Magnolia: Constituents - References.
Continued from previous page.
CONSTITUENTS.—Dr. John Floyd, 1806 [An experimental inquiry into the Medical properties of the Magnolia tripetala and Magnolia acuminata, John Floyd, M.D., Philadelphia, 1806. (A. Thesis presented to the University of Pennsylvania and published in pamphlet form).], found by distillation with water, in the bark of Magnolia Umbrella and Magnolia acuminata, an aromatic oil in very small amount; and by extraction with alcohol, a resin and bitter principles. His chemical examination indicated that the resin was the characteristic constituent.
Coxe, 1825, states in his American Dispensatory, that the fresh bark of Magnolia glauca contains the aforenamed substances, and it is evident that his assertion is upon the authority of Dr. Floyd, although, credit is withheld. These statements were repeated by subsequent writers until 1842.
Dr. Stephen Proctor, 1842 [A. Thesis presented the Jefferson Medical College, Philadelphia, printed in the American Journal of Pharmacy, July, 1842, p. 89.], made an analysis of the bark of Magnolia grandiflora, being led to do so by the botanical relationships between the genera Magnolia and Liriodendron. He sought to find the liriodendrin [See this publication, Vol. II., p. 14, for remarks on liriodendrin.] of Prof. Emmett, and by Emmett's process, employing magnolia bark instead of liriodendron, he obtained "numerous acicular crystals." He did not, however, assert that they were identical with liriodendrin, but that it "appears to be analogous to that of the liriodendrin." He also found a resinous body and a volatile oil.
Dr. W. H. Harrison, 1862 [American Journal Pharmacy, 1862, p. 29.], reports as the result of an analysis of the bark of Magnolia glauca, a resin and volatile oil; from the fruit he obtained much fixed oil and small amounts of fragile transparent crystals that appeared upon the filter paper, when the alcoholic solution of the resinous body obtained by Emmet's process for liriodendrin, was filtered. He states that "the crystals crack under the teeth and when freed from resinous matter have little taste or odor." This was his only description of them. It is evident that they were not the liriodendrin of Emmet, but a new body now known as magnolin.
Wallace Procter 1872 [American Journal Pharmacy 1872, p. 145.], found that an alcoholic tincture of the fruit of Magnolia Umbrella, deposited transparent colorless crystals that were insoluble in cold water; slightly soluble in boiling water; very soluble in alcohol, ether, chloroform, carbon bisulphide and benzine; neutral to litmus paper and not basic. These crystals were obtained by other processes, one being to boil the tincture of the fruit with lime or magnesia, cool, filter, and add water to the filtrate. After some days crystals appeared, some half an inch in length. It seemed that the nearer the crystals were obtained in a state of purity, the less taste was apparent. In this connection, we will say that Prof. J. M. Maisch has supplied us with small specimens of these crystals of magnolin, now yellowish by age, but perfectly tasteless and colorless when recrystalised. Mr. Proctor also found a soft pungent resin, fixed oil, volatile oil, a hard resin but no liriodendrin.
It is therefore recorded that the different species of Magnolia contain in addition to the usual constituents of plants, a volatile oil, resinous matters, and a crystalline body, magnolin, that is not identical with liriodendrin, but no alkaloid has ever been isolated.
Examination of Magnolia Glauca.—In consequence of the fact that previous attention had only been given to the other species with quite uniform results, we thought it necessary to examine only the bark of Magnolia glauca, the result being as follows:
The dried bark of the tree of Magnolia glauca was powdered, percolated with alcohol, and the alcohol distilled. The residue was treated with water and filtered. The insoluble matter was a resinous body, black and shiny upon the surface, of an oily odor, a disagreeable taste in substance, and very bitter in solution, tenacious and sticky at ordinary temperatures, but not thin enough to flow. It was entirely soluble in diluted potash water, and refused to deposit crystals from any solvent. Upon examination it proved to contain three resins, with the following properties:
- All dissolved in alcohol.
- Benzol separated one, (A).
- From the residue, ether extracted another, (B).
- Leaving the third [Solvents applied as above divide the crude, resinous body in that manner. It is scarcely necessary for us to repeat that the study of associated resins and their by-products is, as yet, accompanied by great obstacles.], (C).
