DIETHYLENETRIAMINE AND TRIETHYLENETETRAMINE. 1351 CXLWI.-Diethylenetriamane and l'ricthylenetetramirle. By ROBERT GEORGE FARGHER. THE interaction of ethylene dichloride and a large excess of ammonia has been investigated by Kraut (Annalen 1882 212, 253) who considered that it led almost entirely to ethylenediamine, although the reaction of the alcohol-soluble portion of the mixed hydrochlorides with potassium bisniuth iodide indicated that a small proportion of piperazine was formed. The author had occasion to prepare several kilograms of ethylene-diamine essentially by Kraut's method and it was thought to be of interest to investigate in more detlail the other products of the reaction. The hydrochlorides obtained by evaporation of the product were converted into the corresponding bases and fraction-ally distilled.The portion of' higher boiling point consisted mainly of diethylenetriamine whilst there was also produced although in much smaller quantity triethylenetetrainine. The intermediat 1352 FARGHER DIETHYLENETRXAMINE cyclic bases piperazine and triethylenetriamine appeared to be absent. Of the two bases isolated the former was first obtained by Hofmann (Proc. Roy. Soc. 1860 10 619) admixed with triethylenetriamine by the action of ammonia on ethylene dibromide and was separated by the more sparing solubility of its platinichloride; the second base he obtained by the interaction of ethylenediamine and ethylene dibromide (Zoc. cit.) ethylene dibromide and alcoholic ammonia (Zoc. cit .) and ethylenediamine and ethylene dichloride (Ber.1890 23 3712). For purposes of identification and characterisation a number of derivatives of both have been prepared. . It is of interest to record that the direct union of ethylene with chlorine utilised in the preparation of the ethylene dichloride required in the present experiments shows that electrolytic chlorine from a freshly charged cylinder is considerably more active under identical conditions than that prepared from bleach-ing powder. This is in accordance with the view that chlorine is activated by exposure to an electric discharge (compare Kellner, Zeitsch. Elektrochem. 1902 8 500 ; RUSS Jfonutsh. 1905 26, 627 ; Briner and Durand Zeitsch. Elektroclhenz. 1908 14 706), and that chlorine prepared by electrolysis is more active towards hydrogen (Chapman and MacMahon T.1909 95 135). Contrary to the experience of Russ (Chem. I n d . 1908 31 131)) the increased activity is not lost by heating or by contact with water or solutions of such salts as calcium chloride or potassium chlorate. As an example the fractionation of the products of two experiments may be cited the results being representative of many others. In the first using chlorine from bleaching powder 92 per cent. of the product distilled between 8 4 O and 8 8 O only 4 per cent. passing over a t a higher temperature. In the second using chlorine from a freshly charged cylinder only 7 per cent. distilled between BOO and 90° 25 per cent. passing over between 90° and looo 50 per cent. between looo and 120° and 14 per cent. above that temperature.As an alternative to the Kraut process the reduction of amino-acetonitrile was investigated. The catalytic reduction with hydrogen under pressure in the presence of nickel suboxide had already been claimed to yield ethylenediamine (Brit. Pat. 21383 of 1914). Reduction with sodium and alcohol zinc and hydro-chloric acid and iron and hydrochloric acid also yielded ethylene-diamine although as hydrolysis of the nitrile proceeded simultaneously the yield never exceeded 33 per cent. of the theoretical AND TRIETHYLENETETRBMINE 1353 E x I' E R I M E N T A L. Separation of the Bases. The bases obtained by distilling the mixed hydrochlorides with solid sodium hydroxide preferably under somewhat diminished pressure were freed from water by means of solid sodium hydr-oxide" and then distilled first under the ordinary pressure t o