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tions with alcohol and ether. The aqueous and alcoholic solutions manifest strong alkaline reaction. Conia has a very strong, pungent, repulsive odor, which affects the head, a most acrid and disagreeable taste, and very poisonous properties.

2. Conia is a strong base; it accordingly precipitates metallic oxides from their solutions, in a similar way to ammonia, and forms salts with acids. The salts of conia are soluble in water and in spirit of wine, but nearly insoluble in ether. Hydrochlorate of conia crystallizes readily; the smallest quantity of this base, brought in contact with a trace of hydrochloric acid, yields almost immediately a corresponding quantity of non-deliquescent rhombic crystals (Tu. WERTHEIM). The solutions of the salts of conia turn brownish upon evaporation, with partial decomposition of the conia. The dry salts of conia do not smell of the alkaloid; when moistened, they smell only feebly of it; but upon addition of solution of soda, they at once emit a strong conia odor. When salts of conia are distilled with solution of soda, the distillate contains conia. On neutralizing this with oxalic acid, evaporating to dryness, and treating the residue with spirit of wine, the oxalate of conia formed is dissolved, whilst any oxalate of ammonia that may be present is left undissolved. As conia is only sparingly soluble in water, and dissolves with still greater difficulty in solutions of alkalies, a concentrated solution of a salt of conia turns milky upon addition of solution of soda. The minute drops which separate unite gradually, and collect on the surface.

3. If an aqueous solution of a salt of conia is shaken with solu tion of soda and ether, the conia is dissolved by the ether. If the latter is then allowed to evaporate on a watch-glass, the conia is left in yellowish-colored oily drops.

4. Concentrated nitric acid imparts a fine blood-red tint to conia; sulphuric acid, a purple-red color, which subsequently turns to olive-green.

5. Terchloride of gold produces a yellowish-white precipitate, insoluble in hydrochloric acid; chloride of mercury, a copious white precipitate, soluble in hydrochloric acid. Bichloride of platinum does not precipitate aqueous solutions of salts of conia, the conia compound corresponding to ammonia-bichloride of platinum being insoluble in spirit of wine and ether, but soluble in water. 6. To solution of iodine in iodide of potassium and water, and to solution of tannic acid, conia comports itself the same as nicotina.

7. Chlorine water produces in a mixture of water and conia a strong, white turbidity.

8. If an aqueous solution of conia is mixed with a solution of albumen, the albumen coagulates. Aniline is the only other vola tile vegeto-alkali which shows this reaction.

The volatile alkaloids are easily recognised when pure; the great object of the analyst must accordingly always be to obtain them in that state. The way of effecting this is the same for nicotina as for conia, and has already been given in the foregoing paragraphs, viz., to distil with addition of solution of soda, neutralize with oxalic acid, evaporate, dissolve in alcohol, evaporate the solution, treat the residue with water, add solution of soda, shake the mixture with ether, and let the latter evaporate spontaneously. Conia is distinguished from nicotina chiefly by its odor, its sparing solubility in water, and its comportment with chlorine water, and bichloride of platinum.

II. NON-VOLATILE ALKALOIDS

The non-volatile alkaloids are solid, and cannot be distilled over with water.

FIRST GROUP.

NON-VOLATILE ALKALOIDS WHICH ARE PRECIPITATED BY POTASSA OR SODA FROM THE SOLUTIONS OF THEIR SALTS, AND REDISSOLVE READILY IN AN EXCESS OF THE PRECIPITANT.

Of the alkaloids of which I propose to treat here, one only belongs to this group, viz.,

MORPHIA, OR MORPHINE (C34 H19 N OG Mo).

§ 235. +

1. Crystallized morphia (Mo + 2 aq.) usually appears in the form of colorless, brilliant four-sided prisms, or, when obtained by precipitation, as a white crystalline powder. It has a bitter taste, and dissolves very sparingly in cold, but somewhat more readily in boiling water. Of cold alcohol it requires about 90 parts by weight for solution; of boiling alcohol from 20 to 30 parts. The solutions of morphia in alcohol as well as in hot water manifest distinctly alkaline reaction. This alkaloid is nearly insoluble in ether; it dissolves in amyl-alcohol in the cold, but more freely with the aid of heat. At a moderate heat the crystallized morphia loses the two equivalents of water.

