3fESSRS. MORLLEY AND ABEL ON IX.-Ort the Aclion of Iodide of Ethyl on Tohidine. BY~~EGINALD AND JOHNS. ABEL, I MORLEY ASSISTANTS IN THE ROYAL COLLEGE OF CHEMIBTRY. Chemists are acquainted with the results obtained by Dr. Hof-mann in his researches on the organic bases which led him to establish the existence of four groups of bases derived from ammo- nia by the replacement of its several hydrogen equivalents by organic radicals. He pointed out at the same time a simple method of ascertaining in what group an organic base has to be classified. This method as is well known consists in treating the substance under examination with the iodide of an alcohol radical. The experiments to which we are about to refer undertaken at THE ACTION OF IODIDE OF ETHYL ON TOLUIDIHE.his invitation and carried out wider his kind superintendence refer to the examination in this direction of an orgauic base which has repeatedly claimed the attention of the facul ty-viz. Toluidiae. The origin of this body derived step by step from toluylic acid toluol and nitrotoluol places the substance on the same line with the aniline the formation of which from benzoic acid benzol and nitrobenzol is well known. The perfect homology of toluidine and aniline is moreover nnequivocally proved by their physical proper- ties. The constitution of aniline has been established it may be said beyond any doubt it has been proved that in its salts the substance may be received as ammonium in which 1 equiv. of hydrogen is replaced by 1equiv.of the hydrocarbon C1 H, to which the name of Phenyl has been given or in the free state as ammonia 1 equiv. of hydrogen of which is replaced by the same radical. Salts. Free Rases. H Aniline c1 Aniline N 1 I"f 1 salt c,!2H5 Cl H5 If toluidine is a perfect homologue of aniline its constitutioii must be perfectly similar ; so that if the latter has in fact this con- stitution toluidine must be represented by the formula H" p, Cl* H when it becomes arnmonia in which 1 equiv. of hydrogen is re-placed by toluyl C, H ; and it is this constitution which has been assumed by Dr. Hofmann in his papers on the bases. It re-mained to verify this assumption experimentally. This verification forms the subject of the present communication.We rapidly pass over the preparation of toluol from coal naphtha although we had to perform an immense number of distillations until the hydro- carbon at last boiled stationary at 111' C. (231°08F.) The con- version of toluol into nitrotoluol is attended with difficulties heat must be carefully avoided otherwise a considerable quantity of dinitrotoluol is produced which forms far more readily than dini- trobenzol. The reduction of nitrotoluol by means of sulphuretted hydrogen lastly is an operation tedious in the extreme; it can be accomplished only by a series of supersaturations and distillations. The purification of the toluidine mils effected in the form of oxalate. On account of the facility with which it was obtained we selected from among the alcohol-iodides iodide of ethyl as the substance to the action of which the toluidine was to be submitted.We now proceed to describe the results obtained in this reaction. ETHYLOTOLUIDLNE. A portion of the toluidine was sealed up in a tube with excess of iodide of ethyl and exposed to the temperature of the water-bath for two or three days. The toluidine mixed with the iodide and the whole became one crystalline mass; towards the latter part however an oily layer separated on the upper surface of the liquid. The tube was now opened and the excess of iodide of ethyl ctis- tilled off in a water-bath when iodide of ethylotoluidine remained as a heavy oil possessing a peculiar alliaceous smell; this oil was decomposed by distillation with a strong solution of potassa at a high temperature when a colourless oil distilled over lighter than water and possessing a peculiar odour.This oil the new base was separated from the water with which it had distilled over and dried over stick potash. When thus rectified its boiling point was found to be 21;' C. (422O.6F.) tlie spec. grav. being 0.9391 at 15O.5 C. (60' F,) From the comparison of the boiling points of aniline (about 180' C.} and toluidine (200° C.) we might have expected that by the introduction of 4 equivs. of carbon and hydrogen into the latter base its boiling point would have been raised about 40°C. It appears however that this rule does not hold good in all cases of this kind Dr. Hofmann having observed a similar comportment with ethylaniline.Platinum-salt of EthylotoZuidine.