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soluble in water but insoluble in solutions of caustic alkalis. The violet-colour changes to yellow when the alkaline solutions are boiled, and phenylmethylketopyrazolone and diphenylhydrazineacetylglyoxylic acid are probably formed. The latter compound melts at 212°, dissolves in alkalis, and dyes silk yellow. Phenylhydrazine phenylmethylketopyrazolone is formed when equivalent quantities of rubazonic acid and phenylhydrazine are boiled together in acetic acid. The compound crystallises in golden needles and melts at 155°.


On distillation with zinc-dust, phenylmethylpyrazolone yields aniline, benzene, ammonia, methyl cyanide, and phenylmethylpyrazine, CN,HPhMe [13]. Antipyrine, CN,HPh Me2O [Ph: Me 1:23], has been already described (Abstr., 1884, 1153, 1378). The picrate melts at 188°. The ferrocyanide and the platinochloride, (C1H12N2O)2,H2PtCl + 2H2O, crystallise in prisms. Ferric chloride gives a deep brownish-red coloration with a neutral solution, and sodium nitrite gives an intense emerald coloration with a slightly acid solution of antipyrine. The formation of methylantipyrine, C1N,PhMe,O [1:2:34], has already been mentioned. This substance melts at 82-83°, and boils at 286° under 153 mm. pressure. The base is freely soluble in water, alcohol, and chloroform. The aqueous solution gives a violet-red coloration with ferric chloride and a white precipitate with potassium ferrocyanide. The picrate melts at 94°. Di-antipyrine, C,N,PhMe2O - C1N2PhMe2O, prepared by the action of methyl iodide and methyl alcohol on dis-phenylmethylpyrazolone, melts at 245° and dissolves freely in chloroform. The picrate is deposited from alcohol in needles and melts at 161°; the hydrochloride, C2H22N,O2,2HCl + 2H2O, forms monoclinic crystals. The platinochloride crystallises in prisms and melts about 232-236° with decomposition.

The nitroso-, nitro-, and benzylidene-compounds have been previously described (loc. cit.). Antipyrine dibromide, CH12N2OBr2, is formed when bromine is added to a solution of antipyrine in chloroform. It is unstable and easily loses hydrobromic acid, forming bromantipyrine. It is soluble in alcohol and chloroform and melts about 150°. Bromantipyrine, C3N,PhMe OBr, is deposited from hot water in needles, and is soluble in alcohol, chloroform, and hot toluene. The compound melts at 117°. W. C. W.

Alkaloïds. By O. DE CONINCK (Compt. rend., 104, 513-515).— Equal volumes of sparteïne, alcohol, and ethyl iodide heated together in sealed tubes at 100° for several hours yield needles of the ethylspartylammonium iodide, CH,EtN2I2, described by Mills. The corresponding methyl-derivative forms white crystals. If either of these compounds is dissolved in a slight excess of warm alcohol, the solution rapidly becomes rose-coloured, but if some drops of potassium hydroxide solution of 45° are now added, no deep coloration is produced. It follows that sparteïne differs from the pyridines and dipyridines.

Nicotine reacts readily with ethyl iodide and yields a yellow, translucent solid which dissolves in warm, absolute alcohol, forming a deepbrown solution. If this is mixed with potash of 45°, and heated on a water-bath for 10 hours, a garnet-red coloration is produced which

afterwards changes to carmine. When the solution is mixed with an excess of hydrochloric acid and is poured into acidified water, there is no change of colour and no fluorescence, but after 24 hours the liquid becomes yellow.

It is evident from this behaviour that nicotine is related to the pyridic and dipyridic alkaloïds.

C. H. B. Strychnine. By C. STOEHR (Ber., 20, 810-814).-In order to obtain evidence on the view of Hanssen that strychnine contains a phenylpyridine-group as well as a quinoline-group (this vol., p. 505), the author has distilled strychnine with alkali and obtained, in addition to a hydride of pyridine, not fully examined, 7-picoline, identified by analyses of its auro- and mercuro-chlorides, and crystalline form, as also by the melting point of the latter. Experiments to obtain methyl chloride as a product of the decomposition of strychnine were unsuccessful. It is shown that strychnine does not contain a hydroxyl-group, in that by treatment with phosphorus pentachloride the atoms of oxygen remain intact, whilst three hydrogen-atoms are displaced by chlorine to form a trichloro-derivative, C2HCl3N2O2, the hydrochloride and sulphate of which crystallise in leaflets.

V. H. V.

Phenylpiperidine. By E. LELLMANN (Ber., 20, 680–681).— Phenylpiperidine, C,NH,Ph, is obtained by heating bromo- or iodobenzene with piperidine (3 mols.) at 250-270° for several hours. Piperidine hydrobromide (or hydriodide) is formed at the same time. Phenylpiperidine is slightly heavier than water and reacts strongly


Dinitrophenylpiperidine is readily prepared by the action of orthoparadinitrochlorobenzene on piperidine. It crystallises from alcohol in orange-coloured needles melting at 92°. From nitroparadichlorobenzene a compound, probably chloronitrophenylpiperidine, is obtained; it forms small red plates which melt at 51°.

