256 GODDARD AND GODDARD : XXXI.-Organo-derivatives of Thallium. Part I V. Action of Thallium Chlorides on the Grignard Reagent and on Organo-derivatives of Tin Lead, and Bismuth. By DOROTHY GODDARD and ARCHIBALD EDWIN GODDARD. MEYER and BERTHEIM (Ber. 1904 37 2051) attempted to obtain thallium diphenyl bromide by the action of thallic chloride on magnesium phenyl bromide but failed to isolate any product pure for analysis. After considerable difficulty the authors have obtained this compound in a pure state and find it to be very sparingly soluble in organic solvents with the exception of pyridine, and to remain unmelted at 290". In the tolyl series thallium di-o-tolyl chloride and the di-p-tolyl bromide have also been isolated these again showing extreme insolubility.The compound resulting from thallic chloride and magnesium cr-naphthyl bromide namely, thallium di-u-naphthyl bmnide melts a t 272" t!his agreeing with the authors' observation in previous work that the heavier the grouping attached to thc thallium atom the lower the melting point! of the resulting substance. Thallous bromide reacts with magnesium phenyl bromide causing a quantitative reduction to metallic thal-lium. This reducing action of the Grignard reagent has also been noticed in the case of tellurium compounds (Lederer Ber. 1916 49, 1615). The reaction is all the more remarkable when compared with the behaviour of lead dichloride which under the same conditions gives rise to lead tetraphenyl (Pfeiffer and Truskier Ber. 1904 37, 1125). It was shown (Goddard this vol.p. 39) that triphenyl-bismuthine and thallic chloride react in dry ether to produce diphenylchlorobismuthine and thallium diphenyl chloride. This reaction is now being extended to other organo-derivatives of the types MR ; MR ; R,M*Hal. ; R2MR' ; R,M*Hal. and R,MR=Hal. Tin tetraet'hyl and thallic chloride in ether react according to the equation SnEt + TlCl = Et2T1C1 + Etf2SnC12. If the solution containing the latter two substances be boiled with water the thallium &ethyl chloride will gradually disappear and thallous chloride be produced. The reaction with tin tetraphenyl is more complicated and is best represented as follows : (1) 3Ph,Sn + 2TlC13 = 2Ph2T1C1 + 2Ph3SnC1 + Ph,SnC& (2) P&SnC12 + H20 = Ph,Sn(OH)Cl + HC1. Indications of the presence of tin diphenyl chloride were traced, but Aronheim (Annulen 1878,194,154) showed that the compoun ORGANO-DERIVATIVES OF THALLIUM.PART IV. 257 yields the hydroxychloride with water and this probably accounts for the isolation of the latter compound. The reaction was carried out in xylene no change taking place in alcoholic solution. Thallous chloride failed to react with tin tetraphenyl. In the case of lead triethyl chloride we have the following reaction : (1) Et3PbC1 + TlCl = Et,PbCl + EtTlCl, (2) EtTlC1 = TlCl + EtC1. The assumption is made tha,t under the conditions of experiment the unknown thallium ethyl dichloride is not stable since only lead diethyl chloride and thallous chloride were isolated. Thallic chloride and lead tetraphenyl react to give lead diphenyl chloride and thallium diphenyl chloride this being equivalent to chlorination of the lead compound and similar to the chlorination of triphenylstibine by thallic chloride (Goddard loc.cit.). The diffi-culty of the separation of the two chlorides thus formed was over-come when it was observed that the unknown thallium diphenyl oxide or hydroxide is soluble in alcoholic potash whereas the lead compound is insoluble. Tri-p-tolylbismuthine gives rise to thallium di-p-tolyl chloride and a tervalent bismuth derivative probably di-p-tolylchlorobis-muthine. In the case of tri-a-naphthylbismuthjne the presence of di- a-naphthylchlorobismuthine was shown (Challenger and Allpress, T. 1921 119 913) and thallium di-u-naphthyl chloride isolated.Metallic thallium with lea,d tetraphenyl in xylene solution gavc only small quantities of t'hallic hydroxide no organic thallium compound being isolated. Investigations on these double decompositions with other organo-metallic derivatives are proceeding. E X P E; R I M E N T ,4 L . Thallium Diphenyl Bromide. To a solution of 23.8 grams of bromobenzene and 3.2 grams of magnesium ribbon in dry ether 10.3 grams of thallic chloride in the same solvent were slowly added. The mixture was cooled in ice during the addition and after the vigorous reaction had subsided, the product was heated on the water-bath for half an hour cooled, and decomposed with water. After filtering the dried residue was extracted with pyridine when transparent microscopic needles (2.5 grams) were obtained which did not melt a t 290".These were treated with boiling acetic