2. Morphia neutralizes acids completely, and forms with them the SALTS OF MORPHIA. These salts are readily soluble in water and in spirit of wine, but insoluble in ether and amyl-alcohol; their taste is disagreeably bitter. Most of them are crystallizable.

3. Potassa and ammonia precipitate from the solutions of salts

+

of morphia-generally only after some time-Mo + 2 aq., in the form of a white crystalline powder. Stirring and friction on the sides of the vessel promote the separation of the precipitate, which

redissolves with great readiness in an excess of potassa, but more sparingly in ammonia. It dissolves also in chloride of ammonium and, though with difficulty only, in carbonate of ammonia.

4. Carbonate of potassa and carbonate of soda produce the same precipitate as potassa and ammonia, but fail to redissolve it upon addition in excess. Consequently if a fixed alkaline bicarbonate is added to a solution of morphia in caustic potassa, or if carbonic

+

acid is conducted into the solution, Mo+ 2 aq. separates,-especially after previous ebullition-in the form of a crystalline powder. A more minute inspection, particularly through a magnifying glass, shows this powder to consist of small acicular crystals; seen through a glass which magnifies 100 times, these crystals present the form of four-sided prisms.

5. Bicarbonate of soda and bicarbonate of potassa speedily produce in solutions of neutral salts of morphia a precipitate of hydrat ed morphia, in the form of a crystalline powder. The precipitate is insoluble in an excess of the precipitants. These reagents fail to precipitate acidified solutions of salts of morphia in the cold.

6. The action of strong nitric acid upon morphia or one of its salts, in the solid state or in concentrated solutions, produces a fluid varying from red to yellowish-red. Dilute solutions do not change their color upon addition of nitric acid in the cold, but upon heating they acquire a yellow tint.

7. If morphia or a compound of morphia is treated with pure concentrated sulphuric acid, and heat applied, a colorless solution is obtained; if, after cooling, 8 to 20 drops of sulphuric acid mixed with some nitric acid are added, and 2 or 3 drops of water, the fluid acquires a violet-red coloration (gentle heating promotes the reaction); and if from 4 to 6 clean lentil-sized fragments of binoxide of manganese are now added, or a fragment of chromate of potassa (OTTO), the fluid acquires an intense mahogany-brown color. If the fluid is then diluted with 4 parts of water, properly cooled in a test tube, and ammonia added until the reaction is almost neutral, a dirty-yellow color makes its appearance, which turns brownish red upon supersaturation with ammonia, without depositing an appreciable precipitate (J. ERDMANN).

8. Neutral sesquichloride of iron imparts to neutral solutions of salts of morphia a beautiful dark blue color, which disappears upon the addition of an acid. If the solution contains an admixture of animal or vegetable extractive matters, or of acetates, the color will appear clouded and less distinct.

9. If iodic acid is added to a solution of morphia or of a salt of morphia, IODINE separates. In concentrated aqueous solutions the

* Mix 6 drops of nitric acid of 1:25 sp. gr. with 100 cubic centimetres of water, and add 10 drops of this mixture to 20 grammes of pure concentrated sulphuric acid

separated iodine appears as a kermes-brown precipitate, whilst tc alcoholic and dilute aqueous solutions it imparts a brown or yellow ish-brown color. The addition of starch-paste to the fluid, no mat ter whether made before or after that of the iodic acid, considerably heightens the delicacy of the reaction, since the blue tint of the. iodide of starch remains still perceptible in exceedingly dilute solutions, which is not the case with the brown color imparted by iodine. As other nitrogenous bodies (albumen, caseïne, fibrine, &c.) likewise reduce iodic acid, this reaction has only a relative value; however, if ammonia is added after the iodic acid, the fluid becomes colorless if the separation of iodine has been caused by other substances, whilst the coloration becomes much more intense if it is owing to the presence of morphia (LEFORT).*

SECOND GROUP.

