34 MORQAN, MICKLETHWAIT, A S D WHI I'BY :IV.-Organic Derivatives of Antimony. Part I.Ti-icurnphoylst ib ine Chloride and Triphenylst ibirieHydroxynitmte and Hpdroxysulphate.By GILBERT T. MORGAN, FRANCES M. G. MICKLETHWAIT, andGEORGE STAFFORD WHITBY, B.Sc., A.R.C.S.A COMPARATIVE study of the interactions taking place betweensodium camphor and the trichlorides of phosphorus, arsenic, andantimony has shown that in the case of the arsenic compound theprincipal products are dicamphorylarsinic and tricamphoryl-arsinic acids (Trans., 1908, 23, 2144; 1909, 95, 1473). Theexperiments with phosphorus trichloride are still in progress ; thepresent communication deals with the case of antimony trichloride.The interaction of sodium camphor and antimony trichloride i35 ORGANIC DERiVATIVES OF ANTIMONY.PART I.dry toluene does not lead to the production of any SUbshncessoluble in aqueous alkali hydroxides or carbonates. The onlyproduct definitely isolated and identified is tricamphorylstibinechloride, (C,H150)3SbC12. This substance undergoes destructivehydrolysis so readily that the resulting tricamphorylstibine oxide,(C,,H,,O),SbO, is always more or less contaminated with hydratedantimonic oxide arising from the decomposition of the chloride intohydrochloric and antimonic acids and camphor.As one object of this research was to obtain an organic derivativeof antimony sufficiently stable and soluble for employment as atherapeutic agent, attention was now directed to triphenylstibinechloride, (C,H,),SbCl,, obtained by &tichaelis and Reese by theinteraction of chlorobenzene, antimony trichloride, and sodium(dnnalen, 1886, 233, 43).As these investigators have stated that this aromatic antimonyderivative is possessed of considerable stability, attempts were madeto convert this substance into compounds dissolving more readilyin aqueous solutions.When treated with alcoholic silver nitrate, triphenylstibinechloride loses its chlorine quantitatively in accordance with thefollowing equation :(C,H,),SbCI, + ZAgNO, = 2AgCI + (C,H,),Sb(NO,),.The triphenylstibine nitrate is not stable under these conditions,and undergoes partial hydrolysis into a definitely crystalline sub-stance, triphenylstibine hydroxynitrate, (C,H,),Sb('OH)*NO,, whichmay be recrystallised from hot water without further hydrolysis.I n connexion with the formation of this substance, it is of interestto note that Michaelis and Reese describe a triphenylstibine nitrate,prepared by dissolving triphenylstibine in hot fuming nitric acid(Zoc.cit., p. 52), which is stated to be insoluble in water, butcrystallisable from alcohol.The substitution of silver sulphate for silver nitrate in theforegoing reaction leads to the production of the corresponding tri-PhenYlstibine hydroxysulphat e, ( C,H,),Sb (OH)*SO,*Sb (OH) (C,H5)3,which is less soluble in water than the hydroxynitrate.E x P E R I fii E N T A L.Tricamphorylstibine Chloride,--Oa adding a toluene solution ofantimony trichloride to sodiuin camphor suspended in the samemedium, considerable heat was generated, and a bulky precipitatewas produced.The mixture was warmed on the water-bath andleft for a few days, after which it was treated with water, whena white precipitate of antimony oxides separated, The tolueneD 36 MORGAN, MICRLETHWAJT, AND WRITBY :solution which drained from this precipitate was distilled in steam,and the residue extracted with benzene. From the concentratedbenzene extract, a substance separated in colourless, ice-likecrystals, this separation being promoted by t.he addition of lightpetroleum. After repeated crystallisation from benzene, theproduct melted and decomposed a t 244O, although when rapidlyheated it sometimes remained unchanged a t 24'7-248O :0.1314 gave 0.2660 CO, and 0.0840 H,O.C = 55-21 : H = 7.10.0.1830 ,, 0.3706 CO, ,, 0.1116 H20. C=55*22; H=6*77.0'2235 ,, 0'0591 Sb,S,. Sb=18*85.0.2483 ,, 0'1106 AgCl. C1=11*02.C,H,,O,ClSb requires C = 55-90 ; H = 7.0 ; Sb = 18.63 ;C1=11.02 per cent.0.3120, in 25 C.C. chloroform, at ZOO, gave ~ , + 9 . 