By the action of phosphorus pentachloride, the hydroxyl group is replaced by chlorine.
Molybdenum trichloride, MoC1 31 is obtained when the pentachloride is heated to a temperature of about 250° C. in a current of hydrogen.
Molybdenum pentachloride, MoC1 5r is obtained when molybdenum is gently heated in dry chlorine (L.
Thionyl chloride, SOC1 21 may be obtained by the action of phosphorus pentachloride on sodium sulphite; by the action of sulphur trioxide on sulphur dichloride at 75 -80° C. (Journ.
It may also be obtained by distilling chlorsulphonic acid with phosphorus pentachloride: 2S0 2 C1.
Again, when tungsten hexachloride is converted into vapour it is decomposed into chlorine and a pentachloride, having a normal vapour density, but as in the majority of its compounds tungsten acts as a hexad, we apparently must regard its pentachloride as a compound in which an odd number of free affinities are disengaged.
Foerster and by Pullinger; the phosphoplatinic compounds formed primarily from platinum and phosphorus pentachloride; and also the " ammino " compounds, formed by the union of ammonia with the chloride, &c., of these metals, which have been studied by many chemists, especially S.
Of the halogen compounds of phosphorus, the trichloride was discovered by Gay Lussac and Thenard, while the pentachloride was obtained by Davy.
It is also prepared by the action of phosphorus pentachloride on potassium nitrite or on nitrogen peroxide.
Long digestion of the acid with excess of phosphorus pentachloride results in the formation of the acid chloride, C 6 (0001),, which crystallizes in needles, melting at 190° C. By heating the ammonium salt of the acid to 150-160° C. as long as ammonia is evolved, a mixture of CO paramide (mellimide), C6 (CO > NH) 3, and ammonium euchroate is obtained.
Nascent hydrogen reduces them to primary alcohols, and phosphorus pentachloride replaces the carbonyl oxygen by chlorine.
Columbium trichloride, CbC1 3, is obtained in needles or crystalline crusts, when the vapour of the pentachloride is slowly passed through a red-hot tube.
Columbium pentachloride, CbC1 5, is obtained in yellow needles when a mixture of the pentoxide and sugar charcoal is heated in a current of air-free chlorine.
Columbium oxychloride, CbOC1 3r is formed when carbon tetrachloride, and columbic acid are heated together at 440° C.: 3CC14+Cb205 = 2CbOC1 3 +30001 2, and also by distilling the pentachloride,in acurrent of carbon dioxide, over ignited columbic acid.
It is probably a hydroxy-compound, since it gives a red-brown colour with ferric chloride, reacts with phenyl isocyanate and with phosphorus pentachloride, and with benzoyl chloride yields dibenzhydroxamic acid, C 6 H 5 CO NH O.
The chloride is very hygroscopic. By heating in hydrogen it yields the trichloride, UC1 3, and by direct combination with chlorine the pentachloride, UC1 5.
The synthesis of piperine follows from the interaction of piperyl chloride (formed from piperic acid and phosphorus pentachloride) and piperidine (L.
It behaves as a strong acid and on treatment with phosphorus pentachloride at high temperatures gives triazole.
By heating with phosphorus pentachloride an alkyl group is eliminated and a chlorcarbonic ester formed.
On heating piperidine with phosphorus pentachloride to 200°C. in a sealed tube pentamethylene dichloride is obtained, and this on treatment with potassium phthalimide gives a condensation product of composition, C 6 H 4 [CO] 2 N(CH 2) 5 N[CO] 2 C 6 H 4, which is finally hydrolysed by hydrochloric acid.
Phosphorus pentachloride decomposes it into carbon monoxide and dioxide, the reaction being the one generally applied for the purpose of preparing phosphorus oxychloride.
An impure oxalyl chloride, a liquid boiling at 70° C:, has been obtained by the action of phosphorus pentachloride on ethyl oxalate.
Its ethyl ester, known as oxamaethane, crystallizes in rhombic plates which melt at 114-115° C. Phosphorus pentachloride converts it into cyan-carbonic ester, the ethyl oxamine chloride first formed being unstable: ROOC CONH2 -R000 C(C1 2) NH 2 --)CN COOR.
Tantalum pentachloride, TaC1 5, is obtained as light yellow needles by heating a mixture of the pentoxide and carbon in a current of chlorine.
It is the carboxylic acid corresponding to tropine, for it yields the same products on oxidation, and by treatment with phosphorus pentachloride is converted into anhydroecgonine, C9H13N02, which, when heated to 280° C. with hydrochloric acid, splits out carbon dioxide and yields tropidine, C8H13N.
Duppa (Annalen, 1865, 136, p. 12) by acting with phosphorus pentachloride on oxyisobutyric ester (CH 3) 2 C(OH) 000C 2 H 5.
It combines with ammonia to form AlC13.3NH3; and forms double compounds with phosphorus pentachloride, phosphorus oxychloride, selenium and tellurium chlorides, as well as with many metallic chlorides; sodium aluminium chloride, AlC1 3 ï¿½NaC1, is used in the production of the metal.
Sodium amalgam reduces them to secondary alcohols; phosphorus pentachloride replaces the carbonyl oxygen by chlorine, forming the ketone chlorides.
Benzoyl chloride, C 6 H S 0001, is formed by distilling a mixture of phosphorus pentachloride and benzoic acid; by the action of chlorine on benzaldehyde, or by passing a stream of hydrochloric acid gas over a mixture of benzoic acid and phosphorus pentoxide heated to 200°C. (C. Friedel, Ben.
It is a thick oil which sets at - 20° C. to a mass of crystals of melting point o C, and boiling point 236-237°C. Oxidation with ferric chloride converts it into dicarvacrol, whilst phosphorus pentachloride transforms it into chlorcymol.
