| Revision as of 00:48, 20 January 2011 editKupirijo (talk | contribs)Extended confirmed users9,146 edits Category:Quaternary phosphonium compounds← Previous edit |
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{{chembox |
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| Name = Tetrakis(hydroxymethyl)phosphonium chloride |
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| ImageFile = Tetrakis(hydroxymethyl)phosphonium chloride.png |
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| verifiedrevid = 408885713 |
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| OtherNames = Tetrahydroxymethylphosphonium chloride, THPC |
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| Name = Tetrakis(hydroxymethyl){{SHY}}phosphonium chloride |
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| Section1 = {{Chembox Identifiers |
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| ImageFile = Tetrakis(hydroxymethyl)phosphonium chloride.png |
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| CASNo = 124-64-1 |
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| PIN = Tetrakis(hydroxymethyl)phosphonium chloride |
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| PubChem = 31298 |
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| OtherNames = Tetrahydroxymethylphosphonium chloride, THPC |
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| Section1 = {{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 124-64-1 |
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| ChEMBL = 2131547 |
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| EC_number = 204-707-7 |
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| RTECS = TA2450000 |
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| UNNumber = 2810 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 58WB2XCF8I |
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| ChemSpiderID =29038 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| PubChem = 31298 |
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}} |
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| Section2 = {{Chembox Properties |
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| C=4|H=12|Cl=1|O=4|P=1 |
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| Appearance = white solid |
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| Section2 = {{Chembox Properties |
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| Density = 1.341 g/cm<sup>3</sup> |
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| Formula = (HOCH<sub>2</sub>)<sub>4</sub>PCl |
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| MeltingPtC = 150 |
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| MolarMass = 190.56 g/mol |
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}} |
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| Appearance = cyrstalline |
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| Section7 = {{Chembox Hazards |
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| Density = 1.341 g/cm³ |
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| ExternalSDS = |
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| Solubility = N/A |
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| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS07}}{{GHS08}}{{GHS09}} |
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| MeltingPt = 150 °C (423 K) |
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| BoilingPt = N/A |
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| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|301|302|311|312|314|315|330|334|411}} |
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}} |
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| PPhrases = {{P-phrases|260|261|264|270|271|273|280|284|285|301+310|301+312|301+330+331|302+352|303+361+353|304+340|304+341|305+351+338|310|312|320|321|322|330|332+313|342+311|361|362|363|391|403+233|405|501}} |
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| Section7 = {{Chembox Hazards |
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}} |
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| ExternalMSDS = |
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| RPhrases = {{R21}} {{R25}} {{R38}} {{R41}} {{R42/43}} {{R51/53}} |
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| SPhrases = {{S22}} {{S26}} {{S36/37/39}} {{S45}} {{S60}} {{S61}} |
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'''Tetrakis(hydroxymethyl)phosphonium chloride''' (THPC) is a ] with the chemical formula Cl. The cation (CH2OH)4P<sup>+</sup> is a four-coordinate phosphorus compound with the phosphorus atom carrying a positive charge. THPC has industrial applications as precursors to fire-retardant materials and synthetic applications as precursor to the useful ligand, tris(hydroxymethyl)phosphine. |
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'''Tetrakis(hydroxymethyl)phosphonium chloride''' (THPC) is an ] with the chemical formula Cl. It is a white water-soluble salt with applications as a precursor to fire-retardant materials<ref name=Ullmann>{{Ullmann|doi=10.1002/14356007.a19_545.pub2|title=Phosphorus Compounds, Organic|year=2006|last1=Svara|first1=Jürgen|last2=Weferling|first2=Norbert|last3=Hofmann|first3=Thomas|isbn=3527306730}}</ref> and as a microbiocide in commercial and industrial water systems. |