Resin A,—This is obtained by extracting by means of carbon disulphide, the crude resin of Magnolia tree bark, filtration and evaporation of the solvent. The residue contains some impurities, and should be again exhausted with carbon disulphide (or benzol,) and after some days the solution filtered and again evaporated, stirring until the menstruum is dissipated.
This produces a resinous body of a green color and a peculiar, disagreeable, heavy odor. It is a thick liquid at ordinary temperatures, flowing slowly at 60 ° Fah., and at low temperature it becomes tough, but not brittle. To the taste, in substance it is nauseating and slightly bitter, but, in alcoholic solution it is intensely bitter.
The resin dissolves freely in carbon disulphide, benzol, concentrated sulphuric ether, absolute alcohol, chloro. form, or any mixture of these liquids. Concentrated aqueous solution of caustic potash seems not to affect it, but dilute solution dissolves it slowly. Concentrated ammonia water disintegrates it, dissolving a portion; dilute ammonia water dissolves it quite readily.
This resin refuses to crystallize from any solvent. It has the specific gravity 1.047.
Resin B.—After separation of resin "A," extract the residue with concentrated sulphuric ether, filter and evaporate the filtrate. This produces a dark brown resin that is brittle at 3-2° Kali., but becomes waxy when, warmed. It melts, forming a sticky tenacious liquid at increased temperature, and chars at high heat, leaving a carbonaceous residue. It is nearly tasteless when chewed, but in alcoholic solution is very bitter. It has but little odor.
Carbon disulphide and benzol do not dissolve it. Concentrated sulphuric ether, absolute alcohol and chloroform or mixtures of these liquids, dissolve it freely with brownish, yellow color. Concentrated ammonia partly dissolves it; dilute ammonia freely. Strong solution of caustic potash scarcely affects it; dilute, dissolves it freely.
This resin refuses to crystallize from any solvent. It has the specific gravity 1.141.
Resin C.—After separation of resin "A" and resin "B", dry the insoluble matter, and extract it with absolute alcohol; filter and evaporate the alcohol. The residue is a brown, brittle resin, easily powdered, at ordinary temperatures, of a bitter taste ia alcoholic solution, but less so than cither of the others.
It is insoluble in ether, benzol and carbon disulphide [The crude mixture of resins dissolves in these menstruums. It is scarcely necessary for us to say that under these conditions the real menstruum is a liquid of which the resins "A" and "B" are a part, and which differs in solvent action from the liquid employed to dissolve them severally.]; slightly soluble in chloroform, and very soluble in absolute alcohol, forming a brownish, yellow liquid. Concentrated or dilute ammonia water dissolves it freely. Concentrated aqueous solution of caustic potash scarcely affects it, but the dilute solution dissolves it readily.
This resin refuses to crystallize. It has the specific gravity 1.162.
Resume.—By a comparison of the above it will be seen that the resin of least specific gravity, ("A"), is the softest, and that their consistence increases with their gravity, "C" being brittle at ordinary temperatures.
The accompanying table gives a comparison of the actions of reagents upon the resins. No ultimate analysis was made of them.
|Resin A.||Resin B.||Resin C.|
|Sulphuric Acid.||Black at once.||Black at once.||Brown at once.||Black at once.||Brown at once.||Black at once.|
|Nitric Acid.||Resin slowly turns red. Colorless liquid||Effervesces, forming red liquid.||Resin turns red.||Effervesces, forming red liquid.||Red liquid.||Effervesces, forming red liquid.|
|Hydrochloric Acid.||No change.||Turns brown.||No change.||No change.||Brown.||Brown.|
|Solution Ferric Chloride.||No change.||Turns brown.||No change.||Turns dark brown.||No change.||Dissolves with effervescense, forming red liquid.|
|Solution Potassium Bichromate.||No change.||No change.||No change.||No change.||No change.||No change.|
|Solution Potassium Bichromate, then Sulphuric Acid.||Turns brown.||Effervesces, forming red liquid, if resin is in small quant's.||Turns brown.||Effervesces, forming green liquid.||Effervesces, forming green liquid.||Effervesces, forming green liquid.|
|Bromine.||Turns red.||Forms red liquid, with effervescense.||Forms red solution.|
[image:11941 align=left hspace=1]Glucosid.—The filtered aqueous solution from the resins, deposited after standing some days, crystals of a tasteless. odorless, substance that recrystallized from alcohol by spontaneous evaporation, in transparent groups. This substance was soluble in ether and alcohol, but insoluble in water or acidulated water. It was extracted from dilute sulphuric acid, by agitation with sulphuric ether, and, upon boiling with dilute sulphuric acid, neutralization with carbonate of barium and filtration gave a heavy precipitate with Fehling's solution. Upon comparison with the Magnolin of Proctor, it was found to differ in this latter reaction from that substance, although resembling it in appearance. We did not obtain enough for a combustion and do not presume to affix a name.
