EDITORIAL.
PHARMACEUTICAL CONVENTION.
As heretofore, so now, the best and the only prospect of progress in the profession lies in itself. It best knows its necessities and requirments, and it can best devise the remedies that will meet them. It is in the union of its members, in mutual association and intercourse, in the formation of a public opinion of its own, which, {160} operating first upon the members of the profession, will necessarily have its weight upon the public opinion of the community, that lie our best hopes. Pharmacy is at once a liberal art, and a trade. In individuals, particularly in a community like ours, the spirit of trade is apt to be in the ascendant. Science is estimated at its money value, for what it brings in, rather than for what it is. But when the best men of a profession meet together, science resumes its proper position; they are encouraged in their noblest aims, and that encouragement is spread widely among their fellows. Individuals struggling, isolated throughout the country, feel that there is a tribunal to which they can appeal, and by which they will be judged, and its influence will be felt too by another class, as a restraint, if not an encouragement. Success, obtained by worthy means, loses much of its value, when it costs the esteem of those with whom we are most intimately connected.
It is from such considerations that we look upon the approaching convention at Philadelphia, as a step in a very important movement. A great deal depends upon its success, and every one who has the interest of pharmaceutical science at heart, should do all he can to promote it.
To prove all that is hoped for by its friends, the convention should be a national one, not only in name, but in reality. Every institution and society entitled under the requisitions of the call, should appoint delegates, and above all, they should appoint delegates who will attend. But there are many apothecaries scattered through the country, in places not entitled to appoint delegates, who may be enabled to be present at the meeting of the convention, and we are glad to see that our Philadelphia brethren are prepared to welcome them in a liberal and cordial spirit. They will both receive and communicate benefit. Their presence will add weight and authority to the convention; while, independent of its official proceedings, they cannot but derive advantages from acquaintance and intercourse with the numerous able members of the profession who will, as delegates, attend the meeting.
Great care should be exercised in the selection of delegates; they should not only, above all, be men who will attend, but men who have at heart the position and advancement of pharmaceutists.
We hope that their election will take place as early as possible, that they may have time fully to consider the objects of the convention, and the wants and wishes of the institutions they represent. It would be well, too, if early notice of their election should be communicated to Mr. Proctor, or some other of the members residing at Philadelphia, and their names should be published. The convention will have much to discuss and determine upon, while its duration will necessarily be limited. Were the names of its members early announced, an interchange of opinion might take place between, not to forstall the active of the convention, but to promote and expedite it. For this purpose, if deemed desirable our own columns are freely tendered.
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NEW YORK JOURNAL OF PHARMACY. JUNE, 1852.
ON THE PREPARATION OF PURE BARIUM COMPOUNDS. BY HENRY WURTZ.
The preparation of the compounds of barium in a state of absolute purity is a subject which has not generally received much attention from Pharmaceutical chemists, in consequence of the hitherto limited application of these compounds, except in chemical analysis. The time, however, is undoubtedly close at hand, when new developments in the arts, will create a demand for pure barium compounds, as well as for very many other products now considered as pertaining exclusively to the laboratory. Indeed, efforts have already been made to introduce the chlorate of barytes to the notice of pyrotechnists as a means of producing a green fire unequalled in beauty, and the pure carbonate has been for some time in use in England, in the manufacture of superior varieties of plate and flint glass. The precipitated or purified native sulphate is also preferred as a water color pigment to white lead, being far more durable than the latter. I may here be permitted to mention a practical application of the carbonate which has occurred to myself. I have found that sulphate of lime is totally precipitated from its solution by mixing therewith an equivalent quantity of the precipitated or finely pulverized natural carbonate of barytes, {162} of course with the formation of sulphate of barytes and carbonate of lime. It is by no means improbable that this property may be made available in removing sulphate of lime from spring or sea water which is to be used in steam boilers, thus preventing the formation of the troublesome incrustation which so often occurs, especially when it is considered that the sulphate of barytes which would be formed, might easily be reconverted into carbonate and used over again. Again, sulphate of lime might be removed in the same way from the brine in salt works, thus contributing to the purity of the salt produced.
Recent improvements in chemical analysis have greatly increased the usefulness of barium compounds in the laboratory, especially of the carbonate, to which the late investigations of Professor H. Rose, and of Ebelmen have given a place in the very first rank among the reagents valuable to the chemist. Any suggestion, therefore, concerning the preparation of barium compounds in a pure state, cannot be considered as useless.
The sulphate of baryta is the only compound which occurs in sufficient abundance to be an economical source of the other barium compounds, and the enormous though illegitimate use of this substance in the adulteration of white lead, is so far fortunate as to render it an easy matter to obtain it in any required quantity, already in a state of fine powder which is so desirable in chemical operations.
The sulphate of baryta is always reduced to the state of sulphide of barium, by exposing it to a red heat in intimate admixture with some carbonaceous substance, such as powdered charcoal, rosin, oil or flour. It is exceedingly difficult, however, if not impossible, to effect in this manner a complete decomposition of the sulphate. Indeed, it is probable that in most cases the quantity of sulphide obtained, is not more than half that which is equivalent to the sulphate employed. A modification which promises to be far more economical was proposed by Dr. Wolcott Gibbs. His proposal was to submit the sulphate to the action of a current of common coal gas at a red heat. It is evident that in this way a perfect decomposition {163} may readily be accomplished, especially if the powdered sulphate is stirred during the operation, so as to expose fresh surfaces to the action of the gas.
