Hypophosphorous acid: Difference between revisions
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== Uses == | == Uses == | ||
Hypophosphorous acid is used in the formulation of pharmaceuticals, discoloration of polymers, water treatment, retrieval of precious or non-ferrous metals. Its main use is for electroless plating, i.e. deposition of metal films from solution. In organic chemistry, H<sub>3</sub>PO<sub>2</sub> best known for their use in the reduction of [[Diazonium salt|arenediazonium salts]], converting ArN<sub>2</sub><sup>+</sup> to Ar-H.<ref name="robison">Robison, M. M.; Robison, B. L. (1956). "[http://www.orgsyn.org/orgsyn/prep.asp?prep=cv4p0947 2,4,6-Tribromobenzoic acid]". ''[[Org. Synth.]]'' '''36''':94; ''Coll. Vol.'' '''4''':947.</ref><ref name="kornblum">Kornblum, N. (1941). "[http://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0295 3,3'-Dimethoxybiphenyl and 3,3'-dimethylbiphenyl]". ''[[Org. Synth.]]'' '''21''':30; ''Coll. Vol.'' '''3''':295.</ref> When | Hypophosphorous acid is used in the formulation of pharmaceuticals, discoloration of polymers, water treatment, retrieval of precious or non-ferrous metals. Its main use is for electroless plating, i.e. deposition of metal films from solution. In organic chemistry, H<sub>3</sub>PO<sub>2</sub> best known for their use in the reduction of [[Diazonium salt|arenediazonium salts]], converting ArN<sub>2</sub><sup>+</sup> to Ar-H.<ref name="robison">Robison, M. M.; Robison, B. L. (1956). "[http://www.orgsyn.org/orgsyn/prep.asp?prep=cv4p0947 2,4,6-Tribromobenzoic acid]". ''[[Org. Synth.]]'' '''36''':94; ''Coll. Vol.'' '''4''':947.</ref><ref name="kornblum">Kornblum, N. (1941). "[http://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0295 3,3'-Dimethoxybiphenyl and 3,3'-dimethylbiphenyl]". ''[[Org. Synth.]]'' '''21''':30; ''Coll. Vol.'' '''3''':295.</ref> When diazotized in a concentrated solution of hypophosphorous acid, an [[amine]] substituent can be removed from arenes, selectively over alkyl amines. | ||
===DEA List I chemical status=== | ===DEA List I chemical status=== | ||
Because hypophosphorous acid can reduce elemental [[iodine]] to form [[hydroiodic acid]], which is a reagent effective for reducing [[ephedrine]] or [[pseudoephedrine]] to [[methamphetamine]],<ref name="ARKIVOC">Gordon, P.E.; Fry, A.J.; Hicks, L.D. ''Further studies on the reduction of benzylic alcohols by hypophosphorous acid/iodine.'' 23 August 2005. [http://content.arkat-usa.org/ARKIVOC/JOURNAL_CONTENT/manuscripts/2005/EJ-1559CP%20as%20published%20mainmanuscript.pdf ARKIVOC 2005 (vi) 393-400]. [[ISSN|ISSN 1424-6376]].</ref> the [[Drug Enforcement Administration|United States Drug Enforcement Administration]] designated hypophosphorous acid (and its salts) as a [[DEA list of chemicals|List I precursor chemical]] effective November 16, 2001.<ref name="66 CFR 52670">[http://frwebgate.access.gpo.gov/cgi-bin/getdoc.cgi?dbname=2001_register&docid=01-26013-filed 66 FR 52670—52675.] 17 October 2001.</ref> Accordingly, handlers of hypophosphorous acid or its salts in the | Because hypophosphorous acid can reduce elemental [[iodine]] to form [[hydroiodic acid]], which is a reagent effective for reducing [[ephedrine]] or [[pseudoephedrine]] to [[methamphetamine]],<ref name="ARKIVOC">Gordon, P.E.; Fry, A.J.; Hicks, L.D. ''Further studies on the reduction of benzylic alcohols by hypophosphorous acid/iodine.'' 23 August 2005. [http://content.arkat-usa.org/ARKIVOC/JOURNAL_CONTENT/manuscripts/2005/EJ-1559CP%20as%20published%20mainmanuscript.pdf ARKIVOC 2005 (vi) 393-400]. [[ISSN|ISSN 1424-6376]].</ref> the [[Drug Enforcement Administration|United States Drug Enforcement Administration]] designated hypophosphorous acid (and its salts) as a [[DEA list of chemicals|List I precursor chemical]] effective November 16, 2001.<ref name="66 CFR 52670">[http://frwebgate.access.gpo.gov/cgi-bin/getdoc.cgi?dbname=2001_register&docid=01-26013-filed 66 FR 52670—52675.] 17 October 2001.</ref> Accordingly, handlers of hypophosphorous acid or its salts in the United States are subject to stringent regulatory controls including registration, recordkeeping, reporting, and import/export requirements pursuant to the [[Controlled Substances Act]] and 21 CFR §§ 1309 and 1310.<ref name="66 CFR 52670"/><ref name="21 CFR 1309">[http://www.access.gpo.gov/nara/cfr/waisidx_06/21cfr1309_06.html 21 CFR 1309]</ref><ref name="CSA">[http://www.usdoj.gov/dea/pubs/csa.html 21 USC, Chapter 13 (Controlled Substances Act)]</ref> | ||
== Inorganic and organic derivatives == | == Inorganic and organic derivatives == | ||
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== Sources == | == Sources == | ||
* | *Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), "Advanced Inorganic Chemistry" (6th ed.), New York: Wiley-Interscience, ISBN 0-471-19957-5. | ||
* [http://www.chemicalland21.com/arokorhi/industrialchem/inorganic/HYPOPHOSPHOROUS%20ACID.htm ChemicalLand21 Listing] | * [http://www.chemicalland21.com/arokorhi/industrialchem/inorganic/HYPOPHOSPHOROUS%20ACID.htm ChemicalLand21 Listing] | ||
*D. E. C. Corbridge "Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology" 5th Edition Elsevier: Amsterdam. ISBN 0-444-89307-5. | *D. E. C. Corbridge "Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology" 5th Edition Elsevier: Amsterdam. ISBN 0-444-89307-5. | ||
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<references/> | <references/> | ||
[[Category:Phosphorus compounds]] | [[Category:Phosphorus compounds]] | ||
Latest revision as of 16:12, 9 August 2012
Editor-In-Chief: Henry A. Hoff
Overview
Hypophosphorous acid is a phosphorus oxoacid and a powerful reducing agent. Inorganic chemists refer to the free acid by this name (also as "HPA") although its official IUPAC name is phosphinic acid. See Phosphinic acid. It is a colorless low-melting compound, which is soluble in water, dioxane, and alcohols. The formula for hypophosphorous acid is generally written H3PO2, but a more descriptive presentation is HOP(O)H2 which highlights its monoprotic character. Salts derived from this acid are called hypophosphites.
