concentrated on a water-bath to a small bulk, when a very dark brown, thick liquid was obtained. This liquid readily reduced Fehling's solution, gave an abundant green-black precipitate with ferric chloride, and an intense yellowish-brown color with alkalies. It apparently contained a considerable amount of tannin, but nothing crystalline.

The filtrate from the precipitate produced by basic lead acetate was deprived of lead by hydrogen sulphide, filtered, and the filtrate concentrated on a water-bath to a small bulk. The clear syrupy liquid thus obtained had a yellowish-brown color, and contained a large amount of glucose, for a portion of it when treated with a solution of phenylhydrazine acetate readily yielded a crystalline osazone melting at 205° C. Nothing crystalline separated from this liquid, even after standing for several weeks. It has been stated by Thal* that eriodictyon contains the glucoside ericolin," and indeed in such an amount that an extract from five small leaves of the plant, when heated with a few drops of dilute sulphuric acid, not only developed an exceptionally strong odor of its hydrolytic product "ericinol," but that "an oily layer of ericinol appeared on the surface of the liquid, which could be detected even with the naked eye." This, however, is followed by the significant remark that "as he experienced much difficulty in his investigations on account of the readiness with which the ericolin became decomposed, he cannot regard them as exhaustive, and must admit that they are possibly not free from errors."

Notwithstanding the extremely unsatisfactory character of the evidence which has been adduced for the existence of the so-called "ericolin" in eriodictyon, and the equally indefinite chemical character of ericolin itself, it was considered of interest to ascertain whether the above-mentioned aqueous liquid, when heated with dilute sulphuric acid, was capable of yielding anything corresponding to the hydrolytic product of ericolin, which, under the name of " ericinol," has been described as a volatile, colorless, oily liquid, possessing a peculiar not unpleasant odor, and becoming dark brown on exposure to the air. Accordingly, about one-third of the purified, concentrated aqueous liquid, obtained as above described, was diluted with water, and such an amount of sulphuric acid added as to correspond to about 5 per cent. of the weight of liquid employed. This mixture was first boiled for 5 hours in a flask provided with a reflux condenser, when a quantity of black, resinous matter separated. Steam was then passed through the liquid until all volatile substances were completely removed, when a clear distillate, having an acid reaction and an odor recalling that of furfural, was obtained. The distillate was repeatedly extracted with ether, the ethereal liquid washed, dried, and the ether removed. The residue consisted of a few drops of a clear liquid, which contained a little acetic acid, and had an odor suggestive of furfural. With

*Pharm. Zeit. für Russland, 1883, xxii, p. 257.

aniline it instantly afforded the intense carmine-red color which is characteristic of furfural when brought in contact with this base.* It also afforded an immediate precipitate with phenylhydrazine acetate. This odorous volatile substance therefore appeared to consist essentially of furfural, which was doubtless produced by the action of the sulphuric acid on the carbohydrates contained in the liquid.

From the results of the preceding experiment it appears highly probable that the peculiar odor observed by Thal, and attributed by him, as well as by previous investigators, to the so-called "ericinol," was really due to furfural, which would obviously be produced from a great variety of plant extracts when heated with a dilute mineral acid. The fact that "ericolin" has never been obtained in any other form than an amorphous, brown powder or a sticky extract, in which even the complete absence of sugar does not seem to have been proved, and that its assumed product of hydrolysis, "ericinol," has apparently never been chemically characterized or submitted to analysis, lends further support to the view that no definite glucoside is known to exist which is entitled to the specific designation of ericolin. It is certain that there is at present no known constituent of eriodictyon leaves to which this name should be applied.

The liquid from which the furfural had been removed by distillation was of a brown color, and contained about 20 Gm. of a hard, black resin. This was found to be insoluble in the usual organic solvents, but dissolved slowly in alkalis, and appeared to contain nothing crystalline. The clear aqueous liquid from which the resin had been separated was repeatedly extracted with ether, but this removed only a trace of a brown-colored syrup. The sulphuric acid contained in the aqueous liquid was then removed by means of barium hydroxide and filtering, and from the sugar contained in the filtrate an osazone was prepared. As the latter melted at 206° C., it was evidently glucosazone, and indicated that by the treatment with sulphuric acid no appreciable amount of a sugar had been formed which differed from that contained in the original aqueous liquid.