The mass obtained after the reduction of the sulphate is submitted to the action of boiling water, and a solution obtained, which, according to Professor H. Rose,[12] contains principally hydrate of baryta and sulphohydrate of sulphide of barium BaS. HS. formed by the reaction of equal equivalents of water and proto-sulphide of barium. It almost invariably contains also a quantity of lime, probably in the form of sulpho-hydrate of sulphide of calcium, or of hydrate of lime, proceeding from the almost constant concurrence of sulphate of lime with native sulphate of baryta. From the presence of this lime originates the principal difficulty in preparing pure barium compounds from this substance. Thus when the carbonate is prepared from the solution by precipitation, with carbonate of soda, or a current of carbonic acid gas, it is found contaminated with carbonate of lime, which is fatal to its use as a reagent in analysis. Also in examining many specimens of commercial chloride of barium, which is prepared from this solution by the addition of chloro-hydric acid, boiling to separate sulpho-hydric acid gas which is evolved, filtration to separate the sulphur which is precipitated and crystallization, I have always found it to contain a small quantity of chloride of calcium, which I have found it impossible to separate entirely by repeated recrystallizations. It has been proposed[13] to separate the chloride of calcium from chloride of barium by the use of very strong alcohol, in which the latter when anhydrous, is insoluble. This method is rather expensive and troublesome as it involves the evaporation to dryness of the chloride of barium solution, the reduction of the previously ignited residue to a very fine powder and digestion in strong alcohol. Attempts were made after some previous experimentation, in which it was found that an {164} aqueous solution of oxalate of baryta precipitated chloride of calcium, but not chloride of barium, to separate the lime from a chloride of barium solution by addition of oxalate of baryta, or simply of a little oxalic acid, but it was soon found that oxalate of lime was somewhat soluble in a solution of chloride of barium, so that a solution of oxalate of baryta, gave no precipitate in a mixture of solutions of chloride of barium and chloride of calcium. It was found also that the precipitate formed by a little oxalic acid in a lime solution, could be re-dissolved by addition of chloride of barium. It may also be mentioned, though irrelevant to the subject, that it was found that oxalate of lime was soluble in solutions of chloride of calcium, of ammonia, and of chloro-hydrate of ammonia.
[12] Poggendorff’s Annalen, 55,416.
[13] Gmelin’s Handbuch, 2,158.
The well known property of carbonate of baryta which the recent investigations of Professor H. Rose have rendered so important in the analysis of phosphates, of completely precipitating lime from its solution by a sufficiently long contact therewith, furnishes us, however, with a perfectly easy and cheap method of purifying the chloride of barium solution. In fact a solution of chloride of barium to which chloride of calcium has been added, having been treated with a little carbonate of baryta, and allowed to stand in contact with it for two days, with occasional agitation, was found on filtration to be free from lime. The only objection to this method, is the considerable length of time required; but I must here describe an elegant modification which was communicated to me by Dr. Wolcott Gibbs, and tested by him in his laboratory; that is to add first to the solution of chloride of barium containing lime, a little solution of hydrate of baryta and then to pass through it a current of carbonic acid gas. The precipitate immediately formed contains of course all the lime.
The only impurity which is prevalent in commercial chloride of barium besides lime, is strangely enough, a trace of lead which is almost always present and sometimes in such quantity that the solution is immediately blackened by sulphuric {165} acid.[14] This is, however, very easily removed, either before or after the separation of the lime by the process of Dr. Gibbs, by passing a little sulpho-hydric acid gas into the solution, gently heating for a short time and filtering.
Commercial chloride of barium thus purified is probably the most convenient source of the other compounds of barium when required pure. Thus pure carbonate of baryta may be prepared from it by precipitation with carbonate of ammonia, or with carbonate of soda, which is free from silica, sulphuric acid and phosphoric acid.[15]
[14] It may be that leaden pans are used for the evaporation or crystallization of the commercial chloride of barium, which would sufficiently account for the presence of lead in the product.
[15] New York Journal of Pharmacy, 136.
RESULTS OF THE EXAMINATION OF SEVERAL PARCELS OF ALEPPO SCAMMONY. BY B. W. BULL.
Since the publication of an article upon Virgin Scammony in a previous number of this Journal, I have had an opportunity of examining four different varieties of scammony received from Constantinople, under the names, Aleppo Scammony, first; Aleppo Scammony, second; Tschangari Scammony and Skilip Scammony.
No. 1. Aleppo Scammony, first. This occurs in large amorphous pieces weighing one or more pounds; is not covered with any calcareous powder. The fractured surface presents a dark greenish resinous appearance. The specific gravity will be found below. The caseous odor is not so decided in this {166} specimen as in some of the other varieties, confirming, as will be seen from its composition, as adduced farther on, the remark made in the article above alluded to, in regard to the insecurity of relying upon the odor as a means of judging of the quality of scammony.
No. 2. Aleppo Scammony, second. Of this a sample of about one pound was received. This is in amorphous pieces; it differs from the previous specimen in its fracture which is non-resinous and horny, it is of a much lighter color, and has a grayish tinge. The scammony odor is more decided. This variety receives the prefix Aleppo improperly, as it does not come from that locality, and is said to be made by pressing the root, though the quantity of insoluble organic matter which it contains, seems to indicate some other impurity, intentionally added.
No. 3. Tschangari Scammony, derives its name from the place of production. It appears to be a variety not found in market here. It resembles in fracture the last mentioned, and is like that, in amorphous pieces. Its odor is more decided than that of any of the others.
