S2CID 205296677.
  5. [5]
    Deborah Zamble; Rowińska-Żyrek, Magdalena; Kozlowski, Henryk (2017). The Biological Chemistry of Nickel. Royal Society of Chemistry. pp. 73–74, 83. ISBN 9781788010580.
  6. [6]
    Bretherick, L. (2016). Bretherick's Handbook of Reactive Chemical Hazards. Elsevier. p. 19. ISBN 9781483162508.
  7. [7]
    Pan, Baobao; Lam, Shu Kee; Mosier, Arvin; Luo, Yiqi; Chen, Deli (2016). "Ammonia Volatilization from Synthetic Fertilizers and its Mitigation Strategies: A Global Synthesis". Agriculture, Ecosystems & Environment. 232: 283–289. doi:10.1016/j.agee.2016.08.019.
  8. [8]
    Kiss, S.; Simihaian, M. (2013). Improving Efficiency of Urea Fertilizers by Inhibition of Soil Urease Activity. Springer Science & Business Media. pp. 105–108. ISBN 9789401718431.
  9. [9]
    Krishnamurthy, Ramanarayanan; Jiménez, Eddy I.; Gibard, Clémentine (2020). "Prebiotic Phosphorylation and Concomitant Oligomerization of Deoxynucleosides to form DNA". Angewandte Chemie International Edition. 60 (19): 10775–10783. doi:10.1002/anie.202015910. ISSN 1521-3773. PMID 33325148. S2CID 229281953.
  10. [10]
    Song, Emilie Yeonwha; Jiménez, Eddy Ivanhoe; Lin, Huacan; Vay, Kristian Le; Krishnamurthy, Ramanarayanan; Mutschler, Hannes (2020). "Prebiotically Plausible RNA Activation Compatible with Ribozyme-Catalyzed Ligation". Angewandte Chemie International Edition. 60 (6): 2952–2957. doi:10.1002/anie.202010918. ISSN 1521-3773. PMC 7898671. PMID 33128282.
  11. [11]
    Karki, Megha; Gibard, Clémentine; Bhowmik, Subhendu; Krishnamurthy, Ramanarayanan (2017-07-29). "Nitrogenous Derivatives of Phosphorus and the Origins of Life: Plausible Prebiotic Phosphorylating Agents in Water". Life. 7 (3): 32. Bibcode:2017Life....7...32K. doi:10.3390/life7030032. PMC 5617957. PMID 28758921.

Other reading

  • H. N. Stokes (1894). "On Diamidoorthophosphoric and Diamidotrihydroxyphosphoric Acids". American Chemical Journal. 16 (2): 123.
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