Art. XLII.—On Certain Properties of the Tutu Plant (Coriaria ruscifolia).* See former paper on same subject, by Mr. Skey. (Trans. N. Z. Inst., Vol. ii., p. 153.)

Transactions and Proceedings of the Royal Society of New Zealand, Volume 3, 1870, Page 237

Art. XLII.—On Certain Properties of the Tutu Plant (Coriaria ruscifolia).* See former paper on same subject, by Mr. Skey. (Trans. N. Z. Inst., Vol. ii., p. 153.) By H. G. Hughes, M.P.S., Hokitika. [Read before the Wellington Philosophical Society, November 12, 1870.] During the past year I have devoted my leisure to the investigation of the properties of the Tutu plant, and communicated my results from time to time to Dr. Hector and Mr. Skey, who kindly assisted me with their criticisms. The following paper embodies a brief account of my experiments, which circumstances have unfortunately prevented my completing as I wished to have done. About three-quarters of a pound of the fresh ground shoots were treated with successive quantities of distilled water slightly acidulated. After filtering and adding the acetate of lead in excess, it was submitted to the action of sulphuretted hydrogen, again filtered, and evaporated to the consistency of an extract. This extract was well washed with successive quantities of alcohol, filtered, evaporated, and ammonia added, when a precipitate resembling Kermes mineral was separated (resinous matter). It was still further concentrated, distilled water added, and again filtered from precipitate; evaporation continued, again treated with alcohol, filtered and evaporated to a syrupy consistence. On cooling, a few crystals formed with difficulty. This thick solution possessed very active properties, and a quantity of it, certainly not more than one-twelfth of a grain (I was scarcely aware of having tasted it), in five minutes time produced a most disagreeably irritating sensation in the throat, extending to the stomach, with pain across the region of the stomach, and accompanied by nausea. In a quarter of an hours time, vomiting came on, which continued more or less for two hours. Very unpleasant sensations continued for two hours more, when, after great flushing of the face, with all but intolerable heat, the effects passed away. Of course, not anything was taken to counteract the poison. On the addition of a little ether to the thick solution, a quantity of acicular crystals immediately made their appearance, but became redissolved as the ether slowly volatilized. The whole was afterwards shaken up with ether, the ethereal solution separated. Upon spontaneous evaporation, three or four drops of a fine yellow-coloured fragrant oil was as residue. The fragrancy increased upon the application of a gentle heat. Upon evaporating the thick alcoholic solution, crystals of supposed alkaloid formed. These were redissolved and recrystallized until their solution in alcohol was perfectly colourless. During the final evaporation of an alcoholic solution, an accident occurred, and they were lost, having been burnt. The residue was black and charred (carbonaceous).

The experiment was made with the view of isolating an alkaloid. A resin was separated (the powder before mentioned); it was combustible, burning with a clear flame. Besides, a bright yellowish-coloured fragrant oil. This fragrant oil was also obtained by distilling the expressed juice of the fresh and succulent young shoots. It comes over with the water, rendering it very fragrant. A solution of sodium chloride added to this fragrant water (it being previously shaken up with a little potash) immediately curdles it. About three ounces of leaves were exhausted by percolation with precipitate and benzine successively. The benzine solution contained nothing of importance. The alcoholic solution was treated the same as that of the young shoots; it contained the fragrant oil, it was also poisonous, but lime was substituted this time for the acetate of lead. This time no alkaloid was found, and altogether it was a most unsatisfactory experiment. I thought the principles were lost. Three-quarters of a pound of the bark was next examined. It was in a bad condition, and had been taken off a part of the trunk of a tree near the ground; it had been submerged during a flood of the Hokitika River. This was treated in the same manner as the young shoots, with the exception that lime was used, but yielded nothing besides a trace of the fragrant oil and some resinous matter. Some of the seeds of the fruit (three quarters of an ounce), all that could be obtained the season being so far advanced, were macerated in alcohol and evaporated. To this alcoholic extract a little powdered lime was added and mixed. It was then well washed with spt. vin., ether, and chloroform, in succession. Neither of the latter two yielded anything upon spontaneous evaporation. The alcoholic solution evaporated; the residue was treated with acid sulph. dil. filtered, and pot. carb. added in excess caused a flocculent precipitate. The solution separated, the precipitate was treated with alcohol, and filtered. As the solution became more concentrated, a heavy olive-coloured oily fluid separated. Some shoots of the tree gathered 3rd December, 1869, yielded this oily fluid. It is of a most poisonous nature, half a drop administered to a terrier exciting most severe symptoms, (vomiting and convulsions). After further concentration, ether was added, when a yellowish precipitate formed, the oily fluid separating of a clear olive-green colour. As the ether volatilized the precipitate was redissolved by the alcohol; the oily fluid remained. Chloroform added caused a pure snow-white precipitate, which floated, the oil still remaining unaffected. It was then separated from the precipitate, dissolved in alcohol, and filtered. Upon evaporating spontaneously it deposited feathery crystals of a dingy colour (impure or contaminated with the oily fluid). Before all the alcohol had evaporated, chloroform always gave a pure snow-white precipitate. The crystals were extremely deliquescent. I thought this oily-looking fluid was a liquid alkaloid

