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forms. It is very soluble in dilute alcohol and in benzene, the alcoholic solution being dextrogyrate, whilst the benzene solution is feebly lævogyrate. It alters readily and becomes yellow when heated. It is decomposed by boiling alkalis, and its salts are much more soluble than those of the a-derivative.

Another isomeride exists, and will be described in a subsequent paper. C. H. B.

Anemonin. By HANRIOT (Compt. rend., 104, 1284-1286).—Anemonin was obtained by Heyer from various species of anemones. The author prepared it by distilling Anemone pulsatilla in a current of steam until the distillate no longer gave a yellow coloration with potash. The distillate was redistilled and allowed to remain in a cool place for several months, when it deposited the anemonin, which was purified by solution in alcohol and recrystallisation from benzene, from which it separates in slender needles of the composition C16H12O6. A product is also obtained which has practically the same composition, but is insoluble in alcohol.

Anemonin melts at 156°, and decomposes at 270° with partial sublimation of anemonin and a liquid which appears to be an aldehyde. With zinc-dust or with hydriodic acid in sealed tubes, it gives no distinct reaction, but a small quantity of a hydrocarbon is formed which seems to be cymene or cumene.

If anemonin is dissolved in chloroform and treated with excess of bromine it yields the compound C16H12O6Br; this crystallises from benzene in octahedra which do not melt without decomposition.

When treated with nascent hydrogen in an acid solution anemonin yields hydroanemonin, C15H2006, which crystallises from boiling petroleum in large, colourless lamella which contain 1 mol. H2O, melt at 78°, and distil without decomposition at 210-212° under a pressure of 10 mm. Hydroanemonin is much more stable than anemonin. It is insoluble in cold solutions of the alkalis, yields no derivative with acetic anhydride, and no chlorine-derivative with phosphorus pentachloride. The latter reagent only partially converts it into anemonin. C. H. B.

Action of Acetic Anhydride on Methylpyrroline and Benzylpyrroline. By G. CIAMICIAN and P. SILBER (Ber., 20, 1368-1370). -Ciamician and Dennstedt have already described (Abstr., 1885, 378) a monacetyl-derivative of methylpyrroline. By using a very large excess of anhydride and heating for eight hours at 250°, the authors have obtained diacetomethylpyrroline, C,NH,MeAc. This crystallises in colourless needles melting at 133-134°, and is easily soluble in ether, alcohol, benzene, chloroform, and boiling water.

The authors obtained a benzylpyrroline by heating the potassium compound of pyrroline with benzyl chloride. It is solid at ordinary temperatures, but melts with the warmth of the hand to a colourless liquid which boils at 247° (uncorr.). It is almost insoluble in water, easily soluble in alcohol and ether. When heated at 240° for some hours with a large excess of acetic anhydride, it yields diaceto-benzylpyrroline, C,H,C,NH2Ac2, which crystallises in colourless needles, is soluble in alcohol, and melts at 129-130°.

L. T. T.

Action of Propionic Anhydride on Pyrroline. By M. DENNSTEDT and J. ZIMMERMANN (Ber., 20, 1760-1762).-It has been shown that two isomeric acetyl-derivatives are obtained by the action of acetic anhydride on pyrroline; a similar result is obtained by heating pyrroline with propionic anhydride and sodium propionate in a reflux apparatus, when two propionylpyrrolines are obtained, of which one only distils with steam. The yield is not good.

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Propionylpyrroline, C,NH, COEt [COEt 1], is a viscid, yellowish oil which distils at 192-194°, can also be distilled with steam, and is decomposed by alkalis into pyrroline and propionic acid.


The isomeric propionylpyrroline, [COEt 2 or 3], crystallises in colourless needles, melts at 52°, boils at 222-225°, is soluble in alkalis without decomposition, and yields a white, crystalline silver-derivative, C.NH,Ag COEt [Ag: COEt 1: 2 or 3].


Dipropionylpyrroline, C,NH,(COEt)2, obtained by heating 5 grams of pyrroline with 50 grams of propionic anhydride at 260°, crystallises in colourless plates, and melts at 126-117°. A. J. G.

Preparation of Halogen-derivatives of Pyridine Bases from the Pyridinecarboxylic Acids. By G. PFEIFFER (Ber., 20, 13431353).—It is well known that the pyridine bases are very indifferent towards substitution-reagents, and very few substitution-products are at present known. The author finds that halogen substitution-products may easily be made through the mediation of the carboxylic acids. Bromine does not act on collidinedicarboxylic acid in either alkaline or acid solution, but when added to a neutral solution of the potassium salt, carbonic anhydride is evolved and symmetrical dibromocollidine, CBr CMe CMe CBr:CMe »N, is obtained. This forms snow-white, nacreous crystals soluble in alcohol and ether, almost insoluble in water. It melts at 81° and boils at 262-263° under a pressure of 726 mm. and volatilises slowly even at ordinary temperatures. It is a feeble base, dissolves in hot concentrated hydrochloric acid, and the solution on cooling deposits small, polyhedric crystals of the hydrochloride CNH,Br2, HCl. This is easily soluble in water, and the aqueous solution decomposes on boiling. The dry substance sublimes slightly when rapidly heated, but decomposes into its components even at 100°, very rapidly at about 200°. With bromine it yields a dibromide, CNH,Br2, Br2HCl. The platinochloride forms orange needles containing 2 mols. H2O which it loses at 120°: the dichromate melts at 146°; the picrate at 159-160°; the aurochloride forms yellow needles. When oxidised with permanganate the base yields dibromopyridinetricarboxylic acid, C5NBг2(COŎH), crystallising in needles soluble in boiling water, sparingly so in alcohol and ether. It melts with decomposition at 204-206°. The monopotassium salt,

