blue-green non-fluorescent colour to vegetable preparations made in copper vessels.

When phyllorubin is dissolved in chloroform and treated with a current of dry hydrogen chloride, phyllocyanin is first formed (giving the same spectrum as the alcoholic tincture of chlorophyll), and afterwards a greenish-blue colouring matter, the spectrum of which is identical with that of the fresh leaf. The same substance is formed by treating phyllorubin with other dehydrating reagents, such as sulphuric and phosphoric acids. It should therefore be considered as an ether (hydroxy-derivative?). It separates from the chloroform solution in crystalline plates with metallic lustre, and its behaviour with reagents is the same as that of chlorophyll. The chloroform solution is non-fluorescent, but either alcohol or glycerol gives a fluorescent solution with displaced spectrum.. J. M. H. M.

Identity of Phenylmethylpyrazoloneazobenzene with Phenylhydrazineketophenylmethylpyrazolone: Inner Anhydride Formation of Diphenylhydrazineacetylglyoxylic Acid and Diphenylhydrazinedihydroxytartaric Acid. By L. KNORR (Ber., 21, 1201–1205).-Phenylmethylpyrazoloneazobenzene (Abstr., 1887, 602) is identical with phenylhydrazinephenylmethylketopyrazolone (ibid., 603) Both compounds melt at 155°; they crystallise from hot alcohol in orange-red, shining needles, which dissolve in hot dilute soda, forming a deep yellow solution, from which they are precipitated in the form of the sodium salt by the addition of strong soda. When the alkaline solution of either compound is acidified, the original substance, melting at 155°, is obtained. On warming a nitric acid solution of either compound, the whole suddenly solidities to a mass of fine, yellow needles. This new substance is phenylmethyl-CMe:N-.

ketopyrazolonehydrazone, N2HPh= C<CO-NPh>. Its solubility in soda is probably owing to the formation of the sodium salt of diphenylhydrazineacetylglyoxylic acid, and on acidifying the free acid is converted into the inner anhydride. Similarly, on acidifying, an alkaline solution of the osazone of acetylglyoxylic acid (loc. cit.), the inner anhydride phenylhydrazine phenylmethylketopyrazolone is obtained. Diphenylhydrazinedehydroxytartaric acid (Ziegler and Locher, Abstr., 1887, 578) is converted into the inner anhydride when its alkaline solution is poured into acetic acid, or when the acid is crystallised from acetic acid. This anhydride,

C(COOH)N,

N,HPh:C-CO-NPh

phenylhydrazineketophenylpyrazolonecarboxylic acid, melts at 230232°, and loses 1 mol. of carbonic anhydride when carefully heated at 230°; a brown oil is thus obtained, which solidifies on cooling, and yields brown-yellow crystals, melting at 150° after recrystallisation from alcohol. This compound is probably phenylhydrazineketophenylCH N pyrazolone, N2HPh•C<CONPh>; on heating a few degrees above 230°, it is completely decomposed. The same substance appears to be

formed by boiling the osazone of glyoxalcarboxylic acid (Nastvogel, Inaug. Diss., Würzburg, 1887) with acetic anhydride. F. S. K.

Pyrazoles and Pyrazolines. By L. KNORR and H. LAUBMANN (Ber., 21, 1205-1212).—1.3.5-Triphenylpyrazole,

CPh N

CH:CPhNPh,

is obtained by warming dibenzoylmethane with an excess of phenylhydrazine. It crystallises from ether in large, well-defined plates, melting at 137--138°, and from dilute alcohol in leaflets which contain varying quantities of alcohol, according to the concentration of the solution, and yield the pure pyrazole when gently heated. It is insoluble in water and dilute acids, sparingly soluble in cold ether and alcohol, but dissolves readily in hot alcohol or ether, in chloroform, benzene, and glacial acetic acid. Triphenylpyrazole has only a feebly basic character, and is completely precipitated from its solution in concentrated sulphuric or nitric acid by the addition of water. It remains unchanged when heated with 20 per cent. hydrochloric acid at about 300°.

19

Triphenylpyrazole methiodide, CH9N2I is formed when the pyrazole is heated with an excess of methyl iodide and methyl alcohol at 110°. It forms white needles, which melt at 176° with decomposition, and are sparingly soluble in cold, more readily in warm water. It dissolves in alcohol and chloroform, but is insoluble in alkalis, ether, and benzene. When heated, it yields methyl iodide and triphenylpyrazole.

CHPh NMe

Triphenylmethylpyrazine, <CH, CHPh>NPh, is produced by the action of sodium on a boiling alcoholic solution of the preceding compound. It melts at 109-110° or when placed in boiling water; it is insoluble in water, and only sparingly soluble in cold alcohol and light petroleum, but dissolves readily in hot alcohol, ether, and benzene, the solutions showing a slight blue fluorescence. This compound does not show the reactions of pyrazolines, and it yields a brown resinous product when treated with concentrated nitric acid.

