Cooley's Cyclopaedia of Practical Receipts Volume I Part 30

ACONITE, ditto, ditto 350

CONEINE, ditto, ditto 460

IV.

NICOTINE yields half its nitrogen as Ammonia 1049

IV. Dr Guy, as well as others, have made researches, having for their object the determination of the exact temperature at which the poisonous alkaloids melt and sublime. A very minute speck of the substance is placed on a porcelain plate or copper disc, and a square or oval of microscope-covering gla.s.s is placed over it, supported by a thin ring of gla.s.s or any other convenient substance.

Heat is then applied to the plate or copper, and the temperature, as indicated by a thermometer at which the substance fuses or volatilises, is carefully noted.

CANTHARIDINE sublimes as a white Fahr. Cent.

vapour without change of form or colour. 212 100

Sublime. Melt.

/---------- /---------- Sublime, melt and Fahr. Cent. Fahr. Cent.

MORPHINE } yield carbonaceous { 330 165 340 171 STRYCHNINE} residue. { 345 174 430 224

Melt. Sublime.

/---------- /---------- Fahr. Cent. Fahr. Cent.

ACONITINE } { 140 60 400 204 ATROPINE } Melt, change { 150 66 280 138 VERATRINE } colour, sublime, { 200 93 360 182 BRUCINE } and { 240 116 400 204 DIGITALIN } deposit carbon. { 310 154 310 154 PICROTOXIN} { 320 160 320 160 SOLANINE } { 420 215 420 216

_Selmi's method of extracting poisonous alkaloids in forensic investigations._ The alcoholic extract of the viscera, acidified and filtered, is evaporated at 65 C., the residue taken up with water, filtered to separate fatty matters, and decoloured by means of basic acetate of lead, leaving the solution in contact with the air for 24 hours. It is then filtered, the lead precipitated by means of sulphuretted hydrogen, and the solution after concentration repeatedly extracted with ether. The ethereal solution is then saturated with dry carbonic anhydride, which generally causes a precipitate of minute drops adhering to the sides of the vessel, and containing some of the alkaloids. The ethereal solution is then poured into a clean vessel, mixed with about half its volume of water, and a current of carbonic anhydride pa.s.sed for about twenty minutes, which may cause the precipitation of other alkaloids not precipitated by dry carbonic anhydride. Usually the whole of the alkaloids present in the ether are thrown down by these means, but if not, the solution is dehydrated by agitation with Barium oxide, and then a solution of tartaric acid in ether added to the clear liquid, taking great care not to employ excess of acid. This throws down any alkaloid that may remain. In order to extract any alkaloids that may still remain in the viscera, they are mixed with Barium hydrate and a little water, and then agitated with purified amylic alcohol; the alkaloids may subsequently be extracted from the alcohol by agitation with very dilute sulphuric acid.

A knowledge of the different solubilities of the alkaloids will be found an important auxiliary in their a.n.a.lysis. The following is a summary of the relative solubility of the most important of them. The figures denote the number of parts of the liquid required for their solution:--

_Absolute alcohol._--Strychnine insoluble; brucine soluble.

_Amylic alcohol._--Solanine (1061); digitalin sparingly soluble; morphine (133); strychnine (122); veratrine, brucine, atropine, aconitine, and picrotoxin, freely soluble.

_Benzol._--All the poisonous alkaloids, except solanine, are soluble in benzol.

_Chloroform._--Solanine (50,000); morphine (6550); strychnine (8); the rest freely soluble.

_Ether._--Solanine (9000); morphine (7725); strychnine (1400); aconitine (777); brucine (440); veratrine (108); atropine, picrotoxin,[26] and digitalin, very soluble.

[Footnote 26: Digitalin and picrotoxin, although not alkaloids, are inserted in the above list, because they have a general similarity in chemical properties to them; and for the convenience of the toxicologist.]

_Water_ (_cold_).--Strychnine (8333); veratrine (7860); morphine (4166); aconitine (1783); solanine (1750); brucine (900); atropine (414); picrotoxin (150); digitalin very soluble.

The princ.i.p.al Alkaloids and their Salts, in the state of powder, or with 'conia' and 'nicotia,' in the state of an oily looking liquid, may be thus distinguished:--

1. _a._ The powder is treated with nitric acid:--It is coloured red; probable presence of Brucia, Delphia, Morphia, or commercial Strychnia. If the reddened acid becomes violet on the addition of 'protochloride of tin,' it is BRUCIA; if it becomes black and carbonaceous, it is DELPHIA.

