Progress in Alkaloidal Chemistry During the Year

1904.*

By H. M. Gordin.

Hydrastinine. C. Liebermann and F. Kropf have prepared anhydrohydrastinine acetone by condensing hydrastinine with acetone. The reaction is the same as with cotarnine (see this Review page 160). The anhydrohydrastinine acetone melts at a lower temperature (72°) than hydrastinine itself (116°-117°), and forms a hydrochloride and a platinum salt which were obtained by the same methods as the corresponding cotarnine compounds.

In the same way was obtained a condensation product of hydrastinine with acetophenone. The anhydrohydrastinine acetophenone is easily soluble in alcohol with fluorescence and crystallizes in prisms melting at 74°. It also forms a platinum salt.

Ber. Dtsch. Chem. Ges. 1904, 214.

J. J. Dobbie and C. K. Tinkler investigating the absorption spectra of hydrastinine and its salts in different solvents draw the following conclusions in regard to the constitution of this base:

1. In the solid state or in solution in dry ether or chloroform hydrastinine is colorless and must be assumed to have the carbinol form.

2. In the colored aqueous or alcoholic solutions the alkaloid and its salts have the ammonium hydroxide form

3. Dissolved in little alcohol the alkaloid exists in both forms, but the addition of much alcohol changes the colorless carbinol form completely to the colored ammonium form.

4. Alkalies added to the colored solutions of hydrastinine salts cause a reverse change from the ammonium form to the carbinol form.

The complete conversion of the amonium form into the carbinol form in solution by the addition of alkali can be noticed by the fact that the fluorescence of the solutions disappears completely when the transformation is complete.

The author draws the conclusion that the open chain aldehyde formula proposed by Roser for hydrastinine, not explaining these differences in the spectra, cannot be correct.

сон.

C7H402

CH2.CH2.NH.CH3

Roser's formula.

Journ. Chem. Soc. 1904, 1005.

Isopilocarpine. H. A. D. Jowett finds that upon melting isopilocarpine, C11 H16N2O2, with patassium hydrate normal butyric acid is formed, not, as previously reported, isobutyric acid.

Proc. Chem. Soc. 1904, 14.

Lupinidine. R. Willstätter and W. Marx have investigated the composition and properties of lupinidine. The conclusions arrived at are as follows:

1. Lupinidine is identical with sparteine both alkaloids having the same formula, C15H26N2, and agreeing also with regard to boiling point, specific gravity, solubilities etc.

2. The boiling point under 18 m. m. pressure is 180.5° and under 13 m. m. pressure 170.5°. The specific rotation in pure condition is [«]20°= −5.96°. Dissolved in 99% alcohol (C=14.206) the specific rotation is [«]20°= −16.41°.

3. Judging from the empirical formula and the behavior towards potassium permanganate there cannot be any double bindings in sparteine and the molecule must be made up of one aromatic ring or four saturated rings.

4. There are only three alkaloids present in the various lupinus plants: lupinine, C10H19N2, in Lupinus luteus and Lupinus niger,

sparteine, C15H26N2 in Lupinus luteus and Lupinus niger, and lupanine C15H24N2O in Lupinus albus, Lupinus angustifolius and Lupinus perennis.

5. Sparteine is very difficultly volatilized with steam, has a very feeble odor, is easily soluble in benzol or ligroin and does not form a hydrate. On titrating sparteine with acids the amount of acid consumed varies with the concentration of the alkaloidal solution.

The statements of other investigators with regard to these points were found to be incorrect, Ber. Dtsch. Chem. Ges. 1904, 2351.

Lupinus Alkaloids. According to E. Schmidt the alkaloids of Lupinus perennis consist chiefly of d-lupanine, C15H24N2O, mixed sometimes with oxylupanine, C15H24N2O2, and sometimes with other alkaloids. Seeds obtained from the same source and apparently having the same morphological characteristics have yielded at different times different alkaloids.

On the suggestion of E. Schmidt some analyses and molecular weight estimations of lupinine were carried out by G. Fr. Bergh. The results obtained corroborated the statements of Willstätter and Fourneau with regard to this alkaloid (Arch. d. Pharm. 240, 335.) Arch. d. Pharm. 1904, 409.

