Phosphorus trichloride determination

Phosphor-athcr, m. phosphoric ether (ester of phosphoric acid, specif, ethyl phosphate), -basis, phosphorus base, -bestimmung, /. determination of phosphorus, -blei, n. lead phosphide Min.) pyromorphite. -bombe, f. phosphorus bomb. -brandgranate, /. phosphorus incendiary shell, -brei, m. phosphorus paste, -bromid, n. phosphorus bromide, specif, phosphorus pentabromide, phos-phorus(V) bromide, -bromijr, n. phosphorus tribromide, phosphorus(III) bromide, -bronze, /. phosphor bronze, -calcium, n. calcium phosphide, -chlorid, n. phosphorus chloride, specif, phosphorus pcntachloride, phosphorus(V) chloride, -chloriir, n. phosphorous chloride (phosphorus trichloride, phosphorus(III) chloride), -dampf, tn. phosphorus vapor or fume, -eisen, n. ferrophos-phorus iron phosphide, -eisensinter, m. diadochite. 

The product of interaction of sodium azide and phosphorus trichloride occasionally exploded on warming from 0°C to ambient temperature, but was examined safely in solution. The structure of the explosive product is determined as the title compound [1], rather than pentaazidophosphorane as originally reported [2], It contains some 82% of nitrogen. 

Results. Phosphorus (1 g.) and phosphorus trichloride (1 ml.) were used. The weight of di-isopropyl phosphorofluoridate obtained was 5-5 g. (62 per cent). The purity, determined by fluorine analysis1 on 50 mg. of the active product, was 98-5 per cent. 

Another phosphorus containing CDA (87) has also been described for the estimation of the enantiomeric excess of chiral amines80. The phosphorus CDA 87 is formed quantitatively and instantaneously in situ in an NMR tube by reaction of phosphorus trichloride (PCI3) with the chiral diamine 88. Addition to the NMR tube of the chiral amine (IC-NIIo) for which the ee is to be determined gives the diastereomeric phosphorous derivatives ... 

The first synthesis of a cyclodiphosph(III)azane (13) (Scheme 4) was reported by Michaelis and Schroeter who correctly identified (13) as a dimer by molecular weight determinations. These results have been confirmed by more recent work which also shows that the reaction proceeds via an acyclic diphosphinoamine, CljPNPhPClj. The synthesis of cyclodiphosph(IH)azanes by the reaction of phosphorus trichloride with relatively bulky primary alkylamines and related routes has been widely studied. Examples of this work, leading to (14)... 

Hydrolysis of Phosphorus Trichloride. Pour 3 ml of distilled water into a test tube and add a small amount of phosphorus trichloride dropwise. What do you observe Write the equation of the hydrolysis reaction. Determine the composition of the hydrolysis products. 

The reaction of phosphorus trichloride with tgrt-bufylamine was reported to give a dicoordinate phosph(III)azene Bu N=P-NHBu which can be deprotonated to the [Bu NPNBu ] anion. The crystal structure ofK[Bu NPNBu ] has been determined. The anion has also been found in a gallium and a lithium complex. In monomeric form, the [RN P NMes] anion can be obtained when R = mesityl (Mes = 2,4,6-Me3C6H2), tert-butyl and 1-adamantanyl, as dimeric lithium ring compounds (3) ... 

Cahours has experimentally determined the value of J at pressures near to atmospheric pressure and for temperatures between 182 C. and 336 C. Troost and HautefeuiUe on the one hand and Wurtz on the other have made analogous determinations at pressures below an atmosphere finalfy Wilrtz determined the vapor density of a mixture which instead of enclosing a molecule of phosphorus trichloride for one molecule of chlorine contained an excess of trichloride by joining to all these experimental deter-minations an old observation of Mitscherlich forty-three values of the density J are obtained imder most diverse conditions all these valueS save onC arC as shown by GibbS very exactly repre-... 

Of particular interest in the latter case is the use of N-NMR spectroscopy for the determination of J( P, N) data, of which there are few examples for systems having two coordinate sp -hybridised nitrogen linked to phosphorus. " Various acyclic bis(aminophosphines) have also been reported, including the imino-functional system (96), the bis(phosphino)-hydrazines (97) and -ureas (98), and the l,8-bis[bis(dialkylamino)phosphino]naphthalenes (99). There has also been significant activity in the synthesis of cyclic aminophosphines. An improved route to the four-membered ring system (100) is afforded by the reaction of phosphorus trichloride with t-butylamine in a 1 3 mole ratio in THF. Treatment of this with ammonia in THF/triethylamine at — 78°C gives (101),... 