If the powder is fusible without decomposition, and strongly decomposes iodic acid, it is MORPHIA; if it is not fusible without decomposition, and does not decompose iodic acid, it is STRYCHNIA.

_b._ If instead of a red, the powder strikes a green colour with nitric acid, it is SOLANIA; if it is insoluble in 'ether,' and not reddened by 'nitric acid,' it is EMETIA; if soluble in ether, not reddened by 'nitric acid,' but melts and volatilises when heated, it is ATROPIA; if it is thus affected by ether or nitric acid, but does not volatilise, it is VERATRIA.

(See 2, _below_.)

2. _a._ The powder, or (with 'conia and nicotia') concentrated liquor, is treated with a drop or two of concentrated sulphuric acid:--A red colour is produced; probable presence of Brucia, Nicotina, Salicine, or Veratria.

If the reddened mixture has at first a roseate hue, turning deep red on the addition of nitric acid, it is BRUCIA; if the original substance moistened with solution of pota.s.sa evolves the odour of tobacco, it contains NICOTINE; if the red colour produced by the acid is permanent and of an intense blood-hue, and the powder agglutinates into lumps like resin, it is SALICINE; if the colour is at first yellowish, changing to blood-red, and ultimately to crimson and violet, it is VERATRIA.

_b._ If instead of the substance being 'reddened' by strong sulphuric acid, no particular action ensues in the cold, it contains either Conia or Strychnia; if a small fragment of b.i.+.c.hromate of pota.s.sa being now dropped in, produces a rich violet colour, it is STRYCHNIA; if the original matter on being heated, or treated with solution of pota.s.sa, evolves a penetrating, disagreeable odour, somewhat a.n.a.logous to that from 'hemlock,' or to a mixture of those from tobacco and mice, it is CONIA.

"_Reactions with ceroso-ceric oxide._ This oxide exhibits characteristic colours with several alkaloids, especially with STRYCHNINE. When strong sulphuric acid is poured upon strychnine, and then a small quant.i.ty of ceroso-ceric oxide added, a fine blue colour is produced, similar to that which strychnine exhibits with pota.s.sium b.i.+.c.hromate, but much more permanent. The blue colour gradually changes to cherry-red, and then remains unaltered for several days. This reaction is capable of detecting one part of strychnine in a million parts of liquid. BRUCINE similarly treated acquires an orange-colour, gradually changing to yellow; MORPHINE, olive-brown, finally brown; NARCOTINE, brown cherry red, finally wine-red; CODEINE, olive-green, finally brown; QUININE, pale-yellow; CINCHONINE and THEINE remain colourless; VERATRINE becomes reddish-brown; ATROPINE, dingy yellowish-brown; SOLANINE, yellow at first, finally brownish; EMETINE, brown; COLCHICINE, first green, then dirty brown; ANILINE, after a long time, acquires a blue colour extending from the edges inwards; CONINE becomes light-yellow. PIPERINE colours the sulphuric acid blood-red, and is turned dark-brown, almost black by the cerium oxide" (Sonnenschein).

"_Reactions with picric acid._ This acid is a very good precipitant for alkaloids, affording a very delicate test for many of them, and may perhaps also serve for separating them one from another. The precipitation takes place even in solutions containing a large excess of sulphuric acid, and is sometimes complete. _Precipitated_ are, BRUCINE, STRYCHNINE, VERATRINE, QUINIDINE, CINCHONINE, and most of the opium alkaloids; _not precipitated_, MORPHINE, ATROPINE (English), PSEUDO-MORPHINE, CAFFEINE, and all glucosides" (Hager).

The presence of one or more of the alkaloids being shown by any of the preceding methods, a portion of the original clear solution or powder, or of the precipitates or filtrates above referred to, must be treated with their characteristic tests, as given under the individual notices of these articles, so as to set at rest all doubt as to their ident.i.ty. No single test must ever be relied on as a positive proof. The presence of Brucia, Morphia and Strychnia may be determined in substances which after being mixed with the salts of these alkaloids have undergone the acetous, vinous, or putrefactive fermentation, as shown by Orfila, MM. Larocque and Thibierge, and many other eminent chemists and toxicologists, and confirmed, in numerous cases, by our own experiments. Opium and morphia may thus be readily detected in beer, wine, soup, and milk. A paper by Professor DRAGENDORF in the 'American Chemist' for April, 1876, may be consulted with advantage.