acid and recrystallised twice from pyrid-ine before being pure for analysis (Found T1 = 46.78 ; Br = 17.79 258 GODDARD AND GODDARD : C,,H,,BrTl requires T1= 4658; Br = 18.25 per cent.). The compound is insoluble in alcohol chloroform benzene acetone, light petroleum acetic acid or ethyl acetate. Thallium Di-0-tolyl Chloride. This compound was prepared by the addition of 4% grams of thallic chloride in dry ether to a solution of 10.0 grams of o-bromo-toluene and 1.4 grams of magnesium in the same solvent. The reaction was carried out a t room temperature a vigorous effer-vescence taking place and a yellow solid separating the mixture being allowed to stand for three days.After decomposition the solid was extracted first with pyridine then three times with boiling dilute hydrochloric acid and twice with boiling glacial acetic acid finally with boiling pyridine. Slender microscopic needles were obtained which did not melt a t 290" (Found T1= 47.98; C1= 8-32 C14H,,C1T1 requires T1 = 48.39; C1 = 8.41 per cent.). The compound was insoluble in all organic solvents. Thallium Bi-p-tolyl Bromide. The reaction was carried out with the same quantities as for the ortho-compound but the Grignard solution was heated for an hour, and then decomposed on cooling a greasy yellowish-grey product being isolated. This was boiled for half an hour with 40 C.C. of pyridine filtered the solution evaporated to 7 c.c. and the bromide thrown out with ether.The substance was further washed with ether to remove the last traces of ditolyl and then boiled with glacial acetic acid when pale yellow needles were obtained (Found T1= 43.43 ; Br = 16.94. C,,H,,BrTl requires T1= 43.77 ; Br = 17-15 per cent.). The substance is insoluble in all organic solvents with the exception of pyridine. Thallium Di-a-mphthyl Bronzide. To the solution of 33.6 grams of a-bromonaphthalene and 3.9 grams of magnesium in dry ether 12.5 grams of thallic chloride in the same solvent were slowly added with vigorous shaking the mixture being cooled in water. After the reaction had moderated, the whole was allowed to stand a t room temperature for one hour, and then decomposed with water. The residue was taken up in pyridine the solution on cooling depositing an oil.The latter solidified to a dark brown mass on the addition of water and this was boiled with chloroform the addition of light petroleum t'hrow ORGANO-DERIVATIVES OF THALLIUM. PART IV. 259 ing out a pale fawn solid. After filtering and washing with boiling chloroform until the washings were no longer coloured the resulting compound melted at 272" (Found T1= 37.15 ; Br = 14.81. C,,HI4BrT1 requires T1 = 37.92; Br = 14-85 per cent.). The compound is completely soluble in cold pyridine moderately soluble in ethyl acetate slightly soluble in alcohol carbon tetra-chloride or glacial acetic acid and insoluble in toluene. Action of Thallous Bromide on Magnesium Phenyl Bromide. To a solution prepared with 16.47 grams of bromobenzene and 2-52 grams of magnesium in dry ether 25.2 grams of thallous bromide were added in small quantities and the whole was boiled for seven hours and allowed to stand for a week.After decomposition, 18 grams of fmely divided metallic thallium were obtained and as the original thallous bromide should have yielded 17.8 grams quantita-tive reduction had occurred. Action of Thullic Chloride on (a) Tin Tetraethyl (b) Tin Tetraphenyl. (a) To a solution of 2.75 grams of tin tetraethyl in 50 C.C. of ether, 3.6 grams of thallic chloride in 9 C.C. of the same solvent were added. A slight turbidity ensued and the whole was boiled for half an hour, when shining crystals separat,ed together with a granular powder. The mixture was filtered hot a'nd 1.35 grams of residue were obtained.This had an intolerable smell and on fxeatment with water yielded thallium diethyl chloride and thallous chloride. The evaporated filtrate yielded a solid which softened appreciably at 84-85", indicating the presence of tin diethyl chloride and hally melted above 100". On treatment with aqueous ammonia thallic hydroxide was obtained and also a white solid which was probably tin diethyl oxide but the quantity was not sufficient for further investigation. ( b ) To a suspension of 3.0 grams of tin tetraphenyl in 30 C.C. of xylene 3.32 grams of thallic chloride in 6 C.C. of ether were added. The mixture was boiled for half an hour and a bulky white solid separated which was filtered after cooling when 4.95 grams of a substance not melting at 260" were obtained.This was boiled with absolute alcohol and atered hot the residue (1.35 grams) being un-changed tin tetraphenyl (m. p. 221"). Evaporation of the alcoholic filtrate