LXV.-The Actio?L of Chromium Oxychloride on Orthosubstituted Toluenes. By CHARLES M. STUART M.A. Bellow of St. John's College Cam-bridge and W. J. ELLIOTT Scholar of Christ's College Cambridge. IT is well known that the action of chromium oxychloride on the homologues of benzene gives rise to the formation of solid compounds which consist of 1 molecule of the hydrocarbon combined with 2 molecules of the oxychloride and which are decomposed by water with the formation of aldehydes. V. v. Richter (Berichte 19 224) has examined the action of chromium oxychloride on orthonitrotoluene ; but although he succeeded i n showing the production of a small quantity of orthonitrobenz-aldehyde he found that for the most part orthonitrotoluene was re-formed. We have examined the interaction of ortho-haloi'd derivatives of toluene and chromium oxychloride.Ten grams of the substituted toluene dissolved in carbon bisulphide were added very gradually to a solution of 25 grams of chromium oxychloride in the same liquid which was kept cool by a stream of water. The mixture was allowed to stand three days ; the solid was then filtered off and added to water. A heavy oil separated and the solution contained in all cases a salt of chromium and chromic acid. The chromic acid was reduced by a current of sulphur dioxide. Orthoclilorotoluene and Chromium Ozychloride. The chief part of the oil which separated distilled at 205" to 210". The substance formed a crystalline compound with sodium hydrogen sulphite solution and gave with malonic acid an acid melting at 192" with effervescence namely orthochlorobenzal malonic acid.0.5011 gram take 36 C.C. N/10 AgNO solution = 25.50 p. c. C1. Theoryfor C,H4C1*COH = 25.25 ,, It is therefore orthochlorobenzaldehyde. I n this experiment we were unable to isolate any othtr compound. Orthobromotoluene and Cliromium Oxycl~loride. When the oil which separated was distilled it came over in two fractions ; the first a t 215-220" the second a t 285-235" 504 ACTION OF CHROJlIUJI OXYCHLORIDE ON TOLUEbTS. The first fraction (215-220") gave with sodium hydrogen sulphite solution a crystalline precipitate and with malonic acid an acid melting a t 198" with effervescence namely orthobromobenzalmalonic acid. 0.1843 gram required 10 C.C. N/10 AgNO3 solution = 43-40 p. c.Br. Theory f o r C6H4Br.COH = 43.24 ,, It is therefore orthobromobenzalde hyde. The second fraction (225-235') was shaken with sodium hydrogen sulphite solution and then with ether. The residue obtained by distilling off the ether from the ethereal solution was found to contain both chlorine and bromine. 0.1604 gram required 20 C.C. N/10 AgX03 solution beforc boiling with PbO, and 13.4 C.C. after boiling with PbO?. 0.2496 gram gave 0.3149 gram CO and 0.0662 gram H,O. Ttieory for, Pound. C,H4B r - CMO,. C. . 34.41 C . . 35.00 H . 2.92 H 2.07 C1. 29.65 BI= . 33.33 Br 32.91 C1. 29.58 When boiled with potash solution it is converted into the aldehyde. It is partially decomposed Its formula is therefore C6H4Br.CHCl,. on distilla tion with evolution of hydrogen chloride.Orthiodotoluene and Chronrium Oxychloride. When the oil was distilled the temperature rose slowly to 270". The distillate was shaken with sodium hydrogen sulphite solution. The larger portion remained as an oil. The aqueous solution was shaken with ether in order to extract all oil that remained. Hydrogen chloride was then added and the solution boiled; a slight smell of aldehyde could be detected and there were drops of oil on t,he condensing tube. A trace of aldehyde only is produced. Thc oil which remained after shaking with sodium hydrogen sul-phite solution was shaken with sodium thiosulphate solution in order to remove all free iodine. The residue boiled with decomposition a t 243-2 50". 0.3764 gram required 38 C.C. NjlO AgNO solution.12.7 C.C. NjlO Na,S20J solution. 0.4475 gram gave 0.1013 gram H,O and 0.4747 gram C02 THE JIOLECULAR WEIGHT OF IODINE IN ITS SOLUTIOKS. 805 Theory for Found. CcH4 1.C H Cls. C . . . . . . . . 28.9'2 C . . 29-26 H . . . . . 2.51 H 1.74 I 45.01 I 44.25 C1. 24.35 Cl . 24.42 . . . . . . . . The substance is therefore orthiodobenzal chloride. Wheri boiled wit,h potash it is converted into aldehyde. These experiments therefore prove that the action of water on the solid compounds of chromium oxychloride and ortho-substitu t ed toluenes is to produce in the first instance an ortho-substituted benzal chloride of the formula C6H,X*CC1,H; but that this in the case of tke orthochlorotoluene is entirely and in the case of the ortho-brornotoluene partially decomposed by water with the formation of an aldekyde ; while the orthiodo-compound is scarcely affected. It is extremely probable that the formation of all aromatic aldehydrs by this method is preceded by the formation of derivatives of benzal chloride. For this reason we examined the reaction between orthonitro-toluene and chromium oxychloride. Like V. v. Richter however we found that a trace of orthonitroberizaldehyde only was produced, while not a trace of a compound containing chlorine was formed but the greater part of the orthonitrotoluene was reproduced