_Concluding Remarks._ It is a singular fact that none of the organic bases found in plants have yet been formed artificially, although several a.n.a.logous substances have been thus produced. Closely allied to the alkaloids there also exists an extensive series of neutral proximate principles, which differ from those substances chiefly in the absence of basic properties, and in most of them being dest.i.tute of nitrogen. They are usually bitter, and, like the alkaloids, generally represent the active properties of the plants in which they are found; whilst some of them possess considerable medicinal energy. Of this kind are asparagin, elaterin, gentianin, picrotoxin, salicin, &c. These two cla.s.ses of bodies, though actually distinct, are frequently confounded. See ALKALI, ORGANIC BASES, POISONS, PROXIMATE PRINCIPLES, VEGETABLES, NOMENCLATURE, &c.; also the individual alkaloids under their respective heads.

=ALKALOIDS OF ACONITE=. The nature of the active principle of aconite root does not appear to have been satisfactorily determined. Messrs Groves, Wright, and Williams contend that the _Aconitum napellus_ yields an active crystalline alkaloid, which they distinguish as _Aconitine_, and to which they a.s.sign the formula C_{33}H_{43}NO_{12}; they add that additionally the root contains more or less of another active alkaloid, which they term _Pseudaconitine_, and which is represented by the formula C_{36}H_{49}NO_{11}; they also a.s.sert that the extract of the roots contains varying quant.i.ties of certain decomposition products resulting from the saponification of the above bases by the acids, which are produced by the breaking up of part of the aconitine. The name of these decomposition products is _Aconine_ and _Pseudaconine_. Of _Aconitum ferox_ they report that it yields a comparatively large quant.i.ty of _Pseudaconitine_ and a small quant.i.ty of _Aconitine_. They further affirm that the so-called aconitine of commerce is a mixture of true aconitine and pseudaconitine with variable quant.i.ties of their alteration products, aconine and pseudaconine, and of certain amorphous unnamed alkaloids.

Messrs Paul and Kingzett contest the accuracy of these deductions, and dispute the correctness of the formula given to aconitine. Dr Paul doubts whether the alkaloid to which the active properties of the root are ascribed has ever yet been obtained in an isolated condition. He thinks it probable that the substance obtained from aconite root was to a great extent a salt of an acid, like aconitic acid. For further information the reader is referred to the 'Pharmaceutical Year Book' for 1873, 1874, 1875, 1876, and 1877.

=AL'KANET.= _Syn._ ANCHU'SA, L.; ORCANETTE, Fr.; ORKANET, Ger.; OR'CHANET*, DYER'S AL'KANET, D. BU'GLOSS*. The _anchu'sa tincto"ria_ (Willd.; _lithosper'mum tincto"rium_--Linn.), a deciduous herbaceous plant, with a perennial, dark blood-red root. _Hab._ Asia Minor, Greece, Hungary, &c. It is also largely cultivated in the neighbourhood of Montpellier. The dried root (ALKANET ROOT; RADIX ANCHUSae, R. A. TINCTORIae) is chiefly imported from the Levant. It contains a beautiful blood-red colour, which it freely gives out to oils, fats, wax, spirits, essences, and similar substances, by simply infusing it in them, and is consequently much employed to colour these articles. Wax tinged with it, and applied on warm marble, stains it of a rich flesh-colour, which sinks deep into the stone, and possesses considerable durability. Its spirituous tincture also imparts a deep red to marble.

_Prop._, _&c._ The colouring matter of alkanet was regarded by Pelletier as a fatty acid (ANCHUSIC ACID); but it has since been shown to be a species of resin (ANCHUSINE, PSEUDO-ALKANNINE, P.-ALKANIUM). According to Dr John, good alkanet root contains 5-1/2 per cent. of this substance.

Anchusine melts at 140 Fahr.; is scarcely soluble in water, to which it only imparts a dirty red colour, but is very soluble in alcohol, oils, and acetic acid. Alkalies turn it blue. It is found wholly in the root-bark.