similar to conia. It was soluble in alcohol, but insoluble in both ether and chloroform. The alcoholic solution of this oily substance and white alkaloid possessed very energetic properties,—an all but inappreciable quantity bringing on, almost immediately, a very distressing suffocating sensation, and an unpleasant feeling of roughness and insensibility of the palate. Not any of the fragrant oil was found. Respecting the opinion that the oily-looking fluid is a liquid alkaloid, and at least holds in solution a salt (supposed alkaloid), the following may tend a little to uphold it. It is very remarkable that this oily fluid is perfectly insoluble both in ether and chloroform, and soluble in alcohol and a mixture of alcohol and water; and whatever the poisonous principle or principles may be, that slacked lime made into a thin cream with water instantly destroys it or them, with or accompanied by the evolution of ammoniacal vapour. The fragrant oil is soluble in ether and chloroform, and I imagine it to possess emetic properties only, as will be seen when treating of the antidote. Moreover, a portion of alcoholic extract was mixed with distilled water introduced into a pint retort, and heated in an oil bath. The extract was fragrant, and as a consequence, the fragrancy of the essential oil passed over with the first quantity of water as was intended and was removed. When the extract thickened, a good heat being applied (350° to 400° F.), I found snow-white acicular crystals sublimed in a ring all round the neck of the retort, two inches from the stopper. Watching how they formed, I saw drops of oily fluid, of an olive-green colour (the same oil apparently as that before mentioned), settling very curiously (as drops, I suppose owing to the repulsion of the glass from the high temperature employed, and the low degree of volatility of this oil), on the neck of the retort, which being very hot, these drops, as they slowly volatilized, left snow-white acicular crystals, and similarly to those before mentioned, extremely deliquescent, and very soluble in alcohol. Some were preserved, mounted, and examined with the microscope, and I thought they were oblique rectangular prisms. As far as I was able to judge, these were exactly similar to those before described as having been lost. I imagine that the charring of the first ones, and the extreme deliquescence of these, altogether set aside the opinion of their being ammonium chloride, which was suggested to me by Mr. Skey. The crystals taken from the neck of the retort gave precipitates with the iodide of mercury and tannic acid respectively. An unused portion of the extract experimented upon, was treated with slacked lime (it was the first time that slacked lime was used), when strong ammoniacal vapour was discharged, and the extract became a solid mass. Suspecting the alkaloid, or whatever it was, to be destroyed, just as anticipated, although great and unusual care was used towards isolating the various principles, yet not a trace of anything was found, as was the case with the other portion subjected