Bromotriphenylpyrazole, CH15N2Br, is obtained by treating a chloroform solution of the pyrazole with bromine. It crystallises from alcohol in white, shining, silky needles, which melt at 142°, and dissolve readily in ether, benzene, and hot alcohol, but are insoluble in water and dilute acids. It does not lose bromine when treated with aqueous or alcoholic potash.

Nitrosotriphenylpyrazole, CH16ÑO, is formed when nitrous acid is passed into an ethereal solution of the pyrazole. It crystallises in green needles, which melt at 183°, are sparingly soluble in ether and light petroleum, but dissolve readily in benzene and chloroform. An aqueous or sulphuric acid solution of nitrous acid does not act on triphenylpyrazole:

CPH N

1.3.5-Triphenylpyrazoline, <CH,CHPh <CH2 CHP1>NPh, is obtained by re

ducing triphenylpyrazole with sodium and alcohol, or by warming an alcoholic solution of benzalacetophenone with phenylhydrazine. It crystallises in needles, melting at 134-135°, dissolves readily in ether, benzene, hot alcohol, and glacial acetic acid, with blue fluorescence, but is insoluble in water and dilute acids. It is only acted on at 300° by a 20 per cent. solution of hydrochloric acid, and a solution of this compound in sulphuric acid is turned blue-green by a drop of a nitrite solution. Triphenylpyrazole is formed when gaseous nitrous acid is passed into an ethereal solution of this compound until the blue fluorescence disappears; if the gas is passed for a longer time, the yellow solution becomes deep green, and nitrosotriphenylpyrazole (see above) is obtained; when, however, the triphenylpyrazoline is just covered with a small quantity of ether and nitrous acid passed, a brownishyellow, indifferent substance is produced. This compound is insoluble in water, acids, and alkalis, and dissolves very sparingly in alcohol and ether; it is, however, readily soluble in chloroform and benzene, and crystallises from glacial acetic acid in forms melting at 175176°. It appears to be nitrotriphenylpyrazoline, CaH1N3O2. The same compound, together with triphenylpyrazole, is produced when triphenylpyrazoline, in ethereal solution, is oxidised with nitric acid. Triphenylpyrazoline tribromide, CHIN2Br3, is obtained by treating a chloroform solution of triphenylpyrazoline with bromine. It crystallises from ether, alcohol, or light petroleum, in small needles, melting at 179°, and is reconverted into the pyrazoline by nascent hydrogen. F. S. K.

1.5-Diphenylpyrazoline, By H. LAUBMANN (Ber., 21, 12121213).-1.5-Diphenylpyrazoline, C1HN2, can be obtained by distilling the hydrazine of cinnamaldehyde (Fischer, Abstr., 1884, 1151). It crystallises from alcohol or light petroleum in shining, silky needles, melting at 137-138°. It is insoluble in water, sparingly soluble in light petroleum, dissolves more readily in alcohol, and readily in ether, benzene, and chloroform, the solutions showing a slight blue fluorescence. It gives a pyrazoline reaction similar to that shown by methyldiphenylpyrazoline (Knorr and Blank, Abstr., 1885, 506). Acid solutions of this compound are coloured magenta by oxidising agents. F. S. K.

Decomposition of Anilides at a High Temperature. By C. A. BISCHOFF (Ber., 21, 1257—1265; compare Abstr., 1883, 919).— CÓ CH, Diphenyldiketopiperazine, PhNCH, CO>NPh, is obtained by the action of aniline on chloracetic acid or ethyl chloracetate.

Phenylglycinphenylamidacetic acid, NHPh-CH, CO NPh.CH, COOH, and methylphenylglycinanilide, NHPh.CH, CO NPhMe, are also produced by acting on chloracetic acid with aniline. The former compound is also formed when diphenyldiketopiperazine is boiled with strong acids or alkalis.

Paratoluidine chloracetate, C,H1Me•NH, O·CO-CH,Cl, forms colourless crystals, which melt at 97.5° and are readily soluble in alcohol and ether.

COCH,
CH2

Paraditolyldiketopiperazine, C.H,Me N<CH, CONCH,Me, is produced when the preceding compound is heated; it can also be obtained from ethyl monochloracetate and paratolylglycintoluide,

The last-named compound crystallises from hot alcohol in leafy forms which melt at 134°.

Orthotoluidine chloracetate, C,H,NO,Cl, melts at 95°, dissolves. readily in alcohol and warm water, less readily in ether.