-This was at first prepared by adding excess of hydrochloric acid to the liquid from which the base had been separated and which possessed a strong alkaline reaction. The hydrochlorate thus formed was evapo-rated on a water-bath until when mixed with bichloride of platinum thc double sclt crystallized on cooling. In this manner a considerable quantity of a fine crystalline salt was obtained soluble iri water and when washed with alcohol of ca pale yellow colour. For analysis a portion of the crystals was TEE AC'I'ION OF IODlDE OF ETHYL OK TOLUIDINE dried in the water bath until the weight was constant and burnt as usual The quantity of platinum obtained was slightly too large for ethylotoluidine; a circumstance x-hich we explained by the possible presence of a trace of toluidine in the liquid from uliich the salt was prepared.An attempt to recrystallize the salt only resulted in the total loss of our substance by dcconiposition; a fresh portion of hydro-chlorate was prepared from some of the base evaporated 2nd mixed with bichloride of platinum ; a precipitate was formed which dissolved in excess of the bichloride from which solution the salt could not again be obtained. It was necessary therefore to add the platinum solution very cautiously and when the precipitate was formed alcohol mas added which dissolved the salt but again deposited it on agitation after a short time. In this manner with much trouble suscient platinum-salt was prepared for another determination.The double salt being very soluble in alcohol it was washed with ether; it was found to decompose at 100' C. AS the colour became darker and no constant weight couhl. be arrived at it was dried for analysis in vacuo over sulpliuric acid. 0*1580grm. of platinum-salt gave 0.0460 , platinum = 29.11 per cent. According to the formula C, H, N H C1 Pt Cl, or H the percentage of platinum should be 28.93 per ceiit. The difference is 0.08. Our next step was to confirm the composition of the base by a determination of the carbon and hydrogen. The platinum-salt being so difficult to obtain we burnt the base itself which as it darkens on keeping like aniline toluidine &c. was redistilled for this purpose.0.1425 grm. of substance gave 0.4175 , carbonic acid 0.1255 , water leading to the following percentages Carboii . * 79.90 IIydrogcn . . !)*78 The formula requires the following values Theory. Experiment /-1S equivs. of mrbon . 108= 80.00 79.90 13 , hydrogeu . 13= 9.63 9.78 1 , nitrogen . 14= 10.37 135 100.00 These numbers sufficiently establish the composition of ethyl-toluidine. Ethyfotoluidine forms crystalline compounds with oxalic and mlphuric acids. DIETHYLOTOLUIDJNE A portion of the ethyl-base was next sealed up with an exeess of iodide of ethyl and exposed for two or three days to the tempera- ture of boiling water in order to produce diethylotoluidine. After tha5 time on allowing the tube to cool and gently agitating it beautiful crystals of the iodide of the new base at once formed throughout the whole length of the liquid which dissolved again on placing the tube in the water bath.The excess of iodide of ethyl was again separated as before when the iodide of diethylo- toluidine remained in the flask &om which it crystallized in fine six-sided prisms so soluble in water that they could scarcely be crystallized from it. The salt separated from the aqueous solution in oily drops which assumed the crystalline form on being touched with a glass rod. It appeared to be decomposed by alcohol as also by continued exposure to the atmosphere. For analysis some of the recrystallized salt was dried in vacuo over sulphuric acid (the crystals having been found to decompose in the water bath) dissolved in water and the iodine determined by precipitation with nitrate of silver in the usual manner 0.3130 grm.of iodide gave 0.2520 , iodide of silver orrespo nding to percentage of iodine 1113.445.The formula c,4 I-1, C H i X HI= C, EI18N I c4 H THE ACTION OF IODIDE2 OF ETHYL ON TOLUIDINE requires 43.66 per cent. of iodine; thus proving the crystals to have the above composition. The remainder of the salt was distilled with potash and the base thus obtained on the surface of water from which it was separated. Diethylotoluidineis colourless and possesses a smell like the former compound. After rectification from potash it was found to boil at 229O C.(44AO.2 F.) thus showing another deviation &om the rule. Its spec. grav. at 19O-5C. (GOo F.) was 0.9242. The preparation of the platinum-salt of this base presented insur- mountable diEculties it could not be obtained otherwise than as a resinous mass to crystallize which all attempts were abortive. A combustion of the base was however made 0.1495 grm. of substance gave 0,4435 , carbonic acid 0.1410 , water leading to the following percentages Carbon . . 80.90 Hydrogen . . 10.47 The formula requires the following values Theory. Experiment. /--22 equivs. of carbon . . 132 80.98 80.90 17 , hydrogen . 17 10.43 10.47 1 , nitrogen . 14 8.59 -__. -. 