No. 4. Skilip Scammony. This specimen appears to have undergone some deterioration, and evinces a disposition to mould. Some of the pieces are marked exteriorly, as if placed in a bag when soft, and dried in this way. It is destitute of the caseous odor, and has a mouldy smell. Fracture, non-resinous, and grayish, like the last mentioned varieties.
These three latter varieties are always to be obtained in Constantinople, we are informed, while the first quality Aleppo, is only produced in small quantity, and is soon out of market.
The difference in composition of the different varieties will be found annexed, the numbers referring to those given above. All of them indicate the presence of starch by the test with iodine. {167}
| No. 1. | No. 2. | No. 3. | No. 4. | |
|---|---|---|---|---|
| Specific gravity, | 1.150 | 1.325 | 1.339 | 1.311 |
| Per cent. | per cent. | per cent. | per cent. | |
| Resinous matter, water, and loss. | 86.88 | 55.42 | 64.10 | 34.00 |
| Vegetable substance, insoluble in ether, | 8.10 | 38.00 | 23.17 | 59.43 |
| Inorganic matter, | 5.02 | 6.58 | 12.73 | 6.57 |
| 100.000 | 100.000 | 100.000 | 100.000 |
New York, May, 1852.
WHAT IS MONESIA? BY E. DUPUY, PHARMACEUTIST, NEW YORK CITY.
Dorvault in the Officine gives it “as the product of a foreign bark never found in commerce, but described by Mr. Bernard Derosne, (who, according to the same authority is the only possessor of it,) as being found in voluminous thick pieces, filled with extractive. The color is dark brown, excepting the epidermis which is grayish. It contains tannin and a red coloring matter, analoguous to cinchonic red, also an acrid one and salts.” Virey attributed it to a Chrysophi lum.; Martens says it is the Mohica of the Brazilians; according to Mr. Constant Berrier, it bears in that country sundry other names: furanhem, guaranhem, buranché, etc. Duchesne in his Répertoire des Plantes utiles et Vénéncuses du Globe, and Descourtils in his Flore médicale des Antilles mentions the Cainito Chrysophillum the bark of which is tonic, astringent and febrifuge. In {168} examining some extract of Monesia I was struck with the striking resemblance in its properties with the extract of logwood, (Hematoxylon Campechianum) both possessing the same astringent sweetish taste, precipitating salts of iron, etc. Descourtils, who practiced medicine for a long time in the West India islands, says “it is recommendable in dysentery and diarrhea after the inflammatory period.” and to that effect prescribes the decoction of one ounce of the wood or a drachm of the extract added to an infusion of orange tree leaves, or Cascarilla bark, per diem. Besides, Dr. Wood in the U. S. Dispensatory, mentions its frequent use in some parts of the United States, “in that relaxed condition of the bowels, which is apt to succeed to cholera infantum,” and also in the same complaints as mentioned by Descourtils. Though both the decoction of the wood and the solution of the extract are officinal in our national Pharmacopeia, so far as my means of observation go, they are seldom, if ever, prescribed in New York, and yet I have repeatedly prepared solutions of the Monesia, prescribed by our city practitioners. The extract of log-wood being so similar in its medicinal action, I am strongly inclined to think that it is the same substance, though perhaps obtained from other sources; and as the price of it is so much higher than that of the other, it would be desirable to obtain the results of comparative experiments made to test their relative value, and whether the extract of Hematoxylon Campechianum should not be prescribed as answering for all therapeutical purposes, the mysterious Monesia of Derosne?
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THE PHARMACOLOGY OF MATICO: WITH FORMULA FOR ITS PREPARATION. BY DORVAULT.
As matico is daily attracting more and more the attention of practitioners, its pharmacology demands consideration. It is well known that this new Peruvian plant has been lauded as an efficacious remedy in leucorrhea and gonorrhea, as a vulnerary, and above all as an excellent hemostatic, both external and internal.
We shall, in the present paper, content ourselves with making known the principal pharmaceutical forms which this substance is capable of assuming, reserving all other considerations for a later period. A long and careful experience will be needed to establish the relative value of each of the subjoined forms.
POWDER OF MATICO.
Matico can be easily reduced to an impalpable powder. This powder is of a yellowish green, and its odor, when fresh is more fragrant than that of the plant itself. To preserve it well, it should be kept in well stopped bottles.
Matico powder can be advantageously used externally in sprinkling over bleeding parts, in plugging the nasal fossœ and in epithems for contusions. Internally it may be used moistened with a little sweetened water under the form of electuary or in pills.
INFUSION OF MATICO.
| Bruised matico, | 10 to 20 grammes. |
| Boiling water, | 1,000 grammes. |
Let it infuse until cold and strain it. This infusion is amber-colored, and possesses the aromatic odor of the plant. It is not unpleasant to take, but may be rendered more agreeable by the addition of sugar, or an appropriate syrup.
For external use, lotions, embrocations, lavements and injections, 30, 40 or even 50 grammes of matico may be used to the {170} same quantity of water, and it may be submitted to a slight decoction. If, in this mode of operation, it parts with some volatile oil, it gains a small portion of resin.
DISTILLED WATER, OR HYDROLATE OF MATICO.
| Bruised matico, | 100 parts. |
| Water, | 1,000 parts. |
Draw off by distillation, 500 parts of hydrolate.
The product is colorless throughout the distillation, except the first few drops, which are milky.
Hydrolate of matico has an odor of turpentine stronger than the plant itself. It is covered with globules, or a light layer of a volatile oil, almost colorless, and of the consistence of castor oil.