COOK C,NBr2(COOH)2 + 6H2O,

forms colourless needles soluble in hot water. This salt is not decomposed by mineral acids, and the free acid is best obtained from the silver salt, CNBr.(COOAg),, which forms an insoluble, crystalline powder. Ferrous sulphate gives a carmine coloration. When heated

in glacial acetic solution no decomposition takes place; when the acid is heated alone all three carboxyl-groups are eliminated and Hofmann's 3:5 dibromopyridine formed. When dibromocollidine is heated with sodium ethoxide, 3: 5 diethoxycollidine, CNMes(OEt), is formed; it boils at 217-219° under 726 mm. pressure.

Symmetrical potassium lutidine dicarboxylate yields with bromine dibromolutidine, C,NHMe, Br2. It very closely resembles dibromocollidine in appearance, and melts at 65°.

Quinolinic acid when treated with bromine under like conditions yields 3: 5 dibromopyridine, and the same compound was formed by the action of bromine on pyridinepentacarboxylic acid.

When quinolinic acid in slightly alkaline solution is treated with iodine, diiodohydroxypyridine, C2NH2I(OH) [OH: 1:12:3:57, is formed. This forms light-brown needles sparingly soluble in alcohol, ether, and boiling water (the latter solution having an acid reaction) and melting at 257-259°. When heated very carefully it sublimes in colourless needles, but decomposes if heated rapidly. It dissolves in moderately strong sulphuric acid, but is reprecipitated unchanged on the addition of water. Its acid character is more marked, the sodium compound crystallising with 3H2O in colourless scales. It also forms well-marked compounds with many other metals. L. T. T.

Action of Chloral on a-Picoline. By A. EINHORN and A. LIEBRECHT (Ber., 20, 1592-1594).-When equimolecular proportions of a-picoline and chloral are mixed together, rise of temperature occurs, and a white, crystalline mass is obtained which yields w-trichloro-a-hydroxypropylpyridine, C,NH, CH, CH(OH) CCl3, if it is heated for 8 to 10 hours either with or without zinc chloride. This compound crystallises from dilute alcohol in beautiful, six-sided tables, melts at 86-87°, and yields well-characterised salts with acids. The hydrochloride, CH,NOCI,,HCl, crystallises in compact, long needles, melts at 201-202°, and is soluble in absolute alcohol. When heated with alcoholic potash, the base is converted into a-pyridylacrylic acid, which forms a white, crystalline hydrochloride, CH,NO2,HCl, melting at 220° with decomposition. W. P. W.

Behaviour of the Nitrobenzaldehydes towards Ethyl Acetoacetate and Ammonia. By R. LEPETIT (Ber., 20, 1338—1343).— The author has investigated the action of ammonia and ethyl acetoacetate on the three isomeric nitrobenzaldehydes. When metanitrobenzaldehyde (1 mol.), ethyl acetoacetate (2 mols.), and a slight excess of ammonia are heated in alcoholic solution, ethyl metanitrophenyllutidinehydrodicarboxylate, NO2°C2H1•C2NH2Mе(COOEt)2, is formed. It is easily soluble in alcohol, ether, chloroform, and acetone, crystallises in plates, and melts at 161°. When a small quantity of fuming nitric acid is added to an alcoholic solution and a current of nitrous acid then passed in, ethyl metanitrophenyllutidinedicarboxylate,

NO2 C&H CNMe2(COOEt)2,

is produced. It crystallises in colourless plates, soluble in ether and alcohol, and melting at 65°. The nitrate forms colourless, acicular

crystals melting at 129-130°; the platinochloride, orange crystals melting at 2020. When treated with tin and hydrochloric acid the ethyl salt yields ethyl metamidophenyllutidinedicarboxylate, which is soluble in alcohol and ether, crystallises in plates, and melts at 109110°. This compound is bibasic, and forms a platinochloride,

C19H22N2O,,H2PtCl + H2O,

which crystallises in yellow needles, loses water at 110-120°, and decomposes at about 260° without previous fusion. This amidocompound acts as a primary aromatic amine, and may be diazotised, &c.

Paranitrobenzaldehyde reacts in a similar way, but the reaction does not take place so smoothly, a great deal of secondary products and resinous matter are formed, and the yield is very small. The hydro-compound was not obtained quite pure, but is crystalline and melts at about 118-122°.

