Phosphorous chloride

The labile hydroxyl group is easily replaced by treatment with thionyl chloride, phosphorous chlorides, or even aqueous hydrogen haUdes. At low temperatures aqueous hydrochloric (186) or hydrobromic (187) acids give good yields of 3-halo-3-methyl-l-butynes. At higher temperatures these rearrange, first to l-halo-3-methyl-1,2-butadienes, then to the corresponding 1,3-butadienes (188,189). 

The alkaloid rutaecarpine (111) was synthesized from l-oxo-1,2,3,4-tetrahydro-)3-carboline (183 R = H) by condensation with methyl anthranilate in the presence of phosphorous chloride or by heating... 

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. 

Phosphorus Pentachloride (Phosphoric chloride, Phosphorus perchloride). PC15, mw 208.27 white to pale yel, fuming, deliq, cryst mass pungent, unpleasant odor mp (under press) 148° ordinarily sublimes without melting at 160—165°. Sol with decompn and liberation of much heat in w or ale sol in C disulfide or tetrachloride. Can be prepd by the action of chlorine on P or P trichloride (Refs 9 10)... 

Phosphorus Trichloride (Phosphorous chloride). PCI3, mw 270.73 colorl, clear fuming liq, mp —111.8°, bp 76°, d 1.547g/cc. Decomps rapidly in moist air. -Dissolves in w or ale with decompn and liberation of much heat. Sol in benz, chlf, eth and C disulfide. Prepd by passing a current of dry chlorine over gently heated P, which ignites. The trichloride, admixed with some pentachioride, distills over. A small amt of Pis added and the whole distilled (Refs 9 10)... 

By using a phosphoric diester monotetrazolide, made in situ from the corresponding phosphoric chloride and tetrazole in the presence of triethylamine, die 3 -OH of a suitably protected nucleoside could be phosphorylated to give a fully protected nucleotide [241... 

Two reports are available on the rearrangement of mixed vinyl phosphite esters to produce phosphonate diesters in moderate yield.94 95 In both instances, the vinyl phosphite esters were prepared by reaction of the dialkyl phosphorous chloride with highly enolized carbonyl compounds. The mixed ester products undergo thermal rearrangement to the phosphonate diesters (Figure 6.25). 

By heating phosphoric chloride with phosphoric anhy-... 

By the action of water upon phosphoric chloride and phosphoric oxytrichloride (see pp. 112 and 118). 

Oxatyl has not been united with chlorine to produce oxatylic chloride (OOlloCl) nor has its hydroxyl been replaced by chlorine to form IQQQ. "When treated with phosphoric chloride, it yields carbonic oxide and carbonic anhydride... 

If the anhydride be submitted to the action of phosphoric chloride, an atom of oxygen is replaced by two of eUorine —... 

In order to make the complexes of PC15, care has to be taken that the phosphor chloride is not hydrolysed. These complexes cannot be prepared in aqueous solution, but are easily formed by mixing solutions of PC15 and the second halide in suitable solvents, e.g. POCl3 or AsCI3. 

The molecular formulae of the tri- and pent-oxides are respectively P406 and P4O10 as shown respectively by T. E. Thorpe and A. E. H. Tutton, and by W. A. Tilden and R. E. Barnett. It is assumed that the phosphorus in the trioxide is tervalent because hydrogen chloride converts the oxide into phosphorous chloride, Pd3, and phosphorous acid, P(OH)3 while phosphorus in the pentoxide is assumed to be quinquevalent because water converts the oxide into phosphoric acid, 0 P(0H)3. Since water converts phosphorus tetroxide, P204, into a mixture of phosphorous and phosphoric acids, it has been argued that one phosphorus atom is tervalent, and the other quinquevalent. In the alleged phosphorus tetritoxide, P40, of A. Michaelis, the phosphorus is assumed to be tervalent ... 

J. L. Gay Lussac and L. J, Thenard 2 about 1808, and H. Davy about 1810, prepared liquid phosphorus trichloride, or phosphorous chloride, PC13, by the action of chlorine on phosphorus. If the phosphorus be in excess, the liquid trichloride is formed, and if the chlorine be in excess, the pentachloride is produced as indicated in connection with the la reaction tr s vive between these two elements. H. Davy said ... 

Spectral data for a few illustrative bis- and tris(trifluoromethyl)phenyl trivalent phosphorous chlorides are provided in Scheme 5.55. 

Analogues of phosphorous acid are less well known if ammonia be passed over phosphorous chloride, a white mass is formed, which has not been separated from ammonium chloride, but which is supposed to possess the formula P(NH2)8 it may be named phosphorosamide. 

Ammonia, alkaline dusts and mists, hydrogen chloride, hydrogen fluoride, halogens, nitrogen dioxide, ozone, phosgene, and phosphorous chloride can irritate the eyes and skin. 

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