If the volatile oil be, as authors have advanced, one of the active principles of matico, then the hydrolate must be to a certain extent efficacious. The hemostatic waters of Binelli, Broechieri, Tisseraud, &c., over their property to the volatile oil of turpentine.
The hydrolate may be employed both externally and internally.
EXTRACT OF MATICO.
The one which appears to us the preferable is the hydro-alcoholic. Introduce some rather coarse matico powder into the apparatus for lixiviation, pour on it the alcohol at 56° so as to imbibe all the powder, leave it 24 hours, open the lower cock, pour the same alcohol over the same matico, until the latter is exhausted, and then evaporate the liquid in the vapour bath, till it is brought to the consistence of an extract. The product is black, with a marked odor of matico, and a bitter taste. It is only partially soluble, either in alcohol or water.
The extract of matico may be used internally in the form of pills, lozenges, syrup and electuary, and externally, dissolved or softened in the form of plasters, embrocations, plugs, lavements and injections.
Matico furnishes about 1⁄4 of its weight of the hydro-alcoholic extract.
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SYRUP OF MATICO.
| Bruised matico, | 100 parts. |
| Water, | 1,000 parts. |
Distil till you obtain 100 parts. Draw off the residue from the retort, press the matico, add to the product 700 parts of sugar; mix it so as to have by the addition of the hydrolate a syrup of ordinary consistence; filter it by Demarest’s method.
Thus prepared, matico syrup is brownish, limpid and of an aromatic taste, which is not disagreeable; it contains all the principles, active, volatile or fixed, of the substance.
It may be administered pure, or diluted with water. It is one of the easiest and most efficacious modes of administering matico in cases of internal hemorrhage or of flour albus.
It represents 1-10 of its weight of matico. The spoonful being 30 grammes, would represent 2 grammes; the tea-spoonful being 5 grammes, would represent 1⁄2 gramme.
MATICO PILLS.
| Powdered matico, | 20 grammes. |
| Powdered marsh mallow | 2 grammes. |
| Syrup of gum, | Q. S. |
Make secundum artem 100 pills rolled in lycopodium. They are of a dark green. The weight of each pill from 40 to 50 centigrammes, each containing 20 centigrammes of matico, give from 2 to 25 daily.
EXTRACT OF MATICO PILLS.
Divide secundum artem into 100 pills, which will each contain 10 centigrammes. They are blackish. Being smaller they possess the advantage of being more easily swallowed.
OINTMENT OF EXTRACT OF MATICO.
| Extract of matico, | 5 grammes. |
| Weak alcohol, | 5 grammes. |
| Lard, | 20 grammes. |
Make an ointment, secundum artem.
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TINCTURE OF MATICO.
| Bruised matico, | 100 parts. |
| Alcohol at 85°, | 400 parts. |
Macerate for 10 days, express and filter. The tincture may also be obtained by lixiviation from the powder.
It is used both internally and externally as a vulnerary; it must in the first instance be diluted with water.
Matico not being poisonous, practitioners can trace its application through the widest range.
We will again repeat that we only give these formulæ that they may be experimented on; we shall hereafter give further comments on the choice to be made amongst them.—Bulletin Thèr: 30th January, 1852.
CHEMICAL RESEARCH ON CROTON OIL. BY M. DUBLANC. Director of the Laboratory of the Central Pharmacy of the Parisian Hospitals.
Some interesting researches have been instituted to ascertain,
- a. Whether the croton oil contains within itself an acid volatile at a low temperature?
- b. Is this acid the principle of its action, and can it be preserved if it be separated from the oil, and diminished if it be allowed to evaporate?
In order to answer both questions, the following operations have been instituted by this chemist.
The seeds of croton, deprived of their husks, ground at the mill, and subject to pressure, yield a certain quantity of oil.—If the residuum be mixed with double its quantity of alcohol and pressed again, it yields a liquid which is a mixture of oil {173} and alcohol. This liquid, when distilled, will yield more oil. Both oils are filtered, after having been allowed to settle.
The produce of this first operation is the natural croton oil, such as it exists in the seeds, which is of a brown amber color, viscid, having a peculiar smell, and possessed of great acidity, by which if applied to the skin, it produces an irritation varying in intensity according to its quantity, and the duration of time during which it has been applied. One drop, for instance, causes a blister in twelve hours.
If a piece of litmus paper be dipped in this oil, it turns red, and re acts acid; and the red color, though not deep, resists the action of the air and of a hot furnace.
The oil obtained by distillation from a solution in alcohol is rather more dark, viscid, and acid, than that obtained by simple expression.
The blue paper dipped in the oil obtained by distillation, reddens, and retains the color under the same circumstances as the former.
The second operation, however, offers already a fact which is of great value in deciding the question about the acidity of the croton oil. If you dip the litmus paper in the fluid which is gained by distillation, no traces of a change of color is visible; when, on the other hand, if you dip it in the oil which remains in the distilling apparatus, it changes the color as quickly as if dipped in the oil previous to distillation. The same is the case if the residuum is again acted upon with water or alcohol, the distilled fluid has no traces of acidity.
However, since the contrary opinion is entertained by good authorities, we must add other facts in corroboration of our own.
