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in cold, but somewhat more readily in hot water. It is readily soluble in spirit of wine, both cold and hot, but less so in ether. The taste of quina is intensely bitter; the solutions of quina manifest alkaline reaction. Upon exposure to heat it loses the 6 eq. of

water.

2. Quina neutralizes acids completely. The salts taste intensely bitter; most of them are crystallizable, difficultly soluble in cold, readily soluble in hot water and in spirit of wine. The acid salts dissolve very freely in water; the solutions reflect a bluish tint. If a cone of light is thrown into them, by means of a lens either horizontally or vertically, a blue cone of light is seen even in highly dilute solution.

3. Potassa, ammonia, and the neutral carbonates of the alkalies produce in solutions of salts of quina (if they are not too dilute) a white, loose, pulverulent precipitate of hydrated quina, which immediately after precipitation appears opaque and amorphous under the microscope, but assumes, after the lapse of some time, the appearance of an aggregate of crystalline needles. The precipitate redissolves only to a scarcely perceptible extent in an excess of potassa, but more so in ammonia. It is hardly more soluble in fixed alkaline carbonates than in pure water. If a solution of quina is mixed with ammonia, ether added, and the mixture shaken, the quina which has separated upon the addition of the ammonia, redissolves in the ether, and the clear fluid presents two distinct layers. In this point quina differs essentially from cinchonia; by means of this reaction, the former may therefore be readily detected in presence of the latter, and separated from it.

4. Bicarbonate of soda also produces both in neutral and acid solu. tions of salts of quina a white precipitate. In acidified solutions containing 1 part of quina to 100 parts of acid and water, the precipitate forms immediately; if the proportion of the quina to the acid and water is as 1 150, the precipitate separates only after an hour or two, in the form of distinct needles, aggregated into groups. If the proportion is as 1 : 200, the fluid remains clear, and it is only after from twelve to twenty-four hours' standing that a slight precipitate makes its appearance. The precipitate is not altogether insoluble in the precipitant, and the separation is accordingly the more complete the less the excess of the precipitant; the precipitate contains carbonic acid.

5. Concentrated nitric acid dissolves quina to a colorless fluid, turning yellowish upon application of heat.

6. The addition of chlorine water to the solution of a salt of quina fails to impart a color to the fluid, or, at least, imparts to it only a very faint tint; but if ammonia is now added, the fluid acquires an intense emerald-green color. If, after the addition of the chlorine water, some solution of ferrocyanide of potassium is added, then

a few drops of ammonia or some other alkali, the fluid acquires a magnificent deep red tint, which, however, speedily changes to a dirty brown. This reaction is delicate and characteristic. Upon addition of an acid* to the red fluid, the color vanishes, but reappears afterwards upon cautious addition of ammonia. (O. LIVONIUS, Communicated in a letter to the author; A. VOGEL.)

7. Concentrated sulphuric acid likewise dissolves pure quina and pure salts of quina to a colorless or very faint yellowish fluid; application of a gentle heat turns the fluid yellow, application of a stronger heat brown. Sulphuric acid containing an admixture of nitric acid dissolves quina to a colorless or very faint yellowish fluid.

8. As regards HERAPATH'S quinine reaction, based upon the polarizing properties of sulphate of iodide of quinine, I refer to Phil. Mag. vi. 171.

+

c. CINCHONIA, or CINCHONINE (Co H2 N2 O2 = Ci).

§ 238.

1. Cinchonia appears either in the form of transparent, brilliant, four-sided prisms, or fine white crystalline needles, or if precipitated from concentrated solutions, as a loose white powder. At first it is tasteless, but after some time the bitter taste of the bark becomes perceptible. It is nearly insoluble in cold water, and dissolves only with extreme difficulty in hot water; it dissolves sparingly in cold dilute spirit of wine, more readily in hot spirit of wine, and the most freely in absolute alcohol. From hot alcoholic solutions the greater portion of the dissolved cinchonia separates upon cooling in a crystalline form. Solutions of cinchonia taste bitter, and manifest alkaline reaction. Cinchonia is insoluble in ether.t 2. Cinchonia neutralizes acids completely. The salts have the bitter taste of the bark; most of them are crystallizable: they are generally more readily soluble in water and in spirit of wine than the corresponding quina compounds. Ether fails to dissolve them.