Orthoditolyldiketopiperazine is obtained from toluidine and chloracetic acid or ethyl chloracetate. By heating aniline with malic acid, a -CO-CH:CH-CO, compound, PhNCO-CHICH-CO>NPh, is produced. Similarly ethyl acetylenetetracarboxylic acid yields a compound,

The above compounds will be more fully described in a future publication.

F. S. K.

Pyridine Bases from Coal-tar. By J. MOHLER (Ber., 21, 1006— 1015). The existence of a pyridine hydrate, C,NH,3H2O, seems to be confirmed by the author's experiments. B-Picoline was isolated from a mixture of coal-tar bases, and symmetrical collidine was obtained from the same source by fractional precipitation with potassium ferrocyanide.

Collidine from coal-tar is a colourless liquid which does not change on exposure to the air. It dissolves slowly but to a considerable extent in cold water, and separates again almost quantitatively on warming. The mercurochloride, C,H,Me,N,HC1,2HgCl2, crystallises in prisms melting at 155°, and is only sparingly soluble in water. The aurochloride, C,H1N,HAuCl, forms long, yellow needles which become brittle and dull on exposure to the air; the dry salt melts at 114-115°, but when heated under water it changes to an oil at a lower temperature. The dichromate, (CHN)2,HCr2O,, crystallises from water in long, yellow prisms which decompose at 190°, and are sensitive to light, becoming greyish-yellow coloured in the sunlight. The picrate crystallises in long, silky needles melting at 155-156°. The sulphate, nitrate, and hydrochloride are not deliquescent. The hydrochloride forms slender needles which sublime, with partial decomposition, without melting. The sulphate forms transparent prisms melting at 2030. The nitrate crystallises in hexagonal leaves which melt above 300° with decomposition.

Pyridine ferrocyanide, (CHN)2,H,Fe(CN). + 2H2O, forms monoclinic prisms in combination with domes; it is more sparingly soluble

in water than the ferrocyanides of the homologous bases, and can be employed as a means of obtaining pure pyridine. The ferrocyanides of the picolines are very readily soluble, that of ax'- and of ay-lutidine are more sparingly soluble. The aqueous solutions of the ferrocyanides are tolerably stable in the cold, but decompose when heated

above 70°.

F. S. K.

Distillation of Salts of Pyridinecarboxylic Acids. By F. BLAU (Ber., 21, 1077–1078).-Oh dry distillation, the copper salt of picolinic acid yields an oil from which a strong base, probably a-adipyridyl, was isolated. This compound separates from water in crystals which melt at 70°; it is sparingly soluble in water, but dissolves readily in other solvents. F. S. K.

Amide of Dihydroxyisonicotinic Acid. By S. RUHEMANN (Ber., 21, 1247-1249).-Trichlorcitrazinamide (this vol., p. 255) combines with aniline to form a compound, C18HNO3, which is a strong base, and dissolves very readily in hydrochloric acid; it has also feebly basic properties and dissolves in ammonia. It is very sparingly soluble in alcohol, and is decomposed when boiled with glacial acetic acid.

A crystalline product, CH,N2Os, is obtained by heating a hydrochloric acid solution of the preceding compound. This substance has acid properties and dissolves in ammonia, forming a yellow solution; it decomposes on heating, and its aqueous solution is turned deep brown by ferric chloride. Silver nitrate precipitates from an ammoniacal solution a yellow, gelatinous precipitate which blackens on heating. Heated with potash, ammonia is evolved, and a salt formed which is soluble in ether.

F. S. K.

Quinolinesulphonic Acids. By A. CLAUS (J. pr. Chem. [2], 37, 258-268; compare Abstr., 1887, 737, and this vol., pp. 296 and 501). When quinoline is sulphonated with fuming sulphuric acid containing from 10 to 20 per cent. of anhydride at a temperature not exceeding 125-130°, three sulphonic acids are formed: the meta-, the ortho-, and an acid belonging to the ana-series. At a temperature of between 170-180° only the last two are obtained. These facts explain the contradictory statements of La Coste and Valeur, and Fisher, Bedall, and Riemerschmied. The three acids may be best separated by the fractional crystallisation either of the free acids or of their barium or calcium salts. The meta-acid (4 mols. H2O) is the most soluble, and crystallises in small colourless needles. The potassium (1-2 mols. H2O) and sodium (3 mols. H2O) salts are both somewhat hygroscopic. The calcium salt (4 mols. H2O) crystallises from water in microscopic needles; the barium salt (4 mols. H2O) is only indistinctly crystalline. The silver, lead, and copper salts are described. The sulphochloride forms a sticky mass, and the sulphonamide an indistinctly crystalline powder melting at 119° (uncorr.). On heating the silver salt with ethyl iodide in sealed tubes at 140°, the ethyl salt C,NH, SO,Et is formed. It melts at 275° (uncorr.).

When quinolinemetasulphonic acid is treated with bromine in the