1 7 ~ , whence[a]D = 367.3'.Tricamphorylstibine chloride dissolves only sparingly in alcohol,and is insoluble in water. In acid solutions it is fairly stable, andmay be boiled with 2N-hydrochloric acid without decomposition.On warming with 2N-sodium hydroxide, the chloride was readilyhydrolysed into antimoniu and hydrochloric acids and camphor.Destructive hydrolysis occurred on warming the chloride withaqueous sodium hydrogen carbonate at 55O, and continued heatingwith dilute ammonia led to the liberation of camphor.A similardecomposition took place when the chloride was digested withalcoholic silver nitrate.Triphenylstibine Hydroxynitrute.-O.621 Gram of triphenyl-stibine chloride gave 0.419 gram of silver chloride (the calculatedamount being 0.421 gram) on warming with two molecular pro-portions of silver nitrate in alcoholic solution. The filtrate, onconcentration, furnished white crystals, which, on analysis, gavenumbers corresponding with the partial hydrolysis of the initiallyformed dinitrate. This hydrolysis was brought to a definite end-point by dissolving the white crystals in boiling water, for, oncooling, the hydroxynitrate separated in lustrous, colourless leaflets,softening at 220°, and melting to a yellow liquid a t 224-225O.When carrying out the process on a larger scale, any slightexcess of silver retained in the solution was precipitated by theaddition of sodium chloride.The presence of excess of this saltin the filtrate promoted the crystallisation of the hydroxynitrate,the precipitation, under these conditions, being almost complete :0.2691 gave 0.4932 CO, and 0.0942 H,O.0'3765 ,, 0'1461 Sb&. Sb=27*72.C = 50,OO ; H = 3.80ORGANIC DERIVATIVES OF ANTIMONY. PART I. 370.3300 gave 9.6 C.C. N, a t 2 4 O and 759 mm. N=3.19.C,8H160,NSb requires C = 50.23 ; H = 3-72 ; Sb = 27.9 ;N = 3.26 per cent.Triphenylstibine hydroxynitrate is almost insoluble in coldwater, but dissolves very readily in alcohol, giving rise to a solutionwhich can be diluted with water very considerably without anydepasition of the hydroxynitrate taking place.When reducedwith Devarda’s alloy (Al-Cu couple) in the presence of alkali, tri-phenylstibine is produced, and the whole of the nitrogen iseliminated as ammonia. An estimation of nitrogen by this methodgave 3-62, the calculated value being 3.19 per cent.Triphenylstibine hydroxysulphate was prepared by adding analcoholic solution of triphenylstibine chloride (1 mol.) to it boilingaqueous solution of silver sulphate (2 mols.). The filtrate from thesilver chloride was concentrated to remove the alcohol, when thehydroxysulphate separated in colourless nodular crystals, the solu-tion being then distinctly acid, owing to the liberation of sulphuricacid :0.2602 gave 0.0761 BaXO,. S=4.01.C3,H3,0,SSb, requires S = 3.84 per cent.The hydroxysulphate is almost insoluble in cold water ; itdissolves in cold concentrated sulphuric acid, and remains insolution after considerable dilution with water, this increase insolubility indicating its conversion into the normal sulphate.Triphenylstibine hydroxysulphate melts and decomposes at 252O.Triphenylstibine hydroxgchloride was produced by adding analcoholic solution of triphenylstibine chloride to a large volume ofboiling water and evaporating until crystallisation began. Thecrystalline deposit, when dried and dissolved in benzene, separatedfrom this solvent in transparent, lustrous, colourless spicules,melting at 218O :0.2982 gave 0.1240 Sb,S3. Sb = 29.70.Cl,H1,OCISb requires Sb = 29.73 per cent.The authors desire to express their thanks to the Governmentgrant, which has Grant Committee of the Royal Society forpartly defrayed the expenses of this investigation.ROYAL COLLEGE OF SCIENCE, LONDON,~ O U T H KENSINGTON, S. W