3. Cinchonia, when heated cautiously, fuses at first without loss of water; subsequently white fumes arise which, like benzoic acid, condense upon cold substances, in the form of small brilliant needles, or as a loose sublimate, a peculiar aromatic odor being exhaled at the same time. If the operation is conducted in a stream of hydrogen gas, long brilliant prisms are obtained (HLASIWETZ).

4. Putassa, ammonia, and the neutral carbonates of the alkalies produce in solutions of salts of cinchonia a white loose precipitate

*Acetic acid answers the purpose best.

The cinchonia of commerce usually contains in admixture another alkaloid, called cinchotina, which is soluble in ether. This alkaloid crystallizes in large rhomboidal crystals of brilliant lustre, which fuse at a high temperature, and cannot be sublimed even in a stream of hydrogen gas (HLASIWETZ).

of CINCHONIA, which does not redissolve in an excess of the precipitants. If the solution was concentrated, the precipitate does not exhibit a distinctly crystalline appearance, even though viewed through a lens magnifying 200 times; but if the solution was so dilute that the precipitate formed only after some time, it appears under the microscope to consist of distinct crystalline needles aggregated into star-shaped tufts.

5. Bicarbonate of soda and bicarbonate of potassa precipitate cinchonia in the same form as in 4, both from neutral and acidified solutions of cinchonia salts, but not so completely as the simple carbonates of the alkalies. Even in solutions containing 1 part of cinchonia to 200 of water and acid, the precipitate forms immediately; its quantity increases after standing some time.

6. Concentrated sulphuric acid dissolves cinchonia to a colorless finid, which upon application of heat first acquires a brown, and finally a black color. Addition of some nitric acid leaves the solution colorless in the cold, but upon application of heat the fluid, after passing through the intermediate tints of yellowish-brown and brown, turns finally black.

7. The addition of chlorine water to the solution of a salt of cinchonia fails to impart a color to the fluid; if ammonia is now added, a yellowish-white precipitate is formed.

8. If the solution of a cinchonia salt containing only very little or no free acid, is mixed with ferrocyanide of potassium, a flocculent precipitant of ferrocyanide of cinchonia is formed. If an excess of the precipitant is added, and a gentle heat very slowly applied, the precipitate dissolves, but separates again upon cooling, in brilliant gold-yellow scales, or in long needles, often aggregated in the shape of a fan. With the aid of the microscope, this reaction is as delicate as it is characteristic (CH. DOLLFUS: BILL; SELIGSOHN).

Recapitulation and Remarks.
§ 239.

The non-volatile alkaloids of the second group are altered or precipitated by various other reagents besides those mentioned above; the reactions are, however, not adapted to effect their individual detection and separation. Thus, for instance, bichloride of plati num produces in solutions of the salts of the three alkaloids belong ing to this group a yellowish-white precipitate, chloride of mercury a white precipitate, tincture of galls a yellowish-white flocculent precipitate, solution of iodine in iodide of potassium a reddish brown, phospho-molybdic acid a yellow precipitate, &c.

Narcotina and quina being soluble in ether, whilst cinchonia is insoluble in that menstruum, the two former alkaloids may be most readily separated by this means from the latter. For this purpose

the analyst need simply mix the aqueous solution of the three alka loids with ammonia in excess, then add ether, and separate the solu tion of quina and narcotina from the undissolved cinchonia. If the ethereal solution is now evaporated, the residue dissolved in hydrochloric acid and a sufficient amount of water to make the dilution as 1: 200, and bicarbonate of soda is then added, the narcotina precipitates, whilst the quina remains in solution. By evaporating the solution, and treating the residue with water, the quina is obtained in the free state.*

FROM

THIRD GROUP.

NON-VOLATILE ALKALOIDS WHICH ARE PRECIPITATED BY POTASSA THE SOLUTIONS OF THEIR SALTS, AND DO NOT REDISSOLVE TO A PERCEPTIBLE EXTENT IN AN EXCESS OF THE PRECIPITANT; BUT ARE NOT PRECIPITATED FROM (even somewhat concentrated) ACID SOLUTIONS BY THE BICARBONATES OF THE FIXED ALKALIES: Strychnia, Brucia, Veratria.

a. STRYCHNIA, or STRYCHNINE (C12 H2 N2 O,

§ 240.

