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Baryta is added to the residue, the precipitated barium sulphate removed by filtration, and the excess of baryta precipitated by carbonic anhydride. On acidifying the filtrate with acetic acid, bromoquinolinecarboxylic acid is deposited as a white powder. The pure acid melts at 275°. It is insoluble in water, but dissolves in boiling alcohol and in hot acetic acid. The ammonium salt yields crystalline precipitates with barium and calcium chlorides, and with potassium dichromate, and amorphous precipitates with lead acetate and mercuric chloride. The platinochloride, (CHO2N Br), H2PtCl + 4H2O, is crystalline Reduction with tin and hydrochloric acid converts bromoquinoline carboxylic acid into tetrahydroquinolineanacarboxylic acid,

C,NH10 COOH [COOH = 4];


this forms colourless needles, and melts at 146-147°. The hydro- chloride, CHO2N, HCl + H2O, crystallises in colourless needles** 1 The nitrosamine is deposited from alcohol in yellow prisms, which melt at 186° with decomposition. This tetrahydro-derivative is identical with the tetrahydroquinolinecarboxylic acid described by Fischer and Körner (Abstr., 1884, 1197).

Skraup and Brunner (Abstr., 1886, 811) have recently shown that the carboxyl in quinolinecarboxylic acid from metamidobenzoic acid (which is identical with Fischer's acid) occupies the 4 (ana) position. The quinolinecarboxylic acid which the authors prepared from metamidobenzoic acid differed in many of its properties from the acid which Skraup obtained from the same source. The chief points of difference are as follows:-The acid melts at 338°. The hydrochloride, C10H-O2N,HCl, crystallises in colourless needles or prisms containing 1 mol. H2O. The aqueous solution of the ammonium salt gives with lead acetate a white precipitate insoluble in acetic acid, no precipitate with nickel sulphate, and a pale blue precipitate with copper salts, soluble in excess of the reagent on boiling, and crystallising out on cooling.

Both quinolinecarboxylic acids yield the same tetrahydro-derivative. The following formulæ are proposed for these isomerides.

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Synthesis of Metaquinolinecarboxylic Acid. By M. TORTELLI (Gazzetta, 16, 366).—When a mixture of the stannochloride of amidophthalic acid, C ̧H2(NH2) O1,HSnCl, + 2H2O, and nitronaphthalic acid is heated with glycerol and sulphuric acid, as in Skraup's reaction, it yields a mixture of quinoline- mono- and di-carboxylic acids; these may be separated by repeated sublimation, the latter being gradually converted into the former with elimination of the carbonic anhydride. The monocarboxylic acid crystallises in minute needles which melt at 248.5-250°; it is insoluble in ether, almost insoluble in benzene and cold water, readily soluble in alcohol. Its solutions give various

precipitates with ferrous and ferric, copper, silver, cobalt, and nickel salts. This acid is identical with one recently obtained by Skraup from metamidobenzoic acid (this vol., p. 160). V. H. V.

a-Alkylcinchonic Acids. By O. DOEBNER (Ber., 20, 277-281). The author explains the formation of aniluvitonic acid (2′: 4' methylquinolinecarboxylic acid) from aniline and pyruvic acid by assuming that acetaldehyde is intermediately formed by the splitting up of a molecule of pyruvic acid, and then condenses with aniline and a second molecule of pyruvic acid after the manner of the quinaldine synthesis. The correctness of this assumption has been proved by preparing the whole series of a-alkylcinchonic acids by the action on aniline of a mixture of pyruvic acid with the homologues of acetaldehyde, the reaction being expressed by the general equation -N: CRR-CHO + CMeOCOOH + CHNH, = C2H1<C(COOH)>CH + 2H2O+ H2. These acids, on distillation with lime, are readily converted into the a-alkylquinolines. A more detailed description of these substances will be given later.

If an aldehyde and aniline in alcoholic or ethereal solution are allowed to react with pyruvic acid in the cold, neutral crystalline compounds are formed, which are not related to the quinoline series, and from which aniline can again be readily obtained; these will be described later. If, on the other hand, the mixture in alcoholic solution is heated for four hours on the water-bath in a reflux apparatus, then the a-alkylcinchonic acids are formed and in part separate on cooling, in part are obtained on evaporating the solution. They are readily purified by crystallisation from acetic acid or alcohol.

a-Ethylcinchonic acid, C,NH,Et COOH [2': 4'], prepared from propaldehyde, pyruvic acid, and aniline, crystallises in colourless plates, melts at 173°, and is soluble in both acids and alkalis. The silver salt, C12H0NO2Ag, forms white plates soluble in water. a-Ethylquinoline, C,NH.Et [Et = 2'], prepared by distilling the acid with sodalime, is a colourless oil of quinaldine-like odour, and boils at 245— 246°. The platinochloride, (CHN)2, H2PtCl + 2H2O, crystallises in orange-red needles.