NON-VOLATILE ALKALOIDS WHICH ARE PRECIPITATED BY POTASSA FROM THE SOLUTIONS OF THEIR SALTS, BUT DO NOT REDISSOLVE TO A PERCEPTIBLE EXTENT IN AN EXCESS OF THE PRECIPITANT, AND ARE PRECIPITATED BY BICARBONATE OF SODA EVEN FROM ACID SOLUTIONS, if the latter are not diluted in a larger proportion than 1: 100; Narcotina, Quina, Cinchonia.

+

a. NARCOTINA, or NARCOTINE (C16 H2, NO1 = Na).

$236. ᅡ

16

1. Crystallized narcotina (Na + aq.) appears usually in the form of colorless, brilliant, right rhombic prisms, or, when precipitated by alkalies, as a white, loose, crystalline powder. It is insoluble in water. Alcohol and ether dissolve it sparingly in the cold, but somewhat more readily upon heating. Solid narcotina is tasteless, but the alcoholic and ethereal solutions are intensely bitter. Narcotina does not alter vegetable colors. At 338° F. it fuses, with loss of 1 eq. of water.

2. Narcotina dissolves readily in acids, combining with them to salts. These salts have invariably an acid reaction. Those with weak acids are decomposed by a large amount of water, and, if the acid is volatile, even upon simple evaporation. Most of the salts of narcotine are amorphous, and soluble in water, alcohol, and ether; they have a bitter taste.

* LEFORT (Zeitschrift f. Anal. Chem. I., 134) recommends the following method or the detection of small quantities of morphia: moisten strips of very white unsized paper with the morphia solution, dry, and repeat the operation several times, so as to ensure absorption by the paper of a tolerably large quantity of the fluid; the dried paper contains the morphia in the solid state, most finely divided. Nitric acid, ses quichloride of iron, and iodic acid and ammonia will readily and with positive dis tinctness show the characteristic reactions on paper so prepared.

3. Pure alkalies, and alkaline carbonates and bicarbonates, imme +

diately precipitate from the solutions of salts of narcotine Na + aq. in the form of a white powder, which, seen through a lens magnifying 100 times, appears an aggregate of small crystalline needles. The precipitate is insoluble in an excess of the precipitants. If solution of narcotina is mixed with ammonia, and ether added in sufficient quantity, the narcotine which has separated upon the addition of the ammonia, redissolves in the ether, and the clear fluid presents two distinct layers. If a drop of the ethereal solution is evaporated on a watch-glass, the residue is seen, upon inspection through a lens magnifying a hundred times, to consist of small, distinct, elongated, and lance-shaped crystals.

4. Concentrated nitric acid dissolves narcotine to a colorless fluid, which acquires a pure yellow tint upon application of heat.

5. If a small quantity of pure narcotine is treated with from 4 to 6 drops of pure concentrated sulphuric acid, no coloration is observed, not even on the application of a gentle heat, or, at least, the heated fluid acquires only a barely perceptible yellow tint, but upon adding now, after cooling, from 8 to 20 drops of sulphuric acid mixed with a little nitric acid (§ 235, 7) and 2 or 3 drops of water, the fluid acquires an intense red color. Addition of binoxide of manganese does not materially change the color. If, after dilution, ammonia is added to nearly neutral reaction, the color becomes less intense, in consequence of the dilution. Addition of ammonia in excess produces a copious dark brown precipitate (J. ERDMANN).

6. If the solution of a salt of narcotine is mixed with chlorine water, it acquires a yellow color, slightly inclining to green: if ammonia is then added, a much more intensely colored yellowish-red fluid is obtained.

7. If narcotine or one of its salts is dissolved in an excess of dilute sulphuric acid, some finely levigated binoxide of manganese added, the mixture heated to boiling, and kept in ebullition for the space of several minutes, the narcotine absorbs oxygen and is converted into opianic acid, cotarnine (a base soluble in water), and carbonic acid. Ammonia will now of course fail to precipitate narcotine from the filtrate.

[blocks in formation]

1. Crystallized quina (Q + 6 aq.) appears either in the form of fine crystalline needles of silky lustre, which are frequently aggre gated into tufts, or as a loose white powder. It is sparingly soluble

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