Fluorescent Product of Magnolia Glauca Bark.—This substance resulted from a manipulation that was designed to obtain crystals of an alkaloid, but which resulted in the production of an intensely fluorescent, while, crystalline body. That this substance is an erratic product of decomposition, and not an educt of the plant is assured by the fact that repeated endeavors to obtain it from the recent tincture resulted in failures, and that a reserved portion of the tincture that produced the specimen was not fluorescent and did not yield fluorescent liquids by any manipulation. [Prof. Warder thought that an obscured fluorescense was observed when the tincture was dropped into dilute ammonia water. Our subsequent investigations demonstrated that the phenomenon observed was entirely distinct of it in the cabinet of the from the fluorescense of the substance under consideration.]
The supernatant liquid from which the resins and glucosid were separated gave perceptible reactions with alkaloidal reagents, but we could not separate an organic base from it. In endeavoring to do so we obtained a peculiar body that failed to be reproduced under similar conditions. It had marked properties, but is undoubtedly a product, and not an educt. We therefore record its properties as follows. [Every endeavor to reproduce it resulted in failures. We have deposited a specimen of it in the Philadelphia College of Pharmacy for future investigators to examine if desirous.]
Preparation.—The bark of Magnolia glauca was percolated with alcohol and the alcohol distilled, some water being added towards the end of the process. Upon cooling, water in excess was added, slightly acidulated with hydrochloric acid, and after standing twenty-four hours filtered to separate the resins. [For examination and description of these resins see preceding.]
The filtrate was evaporated to a syrupy condition [This filtrate gave reactions with all the alkaloidal reagents, but being impure, this fact was not considered conclusive evidence of the presence of an alkaloid.], rendered slightly alkaline with ammonia water, and agitated with successive portions of sulphuric ether. The etheral liquids were then evaporated, water, acidulated with hydrochloric acid, being added towards the end of the process. This liquid was filtered [The solution was still much colored, containing resinous bodies, and reacting with alkaloidal reagents After the evaporation it contained much resinuous matter insoluble in water, and the alkaloidal reaction had disappeared.], and evaporated spontaneously, some weeks being necessary to effect this purpose.
The result was a dark red, resinous amorphous mass. It dissolved readily in alcohol, and a very small amount of the solution imparted an intense fluorescense to alkaline water. Investigations showed that it was a mixture of an amorphous resinous body [This resinous substance either possessed fluorescent properties, or it was impossible to entirely free it from the other body.], and a crystalline white substance. In order 10 purify it the mixture was extracted with absolute alcohol and filtered, and the filtrate evaporated. The dark red residue was repeatedly exhausted with benzol [While some other liquids were better solvents than benzol, they took up the coloring matters. The clearest line of demarkation was drawn by benzol, which separated the peculiar substance almost pure white. The crystals from benzol were also superior to those from other solvents.] and the filtered solutions evaporated. The product was a nearly white crystalline crust.
Properties.—This substance when pure is tasteless, white and crystallized readily from most solvents that evaporated spontaneously, but with chloroform tends to produce a glassy deposit. It freely dissolves in anhydrous alcohol, chloroform, sulphuric ether, and officinal alcohol (specific gravity 0,820); sparingly in benzol, carbon disulphide and water. It is more soluble in alkaline than in pure water, and less soluble in acidulated water than in either. The solutions are fluorescent (blue); the alcohol solution being a beautiful azure blue; the alkaline, an intense deep blue. This latter is yellow by transmitted light, but the other solutions are colorless. It was not alkaloidal.
