a
I
ES,~SlIItlL-ASII.ISE.
aoluble i n bcnzole, ulilorofot*in, ether aiid alcohol, insoliible in bisulphide of carbon. I t coiild not be crystallized from any one of these solvc~nts,1101' sublimed without decomposition. Finally, after many iinsuccessfal trials, the following method was foiind t o afford the sylicliiir-acrolein i n a state of pnrity. Iristead of distilliiig the acrolein directly into the \ylidine, the acroleiH i n slight excess was added to a11 alcoholic 5olution of the latter body. The mixture was then digehted for sel-eral hour. upon a v-ater-bath, until the smell of acrolein hail a1ino.t entirely disappeared The resulting mass, which \iat of R dark ret1 color and extremely .;tick?., IWS freed as far as possible froiii t h c ~iirroundingliqnicl, and bvilecl a niiniber of hours with water The longer it was I)oileci wit11 water the less sticky it becaine, until finally it conld be broken into small lunips and reinoved from the flask. These l n m p ~were theii pnlvei-ized in a mortar, returned to the flask and boiled with alcohol nnder a return cooler. This second boiling wit11 alcohol had the result of taking out a large amount of the coloring-matter, but at the tame time of making the mass sticky as before. The boiling wit11 water and afterwards with alcohol had therefore to be repeated alternately many times, until at last a product w a t obtained quite insoluble in alcohol, and which was left hard aiid brittle after boiling with that solvent. The purified body, which was of a reddish-yellow color, could not be made to crystallize from any solvent, nor did it yield crystallizable derivatives. As before stated, bromine enters into combination with it with great energy. Sitric acid converts it into a pastry mass that cannot be sublimed or crystallized. The analysis gave N 8.49 per cent., (theoretical 8.8 per cent.) and showed that the substance was xylidine-acrolein, found according to the equation. C l R H 1 3 N = C ~ H l+, X C,IE,O-H,O
CF,KANTHOL-ANILIXE, (ENANTI-IOL-XYLIDINE AND (EXAN THOL-NAPHTHYLAMINE. HY AIJIERTR. LEEDS. CEnanthol was prepared from castor oil by heating the oil in partial vacuo a t a temperature of about 150". The flask containing the castor oil was connected with a Liebig's condenser. As tho volatile substances were distilled off they were condensed and
aEXANTHOL-ANILINE.
3
collected in a receiver connected with a Bunsen pump. The aenantho1 was purified by subjecting the distillate to a second distillation and collecting that portion that came over a t 1 5 4 O . After two or three such treatments the aenanthol was obtained in a state of purity sufficient for the purposes contemplated in this article. In preparing the following compounds molecular proportions were in each case used, 70 grms. of aenanthol and 57 grms. of aniline were gradually mixed together. The mixture became very hot ; .the temperature rising from 27" to 89". The resnlting liquid mass is very mobile, much more so than either aniline or aenanthol. I n making the cenanthol-xylidine 70 grms. of aenanthol were added to 74 grms. of xylidine. The temperature rose from 27" to 85", and the resulting product was also extremely mobile. 70 grms. of aenanthol were poured 011 to 88 grms. of naphthylamine. The latter melted very rapidly and after combination had taken place the temperature of the liquid had risen to 75'. All €he three compounds were heated on the water bath iinder the return cooler for six hours to ensure complete combination. At the end of that time the flasks containing the three portions were removed and small portions taken from each which were subjected to distillation. The distillate in each case consisted of an uncombined base and some product of decomposition, The method of purification by distillation was thus far abandoned. It was next found that the subfltances could not be purified by any solvent, since the aenanthol-aniline, aenanthol-xylidine, and aenanthol-napthylamine are as soluble in alcohol, ether, benzol, chloroform and carbon bisulphide, as their respective bases. Eventually the most suitable process proved to be the following : Each of the three compounds was dissolved in about 150 grms. of glacial acetic acid and heated several hours on the water bath to ensure complete combination between the acetic acid and the excess of the bases aniline, xylidine, and napthylamine. When the bases were completely changed into their respective acetates, a large excess of water was added which threw down the cenanthol-aniline, etc., while the acetates remained in solution. The percipitated substances were thoroughly washed with water until every trace of acetic acid had disappeared. The three compounds were then dried at a temperature of 100". A portion of each of the three compounds was preserved for analysis while the rest was subjected t o distillation.
4
R E S I D r E FRO31 T H E DISTILLATIOX O F CASTOR 011..
The cnanthul-aniline as finally piirified is a reddifih-colored mobile liqiiiil, having an agreeaide ethereal odor, ahicli resembles neither aniline or cenanthol. Its analys:' yielded C 75.10 per cent., H 10.28 per cent., corresponcling t o the furmula, Cl13 1.1, I?-o=C, H7nTC, lI,,O, i n which C is 75.36 per cent., and H 10.14 per ceilt. The cenanthol-s!-lidine closely resembles enanthol-aniline in allpearmice and sinell. Its formnla was found to be C I SII?, xo=cFI{), N c': II,, 0. Found.
c . ,. . . . . . . . ..;rJ.o4
Calculated.
76.50 10.64 5.96
H . . . . . . . . . . ..10.00
s.. . . . . . . . . . 5.93 T h e acuanthol-napht hy Janiine resembles t lie two preceding conipounds in its appearance and properties, bot was htill more prononnced in its ethereal odor, n-hich resembled that of pineapple. Its forniula ib Cl, H,, 9 0 = C l , H, h' C; H,,O. Fouud .
Cn!culRted.
C . . . . . . . ..50.03 ljer cent.
79.35 per cent. 8.95 '' It will be noted that all tlieke conipoiinds formed synthetically by the direct union of one inolecnle of ananthol with oiie molecule of the aromatic base, no water being eliminated, hare ,z correspondingly elevated heat of combination. They are stable bodies, and were capable of sublimation, with only partial decomposition. The snblimates n-ere not crystalline, and were identical in physical and chemical properties with tlie original substances, yielding on analysis the same formule.
H . . . . . . . . . . . . 9.50
SOLID R E S I D U E FROM THE DISTILLATION O F CASTOR OIL IN VACUO.
BY ALBERT R. LEEDS. I n making enanthol from castor oil there is always left in the flask a highly elastic, sticky substance, which was first investigated by Stansk (Jour. Pr.Chiz., Vol. 63, p. 138.) Although Stanck's results have c e w r been accepted as conclusive, yet no one has reinvestigated the nature of this body, for which reasons I was induced to niake the following research.
