729

cold, additive products of little stability are formed; whilst at the temperature of the water-bath, the sulphonic group is displaced by bromine. A dibromoquinoline which sublimes in needles melting at 255°, and a tribromoquinoline melting at 199, have been thus obtained.

Quinolinemetasulphonic acid when fused with potash yields a hydroxyquinoline, which softens at 165° and melts below 200°; whilst the ana-compound prepared synthetically from amidobenzenemetasulphonic acid yields an hydroxyquinoline, melting sharply at 224° (uncorr.).

green

Sodium quinolineorthosulphonate crystallises in needles with 5 mols. H2O, the potassium salt with 2 mols. H2O, and the copper salt in small needles with 2 mols. H2O. The lead salt is anhydrous. Quinolineorthosulphonic acid cannot be directly brominated, but bromoquinolineorthosulphonic acid may be obtained by heating ethyl The sodium salt orthoquinolinesulphonate with bromine in sealed tubes at 180°. It decomposes at 350° without previously melting. (1 mol. H2O) crystallises in needles; the lead. silver, and potassium The copper salt (2 mols. H2O) forms dark-green salts are anhydrous. prisms. The sulphochloride melts at 88°, the sulphonamide at 185°, and the ethyl salt, C,H,BrNSO,Et, at 98°.

On treating an aqueous solution of bromoquinolineorthosulphonic acid with bromine, a new tribromoquinoline crystallising in yellow prisms and melting at 205° is obtained.

G. T. M.

Cinchoniline. By E. JUNGFLEISCH and E. LÉGER (Compt. rend., 106, 657—660).—Cinchoniline, C19H2N2O, is obtained by treating the dihydriodide (this vol., pp. 380 and 507) with sodium hydroxide, The ethereal solution is washed which is then agitated with ether. with water and concentrated, when it deposits bulky, yellowish Cinchoniline cryscrystals, whieh are purified by recrystallisation.

tallises more readily than its isomerides, and forms very large, colourless, anhydrous, right rhomboidal prisms. It melts without decomposition at 130-4°, and distils in a vacuum without undergoing rapid alteration; rotatory power of a 1 per cent. solution in alcohol = +53-22°; in a per cent. solution [a] = of 97° at 75° [a]D +50.3°. In a 1 per cent. solution in dilute hydrochloric acid containing = +59·15°; if 4 mols. 2 mols. HCl for each molecule of base [a]D The base is only slightly soluble in water, HCl [a]D = +63·10°. but the solution is strongly alkaline to litmus and phenolphthalein. It dissolves readily in ethyl and methyl alcohols, chloroform, benzene, It reduces potassium permanganate in the cold, ether, and acetone. and when decomposed by heat yields the same products as cinchonine.

Cinchoniline forms basic salts which are feebly alkaline to litmus and normal salts which have no acid reaction; the majority of the salts are very soluble in water, and have a remarkable power of forming large crystals. The basic hydrochloride, CHN2O,HCl, is extremely soluble even in cold water, but crystallises from the syrupy solution in very large, oblique, rhomboidal prisms which melt with decomposition at 226°. In an aqueous solution containing 1 per cent, [a] = +50°

at 16°. The platinochloride forms small, orange-yellow prisms containing 1 mol. H2O; the aurochloride, (CHN2O,2HCl, AuC)2 + H2O, crystallises in small, bright yellow, highly refractive prisms. The basic hydrobromide, C19H2N2O,HBr + 3H2O, is much less soluble than the basic hydrochloride, and forms long prisms which melt with decomposition at about 228°. The basic hydriodide is very soluble in water, and forms short, colourless prisms containing 1 mol. H2O. It melts with decomposition at about 221°. The normal hydriodide, obtained by adding an alkaline iodide to a normal cinchoniline salt, forms short, hard, bright yellow anhydrous prisms, insoluble in water containing hydriodic acid. The basic thiocyanate,

C19H22N2O,CNOH + H2O,

forms long, silky, efflorescent needles only slightly soluble in cold water; the basic chromate forms an oily precipitate; the basic oxalate is extremely soluble, and crystallises in large prisms; the normal oxalate is likewise very soluble, and crystallises in needles; the normal picrate is amorphous.

Cinchoniline methiodide, C19H22N2O,MeI, obtained by the action of methyl iodide on the base in presence of anhydrous ether, crystallises from alcohol in short, highly refractive prisms, and from water in long, colourless prisms. Both forms are anhydrous and melt with decomposition at about 233°. The ethiodide, obtained in a similar manner, crystallises from water or alcohol in highly refractive prisms containing 1 mol. H2O. It is very soluble in water, alcohol, and chloroform, but is insoluble in benzene or ether. Cinchoniline ethobromide forms hard crystals, and is soluble in alcohol, but insoluble in ether. C. H. B.