remove most of the ethylenedianiine hydrate and then under 20 mm.There was first obtained a small fraction boiling below 100° which consisted almost entirely of ethylenediamine and after this most of the remaining oil passed over between looo and 120'. The temperature then rose to 155O without remaining constant at any intermediate point and a fraction was collected boiling between 155O and 165O/ZO mm. The first fraction proved to consist almost entirely of diethylenetriamine which distilled at 109O/20 mm. The second fraction on redistillation boiled a t 157O/ 20 mm. and proved t o be triethylenetetramine. Diethylenetriarnine and its Derivatives. Diethylenetriamine dissolves in water with the evolution of heat and apparent formation of a hydrate.The aqueous solution of the base gives copious white precipitates with potassium mercuri-iodide mercuric chloride or phosphotungstic acid soluble in excess of the base but no precipitate with tannic acid. It reduces silver nitrate on warming. The alcoholic solution yields an insoluble carbonate when treated with carbon dioxide. Attempts to titrate the base with standard acid using methyl-orange Congo-red, litmus or cochineal as indicator proved unsuccessful as no definite end-point could be obtained. For analysis it was finally distilled over a little solid sodium hydroxide and was afterwards kept out of contact with moisture or carbon dioxide (Found: C=46*3; €1=13*1; N=40*3.Calc. C=46*6; H=12*7; N=40.75 per cent.). The trihydrochloride (1 Iofmann Proc. Roy. Soc. 1862 11, 420) separates from aqueous alcohol containing excess of hydrogen chloride in bunches of feathery needles which melt at 233O (corr.), sintering from 225O (Found Cl=50*1 50.2; N=19*6. Calc. : C1= 50.1 ; N = 19.8 per cent.). The tripicrate is sparingly soluble even in boiling water and crystallises in glistening flattened prisms which melt and decom-* It is n u t sufieieni; simply to distil over sodium hydroxide. VOL. CXVII. 31 1354 FARGHER DIETHYLENETRIAMINE pose a t 2120 (corr.) (Found N-21.5. C4H,,N,~3C,H30,N, requires N = 21.3 per cent.). The oxaZute crystallises from water in which it is readily soluble, in flattened prisms containing 4H,O. After drying a t l l O o it melts and effervesces a t 1 8 3 O (corr.) (Found loss a t 110°=13*0.2C4Hl3N3,3C2R2O4,4H,O requires H20 = 13.1 per cent. I n dried substance N = 17.5. 2C4H,,N,,3C2H,04 requires N = 17.6 per cent .) . The citrate is practically insoluble in alcohol ether or chloro-form but readily so in water from which it separates in well-defined rhombic prisms containing lH,O. After drying a t l l O o , it melts and effervesces a t 206O sintering from ZOOo (Found loss a t l l O o = 6.3. C,Hl,N,,C6H,07,H,0 requires R,O = 5.8 per cent.). In dried substance N = 14.4. C,H13N,,C6H,07 requires N = 14.2 per cent .). The triacetyl derivative is practically insoluble in alcohol or light petroleum but very readily soluble in water. It separates from 70 per cent.alcohol as a felted mass of needles which in contact with the solvent change to well-defined prisms melting at 220° (corr.) (Found N = 18.0. Cl,H,,03N3 requires N = 18.3 per cent .). The tribenzoyl .derivative is very sparingly soluble in ether, or light petroleum but readily so in water or alcohol. From chloroform it separates in small flattened prisms containing one molecule of the solvent which is gradually lost on exposure t o the air but regained on keeping over chloroform in a desiccator. After removal of the solvent of crystallisation it melts a t 166O (corr.) (Found CHC1,=21.9. After forty-eight hours this had diminished to 16.1 per cent. In dried substance C=71*9; H=6*1; N=10.1. C,H,03N3 requires C=72.2; H=6-1; N=10.1 per cent .) . Triethylenetetramine and its Deriuartivcs.Triethylenetetramine behaves very similarly to diethylenetri-amine in its reactions dissolving in water with evolution of heat, forming an insoluble carbonate when carbon dioxide is passed through its alcoholic solution and giving precipitates with pot,assium mercuri-iodide mercuric chloride and phosphotungstic acid. For analysis it was finally distilled over solid sodium hydroxide (Found C = 48.8 ; H=12*7; N=38.0. Calc. C=49*3; H=12*4; N=38.3 per cent.). The tetrahydrochloride seprates from 70 per cent. alcohol con-taining excess of hydrogen chloride in minute needles (Found: Cl=48*0. It reduces silver nitrate on warming. Calc. C1=48*5 per cent. AND TRTETHYLENETETRAMINE. 