Croton oil was extracted by the action of ether upon the seeds. The ethereal solution containing croton oil in suspension was acid: it was placed in a glass vessel with two openings. One of them admitted a straight tube, and reached to the bottom of the vessel, admitting the introduction of external air: the other communicated with Woulfe’s apparatus, composed, {174}
1. Of the globular tube after Liebig, containing blue solution of litmus.
2. Another globular tube filled with alcohol.
3. An angular tube in connection with a large vessel full of water, giving an inferior running to the liquid, and causing the air to pass across the thick layer of ethereal oil, to lead the volatile principles in contact with the liquor destined to retain them. The apparatus being arranged, it was put in action by causing the water to run which was contained in the large vessel. The vacuum having begun, air was introduced to the bottom of the ethereal liquid, keeping up this action till the ether was totally evaporated. Consequently, the air has agitated the liquid long enough to remove in a state of vapour all the ether which was contained in the mixture. Nevertheless, the tincture of Turnesol, which opposed the passage of the vapours of ether and water, did not change into red, which would have happened if the volatile principles should have contained any acid. Neither did the alcohol which was acted upon by the same current exhibit any sign of acid. The air saturated with ether arrived in the vessel to replace the water had no acid property; its action upon the eye-lids and nostrils was pungent and irritating, but not that of an acid. Another experiment was made with the same apparatus, having always in view to cause a great quantity of air to pass through croton oil. But this time, instead of causing the current to pass through a mass of ethereal solution, it was caused to pass through pure croton oil. The large vessel was this time not quite filled with water, allowing space to introduce on its upper part two sponges, one filled with oil, the other with ether. Things being thus arranged, the liquid was set running, and the air rushed through the oil, coming in at the bottom of the liquid and spreading through the surface, causing a lengthened ebullition. The mass of air employed in this operation was not below two centimetres. The tincture of litmus contained in the globular tubes was not altered; the oil contained in the sponge was neither acid, pungent, or corrosive. The ether acted upon by too much air had disappeared, the {175} sponge was dry. These two proofs appear to be conclusive, and to show that the croton oil does not contain an active volatile acid, otherwise it would have been made manifest by being carried away by the ether in the first case, or by its proper volatility in the second.
Is it, however, possible to separate the active volatile principle from the mere neutral oil? It has been said by several authors that the croton oil was composed of two different oils, but this was a mere statement which required to be proved by facts. To solve this problem, the oil employed in the experiments was obtained by means of ether. The seeds of croton yield by expression 35 per cent.; treated by ether, they yield from 52 to 55 per cent. If treated by ether, the ether obtained by distillation is free from acid, all the acid remaining in the oil. When a certain fixed quantity of this oil is put in contact with ten times its weight of strong alcohol, the alcohol dissolves 6 per cent. of its own weight, and the oil 50 per cent.
The portion of the insoluble oil has lost its color, its smell, a part of its pungency, and all its acidity.
The portion of oil which has been dissolved in alcohol, when separated from this menstruum by evaporation, is more viscid, more colored, more pungent, and acid. The oil which is not dissolved, can be acted upon again by alcohol; by this second operation, it yields some parts to the alcohol, and the remainder loses all its specific qualities. The action of alcohol upon oil in successive operation, can be followed up to its last limits.
Twenty volumes of oil mixed with 100 volumes of alcohol, will be followed by the reduction of five volumes of oil. In the next operation, when the alcohol is renewed, the volume of the columns of oil lowers only three volumes instead of five. By a fourth operation, the oil loses not a single volume. When reduced to this state, the croton oil is slightly amber-colored, without smell, taste, or acidity; it can be taken in the mouth without causing any sensation. It is soluble in all proportions in ether. Its specific gravity is, 92 compared with that of water. {176}
Thus we find by experiments an evident proof of the co-existence of a sweet oil with the pungent croton oil.
All the specific properties of the croton oil are carried over in that dissolved by alcohol.
Is it possible by further processes to separate these active principles from the oily matter that contains them?
To solve this question we resorted to the following experiment:—
We took two kilogrammes of croton oil, and for several days we left it in contact with half a kilogramme of alcohol. A distinct separation took place. The upper part, composed of oil and alcohol, did not represent the exact quantity employed; which is explained by the power which the oil has to dissolve 10 per cent. of alcohol. The upper part being decanted, it was necessary to remove the alcohol, to avoid the inconvenience which might have arisen by employing heat for this purpose. Water was added to this liquid, which having become turbid, ether was added. Thus the oil came with the ether to the surface. The ether was removed by free evaporation. During this lengthened process, the effluvia was so pungent as to affect the eyes and nostrils of the operator, and cause blisters to rise on his face. The oil thus obtained is dark-brown, opaque, thick, possessed of a strong smell and acidity. Applied to the skin, it causes almost instantaneous pain, followed by a blister. It is soluble in all proportions in alcohol and ether. Mixed with nine parts of its volume of olive oil, it forms a liquid possessing specific qualities stronger than those of common croton oil.
These facts prove the mobility of the active principles of croton oil, and the possibility of succeeding in obtaining them free from all fatty matter by chemical ingenuity, a task which will be the object of further experiments.
The results from the above experiments are the following:—
1. That the croton oil does not contain a volatile acid.
2. That the sensible acid in croton oil is fixed or retained in the oil, and cannot be separated from it by a heat at 212° Fahr., or even by distillation. {177}
3. That the acrid volatile principle, which exists in this oil, possesses not the qualities of an acid, and has hitherto withstood the chemical operations which were instituted to extract it.
4. That the active principles of croton oil are capable of being separated from one part of the oil, and concentrated in the other.
5. That croton oil is not homogeneous in its composition, but is formed of two parts, one inert, of which alcohol is unable to dissolve more than one-tenth, and a more soluble part, which carries with it all the active principles.
6. That the greatest degree of concentration of the active principles, is by acting upon a large quantity of oil with a small quantity of alcohol.