a-Isopropylcinchonic acid, C,NH,Pr-COOH [2' : 4'], obtained from isobutaldehyde, pyruvic acid, and aniline, in well-formed crystals, melts at 146°. When heated with soda-lime, it yields a-isopropylquinoline, C,NH.Pr, a colourless oil boiling at 255°; the platinochloride, (C2H3N)2,H,PtCl + 2H2O, crystallises in yellow needles.

a-Isobutylcinchonic acid, CHC,NH, COOH [2': 4'], prepared from isovaleraldehyde, pyruvic acid, and aniline, crystallises in silky, white plates, melting at 186°. When distilled with soda-lime it gives a-isobutylquinoline, C,NH, CH,, as a colourless oily liquid of peculiar odour, boiling at 270-271°. The platinochloride forms large, orangered, anhydrous needles.

a-Phenylcinchonic acid, C,NH,Ph-COOH [2' : 4'], prepared as above from benzaldehyde, crystallises in colourless needles, melts at 202203°, forms a platinochloride crystallising in orange-red needles, and when distilled with soda-lime yields the known a-phenylquinoline.

A. J. G.

Isoquinoline and its Derivatives. By S. HOOGEWERFF and W. A. VAN DORP (Rec. Trav. Chim., 5, 305-312).-Isoquinoline, isolated from coal-tar, can be regarded as a B-derivative of naphthalene. It is best obtained in a state of purity by recrystallising its sulphate from alcohol until the melting point of the salt (205°) is constant; the free base melts at 22° and boils at 240-245°. It forms crystalline combinations with various metallic salts, and unites with the alkyl iodides, to form replaced ammonium iodides such as isoquinolinemethylammonium iodide, C,H,N,MeI, crystallising in plates melting at 158-161°, and the corresponding ethyl compound, C,H,N,EtI, which crystallises in tables melting at 147°. The substances are distinguished from similar derivatives of quinoline in not forming cyanines.

Isoquinoline yields a sulphonic acid, the barium salt,


of which crystallises in needles. On hydrogenation, the base yields a tetrahydro-additive product, C,H1N, a liquid boiling at 232°, and not solidifying at -15°; it absorbs carbonic anhydride to form a crystalline carbonate; a hydrochloride, crystallising in small tables melting at 232°, and a platinochloride in reddish-yellow tables, were also obtained. It seems that these quinoline-derivatives are of therapeutic value.

V. H. V. Acid Morphine Meconate. By D. B. DoTT (Pharm. J. Trans. [3], 17,690). The author has not succeeded in preparing and identifying morphine hydrogen meconate.

Constitution of Brucine. By A. HANSSEN (Ber., 20, 451-460). -With the view of throwing further light upon the constitution of brucine, the preparation and composition of kakotheline, originally obtained by Strecker, have been further investigated. To this substance is ascribed the formula CaH22N4O9, instead of C20H22N4O9, hitherto accepted. When reduced, it yields a base, the analysis of whose hydrochloride pointed to a formula C2H25N3Os, derived from kakotheline by the reduction of one nitro-group and elimination of another. With bromine, kakotheline yields an acid substance, CHNO, the platinochloride of which crystallises in orange-yellow needles, its silver salt in glistening needles; its methyl salt could not, however, be obtained, but the crude product treated with ammonium chloride yielded a base, C19H22Me N2O7, crystallising in yellow, sparingly soluble prisms. In this reaction, the acid seems to be analogous to nicotinic acid, and thus it would appear that in kakotheline, as also in brucine, a pyridine grouping is present. The above acid when oxidised with chromic acid yields the base C16H18N2O4, obtained formerly as a product of decomposition of brucine. According to the author there is present in brucine, besides a quinoline-group, also a dimethoxyphenylpyridine, and in strychnine, a phenylpyridine residue; the stability of brucine seems to indicate a ring-arrangement.

V. H. V. Hydrastine. By J. F. EIJKMAN (Rec. Trav. Chim., 5, 290-298). -Mahla, Power, and more recently Freund and Will (this vol., p. 174),



have examined hydrastine, a principle obtained from the Hydrastis canadensis. The formula assigned to this substance by these chemists is C22H2NO6, that of the author is more in accordance with the formula C2H21NO6, and the results are also confirmed by analysis of the auroand platino-chlorides, as also of the sulphate. The specific rotatory power is [a] =-663, 7200, in chloroform solution, a value practically equal to that of Freund and Will. On decomposition with nitric acid, it yields opianic acid and a 12-carbon nitrogeneous compound, a result more simply explained by the above formula, thus: C2H21NO + H2O + 0 = Č12HNO3 + C10H1005.

V. H. V. Note.-Freund and Will, in a more recent communication than that referred to above, have independently shown the formula to be C21HNO (see this vol., p. 383). A. J. G.