yielded 0.55 gram of thallium diphenyl chloride (Found : T1 = 52.09; C1 = 9.37. Calc. T1 = 51.84; C1 = 9.01 per cent.). The evaporation of the xylene filtrate gave three crops of crystals (a) 0.1 gram (m. p. 187") which contained no thallium and wa 260 GODDARD AND GODDARD : identified with tin diphenyl hydroxychloride; ( b ) 0.3 gram (m. p. 99") which was shaken with cold ether the solution yielding 0.28 gram of tin triphenyl chloride (m. p. 306"); ( c ) 0.2 gram (m. p. 79") which after three crystallisations from light petroleum, softened at 42" and melted at 60". This indicates a mixture of tin diphenyl chloride (m.p. 42") and fin triphenyl chloride. Action of Lead Triethyl Chloride on Thallic Chloride. To a solution of 1.71 grams (1 mol.) of lead triethyl chloride (prepared by the adion of dry hydrogen chloride gas on lead tetraethyl) in 50 C.C. of ether 1.71 grams (1 mol.) of thallic chloride were added. The whole was boiled on the water-bath for one and a half hours and allowed to stand over-night when pale yellow needles mixed with a granular compound separated (0.8 gram). Filtration and evaporation of the atrate yielded a further 0.38 gram of the mixture. The combined solids were boiled for half an hour with absolute alcohol and filtered hot. The residue (0.4 gram) ,was white and was found to be thallous chloride (Found T1= 83-45.Calc. TI = 85.19 per cent.). Evaporation of the alcohol yielded pale yellow needles (0.68 gram) which contained lead and were proved to be lead diethyl chloride (Pound C1= 21.09. Calc., C1 = 21.09 per cent.). Actior~ of l'hallic G'hloride on Lead Z'etraphenyl. A mixture of 3.0 grams of lead tetraphenyl and 1-8 grams of thallic chloride in 60 C.C. of benzene was warmed on the water-bath for two hours. The residue obtained after filtering was boiled for half an hour with excess of alcoholic potash and filtered. The solid remaining (4.0 grams) was organic and contained lead but no t,hallium a.nd by boiling with glacial acetic acid it yielded 1.6 grams of an inorganic lead compound. The alcoholic filtrate deposited long needles (1.7 grams) which did not melt a t 270" and these on boiling with concentrated hydrochloric acid and crystalliskg from pyridine gave pure thallium diphenyl chloride (Found C1= 8.95.Calc. C1 = 9.01 per cent.). Aclion of Thallic Chloride on Tri-p-tolylbismuthine. The solid obtained by shaking together 2.85 grams of tri-p-tolylbismuthine and 1.0 gram of thallic chloride in 50 C.C. of dry ether was filtered off after the mixture had stood half an hour. It was then boiled with acetone aiid the filtrate gave a small quan ORCANO-DERIVATIVES OF THALLTUM. PART IV. 261 tity of a tervalent bismuth compound probably di-p-tolylchloro-bismuthine but the quantity was too small to manipulate. The residue from the acetone was recrystallised from pyridine two crops of crystals being deposited ; (a) consisting principally of inorganic bismuth and thallium salts (0.25 gram) ( b ) small trans-parent needles of thallium di-p-tolyl chloride.The latter were purified by boiling with glacial acetic acid to remove any thallium p-tolyl dichloride and then recrystallised from pyridine (Found : T1 = 48.16 ; C1 = 8-53. C,,H1,CIT1 requires T1 = 48.39 ; C1= 8.41 per cent.). Thallium di-p-tolyl chloride does not melt at 296" and is slightly soluble in alcohol or acetone and insoluble in chloroform, light petroleum toluene or alcoholic ammonia. Action of Thallic Chloride on Tri-a-~phthylbismuthine. To 6.0 grams of tri-a-naphthylbismuthine in GO C.C. of ether 1.91 grams of thallic chloride were added and the whole was boiled for an hour and a half. From the cooled solution 6.2 grams of solid were obtained and evaporation of the ether gave 0.2 gram of a grey mass which contained unchanged thallic chloride bismuth oxychlor-ide and naphthalene. The 6.2 grams were boiled with benzene, the filtrate yielding 3.3 grams of unchanged bismuthine (m. p. 233-234") and on evaporation 1.0 gram of a bismuth compound (m. p. 225") which was found to be a mixture of tri-a-naphthyl-bismuthine and di-a-naphthylchlorobismuthine (m. p. 168O). The benzene residue (1.6 grams) was found to be thallium di-a-naphthyb chloride (Found T1 = 42.47; C1 = 7.39. C,,H,,ClTl requires T1= 42.15; C1= 7-35 per cent.). The compound is fairly soluble in hot pyridine slightly soluble in glacial acetic acid ethyl acetate, chloroform or alcohol and insoluble in ether acetone benzene or carbon tetrachloride. The authors are indebted to the Research Fund Committee of the Chemical Society for a grant which has partly defrayed the expenses of this investigation. THE UNIVERSITY, EDGBASTON BIRMINGHAM. [Received January 6t72 1922.