The method to be used is determined by the practicability of the separation of the chloride from the by-products of the reaction, and the excess of the reagent used. Thus, in the laboratory, phosphorus trichloride is used for the lower fatty acids because their chlorides are more volatile than phosphorous acid. The acid, together with 1.5 times the amount of phosphorus trichloride, as indicated in equation (1), is refluxed, and then the acid chloride is distilled from the viscous phosphorous acid and fractionated. Phosphorus pentachloride is used with aromatic acids as shown in equation (2). The dry, finely pulverized potassium or sodium salt of the acid is mixed with a little more than the calculated amount of the pentachloride and heated until the reaction is finished. The resulting oxychloride (POCI3) is removed by distillation. If the boiling points are too close, then the mixture of aryl acid chloride and phosphorus oxychloride is added to finely chopped ice. The oxychloride decomposes instantly, while the aryl acid chloride does not react appreciably at this temperature. The chloride is either separated or extracted with ether, dried, and then fractionated. 

Overall we determined that the prediction results obtained using the probes were better when compared to those obtained using the cone attachment. We found that it was difficult to distinguish between the carbon disulfide and the phosphorus trichloride, but the other five liquids were easily distinguishable. 

Electrochemical oxidation of dialkylamino substituted diphosphines, e.g. (124), gave phosphenium ions (125) readily. One equivalent of the phosphonium salt (126) and phosphorus trichloride gave the dichlorophosphine (127), but a phosphenium chloride (128) was obtained with two equivalents of (126) another phosphenium chloride (129) was formed from diethyltrimethyl-silylamine and (127). The first diphosphirenium salt (130) has been prepared and the X-ray crystal structure determined. ... 

Apply Phosphorus trichloride is a starting material for the preparation of organic phosphorous compounds. Demonstrate how thermo chemical equations a and b can be used to determine the enthalpy change for the reaction PGl3(l) -f Ghlg) —> PGls(s). 

J.1 Determine the formula weights of each of the following compounds (a) nitric add,HN03 (b) KMn04 (c) Ca3(P04)2 (d) quartz, Si02 (e) gaUium sulfide, (f) chromium (111) sulfate, (g) phosphorus trichloride. 

As mentioned previously, the helicene-based chlorophosphite M,M,R) 25a, which is easily prepared from the reaction ofenantiopure (M,M,R)-[5 -HELOL 24a with phosphorus trichloride, has been successfirUy used to analyze the enantiomeric compositions of a variety of chiral materials such as alcohols, amines, or carboxylic acids. The reaction is conducted in an NMR tube where the analytes are added to the chiral helicene-based chlorophosphite in CDCI3. After 2 h reaction, the diastereomers ratios generated in situ are determined by P-NMR spectroscopy. Notably, this attractive method has proved to be highly efficient for analyzing the enantiomeric purities of a wide range of molecules whose stereogenic centers are far away from functional groups that react with phosphorus atom. The authors... 

Natural L-aspartic acid can be transformed in several steps into triamine 19, which reacts smoothly with phosphorus trichloride to yield diastereomerically pure 20. This triaminophosphine is stable in neutral or mildly acidic aqueous conditions but, interestingly, it suffers a SN2-type hydrolysis upon purification by sihca gel column chromatography with wet ethyl acetate, yielding the desired secondary diaminophosphine oxide in 60% of overall yield from 19. The absolute configuration of the phosphorus atom (i ) could be unequivocally determined by crystallographic analysis. ... 

Chlorine prepared from manganese dioxide and pure HC1 was liquefied and the dry gas evolved from the liquid was admitted to the dry phosphorus in a vacuum. In this ease phosphorus pentachloride was formed in considerable quantity and was removed only by several distillations. It could not be inferred with such confidence that the trichloride was free from pentachloride as that the tribromide was free from bromine. The trichloride was decomposed and oxidised in the manner already described. In the subsequent estimation of the silver chloride less difficulty was experienced in freeing this from occluded chloride, but more difficulty in determining accurately the amount of silver chloride remaining in solution. It was found possible, however, to diminish the solubility by adding an excess of silver nitrate solution and partly washing the precipitated chloride with this solution. 

Experiment.— Determine the vapotur density of phosphorus pentachloride at temperatures between 180 and 240 , and calculate therefrom the degree of dissociation of the pentachloride into trichloride and chlorine. 

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