1355 The tetrapicrate is very sparingly soluble even in boiling water, from which it separates in fern-like clusters of minute rhombic prisms melting and decomposing a t 240° (corr.) (Found N = 20.7.C,H,8N,,4C,H,Q,N3 requires N = 21.1 per cent.). The hydrogen oxalate is sparingly soluble in water and separates in glistening needles which effervesce a t 243O (corr.) and contain lH,O (Found loss a t 110"=3-0. 1€&0 requires 3.2 per cent. In dried material C = 33-3 ; H = 5.5 ; N = 10.9. C6H,,N4,4C,H,O, requires C=33*2; H=5*2; N = l l * l per cent.). The tetrabenzoyl derivative dissolves sparingly in water or alcohol but readily in chloroform. It separates from a mixture of chloroform and alcohol in fine powdery crystals melting a t 2 3 8 O (corr.) .(Hofmann Ber. 1890 23 3717 gives 228-229O) (Found C=72.8; H=6-5; N=9.9.Calc. C=72*55; H=6*1; N = 10.0 per cent.). Methyleneaminoacetonitrile and Aminoacetonatrale. Methyleneaminoacetonitrile was prepared substantially by the process described by Klages (Ber. 1903 36 1511). It was found, however that the time of addition of the cyanide could be materially decreased without detriment to the yield so long as the temperature was maintained below 100 during the first half of the addition and below 1 5 O during the second. It was readily converted into aminoacetonitrile hydrochloride by shaking with the calculated quantity of N-alcoholic hydrogen chloride the yield amounting t o 90 per cent. of the theoretical. Reduction of A ininoacetonitrile Hydrochloride. W i t A Sodium and Alcohol .-Twenty grams of the hydrochloride were added to 60 C.C.of alcohol in which 5 grams of sodium had previously been dissolved 80 grams of sodium were added and, after the first violent reaction had ceased the mixture was heated on the water-bath 250 C.C. of alcohol being gradually added. After about an hour most of the alcohol was removed by distilla-tion a little 90 per cent. alcohol added to ensure that the sodium was all used water added and the mixture transferred to a copper flask and distilled to dryness under somewhat diminished pressure. The distillate was boiled to remove ammonia neutralised with hydrochloric acid and concentrated to crystallisation. The yield of ethylenediamiae dihydrochloride varied from 25 to 33 per cent. of the theoretical. W i t h Iron and Hydrochloric Acid.-Five grams of aminoaceto-3 ~ 1356 WERNER AND FEARON: nitrile hydrochloride were dissolved in 100 C.C.of water 16 grams of iron filings added and 50 C.C. of hydrochloric acid added slowly during an hour with shaking. At the end of the reaction the product was evaporated to dryness distilled from a copper flask with sodium hydroxide and the base in the distillate isolated as hydrochloride. The yield amounted to 10 per cent. of the theoretical. With Zinc and Bydrochloric Acid.-To a solution of 6.8 grams of the hydrochloride in 100 C.C. of water 30 grams of zinc were added and 70 C.C. of concentrated hydrochloric acid added as above the product being then treated as in the previous reduction. The yield of ethylenediamine dihydrochloride amounted to 25 per cent. of the theoretical. I n conclusion the author would thank Messrs. R. R. Baxter and J. A. Goodson for assistance in tJhe preparat>ion of the ethylene dichloride and ethylenedianiin e which formed' the basis of the investigation. WELLCOME CHEMICAL RESEAECH LABORATORIES, LONDON. [Received Septembar 30th 1920.