163 100*00 The results obtained correspond therefore sufficiently with the above formulz.OXIDE OF TRIETHYLOTOLUYLAMMONIUM. It now remained for us to convert the volatile into a fixed base similar to those which Dr. Hofmann has distinguished by the laboratory term ammonium-bases. The formation of such a substance by the introduction of another equivalent of C4 H5 into diethylotoluidine would establish beyond any doubt the perfect homology of aniline and toluidine. MESSRS. MORLEY AND ABFL ON This new base might be called oxide of triethylotoluicline or oxide of triethylotoluylammonium. For this purpose we again sealed up the last base with iodide of ethyl and exposed the tube to a temperature of 100’ C. (212OF.) for some days till fine prismatic crystals of an iodide had formed in the solution.After distilling off the excess of iodide of ethyl as befwe the iodide of the new base remained as a heavy oil :this was decom- posed by heating with freshly precipitated oxide of silver when the liberated oxide of trietliylotoluylammonium at once entered into solution leaving iodide of silver. The solution after filtration was found to possess an extremely bitter taste and to be very alkaline to test-paper. With salts of the metallic oxides a solution of this base behaved in most cases similarly to potash and to Dr. Hof-mann’s oxide of tetrethylammonium thus with salts of baryta strontia lime and magnesia a white precipitate insoluble in excess was formed. The following is a list of the reactions of this substance Barium-saZls.-White precipitate of the hydrate of the earth insoluble in an excess of the base.Strontium-snZts.-Thite precipitate of the hydrate of the earth insoluble in an excess of the base. Calcium-salts.-White precipitate of hydrate of the earth inso- luble in excess of the base. 2Maynesiu.m-saZts.-VVhite precipitate of hydrate of the earth insoluble in an excess of the base. Aluminum-saZts.-VVhite gelatinous precipitate soluble in large excess of the base. Chromium-salts. -Green hydrated sesquioxide insoluble in excess. NickeZ-saZts.-Green protoxide insoluble in excess. Cobalt-salts.-Pink hydrate of protoxide insoluble in excess. Manganese-salts. -Whitish hydrated protoxide insoluble in excess. Salts of Protoxide of Iron.-Green hydrated protoxide insoluble in excess.Sults of Sesquioxide of Iron.-Brown hydrated sesyuioxide insoluble in excess. Zinc-saZts.-H;ydrate of the protoxide soluble in excess. Lead-salts.-White hydrate of protoxide soluble in excess. Silver-salts.-Brown protoxide insoluble in excess. Salts of Suboxide of Mercury ,-Black suboxide insoluble in excess. THE ACTION OF IODIDE OF ETHYL ON TOLUTDlNE. Sults of Protoxide of Mercwy.-White precipitate insoluble in excess. Copper-salts.-Blue hydrated protoxide insoluble in excess becoming black by ebullition. Cachnium-salts.-White hydrated protoxide insoluble in excess. Bis?nuth-saZts.-White hydrated teroxide insoluble in excess. Antimony-salts Teroxide.-\White hydrated teroxide soluble in excess. Salts of Protoxide of Tin.-White hydrated protoxide soluble in excess.Salt oj Binoxide of Tin.-White hydrated binoxide soluble in excess. Gold-salts.-Yellow precipitate of the double salt. Ptatinum-salts.-Yellow precipitate of the double salt. Platinum-Salt.-When the chloride of this base was mixed with bichloride of platinum a copious precipitate of a fine crystalline platinum-salt was produced which was nearly insoluble in cold water but was dissolved readily in hot water from which solution it crystallized in beautifid needles. The salt was thrown upon a filter washed and dried at loooc. Both the original and crystallized salts were analyzed. I. 0.1640 grm. of platinum-salt gave on ignition 0.0410 , platinum. IT. 0-6100grm. of platinum-salt gave on ignition 0.1515 , platinum.Theoretical Experimental percentage. percentage. Platinum . . 24.85 24.91 Recrystallized salt. 0.5212grm. of platinum-salt gave on ignition 0.1292 , platinum. Theory. Experiment. Platinum . 24-85 24.5 It appears therefore that this platinum-salt like some observed by D r. H ofni ann loses platinum by recrystallization. For combustion some of the original salt cuts employed. 76 NESSRS. MORLEY AND ABEL ON THE ACTION OF IODIIX OF KMYL. 0.5300 grm. of platinum-salt gave 0.7600 , carbonic acid 0.2690 , water and 0.1310 , platinum. The numbers required by the formula are shown in the following table together with the numbers obtained by experiment from which it will be seen that little doubt can remain as to the formula of the salt analyzed.-Theory. Experiment. 26 equivs of carbon 156 39.27 39.11 22 1 1 , , , hydrogen nitrogen platinum 22 14 98.7 5.54 3.52 2485 5.64 24*71 3 , chlorine 106-5 26.82 -_I___ 397.2 10000 These experiments establish the existence of the following bases which we place in juxtaposition with those of the homologue phenyl. Phenylamine Aniline H H Eth ylaniline C H5/N Ethylotoluidine C H5\N Cn H5 c14 H c* H5 c4 H Diet hylauiline C H5\ N Diethylotoluidine C H:] N cn H5/ c,4 H Triethylaniline N Triethytoluidine In conclusion we may observe that the combustion of this pla- MR,. WATiTJACE ON R,ED PRUSSTAT’E OF POTASH. tinum-salt as well as all the combustions made in the coinse of this investigation were performed in Dr.Hofrnann’s new gas furnace for organic analysis. It deserves to be mentioned that to ensure complete combustion the liquids were weighed in small open tubes filled with oxide of copper and a little powdered chlorate of potassa the oxygen of which expelled with the last stage of the process ensured the complete combustion of any small particles of carbon that might otherwise have remained unconsumed.