154 NR. WILSON XVIII.-On theAction of Chloride of Cyanogen upon Tohidine. By W. WILSON The perfect homoloy existing between toluidine and ariiline left but little doubt respecting the deportment which the former alka- loid would exhibit when exposed to the influence of chloride of cyanogen ; still the discrepancies which we frequently observe between the various members of one series especially if we rise on the scale of compoimds made it desirable to establish the behaviour of toluidine by experiment. PREPARATION OF TOLTJIDINE. The preparation of toluidine is a process of considerable difficulty inasmuch as the collateral hydrocarbon can be obtained only in comparatively small quantities. The formation of toluol has hitherto been observed in different processes namely in the distillation of tolu-balsam by Deville its discoverer; iii the distillation of dragon's blood (dracyl) by Boudault and Glenard; in the decomposition of toluylic acid by Noad; and lastly it has been met with aniong the hydrocarbons of coal-tar naphtha by Mansfield.I have tried all these methods in order to procure toluol in larger quantities and I find that the source last-mentioned is that which yields this compound most easiIy and in greatest quantity ;-only comparatively minute quantities being obtained by the other processes. The best plan is to select the fraction distilling between looo and 120° C. and to treat this portion with half its bulk of eon-centrated sulphuric acid. I am not prepared to say what substances are removed by this process; the fact is however that a constant boiling-point is more easily reached with than without the use of ON I\IETOLUIDINE sulphuric acid.In all cases a series of tedious distillations is required in order to accomplish this object. The boiling-point of toluol was found to be llOo C. The conversion of toluol into nitro-toluol succeeds without dia- culty in the usual manner. Nitro-toluol was found to boil between 220°and 2,25O,withotit decomposition. Those chemists who have used Zinins' process for the amidation of nitro-compounds are aware how difficult it is to effect the complete conversion of these substances when treated with sulphide of ammo-nium especially if there is but 1equivalent of hyponitric acid present.I have used in my experiments a solution of hydrosulphate of sulphide of potassium with which the nitro-toluol was repeatedly distilled. The advantages which the potassium-compound presents are very remarkable not half the time being required as with sulphide of ammonium; moreover the base once formed has no longer to be separated from the ammonia which in the latter case distils over with it. The toluidine obtained in this manner after having been several times crystallized in the form of oxalate and lastly distilled with caustic lime presents all the properties which its discoverers assigned to it PREPARATION AND ANALYSIS OF METOLUIDINE In subjecting toluidine to the action of chloride of cyanogen. I adopted in the first place the same arrangement that Dr.Hofmann had used in preparing melaniline namely a series of tubes filled with the dry alkaloid through which the chloride of cyanogen was drawn by means of an aspirator. I soon found however that the deportment of toluidine is by no means so simple as that of aniline under similar circumstances. The alkaloid being solid at ordinary temperatures it was necessary to support the action from the very conimencemcnt by the application of heat under the influence of which unless it be very carefully applied the newly formed hydrochlorate appears to undergo some farther metamorphoses. On this account I found it more convenient to introduce toluidine into a slightly bent tube to diffuse it by a gentle heat into a thin laycr over the sides and then to expose this increased surface to the action of the gas.In this manner the heat evolved during the reaction was sufficient to keep the substance in a state of fusion. As soon as the action had ceased the resinous mass consisting almost entirely of hydrochlorate of the new base was dissolved in water to which a small quantity 156 MR. WJLSOY of hydrochloric acid had been added. On mixing the filtered so-lution witb potassa a white precipitate took place which was boiled for some time with the potassa in order to distil off with the aqueous vapours small quantities of toluidine which niight hare escaped the action. The residue was thrown upon a filter sepa-rated by washing froin the chloride of potassium and recrystallized from alcohol.From this solution the new base which I propose to call Metoluidiize a name corresponding to melaniline is deposited iu small crystalline plates. It crystallizes better from a mixture of alcohol and water but by no means with the same facility as melaniline; this substance is but slightly soluble in water but somewhat more so at the boiling-temperature. I have established the composition of metoluidine by analyses of the base itself and by that of the platinum-salt 0.2201 grm. of base gave 0.6048 , of carbon and 0.1454 , of water. These numbers together with those obtained with the platinum-salt lead to the forniula 'SO H17 N3J which requires the follow-ing values Theory. Experiment. r-7 30 equivs. of Carbon .. . 180 75-31 74.54 17 , , Hydrogen . 17 7-11 7-34 3 , , Bitrogen . . 42 17.58 -239 100*00 METOLUIDINE AND BICHLORIDE OF PLATINUM Bletoluidine is readily soluble in hydrochloric acid. The solution yields with bichloride of platinum a dark-yellow precipitate which is insoluble in water and alcohol and may be dried at loo*. On analysis the folloving numbers were obtained I. 0.2685 grm. of platinum-salt gave 0.8980 , , carbonic acid and 0.1025 , , water. 11. 0.1897 , , platinum-salt gave 0.0418 , , platinum. 111. 0.2985 , , platinum-salt gave 0,0659 , , platinum. IV. 0.1096 , , platinum-salt gave: 0.0244 , , platinum. ON METOLUIDINB. These numbers lead to the following percentab.e-comltosition I. XI. 111. IV. -Carbon .40.40 -7 Hydrogen. . 404 --Platinum . -22.03 22.07 22-25 The formula C, H17N,. HCI. Pt C1 requires the following values Theory. Experiment. -30 equivs of Carbon . . . 180.00 40.43 40.40 18 , , Hydrogen. 18.00 4.04 4.24 3 , , Nitrogen . . 42.00 9.43 -3 , , Chlorine . . 106.50 20.93 -1 equiv. , Ylatinuin . . 98.68 22.17 22.15 _I___-1 , , Platinum-salt . 445.18 100*00 The formation of metoluidine is perfectly analogous to that of melaniline; 2 equivalents of toluidine and 1 equivalent of chloride of cyanogen yield 1 equivalent of hydrochlorote of nietoluidine. 2 C, H N + C N C1 = C, 1117N3 13.U. -+ u c Y ToluiclinP. Chloride €X ydr ochIorate oi of Cyauogen. ?kletoluidinc.* * The bzses produced by the action of chloride of cyanogen upon aniline and toluidine exhibit a remarkable analogy with one of the platinum alkaloids obtaiiied by 3%.Reiset which will at once become perceptible if we compare the formula of the chlorides when considered as ammonia compounds Chloride of Reiset’s base { 2 } N IT4 K C1