to distillation with water. It was from the consideration of this strange reaction that it occurred to me that lime would be of avail in cases of poisoning. From another quantity of the shoots of the tree, crystals were obtained of a very mixed character, which gave precipitates with iodide of mercury, also the bichloride of mercury. These had a very peculiar taste, saline and bitter, and very biting, and were poisonous, half a grain causing slight nausea and exciting symptoms similar to the oil, but milder. In all my experiments, the ether, alcohol, chloroform, etc., used, were the commercial articles. Respecting the efficacy of a mixture of lime and water in cases of poisoning, and before giving the report by Dr. G. H. Acheson, of this town, it may be as well to state that nothing was administered by way of general treatment, the antidote only was given, besides what takes place when a mixture of cream of lime with water is added to the simple extract of tutu rendered fluid with a little water and mixed. The extract was prepared by macerating the young, but woody and developed, shoots in water, acidulated with acetic acid, and applying a gentle heat, pressing, and evaporating to the consistency of an extract. These shoots yield extract more poisonous than the succulent ones. Having to handle these wet shoots rather frequently, induced vomiting. The day the extract was prepared, its admixture with lime gave strong ammoniacal vapour. It was very poisonous. About half a scruple was given to a cat; I was obliged to leave her, and on my return, in twenty minutes time, found her dead. On the second day the reactions were similar. On the third day after preparation, the ammoniacal vapour was just perceptible, but readily detected by fumes of hydrochloric acid; it was but slightly poisonous. On the fourth day the exttact had become much thinner, gave no ammoniacal vapour, and was not in the least poisonous. The extract preserved its original consistency until the third day, when it became soft, which condition was much increased by the fourth day. During this time the weather was fine; I do not think the atmosphere was more humid than usual. Three extracts prepared at intervals of five or six days, and in succession, behaved in a similar manner. When the cream of lime is added to good (poisonous) extract, it coagulates or thickens, and appears to swell immediately, strong ammoniacal vapour being at the same time evolved. Should the extract possess fragrancy, owing to some of the fragrant oil not being dispelled during the process of preparation, it is at once destroyed by the lime. It is important to observe that the inert extract on the fourth day after preparation, retained this odour. From what I have seen of its action, it possesses emetic properties only.

Recapitulation.—Acetic acid fixes or preserves the poisonous property (for a time at least), arresting its decomposition. When lime is added to good extract (poisonous), strong ammoniacal vapour is evolved; but on the fourth day, in the lime mixed with it, although possessing the odour of the essential oil, not the slightest trace of ammonia can be detected, the oil also, when destroyed by the lime, not giving any ammoniacal vapour, indicates it to be of a different composition, and a non-nitrogenous oil. The decomposition of the poisonous principle, resulting in the evolution of ammonia, shows nitrogen to be present in it. The fragrant oil comes over at 212° F., the poisonous principle at between 350° and 400° F. The spontaneous decomposition of the extract was carefully watched; there was no other perceptible change than its assuming a more fluid condition. From what has been stated, it is observable that the poisonous principle is very unstable when in a state of extract, decomposes immediately when neutralized with lime, and is fixed (for a time at least) by acetic acid. When the treatment of the plants was prolonged the results were variable and of an indifferent character, which I attributed to the principles decomposing spontaneously when in the presence of water. Also, as the season advanced the results were less satisfactory, as if indicating a smaller amount of the various principles—that is with reference to the shoots, bark and leaves. The young ground shoots (plants growing from the ground) gathered in March, 1869, yielded most of the supposed alkaloid and the other principles. They were, besides, more woody than those subsequently examined. The last examined were collected on the 3rd of December, 1869, and were shoots of the tree, but no trace of alkaloid was found, perhaps owing to the above mentioned supposition. They were macerated for at least twenty-four hours in distilled water, with the application of a gentle heat. Report of Experiments made by Dr. Acheson, with a mixture of Slacked Lime and Water as the Antidote for Tutu Poison. “For some time past I have been experimenting on various animals with a watery extract of tutu, prepared by Mr. Hughes, pharmaceutical chemist, of this town, and, at his request, I now state the result. “I administered to a cat, fifteen grains of the extract; twenty minutes after, the respiration became very frequent, slight twitching of extremities, and in five minutes more, a severe attack of convulsions, which lasted about three minutes. Then, an interruption of ten minutes, followed again by a severe paroxysm, which lasted four minutes; again intermission of ten minutes, which was followed by a severe paroxysm of pure tetanic spasm, in which she expired. In this case, from the commencement of symptoms of poisoning the slightest noise would invariably excite a recurrence of the paroxysm.

