Tetrakis(hydroxymethyl)phosphonium chloride
phosphonium_chloride.png)
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| Names | |
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| Preferred IUPAC name
Tetrakis(hydroxymethyl)phosphonium chloride | |
| Other names
Tetrahydroxymethylphosphonium chloride, THPC
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| Identifiers | |
| ChEMBL | |
| ChemSpider | |
| ECHA InfoCard | 100.004.280 |
| EC Number |
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PubChem CID
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| RTECS number |
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| UNII | |
| UN number | 2810 |
CompTox Dashboard (EPA)
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| Properties | |
| C4H12ClO4P | |
| Molar mass | 190.56 g·mol−1 |
| Appearance | white solid |
| Density | 1.341 g/cm3 |
| Melting point | 150 °C (302 °F; 423 K) |
| Hazards | |
| GHS labelling: | |
    
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| Danger | |
| H301, H302, H311, H312, H314, H315, H330, H334, H411 | |
| P260, P261, P264, P270, P271, P273, P280, P284, P285, P301+P310, P301+P312, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P304+P341, P305+P351+P338, P310, P312, P320, P321, P322, P330, P332+P313, P342+P311, P361, P362, P363, P391, P403+P233, P405, P501 | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Tetrakis(hydroxymethyl)phosphonium chloride (THPC) is an organophosphorus compound with the chemical formula [P(CH2OH)4]Cl. It is a white water-soluble salt with applications as a precursor to fire-retardant materials[1] and as a microbiocide in commercial and industrial water systems.
Synthesis, structure and reactions
[edit]THPC can be synthesized with high yield by treating phosphine with formaldehyde in the presence of hydrochloric acid.[1]
- PH3 + 4 H2C=O + HCl → [P(CH2OH)4]Cl
The cation P(CH2OH)4+ features four-coordinate phosphorus, as is typical for phosphonium salts.
THPC converts to tris(hydroxymethyl)phosphine upon treatment with aqueous sodium hydroxide:[2]
- [P(CH2OH)4]Cl + NaOH → P(CH2OH)3 + H2O + H2C=O + NaCl
Application in textiles
[edit]THPC has industrial importance in the production of crease-resistant and flame-retardant finishes on cotton textiles and other cellulosic fabrics.[3] [4] A flame-retardant finish can be prepared from THPC by the Proban Process,[5] in which THPC is treated with urea. The urea condenses with the hydroxymethyl groups on THPC. The phosphonium structure is converted to phosphine oxide as the result of this reaction.[6]
- [P(CH2OH)4]Cl + NH2CONH2 → (HOCH2)2P(O)CH2NHC(O)NH2 + HCl + HCHO + H2 + H2O
This reaction proceeds rapidly, forming insoluble high molecular weight polymers. The resulting product is applied to the fabrics in a "pad-dry process". This treated material is then treated with ammonia and ammonia hydroxide to produce fibers that are flame-retardant.
THPC can condense with many other types of monomers in addition to urea. These monomers include amines, phenols and polybasic acids and anhydrides.
Tris(hydroxymethyl)phosphine and its uses
[edit]Tris(hydroxymethyl)phosphine, which is derived from tetrakis(hydroxymethyl)phosphonium chloride, is an intermediate in the preparation of the water-soluble ligand 1,3,5-triaza-7-phosphaadamantane (PTA). This conversion is achieved by treating hexamethylenetetramine with formaldehyde and tris(hydroxymethyl)phosphine.[7]
Tris(hydroxymethyl)phosphine can also be used to synthesize the heterocycle, N-boc-3-pyrroline by ring-closing metathesis using Grubbs' catalyst (bis(tricyclohexylphosphine)benzylidineruthenium dichloride). N-Boc-diallylamine is treated with Grubbs' catalyst, followed by tris(hydroxymethyl)phosphine. The carbon-carbon double bonds undergo ring closure, releasing ethene gas, resulting in N-boc-3-pyrroline.[8] The hydroxymethyl groups on THPC undergo replacement reactions when THPC is treated with α,β-unsaturated nitrile, acid, amide and epoxides. For example, base induces condensation between THPC and acrylamide with displacement of the hydroxymethyl groups. (Z = CONH2)
- [P(CH2OH)4]Cl + NaOH + 3CH2=CHZ → P(CH2CH2Z)3 + 4CH2O + H2O + NaCl
Similar reactions occur when THPC is treated with acrylic acid; only one hydroxymethyl group is displaced, however.[9]
References
[edit]- ^ a b Svara, Jürgen; Weferling, Norbert; Hofmann, Thomas (2006). "Phosphorus Compounds, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_545.pub2. ISBN 3527306730.
- ^ M. Caporali, L. Gonsalvi, F. Zanobini, M. Peruzzini "Synthesis of the Water-Soluble Bidentate (P,N) Ligand PTN(Me)" Inorg. Syntheses, 2011, Vol. 35, p. 92–108. doi:10.1002/9780470651568.ch5
- ^ Fischer, Klaus; Marquardt, Kurt; Schlüter, Kaspar; Gebert, Karlheinz; Borschel, Eva-Marie; Heimann, Sigismund; Kromm, Erich; Giesen, Volker; Schneider, Reinhard; Lee Wayland, Rosser (2000). "Textile Auxiliaries". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a26_227. ISBN 3-527-30673-0.
- ^ Weil, Edward D.; Levchik, Sergei V. (2008). "Flame Retardants in Commercial Use or Development for Textiles". J. Fire Sci. 26 (3): 243–281. doi:10.1177/0734904108089485. S2CID 98355305.
- ^ "Frequently asked questions: What is the PROBAN® process?". Rhodia Proban. Archived from the original on December 7, 2012. Retrieved February 25, 2013.
- ^ Reeves, Wilson A.; Guthrie, John D. (1956). "Intermediate for Flame-Resistant Polymers-Reactions of Tetrakis(hydroxymethyl)phosphonium Chloride". Industrial and Engineering Chemistry. 48 (1): 64–67. doi:10.1021/ie50553a021.
- ^ Daigel, Donald J.; Decuir, Tara J.; Robertson, Jeffrey B.; Darensbourg, Donald J. (2007). "1,3,5-Triaz-7-Phosphatricyclo[3.3.1.1 3,7 ]Decane and Derivatives". Inorganic Syntheses. Vol. 32. pp. 40–42. doi:10.1002/9780470132630.ch6. ISBN 978-0-470-13263-0.
{{cite book}}:|journal=ignored (help) - ^ Ferguson, Marcelle L.; O’Leary, Daniel J.; Grubbs, Robert H. (2003). "Ring-Closing Metathesis Synthesis Of N-Boc-3-Pyrroline". Organic Syntheses. 80: 85. doi:10.15227/orgsyn.080.0085
{{cite journal}}: CS1 maint: multiple names: authors list (link). - ^ Vullo, W. J. (1966). "Hydroxymethyl Replacement Reactions of Tetrakis(hydroxymethyl)phosphonium Chloride". Ind. Eng. Chem. Prod. Res. Dev. 58 (4): 346–349. doi:10.1021/i360020a011.