[CONTRIBUTION FROM T E E SECCI6N C)RGANOTERAPIA, INSTITUTO BACTERIOL6GIC0, DIRECCI6N
NACIONAL DE SALUD
PGBLICA]
STUDIES ON ARGENTINE PLANTS. VI. HYDROXYLUPANINE IN LUPIWUB HILARIANUS VENAXCIO DEULOFEXJ
AND
ALEJANDRO GATTI
Received January 9, 1946
Lupinus hilarianus is an Argentine species that grows in some zones of the flat part of the country. From seeda collected from plants growing around the city of Santa FB, we have obtained an alkaloid that was identified by its properties and the preparation of some derivatives as hydroxylupanine. This lupinus alkaloid was first isolated from the seeds of L. polyphyllus by Bergh (1) and later by Beckel (2) from L. angustifolius. Ueno (3) showed that it mas also present in L. albus. Hydroxylupanine is the main constituent of the basic fraction of the seeds of L. hilam'anus. No other pure base could be obtained. A picrolonate was easily obtained from the alkaloid, which is interesting, as no picrate seems to have been described, nor were we able to prepare one. The picrolonate will be useful for identification. EXPERIMENTAL
The seeds employed were air dried; 1?80 g. of seed was finely ground and extracted by covering with 4 liters of 96% alcohol, leaving at room temperature for 48 hours with occasional shaking. The extraction was repeated twice, the last time with heating at 60" for one hour. The ethanolic extracts were united and concentrated to 500 cc. in a vacuum (bath temperature 70"). A syrup waa obtained that was diluted with water to lo00 cc. and evaporated again t o 500 cc. t o eliminate all the alcohol. Ten cubic centimeters of concentrated hydrochloric acid ( d , 1.19) was then added t80the new residue, and a small amount of precipitate filtered and washed with dilute hydrochloric acid (1:lO). The combined acid solutions were well extracted with ether. This ether extract was discarded. The solution was then made alkaline with 20% sodium hydroxide solution and extracted eight times with 60-70 cc. of chloroform. The united chloroform extracts were well dried with sodium sulfate, evaporated to dryness and kept in a desiccator for some days. The residue, well dried, was then dissolved in acetone, a small insoluble portion filtered, evaporated again, the new residue dissolved in .absolute ethanol, and evaporated. The new syrup (13.2 6.) was very viscouEi, and yielded crystals on standing in the desiccator. I n several days the whole mass became crystalline. The crystals were suspended in ether, which dissolved a colored syrup, and filtered. The yield was 7.5 g., m.p. 165". After recrystallization from benzene, white prisms were obtained that melted at 85", and after drying, a t 172-173"; soluble in watJer,chloroform, and acetone; slightly soluble in cold ether and benzene. The literature (4)gives for hydrated hydroxylupanine the m.p. 76-77', and for the anhydrous base 172-174"; specific rotation [ a h +66.3". Observed for this sample, [a],, 64.12" (water, c = 1.6). Anal. Calc'd for CI~HZANZO~: C, 68.18; I€,9.09; N, 10.60. Found: C, 68.23; H, 9.02; N, 10.71. Hydrochloride. This waa prepared by treating a small amount of the base suspended in methanol with hydrochloric acid and healing. On cooling, white prisms melting a t 275" were obtained; Bergh gives the m.p. 273". Aurichloride. A small amount of the alkaloid was dissolved in dilute hydrochloric acid 179
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DEULOFEU AND GATTI
(1 :lo) and treated with a 5% solution of gold chloride. A crystalline precipitate of yellow prisms was obtained that melted a t 210"; Bergh gives 205-206". Picrolonate. A solution of 100 mg. of hydroxylupanine in 3 cc. of absolute ethanol was treated with 140 mg. of picrolonic acid, and the suspension heated to boiling. The picroIonic acid dissolved, and the picrolonate crystallized out immediately. After recrystallization from absolute ethanol, yellow rhombic crystals melting at 174-175" were obtaioed. A n d . Calc'd for CloHsN*Or.CljH,aN20,: N, 15.90. Found: N, 15.56. SUM-MARY
Hydroxylupanine has been found t o be the major alkaloid from the seeds of the Argentine Lupinus hilarimus. Its picrolonate has been prepared. BUENOSAIRES, ARGENTINA.
REFERENCES (1) BERGH,Arch. Pharm., 242,416 (1904);Chem. Zentr., 11, 782 (1904). (2) BECKEL, Arch. Pharm., 248,451 (1910);Chem. Zentr., 11,1307 (1910). (3) UENO,J. Pharm. SOC.Japan, 60,435 (1930);Chem. Abstr., 24, 4043 (1930).
