of water: they are precipitated of a bright yellow on the addition of infusion of galls. A mixture of concentrated sulphuric and nitric acids produces a blood-red colour with narcotine and its compounds. Narcotine is less active as a poison than morphia; but, when administered to a dog in a dose of 23 grains, it speedily produced death. The salts of narcotine have a more bitter taste than those of morphia: the chloride and acetate crystallize with difficulty: most of its other salts form gummy compounds, which do not crystallize. The double salts with platinic chloride and auric chloride are, however, easily procured in crystalline scales. Narcotine is contained largely in the portion of opium which remains undissolved when treated with water. If this residue be digested with acetic acid, and the solution be supersaturated with ammonia, narcotine mixed with colouring matter is thrown down: it may afterwards be purified by solution in alcohol, and treatment with animal charcoal. If any of the acid solutions of narcotine be saturated with chloride of sodium, the liquid becomes turbid, and the narcotine is deposited, in the course of a few days, in crystalline masses. This property has sometimes been taken advantage of, in the separation of narcotine from morphia. When narcotine is distilled with concentrated hydriodic acid it yields rather more than its own weight of methyl iodide, or 3 atoms of the iodide for each atom of narcotine. This is indeed a convenient mode of procuring methyl iodide (Matthiessen and Foster). 22 24 271 Wertheim believed that he had proved the existence of three homologous narcotines, viz., methyl-narcotine ЄHNO,, ethylnarcotine €HNO,, and trityl-narcotine €,HNO,. Matthiessen and Foster, however, who examined a large quantity of narcotine from various sources, found only one kind, to which they assigned the formula €,H,NO,, or CH, less than that obtained by Wöhler and by Blyth. 22 231 Narcotine, under the oxidizing influence of platinic chloride, or of black oxide of manganese, is decomposed, and gives rise to some very remarkable compounds (Wöhler; Blyth, Liebig's Annal. 1. 1 and 29; Anderson, Trans. Roy. Soc. Ed. xx. 359). It appears to split up into a new base, termed cotarnine, and into opianic acid, or into products which are the result of the decomposition of opianic acid : If the oxidation be more energetic, the cotarnine is broken up 558 COTARNINE-MECONINE, 2 2 9 into ethylia and apophyllic acid (H2E16H1N,,?), the latter name being given in consequence of its resemblance in appearance to the pearly crystals of the mineral apophyllite. Opianic acid when treated with potash ley yields meconine and hemipinic acid :— Cotarnine contains all the nitrogen of the narcotine. It forms fusible acicular crystals, which are sparingly dissolved by water, or by a solution of potash; but they are freely soluble in alcohol, ether, and solution of ammonia. Cotarnine is readily obtained by boiling a solution of narcotine in hydrochloric acid, with platinic chloride the liquid becomes of a blood-red colour, and red crystals of the double salt platinic chloride and hydrochlorate of cotarnine [(1H,NO,,HCl),PtCl] are deposited: the base is easily procured by decomposing the salt with an alkali. : 12 It will be unnecessary to enter into any minute description of the properties of the various products obtained by the oxidation of narcotine, for they present but little intrinsic interest, although a knowledge of their composition, and of the mode of their formation, is essential towards the explanation of the rational composition of the group of alkaloids contained in opium. 6. Meconine (ЄH104) may not only be formed by the oxidation of narcotine, but it exists in opium, in small quantity. This substance does not possess basic properties: it is freely soluble in boiling water, and crystallizes in white, inodorous, six-sided prisms, which are sparingly soluble in cold water, but are readily dissolved by alcohol and ether. It fuses at 194° (230°, Anderson), and may be distilled without alteration. It is soluble in concentrated sulphuric acid, and the liquid becomes purple when gently heated. Gerhardt considers this body to be a hydride of opianyl, which stands in the same relation to opianic acid that oil of bitter almonds does to benzoic acid (Gerhardt's opianyl being Є,H,4), as is represented by the following formula: For details upon this subject, vide Anderson, Wöhler, and Blyth, loc. cit., and Matthiessen and Foster, Phil. Trans. 1863, p. 345. NARCEIA-PIPERINE. 10 9 559 Gerhardt's opianyl (EH,) also appears to enter into the formation of two remarkable compounds, derived from ammonia, which present the composition of amides. Anderson has termed them, respectively, opiammon and teropiammon: neither of them possesses basic characters : 23 obtained by evaporating a obtained by the action of (1400) 7. Narceia, or Narceine.-Two substances appear to have been described under this name; one of these, obtained by Pelletier, having the composition (E,,H,NO); the other examined by Anderson, being (Є,H,NO,). The latter is a feeble base, which is soluble in boiling water, and crystallizes from a hot solution as it cools, in delicate silky needles, which are soluble in alcohol, but insoluble in ether: at 197° (92° C.) it fuses, and at a somewhat higher temperature it becomes decomposed. It combines with the dilute acids, forming crystallizable salts. Concentrated sulphuric acid dissolves narceine with an intense red colour, which, when gently heated, passes into green. Iodine colours the base of a deep blue, which disappears on the addition of an alkali. (c) Alkali obtained from the Pepper Tribe. 191 (1401) Piperine (EHNO3; Strecker).