With orthonitrobenzaldehyde the reaction takes place differently. A substance, C19H20N4O5, is always formed as well as the hydro-salt, and the yield of these two substances appears to be better when equimolecular proportions of ethyl acetoacetate and nitrobenzaldehyde are taken than when the usual proportion 2:1 is employed. Ethyl orthonitrophenyllutidinehydrodicarboxylate forms pale-yellow, rhombic plates, is soluble in alcohol and ether, and melts at 119-120°. It is insoluble in dilute acids. When oxidised with nitrous acid so little crystallisable substance was obtained that the non-hydrogenised compound could not be obtained in a pure state. The compound, CH20N.Os (possibly C19H22N.Os), mentioned above is very sparingly soluble in alcohol, crystallises in yellow needles, and melts at 189°: it has basic properties. The hydrochloride, C19H21N,O,Cl, forms a sparingly soluble, yellow powder, loses hydrogen chloride in dry air, rapidly at 100°, and melts with partial decomposition at 150°; it also forms a platinochloride. This compound is unstable, and, when it is boiled with hydrochloric acid, ethyl chloride and carbonic anhydride are evolved, whilst orthonitrobenzaldehyde is amongst the residual products. Attempts at hydrolysis and reduction were unsuccessful. When nitrous acid is passed through alcohol in which the base is suspended, solution takes place, and, after a time, white needles separate which have the same composition, C19HNO, as the base, but are non-basic in character, and decompose at 192°.

With phenylhydrazine all three nitrobenzaldehydes react in the usual way with formation of hydrazides of the constitution NO, CH CH: N2HPh. The ortho-compound forms small, ruby-red prisms melting at 152°; the para-compound dark-red crystals, with a bluish surface fluorescence, and melting at 155°; and the meta-compound scarlet crystals melting at 120°. L. T. T.

Cinchonic Acid. By A. CLAUS and M. KICKELHAYN (Ber., 20, 1604-1606).—Whilst engaged in the preparation of a large quantity of cinchonic acid, obtained by the cxidation of 6 kilos. of cinchonine with nitric acid, the authors have observed that it crystallises in three forms: 1, in the well-known, slender, caffeïne-like needles with

1 mol. of H2O; 2, with 2 mols. of HO in the triclinic forms described by Muthmann and Nef (this vol., p. 598); and, 3, in monoclinic tables also with 2 mols. of H2O. The first form is always obtained when the hot, concentrated solution of the acid is allowed to cool during crystallisation; the third form separates during the slow evaporation of dilute aqueous solutions of the pure acid; whilst the second form, according to the authors' experience, is got by the slow crystallisation of solutions of the acid containing some impurity such as mineral acid, and, after repeated recrystallisation, yields the third form on the slow evaporation of its dilute aqueous solution.

The crystallographic measurements of the third form agree with those of Ditscheiner (Annalen, 173, 84), and, consequently, Muthmann and Nef's conclusions cannot be maintained. The crystals are monoclinic, a b c = 0·2758 : 1:0·5328; ß = 98° 3'; and the following faces were observed: coco, coP, Roo, and Poo. W. P. W.


Synthesis of Quinoline-derivatives. By L. KNORR (Ber., 20, 1397-1399). When ethyl B-phenylamido-a-crotonate is heated at 190-200° it yields y-hydroxy-quinaldine described by Conrad. By the action of dry sodium ethylate on the crotonate the author obtained a compound, CH13NO3, which appears to be Conrad and Limpach's phenyllutidoncarboxylic acid.

L. T. T.

Reactions of Quinoline. By H. WEIDEL (Monatsh. Chem., 8, 120-146). When a mixture of dry quinoline hydrochloride (from 50 grams of quinoline), 50 grams of quinoline, and 10 grams of platinised asbestos, is heated at 170°, and subsequently at 200°, in a gentle current of dry oxygen, the whole becomes dark in colour and thick. It is then dissolved in dilute hydrochloric acid, filtered, and treated with alkali and steam-distilled. The residue is dissolved in very dilute hydrochloric acid, and fractionally precipitated with a concentrated solution of sodium acetate. The last precipitate yielded on further purification dichinolyl, melting at 173°. The yield is 8 per cent.

When quinoline hydrochloride (from 129 grams of base), 93 dry pure aniline, and 25 grams of platinised asbestos are heated together, first at 160°, then for some hours at 175°, and finally at 180°, paramido-a-phenylquinoline (Jellinek, Abstr., 1886, 1045) and a new diquinolyl are obtained. This melts at 138° (uncorr.). It yields two hydrochlorides; the one (with 2 mols. HCI) is colourless, the other (with 1 mol. HCl) yellow. The yield of base is 25 to 40 per cent. of that required by theory. The acetyl-derivative, CisHN,Ac, crystallises from alcohol in lustrous plates, melting at 189° (uncorr.).

Dihydroxyphenylquinoline, CHNO2, is obtained, together with parahydroxy-a-phenylquinoline, by the action of potassium nitrite on amido-a-phenylquinoline, in presence of excess of hydrochloric acid. It crystallises in colourless, lustrous, prismatic needles, insoluble in water, readily soluble in benzene, ether, alcohol, chloroform, and acetone; it melts at 114° (uncorr.).

Parahydroxy-a-phenylquinoline, C1HNO, forms a loose mass of colourless, slender, monoclinic crystals, insoluble in water, readily

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