hydrogen bromide, and it is not reduced by the action of sodium. amalgam. When distilled with soda-lime, it yields a yellow oil, which on rectification forms a colourless, mobile liquid of the composition CH12, boiling at 133-135°, and polymerising on exposure to the air.

W. P. W.

By J. Bou

The

Action of Sulphuric Acid on Terebenthene. CHARDAT and J. LAFONT (Compt. rend., 105, 1177 — 1179). product of the gradual action of 467 grams of sulphuric acid on 9340 grams of French terebenthene boiling at 155-157° (rotatory power -32.2°) was distilled in a current of steam; 79 grams of sulphuric acid remained in the free state, the rest having formed a compound 2C10H16, H2SO4, which is almost though not quite fixed. This compound could not be isolated from the colophene with which it is mixed. It is a neutral substance and does not combine with potassium hydroxide. Alcoholic potash is without action in the cold, but at 150° decomposition takes place with formation of volatile products and the compound C10H16,SO,KH, which crystallises from its aqueous solution in thin lamellæ.

The portion of the original product which distils with steam consists mainly of the unaltered hydrocarbon, without any camphene. The fraction boiling at 175-180° has the composition C10H16, oxidises very readily, and is somewhat lighter than the original terebenthene. It absorbs hydrogen chloride readily yielding a liquid product, and when the latter is distilled in a vacuum, it yields cymene and terpilene hydrochloride, C10H16,2HCl, melting at 48°. The rotatory power of the corresponding terpilene is only one-fifth or one-sixth that of another terpilene obtained from the same terebenthene by a different method.

The fraction boiling below 165° was treated successively four times with sulphuric acid, always with a similar result, but the fraction boiling at 157°, which gradually became smaller and smaller in quantity, diminished in rotatory power, and after a fifth treatment was converted into an easily solidified camphene. This camphene is formed by the decomposition of the small quantity of the sulphur compound which distils over with the water. This fraction, in fact, always contains a small quantity of free sulphuric acid.

When the original product, which is not volatile in steam, is heated at 200-250°, an energetic reaction takes place, water, sulphurous anhydride, and sulphur being produced. The liquid products contain a slightly active lævogyrate compound boiling at 156°, cymene, terpilene, and dextrogyrate camphenols. C. H. B.

Pimaric Acids. By A. VESTERBERG (Ber., 20, 3248-3253).-In a previous paper (Abstr., 1886, 1038) the author showed that the mother-liquor from the preparation of dextropimaric acid contained B-pimaric acid. From the very vigorous lævorotatory power of this acid, the name lavopimaric acid is now given to it; its separation and purification were attended with great difficulty. Lavopimaric acid, C2H3O2, isomeric with dextropimaric acid, crystallises in the rhombic system; axial ratios, a b c = 0·81042: 1: 0·61407; ob

:

served faces: ∞P, coĒco, P/2, 2ř∞, OP. It melts between 140° and 150°, and is insoluble in water, readily soluble in all the other usual solvents, its solubility being greater than that of the dextro-acid. One part of the acid dissolves in 10-8 parts of 98 per cent. alcohol at 15°. A solution of 3.174 parts of lavopimaric acid in 100 c.c. of alcohol has a lævorotatory power [a]D = -272°. It forms readily crystallisable salts, of which the sodium, ammonium, and lead salts are described.

The author considers it very probable that Calliot's pyromaric acid (this Journal, 1874, 457) is a mixture of dextro- and lævo-pimaric acids. A. J. G.

Action of Phenylhydrazine on Santonin. By C. GRASSI (Chem. Centr., 1887, 1163-1164; from Rend. R. Acc. Lincei [4], 3, 521-522).-When a solution of santonin (10 grams) is heated with phenylhydrazine (10 grams) in acetic acid solution (sp. gr. 1.06), a yellow hydrazide, C15H18O2 N2HPh, separates, which melts at 220°, and is not decomposed by acids. Hydrochloric acid dissolves it in the cold with a reddish-yellow colour; on heating, a scarlet precipitate is formed. The hydrazine compound yields a platinochloride. J. W. L. Lakmoïd and Litmin. By W. N. HARTLEY (Proc. R. Dublin Soc., 5, 159). Lakmoïd (Abstr., 1885, 148) is soluble in strong alcohol, insoluble in water. A solution in 50 per cent. alcohol retains its colour with but slight alteration for several months. Litmin is insoluble in strong alcohol, but soluble in spirit of 50 per cent.; the solution was bleached after a time although not exposed to bright light. The photographic spectra of the two substances did not differ markedly. From these results, it follows that the two substances are not identical. Lakmoïd is a better reagent than litmin.

A. J. G.

New Brazilin-derivative. By C. SCHALL and C. DRALLE (Ber., 20, 3365-3366).-Tetramethylbrazilein, CHO,Mes, is prepared by mixing 27 grams of brazilin with 08 gram of sodium (each dissolved in alcohol); 8 grams of methyl iodide is then added, and the whole warmed on a water-bath until the colour changes to a yellowish-brown. The greater portion of the alcohol is distilled off and the rest evaporated on a water-bath. It is washed with water, dissolved in ether, and washed with dilute aqueous soda. It forms a brittle, transparent, amber-coloured mass which becomes crystalline when ether is poured over it. When crystallised from alcohol, it is obtained in colourless crystals melting at 138-139°. The compound has the properties of a phenol alkyl ether; it does not change when exposed to air, and yields an additive product with ammonia. N. H. M.

