Phosphonium, tetrakis

Tetrakis(hydroxymethyl)phosphonium Salts. The reaction of formaldehyde (qv) and phosphine in aqueous hydrochloric or sulfuric acid yields tetrakis-(hydroxymethyl)phosphonium chloride [124-62-1/, Albright Wilson s Retardol C, or the sulfate [55566-30-8] (Retardol S), (C4H 2C4P)2SO [55566-30-8]. 

Finally, a modification has been carried out in which a polyacrylate emulsion is added to a normal tetrakis(hydroxymethyl)phosphonium sulfate [55566-30-8] (THPS), urea, and TMM fire-retardant treatment in an attempt to completely alleviate the strength loss during the finishing. Indeed, better retention of tensile properties is achieved with no loss in fire resistance (85). 

LRC-100Finish. The use of LRC-100 flame retardant for 50/50 polyester cotton blends has been reported (144). It is a condensation product of tetrakis(hydroxymethyl)-phosphonium salt (THP salt) and A/A7,A7 -trimethylphosphoramide [6326-72-3] (TMPA). The precondensate is prepared by heating the THP salt and TMPA in a 2.3-to-l.0-mole ratio for one hour at 60—65°C. It is appUed in conjunction with urea and trimethylolmelamine in a pad-dry-cure oxidation wash procedure. Phosphoms contents of 3.5—4.0% are needed to enable blends to pass the FF 3-71 Test. 

Textile Flame Retardants. The first known commercial appHcation for phosphine derivatives was as a durable textile flame retardant for cotton and cotton—polyester blends. The compounds are tetrakis(hydroxymethyl)phosphonium salts (10) which are prepared by the acid-cataly2ed addition of phosphine to formaldehyde. The reaction proceeds ia two stages. Initially, the iatermediate tris(hydroxymethyl)phosphine [2767-80-8] is formed. 

The salt ia this case is tetrakis(hydroxymethyl)phosphonium chloride [124-64-1]. The corresponding sulfate salt [55566-30-8] is also produced commercially as are urea-containing formulations of both salts. The latter formulations are actually used to flame retard the textiles (see Flame retardants FOR textiles). 

Biocides. Two phosphine derivatives are ia commercial use as biocides. These are tetrakis(hydroxymethyl)phosphonium sulfate [55566-30-8] and tributyl(tetradecyl)phosphonium chloride [8741-28-8]. These compounds are sold by Albright and Wilson Ltd. and EMC, respectively. The preparation... 

Various patents (22—24) have been issued claiming the use of tetrakis(hydroxymethyl)phosphonium sulfate in, for example, water treating, pharmaceuticals (qv), and in the oil industry where this compound shows exceptional activity toward the sulfate-reducing bacteria that are a primary cause of hydrogen sulfide formation and consequent problems associated with souring and corrosion (25). 

Flame Retardants. The amount of research expended to develop flame-retardant (FR) finishes for cotton and other fabrics has been extremely large in comparison to the total amount of fabrics finished to be flame retardant. The extent of this work can be seen in various reviews (146—148). In the early 1960s, a substantial market for FR children s sleepwear appeared to be developing, and substantial production of fabric occurred. In the case of cotton, the finish was based on tetrakis(hydroxymethyl)phosphonium chloride (THPC) or the corresponding sulfate (THPS). This chemical was partly neutralized to THPOH, padded on fabric, dried under controlled conditions, and ammoniated. The finish was subsequently oxidized, yielding a product that passed the test for FR performance. This process is widely preferred to the THPOH—NH process. 

Tetrakis(hydroxymethyl)phosphonium chloride [124-64-1] AcOH and dried at 100° in a vacuum. An 80% w/v aqueous solution has d 7955]. 

The tetrakis(hydroxymethyl)phosphonium chloride so formed is the major ingredient with urea-formaldehyde or melamine-formaldehyde resins for the permanent flame-proofing of cotton cloth. 

Bachman, R.E. and Schmidbaur, H. (1996) Isolation and Structural Characterization of [P(AuPPh3)5][BF4]2 via Cleavage of a P-P Bond by Cationic Gold Fragments Direct Evidence of the Structure of the Elusive Tetrakis [phosphmeaurio(I)] phosphonium(4-) Cation. Inorganic Chemistry, 35, 1399-1401. 

Offshore oil production is one area in which environmental pollution has been highlighted as an issue, particularly in the use of biocides in production waters. Tetrakis-hydroxymethyl phosphonium salts exhibit acceptable environmental profiles [1120], and they are regarded as the preferred products for bacterial control within the oil production industry. 

A development reported recently [519] involves reduction of the cystine disulphide bonds in wool with either thioglycolic acid or tetrakis(hydroxymethyl)phosphonium chloride to form thiol groups, followed by crosslinking with bifunctional reactive dyes. This gave improved insect resistance but had adverse effects on physical properties such as strength, shrinkage and stiffness, thus limiting the potential of the process for commercial use. 