Prof. Robert Warder gave this substance some attention, but without result other than to confirm the foregoing description. There was not enough to make a combustion.
MEDICAL HISTORY AND PROPERTIES.—Schoepf, 1787 [Materia Medica Americana, 1787, p. 91.], ascribes to Magnolia glauca bark, "tonic, subastringent and antifebril properties" and to the seed, "stomachic properties." He states that a decoction is used for diarrhoea and phthisis.
Barton, in his collections, 1798 [He refers to Dr. Duncan's Commentaries, 1793. Vol. xviii p. 445.], classes Magnolia with the native tonics, stating that "The bark of this is an agreeable aromatic, tonic, bitter medicine." He also states that "In Virginia, a spirituous tincture of the cones, or seed-vessels of the Magnolia acuminata, which is commonly called Cucumber-tree, has been used, and we are told advantageously, in rheumatic complaints [Collections for a Materia Medica, part 1st, p. 13 (edition of 1810).], and, that in Florida, associated with Serpentaria, it was used in treatment of intermittent fever.
This mention by Barton really introduced the drug to the notice of the profession, and in 1802, Magnolia glauca was the subject of a thesis by Thomas D. Price (upon graduating from the University of Pennsylvania) which was considered sufficiently important to appear in pamphlet form. In this paper, a number of experimental investigations and clinical cases were tabulated, tending to show that the powdered bark in doses of 30 to 60 grains, reduced the frequency and increased the fullness of the pulse, the conclusion being that it could be used as a tonic or even as an antiperiodic to replace cinchona. Dr. Price also made a number of crude investigations of a pharmacal nature to determine its constituents, but none of them are entitled to recognition, other than that the best solvent employed was proof spirit which extracted the characteristic principles most perfectly.
In 1806, a second inaugural dissertation was presented by Mr. John Floyd, to the University of Pennsylvania, on the medical action of Magnolia Umbrella and Magnolia acuminata, which also appeared in pamphlet form, with a frontispiece engraving, natural size, of the leaf and flower of Magnolia acuminata. The result of these investigations indicated that either the powder of the bark, the infusion, or the resin of these species of Magnolia accelerated the pulse and increased its fullness, the maximum being about 40 minutes after administration [This does not altogether agree with Dr. Price.]. The most marked effect followed the use of the resin, in doses of from 14 to 18 grains,
Coxe [American Dispensatory 1825, and other editions.] states that bark of Magnolia glauca has been used in the cure of intermittent and remittent fevers, as well as those of a typhoid type. However, he did not consider it of primary importance.—Zollickoffer [A Materia Medica of the United States, 1826, p. 107.] accepts the value of the Magnolias as tonics, but presents no experience of his own.—Rafinesque [Medical Flora and Botany of the United States, 1830, p. 31.] states that the Indians of the South, and the settlers, used the bark in substance and in tincture, in intermittents and in rheumatism, and the cones in tincture as a stomachic and prophylactic. He adds however a word of caution, "their use is improper in all inflammatory fevers and the abuse of their tinctures is hurtful."
The New York edition of the Pharmacopoeia (1830) recorded the medicinal uses of the drugs considered, and of Magnolia glauca says, "Tonic, stimulant, diaphoretic. Dose one scruple to one drachm."
In the first edition of the United States Dispensatory, 1833, a synopsis is made of the accepted uses of the various parts of the tree, evidently from the literature we have already presented, as nothing original is offered, and this, in substance, is continued in each revision of that work until the present day.
Dr. Z. S. Wilson [American Journal Pharmacy, 1854, p. 535.], 1854, called attention to the fact that the scalded leaves of Magnolia tripetala, had been used by himself, with satisfaction, as a dressing for blistered surfaces, being less offensive than cabbage leaves.
Résumé.—It will be seen in our paper on the constituents of the magnolia bark, that a volatile oil, bitter resins, and the crystalline substance magnolin are found in the bark of all species. It is probable that the associated actions of these bodies may be of value in certain disease expressions, but, the well known similar effects of other common drugs render it unnecessary for physicians to resort to magnolia at present.
That this striking American tree should have led the early settlers to hope to obtain from it a valuable medicine is not improbable, but it has failed to come into popular use; was not used by the Indians; has remained for fifty years a cumberer of the pharmacopoeia without impressing the medical profession, and presents no striking chemical constituents. We may therefore conclude that it promises little.
