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General ester of phosphonic acid.

Phosphonates or phosphonic acids are organic compounds containing C-PO(OH)2 or C-PO(OR)2 groups (where R=alkyl, aryl). Bisphosphonates were first synthesized in 1897 by Von Baeyer and Hofmann. An example of such a bisphosphonate is HEDP. Since the work of Schwarzenbach in 1949, phosphonic acids are known as effective chelating agents. The introduction of an amine group into the molecule to obtain -NH2-C-PO(OH)2 increases the metal binding abilities of the phosphonate. Examples for such compounds are 'iyot', EDTMP and DTPMP. These common phosphonates are the structure analogues to the well-known aminopolycarboxylates NTA, EDTA, and DTPA. The stability of the metal complexes increases with increasing number of phosphonic acid groups. Phosphonates are highly water-soluble while the phosphonic acids are only sparingly soluble. Phosphonates are not volatile and poorly soluble in organic solvents.

Contents

Phosphonate compounds

  • AEPN: 2-Aminoethylphosphonic acid
  • DMMP: Dimethyl methylphosphonate
  • HEDP: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid
  • ATMP: Amino tris(methylene phosphonic acid)
  • EDTMP: Ethylenediamine tetra(methylene phosphonic acid)
  • TDTMP: Tetramethylenediamine tetra(methylene phosphonic acid)
  • HDTMP: Hexamethylenediamine tetra(methylene phosphonic acid)
  • DTPMP: Diethylenetriamine penta(methylene phosphonic acid)
  • PBTC: Phosphonobutane-tricarboxylic acid
  • PMIDA: N-(phosphonomethyl)iminodiacetic acid
  • CEPA: 2-carboxyethyl phosphonic acid
  • HPAA: 2-Hydroxyphosphonocarboxylic acid
  • AMP: Amino-tris-(methylene-phosphonic acid)

Occurrence in nature

2-aminoethylphosphonic acid: the first identified natural phosphonate.

The naturally-occurring phosphonate 2-aminoethylphosphonic acid was first identified in 1959 in plants and many animals, where it is localized in membranes. Phosphonates are quite common among different organisms, from prokaryotes to eubacteria and fungi, mollusks, insects and others. The biological role of the natural phosphonates is still poorly understood. Bis- or polyphosphonates have not been found to occur naturally.

Properties and uses

Phosphonates are effective chelating agents that bind tightly to di- and trivalent metal ions, preventing them from forming insoluble precipitates (scale) and suppressing their catalytic properties. They are stable under harsh conditions. An important industrial use of phosphonates is in cooling waters, desalination systems, and in oil fields to inhibit scale formation. In pulp and paper manufacturing and in textile industry they serve as "peroxide bleach stabilizers," by chelating metals that could inactivate the peroxide. In detergents they are used as a combination of chelating agent, scale inhibitor, and bleach stabilizer. Phosphonates are also increasingly used in medicine to treat disorders associated with bone formation and calcium metabolism. Furthermore they serve as carriers for radionuclides in bone cancer treatments (see Samarium-153-ethylene diamine tetramethylene phosphonate).

In 1998 the consumption of phosphonates was 56,000 tons worldwide - 40,000 tons in the US, 15,000 tons in Europe and less than 800 tons in Japan. The demand of phosphonates grows steadily at 3% annually. In conjunction with organosilicates, phosphonates are also used to treat "Sudden Oak Death", which is caused by the fungus-like eukaryote Phytophthora ramorum.

Toxicology

The toxicity of phosphonates to aquatic organisms is low. Reported values for 48 h LC50 values for fish are between 0.1 and 1.1 mM. Also the bioconcentration factor for fish is very low.

Biodegradation

In nature bacteria play a major role in the degradation of phosphonates.[1] Due to the presence of natural phosphonates in the environment, bacteria have evolved the ability to metabolize phosphonates as nutrient sources. Some bacteria use phosphonates as a phosphorus source for growth. Aminophosphonates can also be used as sole nitrogen source by some bacteria. The polyphosphonates used in industry differ greatly from natural phosphonates such as 2-aminoethylphosphonic acid, because they are much larger, carry a high negative charge and are complexed with metals. Biodegradation tests with sludge from municipal sewage treatment plants with HEDP and NTMP showed no indication for any degradation. An investigation of HEDP, NTMP, EDTMP and DTPMP in standard biodegradation tests also failed to identify any biodegradation. It was noted, however, that in some tests due to the high sludge to phosphonate ratio, removal of the test substance from solution observed as loss of DOC was observed. This factor was attributed to adsorption rather than biodegradation. However, bacterial strains capable of degrading aminopolyphosphonates and HEDP under P-limited conditions have been isolated from soils, lakes, wastewater, activated sludge and compost.

No biodegradation of phosphonates during water treatment is observed but photodegradation of the Fe(III)-complexes is rapid. Aminopolyphosphonates are also rapidly oxidized in the presence of Mn(II) and oxygen and stable breakdown products are formed that have been detected in wastewater. The lack of information about phosphonates in the environment is linked to analytical problems of their determination at trace concentrations in natural waters. Phosphonates are present mainly as Ca and Mg-complexes in natural waters and therefore do not affect metal speciation or transport.

Phosphonates are one of the three sources of phosphate intake in biological cells (The other two being inorganic phosphate and organophosphate)

Environmental behavior

Phosphonates have a very strong interaction with surfaces, which results in a significant removal in technical and natural systems. Due to this strong adsorption, little or no remobilization of metals is expected.

Synthesis and reactions

Phosphonates can be synthesized using the Michaelis-Arbuzov reaction. In one study a α-aminophosphonate is prepared by condensation of benzaldehyde, aniline, and trimethyl phosphite catalyzed by Copper triflate in a one-pot synthesis.[2]

The phosphonates (and other phosphorus esters) can also be synthesized via transesterification reaction catalyzed by organic catalysts. N-heterocyclic carbenes have been reported to catalyze the reaction efficiently.[3]

In organic synthesis, phosphonates are used in the Horner-Wadsworth-Emmons reaction.

See also

methyl phosphonic acid is used as active ingredient in scale inhibitor.

References

  1. ^ Huang J, Su Z, Xu Y (November 2005). "The evolution of microbial phosphonate degradative pathways". Journal of Molecular Evolution 61 (5): 682–90. doi:10.1007/s00239-004-0349-4. PMID 16245012. 
  2. ^ A novel Cu(OTf)2 mediated three component high yield synthesis of α-aminophosphonates Abhimanyu S. Paraskar and Arumugam Sudalai Arkivoc 06-1838EP) pp 183-189 2006 Article
  3. ^ Singh R, Nolan SP (November 2005). "Synthesis of phosphorus esters by transesterification mediated by N-heterocyclic carbenes (NHCs)". Chemical Communications (43): 5456–8. doi:10.1039/b509783e. PMID 16261245. 
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