42

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It

It is

1. Strychnia appears either in the form of white brilliant rhombic prisms, or, when produced by precipitation or rapid evapora tion, as a white powder. It has an exceedingly bitter taste. is nearly insoluble in cold, and barely soluble in hot water. almost insoluble in absolute alcohol and ether, and only sparingly soluble in dilute spirit of wine. It dissolves freely in amyl-alcohol, more especially with the aid of heat. It does not fuse when heated. It is exceedingly poisonous.

2. Strychnia neutralizes acids completely. The salts of strychnia are, for the most part, crystallizable; they are soluble in water. All the salts of strychnia have an intolerably bitter taste and are exceedingly poisonous.

3. Potassa and carbonate of soda produce in solutions of salts of strychnia white precipitates of STRYCHNIA, which are insoluble in an excess of the precipitants. Viewed under a microscope magni

*The reaction with ammonia and ether, though well adapted to effect the separation of quina from cinchonine, fails to effect the separation of the former vegeto-alkali from the other bases found in bark, which are not as yet officinal, viz., a quinidine, ẞ quinidine, y quinidine, and cinchonidine; since, as G. KERNER (Zeitschrift f. Analyt. Chem., 1, 150) has shown, several of these other vegeto-aikalies are pretty freely soluble in ether. In fact, no qualitative reaction will enable the analyst to fully effect this purpose; but it may be accomplished by means of a simple volumetrica! method, based upon the circumstance that the quina thrown down by ammonia from a solution of the sulphate, requires less ammonia to redissolve it than all the other vegeto-alkalies of the bark. For further particulars I refer to KERNER's paper on the subject.

fying one hundred times the precipitate appears as an aggregate of small crystalline needles. From dilute solutions the strychnia separates only after the lapse of some time, in the form of crystalline needles, which are distinctly visible even to the naked eye.

4. Ammonia produces the same precipitate as potassa. The precipitate redissolves in an excess of ammonia; but after a short time—or if the solution is highly dilute, after a more considerable lapse of time-the stryclinia crystallizes from the ammoniacal solution in the form of needles, which are distinctly visible to the naked eye.

5. Bicarbonate of soda produces in neutral solutions of salts of strychnia a precipitate of strychnia, which separates in fine needles shortly after the addition of the reagent, and is insoluble in an excess of the precipitant. But upon adding one drop of acid (so as to leave the fluid still alkaline), the precipitate dissolves readily in the liberated carbonic acid. The addition of bicarbonate of soda to an acid solution of strychnia causes no precipitation, and it is only after the lapse of twenty-four hours, or even a longer period, that strychnia crystallizes from the fluid in distinct prisms, in proportion as the free carbonic acid escapes. If a concentrated solution of strychnia, supersaturated with bicarbonate of soda, is boiled for some time, a precipitate forms at once; from dilute solutions this precipitate separates only after concentration.

6. Sulphocyanide of potassium produces in concentrated solutions of salts of strychnia immediately, in dilute solutions after the lapse of some time, a white crystalline precipitate, which appears under the microscope as an aggregate of flat needles, truncated or pointed at an acute angle, and is but little soluble in an excess of the precipitant.

7. Chloride of mercury produces in solutions of salts of strychnia a white precipitate, which changes after some time to crystalline needles, aggregated into stars, and distinctly visible through a lens. Upon heating the fluid these crystals redissolve, and upon subsequent cooling of the solution the double compound recrystallizes in larger needles.

8. If a few drops of pure concentrated sulphuric acid are added to a little strychnia in a porcelain dish, solution ensues, without coloration of the fluid. If small quantities of oxidizing agents (chromate of potassa, permanganate of potassa, ferricyanide of potassium, peroxide of lead, binoxide of manganese) are now added -best in the solid form, as dilution is prejudicial to the reaction— the fluid acquires a magnificent blue-violet color, which, after some time, changes to wine-red, then to reddish-yellow. With chromate of potassa and permanganate of potassa the reaction is immediate; on inclining the dish, blue violet streaks are seen to flow from the salt fragment, and by pushing the latter about, the coloration is

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