Paranitrophenylpiperidine, C,NH10 CH, NO2, is prepared by heating parachloronitrobenzene (1 mol.) with piperidine (2 mols.) at 120° in a reflux apparatus. The product is treated with moderately strong hydrochloric acid, filtered, and precipitated with ammonia. It crystallises from hot alcohol in very large, yellow plates melting at 105°. The platinochloride was prepared. Amidophenylpiperidine, C5NH10 C6H4 NH2, is obtained by reducing the nitro-compound with tin and hydrochloric acid. It is obtained from its ethereal solution as a crystalline mass melting at 40°. N. H. M.

Berberine Salts. By C. SCHILBACH (Arch. Pharm. [3], 25, 155 -164). The results obtained by the analysis of various berberine salts confirm the observations of previous investigators as to the composition of the alkaloïd and its salts, except in the case of the hydrochloride, which is shown to have the composition indicated by the formula C20H17NO4, HCI + 4H2O.

J. T.

Action of Potassium Permanganate on Berberine. By E. SCHMIDT and C. SCHILBACH (Arch. Pharm. [3], 25, 164-170).-Berberine, under the action of concentrated nitric acid, yields a tribasic

nitrogenous acid, berberonic acid, CH2N(CO-OH), as has been shown by Weidel, and again by Fürth. It is remarkable that the principal effect of the action of potassium permanganate on berberine should be the production of a non-nitrogenous acid analogous to bemipinic acid, as J. Court has shown in an investigation instigated by one of the authors. The authors in supplementing this investigation, conducted the oxidation in an alkaline solution, and in general followed the course taken by Court. A hot dilute solution of berberine was treated with aqueous potash and then with hot potassium permanganate solution. The slight excess of permanganate was decomposed by a few drops of alcohol. Preliminary tests indicated the formation of only very minute quantities of oxalic acid. On the contrary, carbonic anhydride was freely evolved on adding excess of sulphuric acid, and a strong odour of nitric acid was perceptible. The filtrate from the manganese oxide was neutralised with sulphuric acid, evaporated to dryness, powdered, well shaken with ether, and treated with excess of moderately dilute sulphuric acid. On distilling off the ether, a brown liquid remained which deposited a considerable quantity of crystals when placed over sulphuric acid. To avoid loss, the brown liquid was dissolved in water and the contained acids were precipitated by means of a slight excess of lead acetate. The well-washed precipitate was treated with hydrogen sulphide, the lead sulphide and excess of hydrogen sulphide removed, and the liquid evaporated and set to crystallise over sulphuric acid. The filtrate from the lead precipitate was freed from acetic acid by repeated evaporation and again treated with lead acetate, when a further crop of crystals was obtained. The lead acetate treatment gave crystals much purer than those obtained by direct crystallisation of the ether extract. These crystals, dried at 100°, have a constant melting point of 160-162', and amount to about 30 per cent. of the original berberine. A small quantity of nitrogenous, nodular crystals was obtained by treating the mother-liquor of the ether extract with water, dissolving the precipitate obtained in hot water, and purifying with the aid of lead acetate. No other well characterised compounds were isolated. A considerable portion of the nitrogen of berberine was evidently converted into nitric acid during the oxidation. Another portion appeared in the form mentioned above. A further portion was converted into ammonia, or at least into compounds which gave ammonia on distillation with potash. The copious oxidation product melting at 160-162°, obtained as above, was compared with hemipinic acid, specially prepared by Schilbach from narcotine, and the two compounds were shown to be identical. J. T.

Lactucerin. By G. KASSNER (Annalen, 238, 220-228).Lactucerin can be obtained in a pure state by treating the ethereal solution with an aqueous solution of potassium hydroxide. Alcohol is then added to the ethereal extract, until a small precipitate forms. On the addition of water to the filtrate, lactucerin is deposited in white, microscopic, needle-shaped crystals. Lactucerin purified in this manner melts at 200°, but after it is purified by sublimation in an atmosphere of carbonic anhydride it melts at 210°. The results of


analyses agree with the formula C2H4O2 more closely than they do with Hesse's formula C20H32O2 (Abstr., 1886, 1020). On fusion with potash, hydrogen is evolved and lactucol, C13H20O, is formed according to the equation C2H4O2 + 2H2O = C2H ̧O2 + 2C13H 19 OH +2H2. Lactucol melts at 160-162°, and crystallises in needles. The acetate melts at 198-200°. Solutions of the alcohol and of the acetate in ether, chloroform, and carbon bisulphide are dextrogyrate. These results differ in some important respects from those of Hesse (loc. cit.). W. C. W.

