Tris phosphine oxides

APO. Research on ethylenimine [151 -56-4] led to the development of tris(azitidinyl) phosphine oxide [545-55-1] (APO) as a flame retardant for... 

Chemical Designations - Synonyms-. APO Phosphoric acid triethileneimide Triethylenephosphor-amide Tris (1-aziridinyl) phosphin oxide Chemical Formula-. (CH2CHiN)3PO or C HjjNjPO. Observable Characteristics - Physical State (as normally shipped)-. Solid Color. > ite Odor. Data not available. 

Under similar conditions, perfluoroalkyl iodides react with alkyl phosphates to give fluorinated phosphine oxides, phosphinates, and phosphines [54 (equation 49) The product formed depends upon the stoichiometry and type of iodide used. When sodium alkyl trithiocarbonates are used as substrates, perfluoroalkyl tri-thiocarbonates ate formed [55]. 

Another class of hydrocarbon binders used in propints are the carboxy-terminated polybutadiene polymers which are cross-linked with either tris[l-(2-methyl)aziridinyl] phosphine oxide (MAPO) or combinations with phenyl bis [l -(2-methyl)aziridinyl] phosphine oxide (Phenyl MAPO). Phenyl MAPO is a difunctional counterpart of MAPO which makes possible chain extension of polymers with two carboxylic acid groups. A typical propint formulation with ballistic properties is in Table 11 (Ref 83) Another class of composites includes those using hydroxy-terminated polybutadienes cross-linked with toluene diisocyanate as binders. The following simplified equations illustrate typical reactions involved in binder formation... 

Cobalt, dinitratobis[tris(dimethylamino)phosphine oxide]-angular parameters, 1,57... 

Uranium. tetrathiocyanatotetrakis[tris-(dimethylamino)phosphine oxide]-structure, 1.87 Uranium carbide nuclear fuels dissolution, 6, 928 Uranium complexes, 3,1131-1215 carbamic acid... 

C. Nucleophilic Attack on Other Atoms.—Amidoximes have been shown to react with tris(dimethylamino)phosphine by displacing dimethylamine to give the phosphine oxides (52), but some N-substituted aromatic amidoximes give derivatives of (53). ... 

A. Nucleophilic Reactions of the P=0 Group.—Tris(trifluoromethyl)-phosphine oxide (33) reacts with hexamethyldisiloxane to give a phos-phorane, whose n.m.r. spectrum at — 140 °C shows non-equivalent trifluoromethyl groups. Although this unusual reaction clearly involves nucleophilic attack of the phosphoryl oxygen on silicon at some stage of the reaction, a full study of the mechanism has not been published. Tertiary phosphine oxides can be converted cleanly into dichlorophos-phoranes (34) by treatment with two moles of phosphorus pentachloride. Alkylation of the sodium salt of tetraphenylmethylenediphosphine dioxide (35) with alkyl halides, in dimethyl sulphoxide, has been reported to... 

Trialkylphosphine oxides and tris(dimethylamino)phosphine oxide are undergoing this reaction as well (62). 

A Michael-type addition reaction of phosphine generated from red phosphorus in concentrated aqueous KOH solution has been noted to provide moderate isolable yields of pure organophosphorus products.27 For example, tris-(2-cyanoethyl)phosphine is produced in 45% isolable yield from acrylonitrile, and tris-(2-[y-pyridyl]ethyl) phosphine oxide is isolated in 40% yield from 4-vinylpyridine under these conditions. Excellent yields of the tertiary phosphine oxide, tris-(2-cyanoethyl)phosphine oxide, have been reported using white phosphorus in absolute ethanol with KOH at ice/salt-bath temperatures.28 A variety of solvent systems were examined for this reaction involving a Michael-type addition to acrylonitrile. Similarly, tris-(Z-styryl)phosphine is produced from phenylacetylene under these conditions in 55% isolated yield. It is noteworthy that this last cited reaction involves stereospecific syn- addition of the phosphine to the alkyne. 

A solution of 10 ml of 10 N aqueous KOH diluted to 25 ml with absolute ethanol was added dropwise over a period of 30 min to a well-stirred mixture of 0.4 g-atom (12.4 g) of finely divided white phosphorus, 1.2 mol (85.2 g) of acrylamide, and 200 ml of absolute ethanol under a nitrogen atmosphere. The temperature was maintained at -5 to 0°C by a cooling bath. After stirring for an additional 45 min, the white solid generated was recovered by filtration. This solid was dissolved in 125 ml of hot glacial acetic acid, and the solution was cooled to room temperature. (Any unreacted white phosphorus could be removed at this point by decantation under a nitrogen atmosphere.) The solution was filtered through diatoma-ceous earth, diluted with 600 ml of absolute ethanol, and cooled at 5°C for 30 min. The resultant white solid was collected by filtration, washed with absolute ethanol, and dried to produce the pure tris(2-carbamoylethyl)phosphine oxide in 74% yield. 

Alkyl esters of phosphoric acid and phosphine oxides will extract metals and mineral acids by direct solvation. Tri-//-butyl phosphate (TBP) and tri- -octyl phosphine oxide (TOPO)... 

Tolman and co-workers (67) investigated a series of pyrazolyl-derived ligands for this reaction. Initial investigations centered on the use of tris(pyrazolyl) phosphine oxide (95) as a ligand with chirality derived from camphor. Diastereoselectivities with ethyl diazoacetate are poor, slightly favoring the cis isomer, and enantioselectivities are modest, Eq. 50. The BHT esters greatly increase the diastereoselectivity of this process (96 4) at the expense of enantioselectivity (10% ee for trans isomer). 

Tri-O-acylglycerols (TAGs), 70 281 Trioctylphosphine oxide (TOPO), 79 66 Triode gauge, 20 660-661 Triols, phosphine oxide, 77 501 Triorganohydridosilanes, in silicone chemistry, 22 555... 

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