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==Synthesis== |
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==Synthesis, structure and reactions== |
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THPC can be synthesized with high yield by treating phosphine with formaldehyde in the presence of hydrochloric acid.<ref>{{cite journal | author = Weil, Edward D. ; Levchik, Sergei V. | title = Flame Retardants in Commercial Use or Development for Textiles | journal = ] | year = 2008 | volume = 26 | issue = 3 | pages = 243–281 | doi = 10.1177/0734904108089485}}</ref> |
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THPC can be synthesized with high yield by treating ] with ] in the presence of ].<ref name=Ullmann/> |
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:PH<sub>3</sub> + 4 H<sub>2</sub>C=O + HCl → Cl |
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The cation P(CH<sub>2</sub>OH)<sub>4</sub><sup>+</sup> features four-coordinate phosphorus, as is typical for ]s. |
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THPC converts to ] upon treatment with aqueous ]:<ref>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}}</ref> |
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:PH<sub>3</sub> + 4 H<sub>2</sub>C=O + HCl → Cl |
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:Cl + NaOH → P(CH<sub>2</sub>OH)<sub>3</sub> + H<sub>2</sub>O + H<sub>2</sub>C=O + NaCl |
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==Application in textiles== |
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==Reactions== |
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THPC has industrial importance in the production of crease-resistant and ] ] on cotton textiles and other cellulosic fabrics.<ref>{{cite book|doi=10.1002/14356007.a26_227 |chapter=Textile Auxiliaries |title=Ullmann's Encyclopedia of Industrial Chemistry |date=2000 |last1=Fischer |first1=Klaus |last2=Marquardt |first2=Kurt |last3=Schlüter |first3=Kaspar |last4=Gebert |first4=Karlheinz |last5=Borschel |first5=Eva-Marie |last6=Heimann |first6=Sigismund |last7=Kromm |first7=Erich |last8=Giesen |first8=Volker |last9=Schneider |first9=Reinhard |last10=Lee Wayland |first10=Rosser |isbn=3-527-30673-0 }}</ref> |
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THPC is commonly used to prepare tris(hydroxymethyl)phosphine by treating it with aqueous sodium hydroxide.<ref>Svara, Jürgen; Weferling, Norbert ; Hofmann, Thomas. Phosphorus Compounds, Organic. Ullmann's Encyclopedia of Industrial Chemistry. John Wiley & Sons, Inc, 2008 DOI: 10.1002/14356007.a19_545.pub2</ref> |
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<ref>{{cite journal |author1=Weil, Edward D. |author2=Levchik, Sergei V. | title = Flame Retardants in Commercial Use or Development for Textiles | journal = ] | year = 2008 | volume = 26 | issue = 3 | pages = 243–281 | doi = 10.1177/0734904108089485|s2cid=98355305 }}</ref> A flame-retardant finish can be prepared from THPC by the Proban Process,<ref name="proban process">{{cite web|url=http://www.rhodia-proban.com/uk/faq.asp|title=Frequently asked questions: What is the PROBAN® process?|publisher=Rhodia Proban|access-date=February 25, 2013|archive-date=December 7, 2012|archive-url=https://web.archive.org/web/20121207081548/http://www.rhodia-proban.com/uk/faq.asp|url-status=dead}}</ref> in which THPC is treated with urea. The ] condenses with the hydroxymethyl groups on THPC. The phosphonium structure is converted to ] as the result of this reaction.<ref>{{cite journal |author1=Reeves, Wilson A. |author2=Guthrie, John D. | title = Intermediate for Flame-Resistant Polymers-Reactions of Tetrakis(hydroxymethyl)phosphonium Chloride | journal = ] | year = 1956 | volume = 48 | issue = 1 | pages = 64–67 | doi = 10.1021/ie50553a021}}</ref> |
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:Cl + NaOH → P(CH<sub>2</sub>OH)<sub>3</sub> + H<sub>2</sub>O + H<sub>2</sub>C=O + NaCl |
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:Cl + NH<sub>2</sub>CONH<sub>2</sub> → (HOCH<sub>2</sub>)<sub>2</sub>P(O)CH<sub>2</sub>NHC(O)NH<sub>2</sub> + HCl + HCHO + H<sub>2</sub> + H<sub>2</sub>O |
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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. |
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==Tris(hydroxymethyl)phosphine and its uses== |
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Tris(hydroxymethyl)phosphine is an intermediate in the preparation of the water-soluble ligand 1,3,5-triaza-7-phosphaadamantane (PTA). This is done by treating hexamethylenetetramine with formaldehyde and tris(hydroxymethyl)phosphine.<ref>{{cite journal | author = Daigel, Donald J. | title = <nowiki>1,3,5-triaza-7phosphatricyclodecane and derivatives</nowiki> | journal = ] | volume = 32 | pages = 40–42 | year = 1998 | doi = 10.1002/9780470132630.ch6 | last2 = Decuir | first2 = Tara J. | last3 = Robertson | first3 = Jeffrey B. | last4 = Darensbourg | first4 = Donald J.}}</ref> |
