Tri-n-octylphosphine

Tri-n-octylphosphine oxide [78-50-2] M 386.7, m 59.5-60°, pK jt <0. Mason, McCarty and Peppard [J Inorg Nuclear Chem 24 967 7962] stirred an O.IM solution in benzene with an equal volume of 6M HCl at 40° in a sealed flask for 48h, then washed the benzene solution successively with water (twice), 5% aq Na2C03 (three times) and water (six times). The benzene and water were then evaporated under reduced pressure at room temperature. Zingaro and White [J Inorg Nucl Chem 12 315 7960] treated a pet ether solution with aqueous KMn04 (to oxidise any phosphinous acids to phosphinic acids), then with sodium oxalate, H2SO4 and HCl (to remove any manganese compounds). The pet ether solution was slurried with activated alumina (to remove phosphinic acids) and recrystd from pet ether or cyclohexane at -20°. It can also be crystd from EtOH. 

The possible use of Si NMR for the study of the prototropy and sily-lotropy of pyrazoles has been explored (98MRC110). Another paper reports the use of P NMR for establishing that 3-phenyl-4-benzoylisoxazol-5-one is hydrogen-bonded to tri-n-octylphosphine as the NH-tautomer [96MI(14)653j. 

Capela, R. S. Paiva, A. P. Extraction of silver from concentrated chloride solutions use of tri-n-butyl- and tri-n-octylphosphine sulfides. International Solvent Extraction Conference, Cape Town, South Africa, Mar. 17-21, 2002, 335-340. 

Bis(alkyldithio-/selenocarbamates) of Zn(ID and Cd(II) have previously been used in many applications including the rubber industry 1 and in analysis,382 as well as for single-molecular precursors in the growth of II VI thin films by CVD, as described earlier.181,383 They have also been shown to be good precursors for the preparation of II VI nanoparticles, in a process that involves their decomposition in a high-boiling donor solvent such as tri-n-octylphosphine oxide or 4-ethylpyridine (Figure 47). 

Kopping JT, Patten TE (2008) Identification of acidic phosphorus-containing ligands involved in the surface chemistry of CdSe nanoparticles prepared in tri-n-octylphosphine oxide solvents. J Am Chem Soc 130 5689-5698... 

The molecules producing coordinative saturation need not be chelating. As a by-product to the study of synergism in the extraction of alkali metal chelate salts, Healy (14) isolated crystalline complexes Li(PhCO-CHCOPhJSa where S = tri-n-octylphosphine oxide or N, N-dibutyl-acetamide. 

Compared with the variety of existing carbon or nitrogen nucleophiles that were subjected to nucleophilic addition to there are few examples for phosphorus nucleophiles. Neutral trialkylphosphines turn out to be to less reactive for an effective addihon to Cjq even at elevated temperatures [114], Trialkylphosphine oxides show an increased reactivity. They form stable fullerene-substituted phosphine oxides [115] it is not yet clear if the reaction proceeds via a nucleophilic mechanism or a cycloaddition mechanism. Phosphine oxide addition takes place in refluxing toluene [115], At room temperature the charge-transfer complexes of with phosphine oxides such as tri-n-octylphosphine oxide or tri-n-butylphosphine oxide are verifiable and stable in soluhon [116],... 

Highly monodisperse CdSe/CdS core/shell nanoparticles have been prepared by thermolysis in tri-n-octylphosphine oxide (TOPO) using [Cd(Se2CNMe( Hex))2] (250 °C for 30 min) and [Cd(S2CNMe( Hex))2] (250 °C for 30 min) as single-molecule precursors in a one-pot synthesis [118,119]. [Cd(Se2CNMe(Hex))2] (0.8 g) was dissolved in trioctylphos-... 

To a solution of Fmoc-Thr(Ac3GalN3)-OAll 26 (4.0 g, 5.8 mmol) in dry THF (50 mL) is added at 0°C acetic acid (1 mL) and, subsequently, a solution of tri-n-octylphosphine (3.4 mL, 7.4 mmol) in THF (10 mL). After 2 h, the mixture is concentrated in vacuo. To complete the / /-acetylation, the remainder is stirred with acetic anhydride (2 mL)-pyridine (10 mL) for 6 h, concentrated in vacuo. Toluene (3 x 20 mL) is distilled in vacuo from the residue, which is subsequently purified by flash chromatography on silica gel (100 g) in petroleum ether-ethyl acetate —> ethyl acetate. The product is recrystallized from ethyl acetate-petroleum ether yield, 3.9 g (94%) mp 66-68° C [a]D +36.3° (c 1, CHC13) Rf 0.56 (ethyl acetate). 

Tri-n-octylphosphine oxide (TOPO) has been the most popular phosphine oxide to be used as an extractant for the determination of iron, uranium, plutonium, molybdenum, titanium and thorium among other metals.43 44... 

For tri-n-octylphosphine oxide, for example, the shift in the P=0 stretching frequency from its value for the free extractant is greater for the hafnium complex (85 cm-1) than for the zirconium complex (70 cm-1).297... 

Petkovic, D.M. Kopecni, M.M. Mltrovic, A.A. Solvent extraction of nitric, hydrochloric and sulfuric acid and their uranyl salts with tri-n-octylphosphine oxide, Solvent Extr. Ion Exch. 10 (1992) 685-696. 

Shamsipur, M. Ghiasvand, A.R. Yamini, Y. Solid-phase extraction of ultratrace uranium(VI) in natural waters using octadecyl silica membrane disks modified by tri-N-octylphosphine oxide and its spectrophotometric determination with dibenzoylmethane, Anal. Chem. 65 (1999)4892 1895. 

Among the procedures tried were thionyl chloride and pyridine, phosphorus pentachlo-ride, triphenyiphosphine dibromide in N, N-dimethylformamide, triphenylphosphine and carbon tetrachloride, tris(dimethylamino)phosphine and bromine, o-phenylenephosphoro-chloridite and bromine, tris(dimethylamino)phosphine and carbon tetrachloride, and tri-n-octylphosphine and carbon tetrachloride. 

Peng er a/.6 "71 have proposed the use of greener Cd sources such as cadmium oxide, carbonate and acetate instead of the dimethylcadmium. These workers suggest that the size distribution of the nanocrystals is improved by the use of hexadecylamine, a long-chain phosphonic acid or a carboxylic acid. The method can be extended to prepare CdS nanoparticles by the use of tri-n-octylphosphine sulfide (TOP-S) and hexyl or telradecyl phosphonic acid in mixture with TOPO-TOP. Hyeon and coworkers71 have prepared nanocrystals of several metal sulfides such as CdS, ZnS, PbS, and MnS with different shapes and sizes by the thermolysis of metal-oleylamine complexes in the presence of S and oleylamine (Fig. 7). 

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