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Optical Behaviour of Cocaïne. Method for Determining the Purity of Cocaïne Hydrochloride. By O. ANTRICK (Ber., 20, 310-322).-Analyses of cocaïne hydrochloride pointed to Lossen's formula, C12H2NO1,HCI. Solutions of cocaïne are lævorotatory. Determinations of the specific rotatory power of cocaïne hydrochloride from different sources in dilute alcoholic solution lead to the equations [×]D = 52 180+ 0.1588 × q (q solvent) and [a]D = 67.982 0·15827 × c (c = concentration of solution). When q=0 [a]D 52.180; when q = 100 [a]D = 68·060. To determine the purity of a preparation, the angle is measured at which the plane of polarised light is turned by the solution. A solution is conveniently used in which 100 c.c. (at 20°) contain 10 or 20 grams of dry cocaïne salt to be tested. A 10 per cent. solution should give (with a tube 200 mm. . long) at 20° an angle 13.280°; a 20 per cent. solution an angle 25.927°. When with a 10 per cent. solution the angle is between 13.25° and 13.31°, and with a 20 per cent. solution between 25.90° and 25.96°, the sample is pure. Free cocaïne melts at 98°. The solution in chloroform at 20° has the specific rotatory power [a]D = 15.827 +0.005848 x q. When q = 0 [a] = −15·827.

N. H. M.


Action of Pepsin on Amyloïd. By S. KOSTIURINA (Chem. Centr., 1887, 120).—Working with pure amyloid, the author found, contrary to the usual statements, that it was soluble in pepsin solution acidified with hydrochloric acid. The probable cause of the mistake is that the organs containing amyloïd have not been divided sufficiently fine before being examined. In order to prepare the amyloïd, the diseased organ was cut in small pieces, the blood washed out with water, then boiled with water, alcohol, and ether, and the purified product submitted to the action of pepsin. After acting on diseased liver so purified with pepsin for 48 hours, a residue remained with the properties of amyloïd; this, when finely powdered and again submitted to the action of a strong digestive solution at 40-50° for 48 hours, was almost entirely dissolved, only a very slight residue of nucleïn and tissue remaining. A similar result was obtained with finely chopped diseased spleen. G. H. M.

Vegetable Globulins. By S. H. C. MARTIN (Proc. Physiol. Soc., 1887, 8-9).-Vegetable globulins can be divided into two classes, namely, vegetable myosins and vegetable paraglobulins. The myosins, obtained from the flours of wheat, rye, and barley, have similar properties; they are all readily soluble in 10-15 per cent. sodium chloride solution, and are precipitable from this solution by saturation with sodium chloride or magnesium sulphate. They are soluble in 10 per cent. magnesium sulphate solution, and are coagulated in this solution at a temperature of 55-60°. If the salt is dialysed away from the saline solution of myosins, the latter is precipitated; but the precipitate is no longer a globulin, since it is insoluble in saline solutions. It is soluble in dilute acid and alkalis (0.2 per cent.); it is precipitable from these solutions by neutralisation, the precipitate being soluble in excess of alkali or acid; that is, the myosin has been converted into a proteïd, having the properties of an albuminate. If the saline solution of myosin be placed in an incubator at a temperature of 35-40°, in 12 to 18 hours a fine flocculent precipitate falls, while the globulin disappears from the solution; this takes place more rapidly if the saline solution is diluted. The precipitate exhibits the same properties as the precipitate of the globulin by dialysis; that is, at a temperature of 35-40° the globulin is transformed into an albuminate. The ready transformation of the soluble globulin of wheaten flour into an insoluble albuminate is one of the phenomena which takes place during the formation of gluten (Abstr., 1886, 1065).

The second class of vegetable globulins, the paraglobulins, is in distinct contrast with that of the myosins. Two proteïds of this class have been found, one in papaw juice (Abstr., 1886, 612), the other in the seeds of Abrus precatorius (jequirity). Both these globulins exhibit the following properties: they are soluble in saline solutions, and are precipitated by saturation with sodium chloride and magnesium sulphate. In a 10 per cent. solution of magnesium sulphate, they coagulate between 70° and 75°. When precipitated from their saline solutions by dialysis, they are still soluble in solutions of sodium chloride and magnesium sulphate of 10-15 per cent., not being transformed into albuminates. Nor are they precipitated by long exposure (over three days) to a temperature of 35-40°.

W. D. H.

Physiological Chemistry.

Estimation of the Carbonic Anhydride Expired, and the Oxygen Absorbed in Respiration. By M. HANRIOT and C. RICHET (Compt. rend., 104, 435-437).-The inspired air passes through a meter, and the expired air passes through two meters, between which is the apparatus for absorbing the carbonic anhydride. The difference between the readings of the first and third meter gives the volume of oxygen absorbed, and the difference between the second and third

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