Tetrakis(hydroxymethyl)phosphonium chloride

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Tetrakis(hydroxymethyl)­phosphonium chloride
Tetrakis(hydroxymethyl)phosphonium chloride.png
Names
Preferred IUPAC name
Tetrakis(hydroxymethyl)phosphonium chloride
Other names
Tetrahydroxymethylphosphonium chloride, THPC
Identifiers
ChEMBL
ChemSpider
ECHA InfoCard 100.004.280 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 204-707-7
PubChem CID
RTECS number
  • TA2450000
UNII
UN number 2810
Properties
C4H12ClO4P
Molar mass 190.56 g·mol−1
Appearancewhite solid
Density 1.341 g/cm3
Melting point 150 °C (302 °F; 423 K)
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
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. THPC has applications as a precursor to fire-retardant materials, [1] as well as a microbiocide in commercial and industrial water systems.

Contents

Synthesis, structure, and reactions

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

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

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]

Related Research Articles

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Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated forms which are both hygroscopic. They feature iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while all forms are mild oxidizing agents. It is used as a water cleaner and as an etchant for metals.

<span class="mw-page-title-main">Nickel(II) chloride</span> Chemical compound

Nickel(II) chloride (or just nickel chloride) is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

<span class="mw-page-title-main">Phosphonium</span> Family of polyatomic cations containing phosphorus

In chemistry, the term phosphonium describes polyatomic cations with the chemical formula PR+
4
. These cations have tetrahedral structures. The salts are generally colorless or take the color of the anions.

<span class="mw-page-title-main">Phosphorus trichloride</span> Chemical compound

Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is versatile compound that is widely used as a reagent in organic synthesis and as a ligand for transition metal complexes, including ones that serve as catalysts in organometallic chemistry. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic red-brown solids. The soluble trihydrated (n = 3) salt is the usual compound of commerce. It is widely used to prepare compounds used in homogeneous catalysis.

<span class="mw-page-title-main">Sulfamic acid</span> Chemical compound

Sulfamic acid, also known as amidosulfonic acid, amidosulfuric acid, aminosulfonic acid, sulphamic acid and sulfamidic acid, is a molecular compound with the formula H3NSO3. This colourless, water-soluble compound finds many applications. Sulfamic acid melts at 205 °C before decomposing at higher temperatures to water, sulfur trioxide, sulfur dioxide and nitrogen.

<span class="mw-page-title-main">Palladium(II) chloride</span> Chemical compound

Palladium(II) chloride, also known as palladium dichloride and palladous chloride, are the chemical compounds with the formula PdCl2. PdCl2 is a common starting material in palladium chemistry – palladium-based catalysts are of particular value in organic synthesis. It is prepared by the reaction of chlorine with palladium metal at high temperatures.

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<span class="mw-page-title-main">Phosphine oxides</span> Class of chemical compounds

Phosphine oxides are phosphorus compounds with the formula OPX3. When X = alkyl or aryl, these are organophosphine oxides. Triphenylphosphine oxide is an example. An inorganic phosphine oxide is phosphoryl chloride (POCl3). The parent phosphine oxide (H3PO) remains rare and obscure.

<span class="mw-page-title-main">Hexafluorophosphate</span> Anion with the chemical formula PF6–

Hexafluorophosphate is an anion with chemical formula of [PF6]. It is an octahedral species that imparts no color to its salts. [PF6] is isoelectronic with sulfur hexafluoride, SF6, and the hexafluorosilicate dianion, [SiF6]2−, and hexafluoroantimonate [SbF6]. In this anion, phosphorus has a valence of 5. Being poorly nucleophilic, hexafluorophosphate is classified as a non-coordinating anion.

<span class="mw-page-title-main">TPPTS</span> Chemical compound

3,3′,3′′-Phosphanetriyltris(benzenesulfonic acid) trisodium salt (abbreviated TPPTS), is an organic compound that is also known as sodium triphenylphosphine trisulfonate. The compound has the formula P(C6H4SO3Na)3. This white solid is an unusual example of a water-soluble phosphine. Its complexes are also water-soluble. Its complex with rhodium is used in the industrial production of butyraldehyde.

<span class="mw-page-title-main">Dichlorotris(triphenylphosphine)ruthenium(II)</span> Chemical compound

Dichlorotris(triphenylphosphine)ruthenium(II) is a coordination complex of ruthenium. It is a chocolate brown solid that is soluble in organic solvents such as benzene. The compound is used as a precursor to other complexes including those used in homogeneous catalysis.

<span class="mw-page-title-main">Metal-phosphine complex</span>

A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).

<span class="mw-page-title-main">Tris(trimethylsilyl)phosphine</span> Chemical compound

Tris(trimethylsilyl)phosphine is the organophosphorus compound with the formula P(SiMe3)3 (Me = methyl). It is a colorless liquid that ignites in air and hydrolyses readily.

In organophosphorus chemistry, an aminophosphine is a compound with the formula R3−nP(NR2)n where R = H or an organic substituent, and n = 0, 1, 2. At one extreme, the parents H2PNH2 and P(NH2)3 are lightly studied and fragile, but at the other extreme tris(dimethylamino)phosphine (P(NMe2)3) is commonly available. Intermediate members are known, such as Ph2PN(H)Ph. These compounds are typically colorless and reactive toward oxygen. They have pyramidal geometry at phosphorus.

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<span class="mw-page-title-main">Tris(hydroxymethyl)phosphine</span> Chemical compound

Tris(hydroxymethyl)phosphine is the organophosphorus compound with the formula P(CH2OH)3. It is a white solid. The compound is multifunctional, consisting of three alcohol functional groups and a tertiary phosphine. It is prepared by treating tetrakis(hydroxymethyl)phosphonium chloride with strong base:

References

  1. 1 2 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.
  2. 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
  3. 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.
  4. 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.
  5. "Frequently asked questions: What is the PROBAN® process?". Rhodia Proban. Archived from the original on December 7, 2012. Retrieved February 25, 2013.
  6. 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.
  7. 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)
  8. 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).
  9. 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.