7. That either may be usefully employed in manufacturing croton oil.—Repertoire de Pharmacie.—From the Annals Pharmacy, 1852.
ON ALOINE, THE CRYSTALLINE CATHARTIC PRINCIPLE OF BARBADOES ALOES. BY JOHN STENHOUSE, L.L.D., F.R.S.L., & E.
About two months ago I received from my friend, Mr. Thomas Smith, apothecary, Edinburgh, a quantity of a brownish yellow crystalline substance which he had obtained from Barbadoes aloes. Mr. Smith’s process consisted in pounding the previously dried aloes with a quantity of sand, so as to prevent its agglutinating, macerating the mass repeatedly with cold water, and then concentrating the liquors in vacuo to the consistence of a syrup. On remaining at rest in a cool place for two or three days, the concentrated extract became filled with a mass of small granular crystals of a brownish yellow {178} color. This is the crude substance to which Mr. Smith has given the name of Aloine, and which appears to constitute the cathartic principle of aloes. The brownish yellow crystals obtained in this way are contaminated with a greenish brown substance, which changes to brownish black on exposure to the air, and still more rapidly when it is boiled. In order to purify the crystals of aloine, therefore, they must first be dried by pressure between folds of blotting-paper, and then repeatedly crystallized out of hot water till they have only a pale sulphur yellow color. The aqueous solutions of aloine must on no account be boiled, but simply heated to about 150° F., as at 212° F. aloine is rapidly oxidized and decomposed. By dissolving the purified crystals of aloine in hot spirits of wine, they are deposited, on the cooling of the solution, in small prismatic needles arranged in stars. When these crystals have a pale yellow color, which does not change when they are dried in the air they may be regarded as pure aloine.
Aloine is quite neutral to test-paper. Its taste is at first sweetish, but soon becomes intensely bitter. Aloine is not very soluble either in cold water or in cold spirits of wine; but if the water or the spirits of wine are even slightly warmed, the solubility of the aloine is exceedingly increased: the color of these solutions is pale yellow. Aloine is also very readily dissolved by the carbonated and caustic fixed alkalies in the cold, forming a deep orange yellow solution, which rapidly grows darker, owing to the oxidation which ensues. The effects of ammonia and its carbonate are precisely similar. When aloine is boiled either with alkalies or strong acids, it is rapidly changed into dark brown resins. A solution of bleaching powder likewise gives aloine a deep orange color, which soon changes to dark brown. Aloine produces no precipitate in solutions either of corrosive sublimate, nitrate of silver, or neutral acetate of lead. It also yields no precipitate with a dilute solution of subacetate of lead; but in a concentrated solution it throws down a deep yellow precipitate, which is pretty soluble in cold water, and is therefore difficult to wash. This precipitate is by no means {179} very stable; and when it is exposed even for a short time to the air, it becomes brown.
When powdered aloine is thrown, in small quantities at a time, into cold fuming nitric acid, it dissolves without evolving any nitrous fumes, and forms a brownish-red solution. On adding a large quantity of sulphuric acid, a yellow precipitate falls, which, when it is washed with water to remove all adhering acid and then dried, explodes when it is heated. It plainly, therefore, contains combined nitric acid. I could not, however, succeed in obtaining this compound in a crystalline state, as when it was dissolved in spirits, it appeared to be decomposed. When aloine is digested for some time with strong nitric acid, much nitrous gas is evolved, and it is converted into chrysammic acid, but without the formation of any nitro-picric acid, as is always the case when crude aloes is subjected to a similar treatment. A quantity of aloine was boiled with a mixture of chlorate of potash and muriatic acid. The acid solution was evaporated to dryness, and digested with strong spirits of wine. The greater portion of the spirits was removed by distillation; and the remainder, when left to spontaneous evaporation; yielded a syrup which could not be made to crystallize. Not a trace of chloranil was produced.
When aloine is destructively distilled, it yields a volatile oil of a somewhat aromatic odor, and also a good deal of resinous matter. When aloine is heated on platinum foil it melts, and then catches fire, burning with a bright yellow flame, and emitting much smoke. It leaves a somewhat difficultly combustible charcoal, which, when strongly heated, entirely disappears, not a trace of ashes being left.
A quantity of aloine dried in vacuo was analyzed with chromate of lead in the usual way.
I. 0.2615 grm. aloine gave 0.5695 carbonic acid and 0.14 water.
II. 0.2415 grm. aloine gave 0.5250 carbonic acid and 0.126 water. {180}
| Hydrated aloine. | Found numbers. | |||
|---|---|---|---|---|
| Calculated numbers. | I. | II. | ||
| 34 C | 2550.0 | 59.47 | 59.39 | 59.24 |
| 19 H | 237.5 | 5.54 | 5.97 | 5.79 |
| 15 O | 1500.0 | 35.09 | 34.64 | 34.97 |
| 4287.5 | 100.00 | 100.00 | 100.00 | |
The formula derivable from these analyses is C34 H19 O15, which, as we shall presently see, is = C34 H18 O14 +HO, or aloine with one equivalent of water.
The aloine which had been dried in vacuo was next heated in the water-bath for five or six hours, and was also subjected to analysis.