The main method for obtaining these heterocycles is the interaction of amines with oxymethylphosphines. Frank and Drake (72JOC2752 77JOC4040) isolated 5-aminomethyl-l,3-diphenyl-l,3,5-diazaphosphori-nane (39) by treating tris(oxymethyl) phosphine (40) or tetrakis(oxy-methyl)phosphonium chloride (38) with aniline. The reaction with p-toluidine proceeds in a similar manner [Eq. (24)] (83IZV1379). 

However, compound 57, containing two 1,3-azaphosphetidine fragments, obtained by heating tetrakis(aminomethyl)phosphonium (38) chloride or tris(anilinomethyl)phosphine (40) in ethanol, is described in Eq. (28) (72JOC2752 77JOC4040). A detailed analysis of NMR spectra made it possible to reject a structure with two five-membered rings. 

Tetrakis (dimethylthiocarbamato) tellurium(IV), 24 428 Tetrakis(hydroxymethyl)phosphonium salts, 11 498 hydroxide, 19 67... 

Anion-based organic dye nanoparticles can be also synthesized on the basis of the ion-association method. In this case, hydrophobic phosphazenium cations such as tetrakis[tris(dimethylamino) phosphoranylideneamino]phosphonium cation are effective for ion-pair formation with anionic dyes. A neutral polymer stabilizer polyvinylpyrrolidone (PVP) that is soluble in water is sometimes added for preventing agglomeration... 

Tetrakis(hydroxymethyl)phosphonium nitrate, 1754 Tetramethylammonium chlorite, 1742 Tetramethylammonium pentaperoxodichromate, 3103 Triaminoguanidinium nitrate, 0517... 

Thorpe reaction org chem The reaction by which, in presence of lithium amides, a,(rt-dinitriles undergo base-catalyzed condensation to cyclic iminonitriles, which can be hydrolyzed and decarboxylated to cyclic ketones. thorp re,ak-shan TMPC See tetrakis(hydroxymethyl)phosphonium chloride, thulia See thulium oxide. thu-le-a ... 

World Health Organisation (WHO) (2000) Flame retardants Tris(2-butoxyethyl)phosphate, tris(2-ethylhexyl) phosphate and tetrakis(hydroxymethyl)phosphonium salts. Environmental Health Criteria 218, WHO, Geneva... 

Potassium cyanide-potassiiun nitrite, 0527 Potassium pentacyanodiperoxochromate(5-), 1810 Potassiiun tricyanodiperoxochromate(3-), 1044 Tetrahydroxotritin(2+) nitrate, 4525 Tetrakis(hydroxymethyl)phosphonium nitrate, 1754 Tin(ll) nitrate, 4750 Tin(ll) perchlorate, 4109 Trihydrazinealuminium perchlorate, 0064 Trimethylhydroxylammonium perchlorate, 1323 Triphenylphosphine oxide hydrogen peroxidate, 3755 OXYGEN BALANCE DRUMS... 

Little attention was paid to these reactions until 1921 when Hoffman 174-176) prepared tetrakis(hydroxymethyl)phosphonium chloride by passing phosphine into a warm, aqueous hydrochloric acid solution of formaldehyde. The product was obtained in the form of colourless crystals by evaporation of the reaction solution. 

In the presence of heavy metal salts, such as HgCl2, AgNOs or PtCl4, the reaction between phosphine and formaldehyde is also catalysed by acids weaker than hydrochloric acid. Thus, in this way, phosphonium acetate, oxalate, lactate or fluoride can be obtained directly. According to studies by Raver 178,179) phosphine reacts with formaldehyde even in the absence of acids when metal salts such as HgCl2, NiClj, Crj(S04)3, PtCl4 or finely divided metals are present in catalytic amounts Tetrakis (hydroxymethyl)phospho-... 

Tetrakis( l-hydroxyalkyl)phosphonium salts were prepared from phosphine and various aliphatic aldehydes using similar reaction conditions... 

Tetrakis(hydroxymethyl)phosphonium salts Tetramethyllead see Lead and lead compounds)... 

During formation of the addition compounds 12 and 16, no free formaldehyde accumulates. We assume that the liberated formaldehyde immediately reacts with tris-hydroxymethyl-phosphine, forming the quaternary tetrakis-hydroxymethyl-phosphonium salt 13. The addition compounds 12 and 16 are relatively unstable, but can be purified for analysis. Intermediates 12 and 16 can also be employed in the synthesis of symmetrical or unsymmetrical phosphamethin-cyanines. For example, Klapproth synthesized 18 in 60% yield by condensing 16 with 77. 

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