Metanitroquinoline. By A. CLAUS and A. STIEBEL (Ber., 20, 3095-3097).-Metanitroquinoline, C,NH, NO2, is prepared from 10 grams of nitraniline, 26 grams of picric acid, 14 grams of glycerol, and 14 grams of sulphuric acid. The mixture is afterwards boiled for some hours. The product after being freed from resin, is treated with light petroleum to remove the phenanthroline, which is also formed in

the reaction, and recrystallised from alcohol or water. It forms long, thin, colourless needles, melting at 131 5° (uncorr.). The hydrochloride crystallises in long, yellowish-white needles, melts at 225° with evolution of gas, and decomposes in contact with water. The nitrate crystallises in long, flat needles of a satiny lustre, not very readily soluble in water. The platinochloride forms large, ambercoloured prismatic crystals. Metamidoquinoline, C,NH NH2, prepared by reducing the nitro-compound with stannous chloride, forms long, hair-like, yellowish needles which melt at 186° (uncorr.); it is readily soluble in ether, chloroform, &c. When heated, it yields a sublimate of splendid red needles. It does not distil with steam. (Compare Abstr., 1887, 810). N. H. M.

Constitution of Quinoline-derivatives. By J. FREYDL (Monatsh., 8, 580-583).—The so-called B-amidoquinoline on conversion into the corresponding diazochloride and treatment of the same with potassium cyanide, yields a cyanoquinoline identical with the metacyanoquinoline of Bedall and Fischer. On hydrolysis, this nitrile yields a quinolinecarboxylic acid, identical with that obtained from an amidobenzoic acid by Skraup's reaction. The amidoquinoline is also converted by the diazo-reaction into a chloroquinoline, identical with the compound obtained by La Coste (Abstr., 1886, 159) from metachloraniline by Skraup's reaction. Then in the above group the substituted groupings are in the 2 position as derived from the 1:3 benzenoïd derivatives. V. H. V.

Sulphonation of Quinoline. By G. v. GEORGIEVICS (Monatsh., 8, 577-579).—By the sulphonation of quinoline with Nordhausen acid, La Coste, as also Bedall and O. Fischer, obtained a mixture of the 1:2 and 13 quinolinesulphonic acids, the proportion of each which is formed being dependent on the conditions of the experiment. It is here shown that if the sulphonation is effected with ordinary sulphuric acid, the 1: 4 sulphonic acid is produced, a result confirmed by the conversion of the acid into the corresponding nitrile and carboxylic acid. V. H. V.

Quinoline. By E. LELLMANN and G. LANGE (Ber., 20, 3084-3089; compare Abstr., 1887, 737).-Calcium parabromobenzenesulphonate crystallises is well-formed, monoclinic crystals with 2 mols. H2O: a:b:c= : c = 0·5872 : 1 : 0·5168; B = 85° 14′ 42′′ (compare Goslich, this Journal, 1876, i, 929). Parabromometamidobenzenesulphonic acid crystallises in well-formed prisms with 1 mol. H2O (not 1 mol. H2O, Goslich, loc. cit.).

Orthobromoquinoline-anasulphonic acid, C,NH,BrSO,H [Br: SO,H= 14], is prepared by heating 5 grams of parabromometamidobenzenesulphonic acid, 6 to 7 grams of orthonitrophenol, 20 grams of glycerol, and 25 to 27 grams of sulphuric acid in a reflux apparatus at 155160° for six hours. The product is treated with water, steam-distilled, treated with baryta, filtered, and the filtrate boiled with animal charcoal. By precipitating the barium as exactly as possible with sulphuric acid and carefully evaporating the filtrate, the sulphonic acid

is obtained in small, lustrous plates with 1 mol. H2O. The calcium salt with 6 mols. H2O crystallises in long needles, readily soluble in

water.

Tetrahydroquinoline-anasulphonic acid, C,NH10 SO3H+ H2O, is formed when 5 grams of bromoquinolinesulphonic acid is heated on a waterbath with concentrated hydrochloric acid and tin. It crystallises from dilute solutions in rhombic crystals; a b c = 0·5041 : 1 : 0·7511, and from concentrated solutions is monoclinic crystals; a:b:c= 0.4855: 1:0-5298; B = 55° 10′. When treated with oxidising agents, it shows the reactions characteristic of tetrahydroquinoline-derivatives. The quinolinesulphonic acid previously prepared (loc. cit.) from metamidobenzenesulphonic acid, also yields a tetrahydroquinolinesulphonic acid which completely resembles that just described. N. H. M.