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Tris(hydroxymethyl)phosphine can also be used to synthesize the heterocycle, N-boc-3-pyrroline by ring-closing metathesis using ] (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 ethylene gas, resulting in N-boc-3-pyrroline.<ref>{{OrgSynth | author = Ferguson, Marcelle L.; O’Leary, Daniel J.; Grubbs, Robert H. | title = Ring-Closing Metathesis Synthesis Of N-Boc-3-Pyrroline | volume = 80 | pages = 85 | year = 2003 | prep = v80p0085}}</ref> |
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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 = CONH<sub>2</sub>) |
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THPC can condense with many other types of monomers in addition to urea. These monomers include amines, phenols and polybasic acids and anhydrides. |
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:Cl + NaOH + 3CH<sub>2</sub>=CHZ → P(CH<sub>2</sub>CH<sub>2</sub>Z)<sub>3</sub> + 4CH<sub>2</sub>O + H<sub>2</sub>O + NaCl |
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==Tris(hydroxymethyl)phosphine and its uses== |
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Similar reactions occur when THPC is treated with acrylic acid; only one hydroxymethyl group is displaced, however.<ref>{{cite journal | author = Vullo, W. J. | title = Hydroxymethyl Replacement Reactions of Tetrakis(hydroxymethyl)phosphonium Chloride | journal = ] | year = 1966 | volume = 58 | issue = 4 | pages = 346–349 | doi = 10.1021/i360020a011}}</ref> |
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Tris(hydroxymethyl)phosphine, which is derived from tetrakis(hydroxymethyl)phosphonium chloride, is an intermediate in the preparation of the water-soluble ligand ] (PTA). This conversion is achieved by treating ] with formaldehyde and tris(hydroxymethyl)phosphine.<ref>{{cite book | author = Daigel, Donald J. | journal = ] | volume = 32 | pages = 40–42 | doi = 10.1002/9780470132630.ch6 | last2 = Decuir | first2 = Tara J. | last3 = Robertson | first3 = Jeffrey B. | last4 = Darensbourg | first4 = Donald J. | chapter = 1,3,5-Triaz-7-Phosphatricyclo[3.3.1.1 <sup>3,7</sup> ]Decane and Derivatives | title = Inorganic Syntheses | date = 2007 | isbn = 978-0-470-13263-0}}</ref> |
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==Application in Textiles== |
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THPC has industrial importance in the production of crease-resistant and ] ] on cotton textiles and other cellulosic fabrics. A flame-retardant finish can be prepared from THPC by the ”Proban Process,” in which THPC is treated with urea. The urea condenses with the hydroxymethyl groups on THPC. The phosphonium structure is converted to ] as the result of this reaction.<ref>{{cite journal | author = Reeves, Wilson A.; Guthrie, John D. | title = Intermediate for Flame-Resistant Polymers-Reactions of Tetrakis(hydroxymethyl)phosphonium Chloride | journal = ] | year = 1956 | volume = 48 | issue = 1 | pages = 64–67 | doi = 10.1021/ie50553a021}}</ref> |
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Tris(hydroxymethyl)phosphine can also be used to synthesize the heterocycle, N-boc-3-pyrroline by ring-closing metathesis using ] (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.<ref>{{OrgSynth | author = Ferguson, Marcelle L.; O’Leary, Daniel J.; Grubbs, Robert H. | title = Ring-Closing Metathesis Synthesis Of N-Boc-3-Pyrroline | volume = 80 | pages = 85 | year = 2003 | doi = 10.15227/orgsyn.080.0085}}</ref> |
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:Cl + NH<sub>2</sub>CONH<sub>2</sub> → (CH<sub>2</sub>OH)<sub>2</sub>POCH<sub>2</sub>NHCONH<sub>2</sub> + HCl + HCHO + H<sub>2</sub> + H<sub>2</sub>O |
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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 = CONH<sub>2</sub>) |
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:Cl + NaOH + 3CH<sub>2</sub>=CHZ → P(CH<sub>2</sub>CH<sub>2</sub>Z)<sub>3</sub> + 4CH<sub>2</sub>O + H<sub>2</sub>O + NaCl |
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Similar reactions occur when THPC is treated with ]; only one hydroxymethyl group is displaced, however.<ref>{{cite journal | author = Vullo, W. J. | title = Hydroxymethyl Replacement Reactions of Tetrakis(hydroxymethyl)phosphonium Chloride |journal=Ind. Eng. Chem. Prod. Res. Dev.| year = 1966 | volume = 58 | issue = 4 | pages = 346–349 | doi = 10.1021/i360020a011}}</ref> |
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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. |
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THPC can condense with many other types of monomers in addition to urea. These monomers include amines, phenols, and polybasic acids and anhydrides. |
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==References== |
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==References== |
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{{reflist}} |
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<references/> |
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