Examination of the Yellow Substance (B).

This substance consisted of a slimy mass of apparently semi-solid particles possessing a bright yellow color, together with a little green resinous matter, and amounted to about 10-15 Gm. It was very sparingly soluble in hot, and insoluble in cold water, and could not be crystallized from any solvent. As it evidently represented a mixture of substances it was dissolved in ether, and the ethereal solution, after being washed with water, extracted with successive portions of sodium carbonate solution, in the same manner as described in the treatment of the ethereal extract of the aqueous liquid (A). By this means the substance was found to consist, to

* Ber. d. deutsch. chem. Ges., 1887, 20, p. 541.

a large extent, of homo-eriodictyol, which separated in the form of its mono-sodium compound, together with a trace of eriodictyol, a small amount of a brown and a green resinous substance, both of an acidic nature, and several grams of a green resin, which was inscluble in sodium carbonate solution.

It has already been noted that some years ago Quirini (loc. cit.) obtained from eriodictyon a substance to which he gave the name of “eriodictyonic acid." Although this was described as forming yellow plates, which melt at 86-88° C., it was evidently a mixture, as from its method of preparation it must have consisted to a large extent of homo-eriodictyol, which melts at 223° C.

Examination of the Resins (C).

The cake of soft, dark-green, resinous matter, which had been separated from the aqueous liquid subsequent to the steam distillation, as previously described, was heated on a water-bath until dry, when it weighed 627 Gm., corresponding to 29.2 per cent. of the weight of air-dried leaves. It was then intimately mixed with prepared sawdust, and successively extracted in a Soxhlet apparatus with the following solvents. The extracts thus obtained were dried at 100° C., until of constant weight.

This was a soft, fatty solid, of a dark greenish color, and amounted to 34.7 Gm. When heated, it melted to a clear, dark green oil. It was dissolved in about 500 cc. of boiling ether, and the solution cooled by immersing the flask in cold water. Several grams of a solid substance then separated, which was removed by filtration, washed with cold ether, and allowed to dry, when it was obtained as a pale greenish, amorphous powder. When heated, it melted at 70-75° C., and, on re-solidifying formed a mass resembling paraffin and having the properties of a hydrocarbon. The whole of the substance was then brought into a distilling flask, and distilled under a pressure of 8 Mm., when a clear distillate was obtained, which, on cooling, solidified to a crystalline mass. It was subsequently crystallized from ethyl acetate, when it was obtained in small, colorless plates, which, after drying, melted at 74-5-75° C. On analysis it gave the following result:

0.1564 gave 0.4858 CO, and 0.2071 H2O. C = 84.7 ; H 14.7. C3H72 requires C = 85.4; H

14.6 per cent.

The substance was thus identified as pentatriacontane, which had previously been isolated by the authors from Aethusa Cynapium, Linn.*

The ethereal solution of the petroleum extract, from which the pentatriacontane had been separated by filtration, was then shaken with sodium carbonate solution. This caused the precipitation of an amorphous, pale green substance, which was separated from the ethereal solution, together with the alkaline, aqueous liquid. It was removed from the alkaline liquid by filtration, washed first with ether, then with water, and dried on a tile. As thus obtained, it had the appearance of a dried soap, contaminated with a little resinous matter. It was then dissolved in hot, dilute alcohol, the solution acidified with sulphuric acid, and the mixture cooled and extracted with ether. The ethereal liquid, which had a green color, was washed with water, dried, and the ether removed. The residue thus obtained was dissolved in hot ethyl acetate, and the solution allowed to cool, when a substance of a pale green color separated in the form of nodules, which possessed no definite crystalline form. This solid was collected on a filter, washed with ethyl acetate, and dried, when it melted at 78° C. Although its sharp melting-point indicated that it was a fairly pure substance, it would not separate in a crystalline condition from any solvent, and it was therefore distilled under diminished pressure. A distillate was thus obtained which, after dissolving in hot ethyl acetate, and allowing the solution to cool, yielded the substance in the form of glistening plates. These were removed by filtration, and dried, when they melted at 79° C.