Cholic Acid. By F. MYBIUS (Ber., 20, 683-688; comp. Abstr., 1886, 480, 952).-Iodocholic acid, (C20H40O5I),,KI + H2O, is obtained by adding a concentrated aqueous solution of 1 gram of potassium iodide to a solution of 2 grams of cholic acid and 0.8 gram of iodine in 40 c.c. of alcohol. The mixture is gradually diluted with water until the blue substance separates. This is then collected and washed with water. It forms a matted mass of a bronze-like lustre. When suspended in water (500 c.c.), an indigo-blue liquid is produced. When the latter is heated, it becomes yellow and cholic acid separates; when a few drops of the blue liquid are poured into water, the blue colour disappears in a few moments, and the solution is found to contain free iodine. The substance is therefore decomposed by excessive dilution. Sulphurous acid decolorises the liquid with separation of cholic acid. The solution is also decolorised by adding a few drops of soda solution, with formation of sodium cholate, iodide, and iodate; on adding hydrochloric acid, the blue compound is re-formed. When iodocholic acid is dried in a vacuum, a dark, lustrous, crystalline powder is obtained which dissolves in ether containing alcohol, yielding a yellow solution; this, when evaporated, leaves a yellow, amorphous substance which is anhydrous iodocholic acid. The latter becomes blue in presence of water.


The compound (C2HOI), HI is prepared by adding a small quantity of hydriodic acid to the brown solution of cholic acid and iodine. The liquid at once becomes blue. The compound is isolated in a manner similar to the potassium compound which it completely resembles. The barium compound, (C2H4OI),Bal, and the zinc, cadmium, and ammonium compounds are obtained by using corresponding iodides in the place of potassium or hydrogen iodides.


N. H. M.

Bile Acids. By C. SCHOTTEN (Zeit. physiol. Chem., 11, 268-276). -The author has previously suggested (Abstr., 1886, 565) that the smaller solubility of the salts of cholic acid obtained from human bile as compared with those from the ox, was due to an admixture of choleates. Further researches have led to the conclusion that the second acid in human bile is neither choleïc acid, (C25H12O4), nor the desoxycholic acid (C4H10O4) of Mylius (Abstr., 1886, 480), although both of these resemble the second acid of human bile in the insolubility of their barium salts, but a previously undescribed acid of the formula CHO1, and to which the name fellic acid is given. The insoluble barium precipitate was decomposed by boiling with sodium carbonate, the filtered solution shaken with ether, and then the free


acid obtained by means of hydrochloric acid. The barium salt, (C2H3O4)2 Ba, contains 4 mols. H2O, and is soluble in about 700 or 800 times its weight of water; the magnesium salt, (C23H3O4) Mg + 24H2O, was also prepared; from both of these salts, the free acid was obtained. Fellic acid is not homologous with cholic or choleic acid, the nature of its relations to lithofellic, hyocholic, and chenocholic acids, requires further investigation. In the dry condition, it is strongly electrical, as shown by rubbing it with a pestle. With Pettenkofer's reaction, it gives a red but not a violet colour. It melts at 120°. By heating strongly, it yields a turpentine-like residue. Its taste is bitter.

In opposition to Mylias (Abstr., 1866, 952), the author adheres to the statement he previously made that cholic acid does not give an acetyl compound.

W. D. H.

The Behaviour of Hydrogen Peroxide to Albumin. By C. WURSTER (Ber., 20, 263–267).-Egg albumin is not affected by hydrogen peroxide when in an alkaline or neutral solution, but in an acid solution in the presence of sodium chloride, hydrogen peroxide causes the albumin in a few minutes or hours to be changed into a proteïd, insoluble in water. The rate at which this coagulation occurs varies directly with the fresh condition of the albumin, the concentration of the liquid, and especially the temperature, the most favourable temperature being from 37° to 40°, the mixture being kept in an incubator. For the precipitation, an equal volume of hydrogen peroxide is well shaken with the white of egg, and 1 to 2 c.c. of commercial lactic acid, and 1 to 2 grams of sodium chloride, or 20 c.c. of a 5 per cent. solution added for every 100 c.c. of albumin. The cold mixture remains clear, becomes cloudy when held in the hand, and after 12 hours in the incubator has set into a firm cheesy mass. It is not necessary to use so large an excess of hydrogen peroxide; 3 to 5 c.c. will often suffice, but I. c.c. to the 100 of albumin does not cause complete coagulation. The mother-liquor has a greenish-yellow colour like whey; on evaporating it an acid syrup is obtained, which after repeated drying and beating is found to contain hydrogen peroxide. Alcohol precipitates a peptone-like substance from this syrup. The precipitate caused by the peroxide reminds one more of acid albumin than caseïn. On digestion with artificial gastric juice, it is rapidly and very completely peptonised. It is soluble in solutions of sodium carbonate; on neutralising this solution with acetic acid, a proteïd is precipitated, which blackens an alkaline lead solution, and is insoluble in sodium acetate or tartrate, and is, therefore, not the oxy proteo-sulphonic acid of Brücke and Maly. It is insoluble in salt solutions and in water, soluble in hot alcohol, for the greater part soluble in sodium carbonate solution and in concentrated acids in the cold, wholly soluble in sodium carbonate solution and dilute acids at a temperature of 70-80°. is soluble with ease in caustic alkalis, especially in ammonia.


The precipitate caused by hydrogen peroxide is stated to be a mixture of gelatinous acid albumin with a large quantity of a proteïd very similar to casein.

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