Phosphonium, -, chloride

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]. 

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... 

Tributyl(tetradecyl)phosphonium chloride was developed specifically (26,27) as a broad-spectmm biocide for the control of biological fouling in cooling water systems where it is particularly effective (see Industrialantimicrobialagents). 

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. 

The quaternary salt is now treated with ethoxide ion in the presence of cinnamalde-hyde so that the ylide reacts in situ as it is produced. A solution of sodium ethoxide is prepared by slowly adding 0.75 g of sodium metal to 100 ml of absolute ethanol in a dry Erlenmeyer flask (hood). In a second flask, the phosphonium chloride is dissolved in 150 ml of absolute ethanol, cinnamaldehyde (2.9 g) is added and the flask is swirled while the ethoxide solution is added a transient orange-red color indicates the formation of the ylide. 

The sublimation and evaporation curves of solid and liquid phosphonium chloride (PH4C1), however, meet at a very decided angle at the triple point (Tammann, Kryst. und Schmelz., p. 291). The curves are represented in Fig. 48. 

Salt-free ylides have been prepared from phosphonium chlorides and bromides by treatment with sodamide in refluxing THF. The sodium halide precipitates and is removed by filtration. Allylidene- and benzylidene-trimethylphosphoranes have been obtained as low melting distillable solids from the phosphonium chlorides and butyl-lithium in ether. The allylidenephosphorane on standing at room temperature slowly decomposed to give methylenetrimethylphosphorane. 

T. M. Lamarre and C. H. Martin. Synergistic biocide of tributyl tetrade-cyl phosphonium chloride and 1.5-pentanedial. Patent CA 1269300, 1990. 

Fujiwara, M., Matsushita, T., Kobayashi, T., Yamashoji, Y., and Tanaka, M., Preparation of an anion-exchange resin with quaternary phosphonium chloride and its adsorption behavior for noble metal ions, Anal. Chim. Acta, 274, 293, 1993. 

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). 

Figure 1.6 A. Trimethyl(phenyl)phosphonium chloride (a typical quaternary phos-phonium salt). B. Examples of quasiphosphonium salts.

Phenyl-dibenzophosphole (164) results from the reaction of tetraphenyl-phosphonium chloride with certain lithium dialkylamides a free-radical mechanism... 

PH4CI PHOSPHONIUM CHLORIDE 255.9276 -6.5388E+03 -1.0929E+02 1.6761E-01... 

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 ... 

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. 

Anhydrous hydrogen chloride gas is used to produce phosphonium chloride, PH4CI, which is a flame retardant for cotton textiles. Other major apphcations include manufacture of a number of high purity metal chlorides, ammonium chloride, chlorosulfuric acid recovery of waste metals preparation of alkyl chlorides and chloroacetic acids and as a chlorinating agent in organic syntheses. 

Anhydrous hydrogen chloride combines with ammonia or phosphine to form ammonium or phosphonium chloride ... 

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