Ptomaïnes. By O.. DE CONINCK (Compt. rend., 106, 858-861).— The flesh of cuttle fish, with the sepia bags removed, was allowed to putrefy, and the alkaloids were extracted by Gautier's process. Several of the ptomaïnes described by Brieger were obtained, and two others of the composition C.HN and C10H1SN respectively.

The alkaloid C,HN is a somewhat mobile, yellowish, strongly smelling liquid, very soluble in water, and also readily soluble in methyl or ethyl alcohol, ether, and acetone. When dry, it boils without decomposition at 202°; sp. gr. at 0° = 0·9865. When exposed to air, it becomes brown and absorbs moisture, and then boils at a lower temperature. The hydrochloride, CH1N,HCl, forms deliquescent, white or yellowish radiating masses, very soluble in water at all temperatures. The hydrobromide is similar, but is less deliquescent and less soluble. The platinochloride, (CHN)2, H,PtCl, is deep yellow and almost insoluble in cold water, but soluble in hot water. It is somewhat stable, but decomposes more readily than the platinochlorides of the pyridine bases. Water at 80° or 100° decomposes it with formation of a pale brown powder (CHN)2, PtCl, insoluble in cold water, and almost insoluble in hot water. The aurochloride is pale yellow, and is somewhat stable in the cold, but decomposes on heating.

The salts of this ptomaïne are less stable than those of the pyridine

bases, and more closely resemble the salts of hydropyridines. If a cold solution of the hydrochloride is mixed with excess of gold chloride, some gold is reduced. C. H. B.

Ptomaïnes. By I. GUARESCHI (Chem. Centr., 1888, 45, from Ann. Chim. Farm., 87, 237-249).—The author has made some experiments with the object of excluding, if possible, the objection that has been urged with regard to these bases, namely, that they may not pre-exist, but arise from the action of the reagents (acid, alcohol, &c.) used in their extraction. From putrid fibrin, he has obtained a very satisfactory yield of a base, CH13N, previously described by him, by making the mass alkaline with baryta in the cold, and extracting with ether and chloroform. This base pre-exists in the patrid fibrin. From the chloroform extract, another compound, CH20Ñ2O4, which appears to be an amido-acid, was obtained. It forms beautiful, shining plates melting at 248-250°, soluble in water and alcohol, but not readily soluble in chloroform. The watery solution is neutral or feebly acid, and gives all the general alkaloïd reactions. When a weak hydrochloric acid solution of the base is precipitated with platinum chloride, the platinochloride of the base CH3N is formed.

J. P.. L.

A Cadaveric Alkaloïd behaving like Strychnine. By C. AMTHOR (Chem. Centr., 1888, 43, from Chem. Zert., 11, 288)-An alkaloïd with strychnine-like properties has twice been obtained from parts of a corpse eight days old.

The chief differences between this alkaloid and strychnine are:-(1) It is less poisonous than strychnine when injected subcutaneously in the frog; (2) from alkaline solutions, ether dissolves but a very small quantity, whereas amyl alcohol dissolves it easily; (3) the taste is less bitter; (4) the precipitates with potassium ferrocyanide and ferricyanide, potassium chromate and picric acid are amorphous, those of strychnine crystalline; (5) the blue colour with potassium chromate and sulphuric acid is less persistent and less pure than the colour formed with strychnine. J. P. L..

Hæmoglobin of Dog's Blood. A. JAQUET (Zeit. physiol. Chem., 12, 285-288). Hæmoglobin was prepared from dog's blood, according to the method adopted by Zinoffsky (Abstr., 1886, 165) in the case of horse's blood, and then twice recrystallised. Elementary analysis. gave the following percentage results, which for the sake of comparison are placed side by side with the numbers obtained by

Zinoffsky :

Action of Alloxantin on Blood. By N. KOWALEWSKI (Chem. Centr., 1887, 1296, from Med. Centr., 25, 658-659, 676-678).—The author refers to a former paper (Abstr., 1887, 508) regarding the change into methæmoglobin that hydroxyhemoglobin undergoes by the action of alloxantin, and shows in several instances how this change may take place under the influence of reducing agents. By the action of alloxantin on blood, the former reduces the oxyhemoglobin to hæmoglobin, and is oxidised itself to such compounds as are able to change the reduced hæmoglobin into methæmoglobin. J. W. L.

Physiological Chemistry.