HOP(O)H2 exists in equilibrium with the minor tautomer HP(OH)2. Sometimes the minor tautomer is called hypophosphorous acid and the major tautomer is called phosphinic acid.
Preparation and availability
The acid is prepared industrially via a two step process. Hypophosphite salts of the alkali and alkaline earth metals result from treatment of white phosphorus with hot aqueous solution of the appropriate hydroxide, e.g. Ca(OH)2.
- P4 + 4OH− + 4H2O → 4H2PO2− + 2H2
The free acid may be prepared by the action of a strong acid on these hypophosphite salts.
- H2PO2− + H+ → H3PO2
Alternatively, H3PO2 arises by the oxidation of phosphine with iodine in water.
- PH3 + 2I2 + 2H2O → H3PO2 + 4I− + 4H+
HPA is usually supplied as a 50% aqueous solution.
Uses
Hypophosphorous acid is used in the formulation of pharmaceuticals, discoloration of polymers, water treatment, retrieval of precious or non-ferrous metals. Its main use is for electroless plating, i.e. deposition of metal films from solution. In organic chemistry, H3PO2 best known for their use in the reduction of arenediazonium salts, converting ArN2+ to Ar-H.[1][2] When diazotized in a concentrated solution of hypophosphorous acid, an amine substituent can be removed from arenes, selectively over alkyl amines.
DEA List I chemical status
Because hypophosphorous acid can reduce elemental iodine to form hydroiodic acid, which is a reagent effective for reducing ephedrine or pseudoephedrine to methamphetamine,[3] the United States Drug Enforcement Administration designated hypophosphorous acid (and its salts) as a List I precursor chemical effective November 16, 2001.[4] Accordingly, handlers of hypophosphorous acid or its salts in the United States are subject to stringent regulatory controls including registration, recordkeeping, reporting, and import/export requirements pursuant to the Controlled Substances Act and 21 CFR §§ 1309 and 1310.[4][5][6]
Inorganic and organic derivatives
Numerous derivatives are known in which the two hydrogen atoms directly bound to phosphorus are replaced by organic groups. These derivatives are known as phosphinic acids, and their salts as phosphinates. For example, formaldehyde and H3PO2 react to give (HOCH2)2PO2H. The reaction is akin to the addition of thiols and HCN to aldehydes. Similarly, it adds to Michael acceptors, for example with acrylamide it gives H(HO)P(O)CH2CH2C(O)NH2.
Few metal complexes have been prepared from H3PO2, one example is Ni(O2PH2)2.
Sources
- Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), "Advanced Inorganic Chemistry" (6th ed.), New York: Wiley-Interscience, ISBN 0-471-19957-5.
- ChemicalLand21 Listing
- D. E. C. Corbridge "Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology" 5th Edition Elsevier: Amsterdam. ISBN 0-444-89307-5.
- V. V. Popik, A. G. Wright, T. A. Khan, J. A. Murphy "Hypophosphorous Acid" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.
References
- ↑ Robison, M. M.; Robison, B. L. (1956). "2,4,6-Tribromobenzoic acid". Org. Synth. 36:94; Coll. Vol. 4:947.
- ↑ Kornblum, N. (1941). "3,3'-Dimethoxybiphenyl and 3,3'-dimethylbiphenyl". Org. Synth. 21:30; Coll. Vol. 3:295.
- ↑ Gordon, P.E.; Fry, A.J.; Hicks, L.D. Further studies on the reduction of benzylic alcohols by hypophosphorous acid/iodine. 23 August 2005. ARKIVOC 2005 (vi) 393-400. ISSN 1424-6376.
- ↑ 4.0 4.1 66 FR 52670—52675. 17 October 2001.
- ↑ 21 CFR 1309
- ↑ 21 USC, Chapter 13 (Controlled Substances Act)