Tris hydroxymethyl phosphine

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. 

Tributyiphosphine displaces tris(hydroxymethyl)phosphine, triphenyl-phosphine, and, in poor yield, butylbis(hydroxymethyl)phosphine from the corresponding hydroxymethylphosphonium salts. ... 

A. Preparation.—The preparation of phosphorins from pyrilium salts and tris(hydroxymethyl)phosphine has been extended to include phosphorins with indolyl and pyrrolyl groups as substituents. ... 

The preparation of the bicyclic phosphite (89) from tri(hydroxymethyl)-phosphine and trimethyl phosphite has been reinvestigated following reports that it could not be repeated. The reasons for the difficulties... 

New Chemistry, Including Pulp Bleaching Processes, of the Golden-Aged, Water-Soluble Compound, Tris(hydroxymethyl)phosphine... 

The first copper(I) complex of tris(hydroxymethyl)phosphine ((760) tetrahedral) has been reported by Samuelson and co-workers. This group addressed the question of anion-controlled nuclearity and metal-metal distances in copper(I)-bis(diphenylphosphino)methane complexes, and in this endeavor they reported the structures of complexes (761) (Cu-Cu separation 3.005-3.128 A), (762) (Cu-Cu separation 3.165 A) and (763) (tetrahedral Cu-Cu 3.293 A). 6 They synthesized and provided structural evidence of oxy anion- encapsulated copper(I) complexes of this ligand. The complexes (764) (distorted tetrahedral Cu-Cu 3.143 A), (765) (distorted tetrahedral Cu-Cu 3.424A), (766) (distorted trigonal Cu-Cu 3.170A), and (767) (Cu-Cu 3.032-3.077A) were reported. They studied solid-state emission spectra of these complexes.567 During this pursuit they... 

Bridged bicycles (13), containing different elements, were synthesized using tris(hydroxymethyl)phosphine [Eq. (11)] (65IC1655 70JOC2310 73PS1). 

A series of heterocycles has been obtained from tris-(hydroxymethyl) phosphine [Eq. (78)] (90IZV1133). 

Hoye, P.A.T., Pringle, P.G., Smith, M.B., and Worboys, K., Hydrophosphination of formaldehyde catalyzed by tris(hydroxymethyl)phosphine complexes of platinum, /. Chem. Soc., Dalton Trans., 269, 1993. 

Condensation of tris(hydroxymethyl)phosphine with easily available water soluble secondaiy amines yielded the hydrophihc... 

Solutions of the nickel(O) and palladium(O) complexes of 1,3,5-triaza-7-phosphaadamantane, PTA (82) and tris(hydroxymethyl)phosphine (98) in water catalyze the oligomerization and telomerization of 1,3-butadiene at 80 °C. Although high yields and good selectivities to octadienyl products (87 %) were obtained, the complexes (or the intermediate species formed in the reaction) dissolve sufficiently in the organic phase ofthe monomer and the products to cause substantial metal leaching [17],... 

Another situation is found for the stereochemistry of the products which are obtained from the reaction of [Re02(py)4]Cl with tris(hydroxymethyl)phosphine (THP) which yields both the cis-and traro-isomers of [ReO(py)2(THP)2] (74) with a clear preference for the cw-compound (74b) at longer reaction times, whereas the trara-compound (75) could be isolated exclusively with the more bulky bis(hydroxymethyl)phenylphosphine ligand (Scheme 6). ... 

All presently known phosphamethin-cyanines were prepared according to our original procedure (1964) in which two quaternary salts of a heterocyclic base (e. g. 4) are condensed with tris-hydroxymethyl-phosphine 5 in the presence of a proton-abstracting base The preparation ofbis-[N-ethyl-benzothiazole(2)]-phosphamethin-cyanine-tetrafluoroborate 6 illustrates the synthetic sequence. A mixture of 2 moles of N-ethyl-2-chlorobenzothiazolium-tetrafluoroborate 4 and 1 mole of tris-hydroxymethyl-phosphine 5 in dimethylformamide is slowly reacted with ethyl-di-isopropylamine or pyridine at 0 °C. Addition of water immediately affords the crystalline cyanine dye 6 in ca. 45% yield ... 

Due to danger of explosion, tris-hydroxymethyl-phosphine should not be distilled. In case of an aqueous solution containing benzene, the water and organic solvent can be removed by vacuum distillation (maximum temperature 60 °C). We thank Farbwerke Hoechst A. G. for generous gifts of aqueous P(CH20H)3-solutions. 

Unsymmetrically substituted phospha-methin-cyanines 9 with two different heterocyclic bases can also be synthesized. Here the quaternary salt of one heterocyclic base (e. g. 4) is reacted with tris-hydroxymethyl-phosphine 5 in dimethyl-formamide or glacial acetic acid without the addition of a base. Then one mole of the quaternary salt of the other heterocyclic base (e. g. 10) and the base are added. The base deprotonates the hydroxymethyl groups of the phosphine 5, thus liberating formaldehyde and yielding the phosphine base which then reacts with the second quaternary salt ... 

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. 

Our attempts as well as those of C. C. Price to react 2.4.6-triphenylpyry-lium salts with phosphine, phenylphosphine or tris-hydroxymethyl-phosphine in the hope of isolating phosphorins or their P-substituted derivatives were unsuccessful. In contrast, MarM applying essentially the same principle but using pyridine as base and solvent, succeeded by heating 2.4.6-triphenylpyrylium-tetrafluoro-borate 21 with tris-hydroxymethyl-phosphine 5. He was able to isolate 2.4.6-triphenyl-X -pbosphorin 22, m. p. 171—172 C, as the first X -phosphorin in 20-25% yield. 

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