I. 0.251 grm. aloine dried at 212° F. gave 0.550 carbonic acid and 0.128 water.
II. 0.2535 grm. aloine dried at 212° F. gave 0.564 carbonic acid and 0.129 water.
III. 0.234 grm. aloine dried at 212° F. gave 0.521 carbonic acid and 0.114 water.
| Calculated numbers. | I. | II. | III. | ||
|---|---|---|---|---|---|
| 34 C | 2550 | 61.07 | 60.51 | 60.67 | 60.72 |
| 18 H | 225 | 5.39 | 5.66 | 5.65 | 5.42 |
| 14 O | 1400 | 33.54 | 33.83 | 33.68 | 33.86 |
| 4175 | 100.00 | 100.00 | 100.00 | 100.00 | |
The aloine employed in these analyses was prepared at three different times. These results give C34 H18 O14 as the formula of anhydrous aloine, that dried in vacuo being a hydrate with one equivalent of water.
When the aloine was allowed to remain in the water-bath for more than six hours, it continued slowly to lose weight, apparently owing to its undergoing partial decomposition by the formation of a brownish resin. The loss of weight gradually continued for a week or more, but became very rapid when the aloine was heated to 302° F., when it melted, forming a dark brownish mass, which when cooled became as hard and brittle {181} as colophonium. It still, however, contained a good deal of unaltered aloine, as I ascertained by crystallizing it out with hot spirits and analyzing it. Much of the aloine, however, had been changed, most probably by oxidation, into a dark brown uncrystallizable resin.
BROM-ALOINE.—When an excess of bromine is poured into a cold aqueous solution of aloine, a bright yellow precipitate is immediately produced, the amount of which increases on standing, while at the same time the supernatant liquid becomes very acid from containing free hydrobromic acid. The precipitate, after it has been washed with cold water to remove adhering acid, is dissolved in hot spirits of wine; and on the cooling of the solution it is deposited in bright yellow needles radiating from centres, which attach themselves to the bottom and sides of the containing vessel.
The crystals of brom-aloine are considerably broader than those of aloine, and have a richer yellow color and a higher lustre. Brom-aloine is quite neutral to test-paper, is not so soluble in either cold water or cold spirits of wine as aloine, but dissolves very readily in hot spirits of wine.
I. 0.421 grm. substance dried in vacuo gave 0.547 carbonic acid and 0.103 water.
0.856 grm. gave 0.848 bromide of silver = 42.16 Br.
II. 0.300 grm. substance gave 0.391 carbonic acid and 0.078 water.
0.661 grm. substance gave 0.649 bromide of silver = 0.2762 Br. = 41.78 per cent.
| Calculated numbers. | I. | II. | ||
|---|---|---|---|---|
| 34 C | 2550.00 | 35.73 | 35.43 | 35.53 |
| 15 H | 187.50 | 2.62 | 2.71 | 2.86 |
| 14 O | 1400.00 | 19.63 | 19.70 | 19.83 |
| 3 Br | 2998.89 | 42.02 | 42.16 | 41.78 |
| 7136.39 | 100.00 | 100.00 | 100.00 | |
The brom-aloine employed in these analyses was prepared at two different times. It is plain therefore from these results, {182} that this bromine compound is aloine, C34 H18 O14 in which 3 equivs. of hydrogen are replaced by 3 equivs. of bromine.—The formula of brom-aloine therefore is C34 H15 O14 Br3.
When a stream of chlorine gas was sent for a considerable time through a cold aqueous solution of aloine, a deep yellow precipitate was produced. It contained a great deal of combined chlorine; but as it could not be made to crystallize, it was not subjected to analysis. In the present instance, and in those of several other feeble organic principles, such as orcine, chlorine appears to act some what too strongly, so that the constitution of the substance is destroyed, and merely uncrystallizable resins are produced. Bromine, on the other hand, is much more gentle in its operations, and usually simply replaces a moderate amount of the hydrogen in the substance, so that, as in the case of orcine and aloine, crystalline compounds are produced.
It has long been known to medical practitioners, that the aqueous extract of aloes is by far the most active preparation of that drug. The reason of this is now very plain, as the concentrated extract of aloes obtained by exhausting aloes with cold water consists chiefly of aloine, by much the larger portion of the resin being left undissolved. Mr. Smith informs me, that from a series of pretty extensive trials, from 2 to 4 grs. of aloine have been found more effective than from 10 to 15 grs. of ordinary aloes. Aloine is, I should think, therefore, likely ere long, to supersede, at least to a considerable extent, the administration of crude aloes.
I endeavored to obtain aloine by operating on considerable quantities of Barbadoes, Cape and Socotrine aloes. These were macerated in cold water, and the aqueous solutions obtained were concentrated to the state of thin extracts on the water-bath. I was quite unsuccessful in every instance. The impurities contained in the extracts in these different kinds of aloes appear, when in contact with the oxygen of the air, to act upon the aloine so as effectually to prevent it from crystallizing. Aloine can only, therefore, be obtained in a crystalline state by {183} concentrating the cold aqueous solution of aloes in vacuo; though, after the aloine has once been crystallized, and it is freed from the presence of those impurities which appear to act so injuriously upon it, the aloine may be quite readily crystallized out of its aqueous solutions in the open air.
Though aloine has as yet only been obtained from Barbadoes aloes, I have scarcely any doubt that it also exists both in Cape and Socotrine aloes. The amount of aloine in Cape aloes, is, however, in all probability, much smaller than in either of the other two species; for Cape aloes is well known to be a much feebler cathartic, and to contain a mass of impurities. In corroboration of this opinion, I would refer to the fact already mentioned in a previous part of this paper, viz. that when aloine is digested with nitric acid, it is converted into Dr. Schunck’s chrysammic acid. Now it has been satisfactorily ascertained that all the three species of aloes yield chrysammic acid, of which in fact they are the only known sources. Cape aloes, as might have been expected, yields by far the smallest amount of chrysammic acid together with much oxalic and some nitro-picric acids. There appears, therefore, great reason to believe that all the three kinds of aloes contain aloine.