Phosphorus pentachloride converts them into alkyl chlorides, a similar decomposition taking place when they are heated with the haloid acids.
Considerable interest is attached to the remarkable series of hydrocarbons obtained by Gomberg (Ber., 1900, 33, p. 3150, et seq.) by acting on triphenylmethane chloride (from triphenylmethane carbinol and phosphorus pentachloride, or from carbon tetrachloride and benzene in the presence of aluminium chloride) and its homologues with zinc, silver or mercury.
The tetrachloride, WC1 41 is obtained by partial reduction of the higher chlorides with hydrogen; a mixture of the pentaand hexa-chloride is distilled in a stream of hydrogen or carbon dioxide, and the pentachloride which volatilizes returned to the flask several times.
The pentachloride, WC1 5, is obtained as a product in the preparation of the tetrachloride.
Iodine, antimony trichloride, molybdenum pentachloride, ferric chloride, ferric oxide, antimony, tin, stannic oxide and ferrous sulphate have all been used as chlorine carriers.
The majority of the metallic chlorides are solids (stannic chloride, titanic chloride and antimony pentachloride are liquids) which readily volatilize on heating.
Succinyl chloride, obtained by the action of phosphorus pentachloride on succinic acid, is a colourless liquid which boils at 190° C. In many respects it behaves as though it were dichlorbutyro-lactone, /CC12 C 2 He >O; e.g.
While working on the olefines he noticed that a change takes place in the density of the vapour of amylene hydrochloride, hydrobromide, &c., as the temperature is increased, and in the gradual passage from a gas of approximately normal density to one of half-normal density he saw a powerful argument in favour of the view that abnormal vapour densities, such as are exhibited by sal-ammoniac or phosphorus pentachloride, are to be explained by dissociation.
Fremy), is obtained by decomposing antimony pentachloride with hot water, and drying the precipitate so obtained at 100° C. It is a white powder which is more soluble in water and acids than orthoantimonic acid.
Antimony pentachloride, SbC1 5, is prepared by heating the trichloride in a current of chlorine.
Antimony oxychloride, SbOC1 3, is formed by addition o f the calculated quantity of water to ice-cooled antimony pentachloride, SbC1 5 -}-H 2 0=SbOC1 3 +2HC1.
Antimony nentasulphide, Sb2S5, is prepared by precipitating a solution of the pentachloride with sulphuretted hydrogen, by decomposing "Schlippe's salt" with an acid, or by passing sulphuretted hydrogen into water containing antimonic acid.
The three monochlorpyridines are known, the a and -y compounds resulting from the action of phosphorus pentachloride on the corresponding oxypyridines, and the 1 3 compound from the action of chloroform on potassium pyrrol.
Braun (Ber., 1904, 37, p. 2915) showed that benzoyl piperidine, when heated with phosphorus pentachloride to 200° C. in sealed tubes, yields benzonitrile, and pentamethylene dichloride, thus leading to a simple method of preparing pentamethylene compounds.
Selenium tetrachloride, SeCl 4, is obtained by passing excess of chlorine over selenium; by the action of phosphorus pentachloride on selenium dioxide: Se0 2 +PC1 5 =SeOC1 2 +POC1 3 i 3SeOC12-I-2POC13=3SeC14-1-P205; and by the action of thionyl chloride on selenium oxychoride.
It does not dissociate on heating as do the pentachloride and pentabromide, thus indicating the existence of pentavalent phosphorus in a gaseous compound; dissociation, however, into the trifluoride and free fluorine may be brought about by induction sparks of 150 to 200 mm.
Phosphorus trifluorodichloride, PF3C12, prepared from chlorine and the trifluoride, is a pungentsmelling gas, which at 250° gives the pentachloride and fluoride.
With chlorine it gives the pentachloride, PC1 5, and with oxygen when heated phosphoryl chloride, POC1 3.
Phosphorus pentachloride, PC15, discovered by Davy in 1810 and analysed by Dulong in 1816, is formed from chlorine and the trichloride.
Phosphoryl trichloride or phosphorus oxychloride, POC1 3, corresponding to phosphoric acid, (HO) 3 P0, discovered in 1847 by Wurtz, may be produced by the action of many substances containing hydroxy groups on the pentachloride; from the trichloride and potassium chlorate; by leaving phosphorus pentoxide in contact with hydrochloric acid: 2P 2 0 5 +3HC1= POC13+3HP03; or by heating the pentachloride and pentoxide under pressure: 3PC15+ P205= 5POC1 3.
Thiophosphoryl chloride, PSC1 3, may be obtained by the direct combination of sulphur with the trichloride; from sulphuretted hydrogen and the pentachloride; from antimony trisulphide and the pentachloride; by heating the pentasulphide with the pentachloride; and by dissolving phosphorus in sulphur chloride and distilling the solution: 2P+3S 2 C1 2 = 4S+2PSC1 3.
Nitrogen Compounds.-Phosphorus pentachloride combines directly with ammonia, and the compound when heated to redness loses ammonium chloride and hydrochloric acid and gives phospham, PN 2 H 4, a substance first described by Davy in 1811.
The diamide, PO (NH 2) (NH), results when the pentachloride is saturated with ammonia gas and the first formed chlorophosphamide, PC1 3 (NH 2) 2, is decomposed by water.
Bamberger, Ber., 94, 7, 1955), C,H 5 CH: CH CH: NOH --4[C 6 H 5 CH: CH NH COH] -*C,H,N; by the action of hydriodic acid on the oxydichlorisoquinoline formed when phosphorus pentachloride reacts with hippuric acid; by the distillation of homophthalimide over zinc dust (M.