0.0749 gave 0.2167 CO, and 0.0923 H2O. C = 78.9; H= 13.6. C2H5O2 requires C

54

=

=

79.0; H 13.2 per cent.

The properties and analysis of this substance confirmed its identity with cerotic acid, which existed in the leaves in a free state.

The substance contained in the original ethyl acetate mother liquors from this cerotic acid was distilled under diminished pressure, when it afforded a distillate which, after several recrystallizations from ethyl acetate, melted between 71 and 74° C., and was apparently a mixture of acids. The alkaline aqueous liquid from which the sodium salts of the above-mentioned acids had been separated by filtration was found to contain no fatty acids.

The ethereal solution of the petroleum extract, from which the pentatriacontane had been obtained, and which had been freed from acids by shaking with sodium carbonate solution, was found to contain nothing soluble in dilute mineral acids. The ether was therefore removed, and the residue hydrolysed by boiling it for 3 hours with an alcoholic solution of 20 Gm. of potassium hydroxide, when it was observed that a small amount of ammonia was evolved. The alcohol was then removed, the

*Journ. Amer. Chem. Soc. 1905. 27, p. 1468.

residue poured into water, and the mixture repeatedly extracted with ether. The ethereal liquid, after being washed and dried, was concentrated to about 100 Cc., and allowed to cool, when a considerable quantity of a crystalline substance separated. This was collected on a filter, then distilled under a pressure of 10 Mm., and the distilled product crystallized from ethyl acetate, when it was obtained in the form of extremely handsome, colorless plates. These crystals, after being dried on a tile, melted sharply at 65.2° C., and this melting point was not altered by further recrystallization.

0.0998 gave 0.3110 CO, and 0.1311 H2O. C-85.0; H=14.6.

CsHe requires C-85.3; H=14.7 per cent.

62

This substance is obviously a hydrocarbon. As its melting-point lies between that of nonacosane, CH60 (m. p. 63.5-64° C.), and hentriacontane, CH (m. p. 68.1° C.), and as it also differs in appearance from the latter, it is probable that it is triacontane, CH62. If this supposition be correct, it is apparently the first time that this hydrocarbon has been obtained from any source.

The substance contained in the ethereal mother-liquors from this hydrocarbon was fractionally distilled under 10 Mm. pressure, when the lower boiling portion, on fractional crystallization, yielded a further quantity of triacontane, together with a very small amount of a substance melting at 136-137° C., which afforded the color reaction characteristic of the phytosterols. The fraction of higher boiling-point yielded a substance which melted between 66 and 68° C., and was apparently a mixture of triacontane and pentatriacontane. The total amount obtained of these hydrocarbons was about 15 Gm., which corresponds to 0.7 per cent. of the weight of air-dried leaves.

The alkaline, aqueous liquid from which these neutral substances had been removed by means of ether contained a small amount of a sparingly soluble potassium salt in the form of a flocculent precipitate. This was removed by filtration and decomposed by sulphuric acid. The liberated acid was first distilled under diminished pressure, and then crystallized from ethyl acetate, when it was found to be identical with the cerotic acid previously obtained. The filtrate from this potassium cerotate was acidified with sulphuric acid and distilled in steam. The distillate contained no oily drops, but had an acid reaction, and was found to contain both formic and butyric acids, which were identified by means of their barium salts. The non-volatile acids contained in the steam distillation flask were extracted by ether. On evaporating the ethereal solution a dark green, sticky residue was obtained, which was redissolved in a small quantity of warm ether, a large volume of warm, light petroleum added, the mixture well stirred, and the clear liquid decanted from a soft, dark green resin which was only sparingly soluble in light petroleum. The petroleum was removed from this liquid, the residue distilled under diminished pressure,