Since the above was written, I have learned from Mr. Smith that he has not succeeded in obtaining crystallized aloine from either Cape or Socotrine aloes. Mr. Smith does not doubt that both of these species of aloes also contain aloine, though, most probably contaminated with so much resin, or some other substances, as prevents it from crystallizing. What tends to confirm Mr. Smith in this opinion is the observation he has made, that when the crude crystals of aloine are allowed to remain in contact with the mother liquor of the Barbadoes aloes, they disappear and become uncrystallizable. I have also observed a similar occurrence in the mother-liquors of tolerably pure aloine. These become always darker and darker; so that if we continue to dissolve new quantities of aloine in them, at length scarcely any of it crystallizes out, and the whole becomes changed into a dark-colored magma. {184}
In the year 1846, M. E. Robiquet published an account of an examination he had made of Socotrine aloes. By treating the concentrated aqueous solution of this species of aloes with basic acetate of lead, he obtained a brownish yellow precipitate, which was collected on a filter and washed with hot water. On decomposing this lead compound with sulphuretted hydrogen and evaporating the solution to dryness, he obtained an almost colorless varnish, consisting of a scaly mass, which was not in the least degree crystalline. M. E. Robiquet subjected his substance, which he called aloetine, to analysis, and obtained the following result:—
| 8 C = | 27.7 per cent. |
| 14 H = | 10.8 per cent. |
| 10 O = | 61.5 per cent. |
| 100.0 |
It is plain, therefore, that M. E. Robiquet’s aloetine, if it really is a definite organic principle, which I very much question, is certainly a very different substance from the aloine which has formed the subject of the present notice.—London and Edinburgh Philosophical Magazine.
ON HENRY’S MAGNESIA. BY DR. MOHR.
In England, under this name is sold a calcined magnesia, at a very high price, which is not to be obtained in any other way. Many English travelers, as well as most of their countrymen, believe that they possess a very large knowledge of medicines, because such things as blue pills, calomel, sweet spirits of nitre, and laudanum they administer without medical advice, and {185} bring this magnesia with them to our shops when they wish a recipe to be dispensed, which contains calcined magnesia as one of the ingredients. By such opportunities, I became acquainted with the purity and beauty of this preparation, and its peculiar silky gloss and whiteness. With a view to discover its method of preparation, I made the following research:—
By heating to redness the ordinary carbonate of magnesia, it is not to be obtained. The ordinary magnesia of commerce, which produces by a red heat a fine calcined magnesia, I exposed in a crucible, to a strong white heat. It solidified, and was of a yellow color, and had become so hard that it was only with the greatest labor that it could be powdered and sifted. Prepared in this way, it cannot be used. I now prepared some carbonate of magnesia, observing that Henry’s was very dense, without reference to that result, which was very fine, by precipitation in the heat. The process by which the flocculent magnesia of commerce is obtained, is not explained in any chemical works. Pure sulphate of magnesia, free from iron, was dissolved in distilled water, and a solution of carbonate of soda added to it as long as anything was precipitated by a boiling heat. The ebullition was continued until the mixture ceased to evolve carbonic acid, and set aside for decantation. When decanted, fresh distilled water was added to the precipitate, and the whole again boiled, and afterwards placed on a filter and washed with hot distilled water, until the liquid passing from the filter gave no trace of sulphuric acid. The precipitate, when pressed and dried, was very white and dense. It was exposed to an intense white heat in a closely-covered Hessian crucible for one hour. When the crucible was opened, I found a beautifully white magnesia, finely granulated. Where it had come in contact with the crucible, it had acquired a yellow color, from the peroxide of iron contained in the crucible. The yellow portion alone adhered firmly to the crucible and the rest was perfectly white, and readily removed. In acids, this magnesia was with difficulty dissolved, although ultimately completely soluble therein. By a repetition of this {186} process, an identical result was obtained. The magnesia thus produced in small lumps exhibited by transmitted light a slight rosy tint, and by reflected light, a very white color. In these respects, it agrees perfectly with Henry’s. To determine its comparative density, a cubic inch measure was filled with its powder, and weighed. As the results of three trials, it contained respectively 10,74, 11,19, and 11,18 grammes of the powder. Two experiments with Henry’s magnesia gave 7, and 7,2 grammes. Three of the carbonate of magnesia, prepared by heat, gave 12,68, 12,9, and 12,5 grm. One of the ordinary calcined magnesia gave 1,985 grm.; and one of the ordinary carbonate of magnesia, 1,4 grm.
The calcined magnesia, as above prepared, contains some hard particles, which are very difficult to pulverize. In attempting to powder them, I remarked that this magnesia, which was washed before being burnt until no traces of sulphuric acid could be detected, now afforded an evidence of a small portion still being present. This same observation I have previously made in the preparation of oxide of zinc. To remove this contamination, I recommend that carbonate of magnesia should first be lightly burnt, and then well washed with hot water, and again burnt with a very strong heat.
The above determinations of the density of the magnesias must not be confounded with their specific gravity. To ascertain the latter is a task of great difficulty, for Rose, in attempting it, obtained such discrepant results, that he has withheld them. The specific gravity of Henry’s magnesia, as near as it could be ascertained, is from 2,50 to 2,67. The magnesia prepared according to my process, gave 3,148 as its specific weight.—Buchner’s Repertorium, in Annals of Pharmacy.