G. Fr. Bergh has investigated the alkaloids of Lupinus perennis. The alkaloids were obtained by the following method. The coarsely powdered seeds were extracted with water acidulated with hydrochloric acid, the liquid concentrated and the extract after making it alkaline with sodium hydroxide extracted first with ether and then with chloroform. In this way an ethereal and a chloroform extract were obtained which were worked up separately.

On distilling off the ether from the ethereal extract and treating the residue with a large amount of ether crystals of oxylupanine separated out on the walls of the vessel and a yellowish red sticky mass settled at the bottom. This mass could not be made to crystallize. From the ethereal mother liquor some d-lupanine was obtained.

The chloroform extract after distilling off the solvent was mixed with magnesium oxide, the mass thoroughly dried and then extracted for a month with ether in a Soxhlet apparatus. On distilling off the ether the residue was treated again with a large amount of cold ether which removed some d-lupanine and the remaining oxylupanine recrystallized from a mixture of acetone and water. From fifteen kg.

of the seeds 15 grams oxylupanine and 200 grams d-lupanine were obtained.

Oxylupanine, C15H24N2O2+ 2H2O, forms colorless transparent rhombic prisms and melts air dried at 76°-77°; dried at 50°-60° in vacuum it melts at 172°-174°. When dried under ordinary pressure at 100° the alkaloid becomes brown. The specific rotation is 64.12. The alkaloid forms a di- and a mono-hydrochloride. When the dihydrochloride is melted it is changed to the monohydrochloride. Oxylupanine also forms a hydriodide, a chloraurate and a chloroplatinate. The salts of oxylupanine crystallize less readily than those of d-lupanine.

The two alkaloids can be distinguished from each other by their behaviour with bromine water; with which d-lupanine gives a fine precipitate which on stirring disappears, whereas oxylupanine gives a flocculent amorphous precipitate which does not disappear on stirring.

Monoacetyl oxylupanine C15H23N2O2(CH3CO) was prepared by boiling oxylupanine with acetic anhydride. For analysis it was converted into its crystalline chloraurate.

Oxylupanine iodomethylate, C15H2402N2.CH3I+H2O, was prepared by heating the alkaloid with excess of methyliode in methylalcoholic solution. After converting the iodomethylate into the chloromethylate the latter was converted into the gold and platinum

salts.

On heating oxplupanine with red phosphorus and hydriodic acid it is converted into lupanine.

d-Lupanine forms a hydriodide which crystallizes with two molecules of water of crystallization. The salt cannot be dried under ordinary pressure without decomposition and loses its water of crystallization only when dried in vacuum to 100° for 24 hours. An iodomethylate was prepared by treating d-lupanine in methylalcoholic solution with methyliodide. From the mono-iodomethylate the corresponding gold and platinum salts were prepared.

Other bases could not be found in the seeds.

Arch. d. Pharm. 1904, 242.

Morphine. C. Reichard has found the following color reactions for morphine: On warming some morphine or its sulphate with a little sulphuric acid to which some sodium, arsenite sodium arsenate, antimony trichloride or stannous chloride had been added a perman

ent red color is produced. Several other alkaloids tried did not give this reaction.

On adding a trace of morphine or any of its salts to a concentrated solution of bismuth chloride an intensely yellow color is produced. Many other alkaloids also give color reactions with bismuth chloride but these are more or less different from the morphine reaction. Atropine also gives a yellow color with bismuth chloride but the color disappears on warming the liquid.

Cocaine gives no color reaction with bismuth chloride unless strong sulphuric acid be present but even then the color disappears on warming the liquid.

With a very dilute solution of cobalt nitrate, morphine gives no color whatever, but in presence of concentrated sulphuric acid a deep red or brown-red color is produced which slowly changes at first to a yellowish-red and then to a very permanent brownish-yellow.

Atropine gives with cobalt nitrate in the absence of strong sulphuric acid a grass green color.

With cerium dioxide (obtained by heating cerium nitrate) and sulphuric acid morphine gives on standing at ordinary temperature a blue violet color. Atropine and cocaine do not give the reaction. Brucine brought in contact with cerium dioxide and sulphuric acid in the cold gives a reddish or a reddish-yellow color which after a short while changes to an intense yellow. Chem. Ztg., 28, p. 1102.

L. Knorr continues his investigations on the constitution of morphine. It is known that the three alkaloids morphine, codeine and thebaine are derivatives of 3, 4, 6-trioxyphenanthrene (See this Review 1904 Prog. in Alk. Chem. during 1903)