-This is a substance which is isomeric with morphia; it is possessed of feebly basic properties. It is found in the common white and black pepper, and in long pepper. White pepper easily yields it when treated with alcohol, which extracts a resinous matter with the piperine, from which the latter may be freed by digestion in a solution of potash the piperine which remains undissolved is recrystallized from alcohol, and furnishes colourless prisms, which are fusible at 2120. Piperine is nearly insoluble in cold water; it has an acrid taste, resembling that of pepper: the hydrochlorate is its most stable salt. Concentrated sulphuric acid dissolves piperine, with a red colour; but the base is precipitated unchanged, on dilution with water. Nitric acid acts powerfully on piperine, developing an odour of bitter almonds, whilst a brown resin rises to the surface. On evaporating the solution to dryness, a brown. residue is left, which, when treated with potash, yields a magnificent blood-red liquid; and on distilling this mixture it furnishes 560 PIPERIDINE-STRYCHNOS BASES. piperidine, which is a powerfully alkaline base. The same base is also obtained when piperine is distilled with three times its weight of caustic potash, at a temperature not exceeding 320° (160° C.). The piperidine (Є,H,N), being volatile, passes over, and a yellow, resinoid acid-piperic acid (HЄ12H,1; Strecker)— remains in combination with potassium; €,,H1,NO ̧+KHO= 10/ 12 9 191 Piperidine [(EH10)"H,N]; Sp. gr. of vapour 2.982; Rel. wt. 425; Boiling pt. about 223° (1c6° C.).-This is a remarkable oily base, with a pungent odour, recalling both that of ammonia and that of pepper. It resembles ammonia in alkaline power, and precipitates many metallic oxides from their salts. It combines with the acids, neutralizing them, and forming well-crystallized salts with cyanic acid it forms a compound urea, piperyl-urea; and, if heated with cyanic ether, piperidine forms a compound termed ethyl-piperyl-urea :— : One of the atoms of hydrogen in piperidine may be displaced by ethyl or by methyl, on treating the base with iodide of ethyl or of methyl; and ethylo-piperidine, by treatment with an additional quantity of the hydriodic ether, yields the iodide of an ethyl base corresponding to tetrethylium. Capsicine is the name given to an alkaloid obtained from the capsicum, or Cayenne pepper. It has a burning taste; and as usually prepared, it presents a resinous appearance; but, when quite pure, it may be crystallized. It forms crystallizable salts with acetic, nitric, and sulphuric acids. (d) Alkaloids from the Strychnos Tribe. (1402) The fruit and bark of the Strychnos nux vomica, and other parts of several plants of this tribe, particularly the seeds of the Strychnos ignatii, contain two alkalies closely related to each other both of them act as powerful poisons on the living frame, and speedily occasion death, amid violent tetanic convulsions: these bases are strychnia and brucia. They contain two atoms of nitrogen in each molecule of base. In the nux vomica they occur in combination with lactic acid, and a peculiar vegetable acid. In order to extract them from this fruit, the following method may be adopted :-The rasped seeds are boiled with 4 times STRYCHNIA-SALTS OF STRYCHNIA. 561 their weight of alcohol, acidulated with 1 per cent. of sulphuric acid. The alcoholic liquid is neutralized with lime in slight excess: the acid and colouring matters are thus precipitated, whilst the bases remain in solution; the alcohol is distilled off, and the residue treated with acidulated water, from which, on the addition of ammonia, the strychnia and brucia are precipitated. The two alkalies are separated by converting them into nitrates, and crystallizing; the nitrate of strychnia, being the least soluble of the two, is first deposited. Both strychnia and brucia exert a lefthanded rotatory effect upon a ray of polarized light; but the rotatory power of strychnia is twice as great as that of brucia. : 21 22 2 (1403) STRYCHNIA (EHN, or C12H22N2O4=334) is contained in the St. Ignatius's bean, to the extent of nearly 1 per cent.; and it is one of the active constituents of the upas poison. Strychnia is one of the most powerful of the vegetable bases; it precipitates many metallic oxides from their salts, either completely or partially in the latter case, it forms double salts,-such as the double sulphate of strychnia and copper, which crystallizes in long green needles. Strychnia crystallizes from dilute alcohol, in white anhydrous octohedra, or in square prisms, which do not fuse on the application of heat. It is insoluble in absolute alcohol, ether, and the caustic alkalies; but it is soluble in the essential oils, and in chloroform. Cold water does not dissolve more of it than of its weight; but this solution, even when diluted with 100 parts of water, still possesses a distinctly bitter taste. If distilled with caustic potash, strychnia, like cinchonia and quinia, yields the oily base quinoline. A portion of the hydrogen in strychnia may be displaced by chlorine or by bromine, and the body thus obtained still retains basic properties. Strychnia, when triturated with iodine, forms a peculiar crystalline compound, which is soluble in alcohol, and yields orange-coloured scales [(21H2N2O2)2I3], from which the acids separate strychnia unaltered. This compound is analogous to those which iodine. yields with the opium bases (1395). Strychnia, when pure, is turned yellow by concentrated nitric acid, and yields a nitrate of a new substitution-base, nitro-strychnia. If brucia be present with the strychnia, as is usual in most commercial specimens, the colour produced by nitric acid is deep orange, or red. With ethyl iodide, strychnia yields ethylostrychnium iodide (Є21H ̧‚¤ ̧H ̧, NO,,I), from which oxide of silver separates a hydrated oxide of an ammonium base (Є, H2,,H,,N,,,HO), which is crystallizable: strychnia is therefore a nitrile base. 2 21 2 2 22 59 Salts of Strychnia. - Sulphuric acid forms a neutral and an |