B-Quinolinedisulphonic Acid. By W. LA COSTE and F. VALEUR (Ber., 20, 3199-3201).-B-Quinolinedisulphonic acid, prepared by heating the pure barium salt with the necessary amount of sulphuric acid, crystallises in slender white needles, readily soluble in water, insoluble in alcohol, ether, benzene, and chloroform. (Compare Abstr., 1887, 379.) The barium salt is obtained by treating the potassium salt with barium acetate. The potassium salt (with I mol. H2O), is insoluble in alcohol, readily soluble in boiling water. When this salt is fused with 3 parts of potash at 160°, potassium 3-hydroxyquinolinesulphonate is formed. B-Hydroxyquinolinesulphonic acid crystallises in yellow, lustrous plates, melting at 270-275°; it dissolves readily in hot water, sparingly in alcohol, and still less in chloroform and carbon bisulphide.

B-Dihydroxyquinoline, C,NH,(OH)2, is prepared in a manner similar to the a-compound (Abstr., 1886, 629), except that the temperature is only raised to 250-255°. It crystallises in slightly brown needles, readily soluble in ether, alcohol, benzene, chloroform, and carbon bisulphide, insoluble in water. It melts at 68°, and sublimes at a higher temperature in slender white needles. The salts are stable, but difficult to crystallise. (Compare also Abstr., 1887, 973.)

N. H. M. Tetrahydroquinaldine. By M. MÖLLER (Annalen, 242, 313– 321). Tetrahydroquinaldine has already been described by Jackson (Abstr., 1881, 742), and by Döbner and Miller (Abstr., 1884, 183). The nitronitroso-compound, NO2 CNH NO, crystallises in golden plates, and melts at 152°. Methylhydroquinaldine, C10H12NMe, has been prepared by Döbner and Miller (loc. cit.). It can also be prepared by the action of tin and hydrochloric acid on quinaldine methiodide. Methylhydroquinaldine methiodide, CONH12Me, Mel, crystallises in needles, melts at 2050, and dissolves freely in water and in hot alcohol. Freshly precipitated silver oxide converts it into the ammonium base, CONH12Me, MeOH, a crystalline, hygroscopic compound. The aurochloride crystallises in lemon-coloured needles, and the dichromate in six-sided plates. The platinochloride forms brick-red crystals, soluble in hot water. The base is decomposed by heat, yielding methyl, alcohol, and methyltetrahydroquinaldine

Ethyltetrahydroquinaldine, CNH12Et, is a colourless liquid, boiling at 256°. The platinochloride and methiodide are crystalline. The latter melts at 187° and dissolves in water, but is not acted on by a solution of potassium hydroxide. W. C. W.

Quinaldine Alkyl Iodides. By M. MÖLLER (Annalen, 242, 300312). Quinaldine methiodide and methylquinaldinium hydroxide have been previously described by Döbner (Abstr., 1884, 184), and by Bernthsen and Hess (Abstr., 1885, 558) respectively. In addition to the salts prepared by Bernthsen and Hess, the ammonium base yields an aurochloride, CH,NMeCl, AuCl,, and a dichromate,

(C10NH,Me)2Cr2O7,

crystallising in lemon-coloured needles. The dichromate detonates at 90°. Ethylquinaldinium hydroxide on exposure to the air changes into a carmine-coloured resin. The platinochloride, (CNH„Et)2PtC), is deposited from hot water in ruby prisms. The aurochloride,

C1NH,EtCl,AuCl3,

forms golden needles. The dichromate detonates at 100°. Quinaldinepropiodide forms greenish-yellow prisms, soluble in water and in hot alcohol. It melts at 166-167°. The ammonium base is amorphous. It is soluble in alcohol and ether. The platinochloride, aurochloride, and dichromate are crystalline. Quinaldine butiodide is prepared by heating quinaldine with isobutyl iodide at 115° in molecule proportion. It crystallises in plates, and melts at 172°. The amyl iodide requires a temperature of 140-145° for its formation. It is crystalline, soluble in water and hot alcohol, and melts at 175°.

Orthomethylquinaldine methiodide is deposited from alcohol in yellow needles, and melts at 221°. The ammonium base is tolerably stable, and does not change rapidly on exposure to the air. The platinochloride, dichromate, and aurochloride are crystalline. The base is decomposed by heat, yielding orthomethylquinaldine. Orthomethylquinaldine ethiodide is deposited from alcohol in yellow needles, and melts at 228°. The ammonium base is a stable, oily liquid, and it forms crystalline platino- and auro-chlorides.

Paramethylquinaldine unites with methyl iodide at the ordinary temperature. The compound melts at 236-237°, and dissolves freely in water. The ammonium base is unstable. The platinochloride, dichromate, and aurochloride crystallise in needles.

W. C. W.

Conversion of Indoles into Hydroquinolines. By E. FISCHER and A. STECHE (Annalen, 242, 348-366).—In previous communications (Abstr., 1887, 588 and 976), the authors have described the conversion of methylketole into dimethyldihydroquinoline and dimethyltetrahydroquinoline, which are derivatives of B-methylquinoline. In the preparation of dimethyldihydroquinoline, a monomethyldihydroquinoline is formed as a bye-product. Dihydroethyldimethylquinoline and ethylmethylketole have already been described by the authors (loc. cit.).