- 1787.—Materia Medica Americana, David Schoepf, p. 91.
- 1793.—Barton's Collections for a Materia Medica, Vol. I., p. 14 (edition 1810).
- 1802.—Inaugural Dissertation on Magnolia Glauca, Thos. D. Price, pp. 1 to 40.
- 1806.—Experimental Inquiry into the Medical Properties of the Magnolia Tripetala and Magnolia Acuminata, John Floyd, pp. 1 to 33.
- 1820.—House Surgeon and Physician, Hand, p. 235.
- 1821.—Supplement to the Pharmacopoeia, London, p. 148.
- 1822.—Sequel to the Pharmacopoeia of the United States, Bigelow, p. 253.
- 1825.—The American Dispensatory, Coxe, p. 377 (and other editions).
- 1826.—A Materia Medica of the United States, William Zollickoffer, pp. 105 to 107.
- 1827.—Outlines of Lectures on Materia Medica and Botany, W. P. C. Barton, p. 204.
- 1830.—The Pharmacopoeia of the United States, (Philadelphia), p. 35.
- 1830.—The Pharmacopoeia of the United States, (New York), p. 44.
- 1830.—Medical Flora and Botany of the United States, Rafinesque, Vol. II., p. 31.
- 1830.—Introduction to the Natural System of Botany, Lindley, p. 24.
- 1833.—Prodrome of a Work to Aid in the Teaching of the Vegetable Materia Medica, W. P. C. Barton, p. 67.
- 1833.—Dispensatory of the United States, Wood & Bache, first edition, p. 401.
- 1834.—American Journal of Pharmacy, p. 285.
- 1838.—Flora Medica, Lindley, p. 23.
- 1840.—The Pharmacopoeia of the United States, p. 46.
- 1840.—Pharmacopeé Universellé, Vol. II., p. 7.
- 1843.—American Journal of Pharmacy, p. 89.
- 1843.—General Therapeutics and Materia Medica, Dunglison, second edition, Vol. II., p. 46.
- 1846.—Elements of Materia Medica and Therapeutics, second edition, Pereira, Vol. II., p. 743 (and other editions).
- 1847.—Materia Medica and Therapeutics, Royle (Carson's edition), p. 248.
- 1847.—Medical Botany, Griffith, p. 96.
- 1848.—Dispensatory and Formula, Mayne, (Griffith's revision), p. 276.
- 1849.—Elements of Materia Medica and Therapeutics, Kost, p. 439.
- 1849.—Indigenous Medicinal Plants of South Carolina, Porcher, (Report of the American Medical Association), p. 693.
- 1850.—The Pharmacopoeia of the United States, p. 52. 1850.—Medicinal Plants of the United States, Clapp, (Report of the American Medical Association), p. 726.
- 1852.—The Eclectic Dispensatory, King & Newton, p. 256.
- 1854.—American Journal of Pharmacy, p. 535.
- 1857.—Materia Medica and Therapeutics, Mitchell, p. 577.
- 1860.—The Pharmacopoeia of the United States, p. 60.
- 1862.—American Journal of Pharmacy, p. 29.
- 1870.—The Pharmacopoeia of the United States, p. 59.
- 1872.—Pharmacopoea Homoeopathica Polyglotta, p. 191.
- 1872.—American Journal of Pharmacy, p. 145.
- 1873.—Dictionary of Pharmaceutical Sciences, Sweringen, p. 256.
- 1875.—American Journal of Pharmacy, p. 179.
- 1876.—American Journal of Pharmacy, p. 279.
- 1877.—Encyclopedia of Pure Materia Medica, Allen, Vol. VI., p. 142.
- 1878.—Dispensatory and Pharmacopoeia of North America and Great Britain, Buchanan and Siggins, p. 199.
- 1879.—The National Dispensatory, Stille and Maisch, p. 874, issued in 1882.
- 1880.—The Pharmacopoeia of the United States, p. 215.
- 1882.—Dictionary of Economic Plants, Smith, p. 235.
Drugs and Medicines of North America, 1884-1887, was written by John Uri Lloyd and Curtis G. Lloyd.