Chemistry of Fish; Analysis of American Specimens. By W. O. ATWATER (Amer. Chem. J., 10, 1-20; compare this vol., p. 308). -Tables are given of the composition of the flesh of fish, showing matters extracted by cold water and not coagulated; albumin coagulated from cold water extract; gelatin extracted by hot water; insoluble proteïn; fats, ash, and water; also tables showing the amounts of phosphorie, sulphuric, and hydrochloric acids in the ash. From these data, tables are constructed showing the relative value of various fish as foods. Analyses are also given of fresh and whole fish, and of salted and cured, or canned fish.

H. B.

Occurrence of Fluorine in the Organism. By G. TAMMANN (Zeit. physiol. Chem., 12, 322-326).-The method adopted for the quantitative estimation of fluorine was as follows:-The substance under investigation was treated with powdered quartz and sulphuric acid. A current of dry air carried the silicon fluoride so formed through a narrow tube where it was decomposed with steam and the silieic acid collected on the walls of the tube, hydrofluosilieie acid being also formed; the latter was absorbed in aqueous potash, and evaporated to dryness; the residue was taken up with hydrochloric acid, the potassium silicofluoride precipitated with alcohol, filtered, and titrated with potassium hydroxide solution. Fluorine is well known to be a constant constituent of bone; it is also known to occur in ploughed earth and in wells. Horsford (Annalen, 149, 202) found weighable quantities of fluorine in the human brain, and Salm-Horstman (Ann. Phys. Chem. 114, 510) found that certain plants did not fully develop in the absence of fluorine.

In the present research, plants grown in culture liquids whieh did not contain fluorine, were found to die quickly when fluorine was added to such liquids; thus, the addition of 01 gram of potassium fluoride per litre caused death in these plants in 12 hours.

The different parts of the egg were investigated; the shell contained imponderable traces only; the white contained somewhat larger traces, but still imponderable; the yolk yielded weighable quantities; 84 grams of fresh yolk contained 0·0009 gram of fluorine. Attention

is drawn to the fact that the brain and egg-yolk, tissues that contain much phosphorus, are also richest in fluorine. In other experiments, brain, cow's milk, and blood were found to contain small weighable quantities of fluorine.

From these experiments, certain conclusions are drawn, the chief purport of which is, that fluorine is of greater physiological importance in the animal economy than has hitherto been considered to be the case. W. D. H.

Digestion of Albumin. By J. Boas (Chem. Centr., 1887, 1226, from Zeit. Klin. Med., 12, 231).—A comparative study of the three chief products, syntonin, hemialbumose, and peptone, of the artificial and natural digestion of albumin has been made. In artificial digestion, syntonin is formed at a very early stage with all the three kinds of albumin experimented on (fibrin, egg albumin, and scraped meat); the amount formed, however, varies considerably.

Hemialbumose is a constant product of fibrin digestion and a frequent product, though in much smaller quantity, of egg albumin digestion; it is altogether absent in the digestion of meat. Hemialbumose must be regarded more as a bye-product of digestion than as an intermediate step in the process, for, like syntonin, it is a product of the action of acid. Any hemialbumose formed is gradually converted into peptone, so that after long prolonged artificial digestion, syntonin and peptone, the first and last terms of the process, alone are present.

As far as the products are concerned, artificial and natural digestion are similar, but essential differences occur in the time of appearance and disappearance of the various modifications of proteïd. The artificial and natural digestion of fibrin are most alike. In artificial digestion, all three modifications are generally present from the beginning to the end of the digestion, but towards the end of natural digestion peptone is the almost exclusive product. J. P. L.

Food of Larval Bees. By A. v. PLANTA (Zeit. physiol. Chem., 12, 327-354).-The substance investigated was the juice or pap, the whitish sticky substance which the working bees store in the cells of the larvae of the queens, drones, and workers. Leuckart (Deutsche Bienenzeitung, 1854, 1855) regarded it as the product of the true stomach of the working bees, which they vomit into the cells, in the same way that honey is vomited from the honey-stomach. Fischer and others regarded it as the product of the salivary glands of the bees. Schönfeld, in numerous papers, references to which are given, has more recently shown that Leuckart's original view is the correct one. He showed that the saliva can be easily obtained from the salivary glands of the head and thorax, and that it is very different from the food-juice deposited in the cells by the bees; and that, moreover, the juice is similar, both chemically and microscopically, to the contents of the bee's true stomach; he showed also from the consideration of certain anatomical and physiological peculiarities of the bee, such as the position of the mouth, the inability of the bee to spit, &c., that the view of this substance being saliva is quite untenable. Certain 3 с

VOL. LIV.