“2nd. I administered to a large dog half a drachm of the extract. Fifteen minutes after, breathing hurried, fœces expelled, vomited several times so severely that I was perfectly persuaded that the poison had been expelled. At the expiration of thirty minutes, tremors and slight twitching of the muscles of the extremities and very much afraid to move out of one position. Then a severe paroxysm of convulsions, gnashing of teeth and frothing at the mouth, the paroxysm lasting about four minutes, then a remission of ten or twelve minutes, which was followed by the most severe and final paroxysm. “In the above two cases, the extract had been prepared but two days. “3rd. On the afternoon of the third day after the preparation of the extract, I administered the same quantity to a similarly sized dog. At the expiration of thirty minutes, it having produced no effect, repeated the dose in a fluid state. The double dose merely produced sickness and slight tremor. “On the fourth day the extract had become very thin and watery, which led me to suppose that spontaneous decomposition had destroyed its poisonous property. I therefore increased the dose to two drachms, yet no symptom of poisoning. “A few days after the above mentioned experiments were made, I, with the assistance of Mr. Hughes, administered about a drachm of fresh extract to two dogs. To one of the dogs the extract was given in a mixture of lime and water. It remained in the stomach for several minutes before vomiting commenced. After the expiration of half an hour from the cessation of vomiting, we determined to administer a drachm of the extract alone, being merely dissolved in a little water. This he retained for twenty minutes without any vomiting taking place. We then administered to him a quantity of lime mixture. He never showed the slightest symptom of poisoning. To the other dog the extract was given in a quantity of water merely. A few minutes after administration, symptoms of poisoning commenced, and in twenty minutes he had a regular attack of pure tetanic convulsions. Immediately after the first paroxysm, we emptied into the stomach a quantity of the lime mixture, after which he had one severe fit, from which he recovered rapidly, and in the course of a very short period he was perfectly free from all symptoms of poisoning. “We administered to a rabbit about thirty grains in the solution of lime, it never evinced the slightest symptom of poisoning.* Tutu does not act as a poison upon rabbits. I kept two of them for two days feeding upon tutu Ieaves, and afterwards gave them several large doses of the poisonous extract. I thought one of them appeared a little stupefied, but it would eat well enough notwithstanding. “In every case in which we administered the lime mixture the animal recovered rapidly, and when the extract was active it invariably gave fumes of ammonia on being mixed with lime.

“From what I have seen I am perfectly persuaded that lime is an antidote against the tutu poison; also, that by the fourth day of the watery extract it is almost inert. “In every case experimented upon the animal remained perfectly conscious, indeed, the mode of attack and the appearance of the animal while in a paroxysm, strongly resembles poisoning by strychnia. “G. H. Acheson., F.F.P.G. “Hokitika, April 5, 1870.” Tutu As a Dye-Wood. Some woollen material, silk, and linen, were boiled for a short time (half an hour to an hour), with some chips (the wood of the tree), afterwards treated with a hot solution of copperas. The colours were pure, from a neutral grey to a deep black, the dye varying in intensity according to the number of times the material was treated with the decoction of the wood. The dye is superior to that of logwood, inasmuch that it is pure. Woollen materials take it readily and well, silk is not so readily affected, and linen takes more time. The wood of the tree may be used as a substitute for log- wood, and this property of the wood of the tree may be studied to advantage and profit. [The results given in the above paper being somewhat at variance with those obtained by Mr. Skey (loc. oit.), they have been carefully re-examined in the Laboratory, and Mr. Skey is of opinion that some of the reactions cited by Mr. Hughes are not satisfactory, for the following reasons:— 1st. That the oil under examination must have been saponified by the processes employed. 2nd. That the temperature used was such as must have produced many side products by destructive distillation, and, among others, acetate of ammonia, the presence of which would sufficiently account for the reactions Mr. Hughes attributes to the presence of an alkaloid. 3rd. That the action of lime, as an antidote, is not due to its decomposing an alkaloid, but to its forming an insoluble soap with the poisonous oil; and Mr. Skey still adheres to his opinion, that dilute acids should be administered in cases of poisoning by tutu. 4th. That the dyeing properties of the juice of the tutu plant are due solely to the abundance of tannin they contain, and are not analogous to the special dye principle of logwood (hæmatoxyline), for which reason he does not think that it can be used for dyeing any shade to which tan bark is not equally applicable. Mr. Skey's views are explained in a paper, which must be deferred for future publication.—Ed.]