In selecting this article, the smaller roots should therefore be chosen, as they possess more bark than the larger ones, in proportion to their weight. Exposure to ammoniacal fumes, or even handling it much with the fingers, changes its red to a crimson or purplish hue.

_Uses_, _&c._ It is much employed by druggists and perfumers to colour oils, lip-salves, plasters, pomatums, &c.; by varnish-makers, to tinge their varnishes and lacquers; by statuaries to stain marble; by dairy-farmers, to colour cheese; by wine-merchants and bottlers (in the form of tincture), to stain beforehand the corks of their port-wine bottles, in order to imitate the effects of age, and as colouring and flavouring for fact.i.tious port wine; and by dyers, and others. A species of crimson rouge was formerly prepared from it (hence its name).

=ALLANTO'IC ACID.= See ALLANTOIN.

=ALLAN'TOIN.= C_{8}H_{6}O_{6}N_{4}. _Syn._ ALLANTO'IC ACID*, AMNIOT'IC A.

AM'NIC A.; ALLANTO'NA, L. A substance discovered by Vauquelin and Buniva in what they imagined to be the liquor amnii of the cow, and hence named by them amniotic acid. It was afterwards shown by Dzondi and La.s.saigne to exist in the fluid of the allantos, and not of the amnios. It has since been produced artificially by Wohler and Liebig.

_Prep._ 1. The allantoc fluid of the ftal calf is evaporated to 1-4th or 1-5th of its volume, and then set aside for some time. The crystals thus obtained are purified by re-solution, digestion with animal charcoal, and re-crystallisation.

2. (Wohler and Liebig.) Uric acid, 1 part; is dissolved in water, 20 parts; and freshly precipitated and well-washed binoxide of lead is added to the solution until the colour ceases to change; the liquid is next filtered while hot, evaporated until a pellicle forms on the surface, and then set aside to crystallise; the crystals being purified as before.

_Prop., &c._ Small, but very brilliant prismatic, transparent, colourless crystals; tasteless; neutral; soluble in 160 parts of cold water, and in much less at 212; nitric acid converts it into ALLANTURIC ACID; oil of vitriol resolves it into ammonia, carbonic acid, and carbonic oxide; hot concentrated solutions of the caustic alkalies change it into ammonia and oxalic acid.

=ALLANTOX'Ic.u.m.= [L.] _Syn._ ALLANTOX'Ic.u.m, L. (prim., Gr.). The poison developed, during putrefaction, in sausages made of blood, liver, &c. "It often proves speedily fatal." (Kraus.)

=ALLGEMEINE FLUSSTINCTUR= (Sulzberger, Salzungen). For the relief of a number of diseases, among which are cholera and sea-sickness. Aloes, 1 part; spirit of wine, 2 parts. (Spau.)

=ALLIA'CEOUS= (-sh'us). _Syn._ ALLIA'CEUS, L.; ALLIACe, AILIACe, Fr.; k.n.o.bLAUCHARTIG, &c., Ger. Garlick-like; an epithet applied to substances having the odour or properties of garlic or onions.

=Alliaceous Plants.= Chives, garlic, leeks, onions, rocambole, shallots, &c.

=ALLIGA'TION.= _Syn._ ALLIGA'TIO, L. In _commercial arithmetic_, a rule for ascertaining the price or value of mixtures, and for determining the proportions of the ingredients that must be taken to produce mixtures of any given price, value, or strength. The first is called ALLIGATION ME'DIAL; the second, ALLIGATION ALTERN'ATE. Its principles and applications are explained under MIXTURES (Arithmetic of).

=ALLOP'ATHY.= _Syn._ ALLOPA'THIA, L. (from ?????, _other_, _different_, and pa???, _affection_ or _disease_, Gr.); ALLOPATHIE, Fr. In _medicine_, the method of curing disease by the use of remedies which tend to produce a condition of the system, either differing from, opposed to, or incompatible with the condition believed to be essential to the disease it is sought to cure. It is commonly employed to distinguish the ordinary system of medical practice from h.o.m.opathy (which see). Hence (an) ALLOP'ATHIST, and the corresponding adjective ALLOPATH'IC (_allopath'icus_, L.).

=ALLOT'ROPY.= _Syn._ ALLOT'ROPISM; ALLOTRO'PIA, ALLOTROPIS'MUS, L.

Literally, a difference in character; another form of the same substance.