long, glistening needles, sparingly soluble in cold ethyl and methyl alcohols, easily in ether, and melts at 68°. Dilute soda does not attack it in the cold, but saponifies it on heating. When heated in a reflux apparatus, carbonic anhydride is evolved, and phenol, isobutylphenol, and isobutylbenzophenoxide, CH1O2, are formed. The latter compound is now being investigated.

When isobutylphenol is treated with phosphoric chloride, isobutylchlorobenzene is formed. The oxidation of this compound proved difficult, potassium chromate and sulphuric acid solution being without action, whilst chromic acid in acetic solution caused complete oxidation. When heated for a long time at 190° with dilute nitric acid, however, it yielded parachlorobenzoic acid. Liebmann's isobutylphenol is, therefore, the para-compound, and from analogy and a consideration of its properties there is little doubt that the acid described above has the constitution [OH: COOH : C‚H, = 1 : 2 : 4]. L. T. T.

a-Methylcinnamic Acid. By P. RAIKOW (Ber., 20, 3396-3397). -In preparing a-methylcinnamic acid (phenylcrotonic acid) by Perkin's method, and recrystallising the product from light petroleum, two acids were obtained having the same composition. The one crystallises in plates melting at 81-82°, the other in needles melting at 74°. When the latter is often recrystallised, it is converted into the acid of higher melting point. The relative amounts of the two acids is influenced by the temperature at which the reaction between the benzaldehyde, propionic acid, and sodium acetate takes place. At 135°, 24 per cent. of the plates and 30 per cent. of the needles are obtained, whilst at 175° only the needles (56 per cent.) are formed. The two acids differ only slightly in solubility. N. H. M.

Benzeneazomalonic Acid. By R. METER (Ber., 21, 118-119). -Benzeneazomalonic acid, prepared from diazobenzene chloride and ethyl malonate, is identical with the phenylhydrazide of mesoxalic acid.

J. W. L.

Action of Phthalic Anhydride on Amido-acids. By L. REESE (Ber., 21, 277-278).-a-Leucinphthaloic acid (this vol., p. 148) can be obtained by adding the calculated quantity of phthalyl chloride to a boiling solution of leucine in alcoholic potash, and continuing the boiling of the alkaline solution for one minute; on cooling, the potassium salt crystallises in small, slender, concentricallygrouped needles, and yields the acid on treatment with dilute sulphuric acid and extraction with ether.

Phthalyldisarcosine, C14H16N2O6, is formed when phthalic anhydride (5 parts) is heated at 140-150° with sarcosine (6 parts). It crystallises in lustrous needles, melts at 168°, and is readily soluble in water and boiling alcohol, sparingly soluble in ether, and insoluble in chloroform and light petroleum. A sodium salt could not be prepared, since the compound is decomposed into its constituents by the action of alkalis; a similar decomposition also occurs when it is heated with concentrated hydrochloric acid. W. P. W.

Azotoluenesulphonic Acid. By J. V. JANOVSKY (Ber., 21, 119– 122). By appropiate manipulation, it is possible to directly sulphonate azotoluene.

Azotoluenesulphonic acid,

C&H,Me N2 C&H,Me SO2H [Me: N2: Me: SO,H=4:1:4:3],

is obtained by the action of fuming sulphuric acid on parazotoluene, care being taken that the temperature is kept below 100°; the best result is obtained by the employment of an acid containing about 24 per cent. SO3, when the temperature produced by the reaction does not exceed 80°. It crystallises with 5 mols. H2O in orangered tables, sparingly soluble in cold water. The potassium (with 5 mols. H.O), sodium (4 mols. H2O), calcium, barium (11 mols. H2O), lead and zinc salts are described. When nitrated, it yields a nitroacid, NO2 CH12N2SO2H + H2O, crystallising in small, yellow needles, readily soluble in hot water; several salts were prepared. The corresponding amido-acid crystallises in pale-yellow needles, and together with the hydrazo-acid also obtained, will be described later. A bromo-acid, CH,BrN, SO,H, was prepared, crystallising in tufts of long needles; the potassium and calcium salts are described. Proof of the constitution assigned above to the sulphonic acid is obtained when it is treated with tin and hydrochloric acid, paratoluidine hydrochloride, and paratoluidineorthosulphonic acid [Me: SO,H: NH, 1:2:4] being formed. A. J. G.

Ethylindole. By A. PICTET and L. DUPARC (Ber., 20, 34153422).-3'-Ethylindole is prepared as follows:-30 grams of aniline is added to 50 grams of zinc chloride, and the whole mixed with 35 grams of lactic acid; 200 to 300 grams of sand being added to prevent frothing. It is then heated in a copper retort. The oily products of several fractions are united, dissolved in ether and shaken with small amounts of dilute hydrochloric acid until no more basic substance is dissolved; the ethereal solution is then distilled. It is a bright yellow oil, boiling at 282-284° (corr.), very sparingly soluble in water, readily soluble in alcohol, ether, benzene, and chloroform, &c.; it distils readily with steam. When the alcoholic solution is treated with hydrochloric acid and a chip of pine, it gives an intense red colour. The solution in chloroform gives, on addition of a few drops of a dilute solution of bromine in chloroform, an intense violet coloration, resembling that of potassium permanganate. The picrate melts at 143°. Ethylindole resembles scatole in its general behaviour.

The basic substance formed in the preparation of ethylindole is quinaldine (compare Wallach and Wüsten, Ber., 16, 2067).

Propionylorthotoluidine, C,H,Me NH COEt [Me: NH.CÓEt=1:2], is readily obtained by boiling orthotoluidine with propionic acid for six hours. It crystallises from benzene in white needles an inch long, melts at 87°, and is readily soluble in alcohol, ether, and glacial acetic acid, &c., sparingly soluble in hot water. It boils at 298299° (corr.) under 730 mm. pressure. When oxidised with potassium permanganate, it is converted into propionylorthamidobenzoic acid, COOH CH NH-COEt. This crystallises from water in white, flat

needles, melts at 117°, decomposes at 180° and is readily soluble in alcohol, ether, and in hot water. The silver salt crystallises from water in small, white needles.

N. H. M.

Dimethylindole. By L. WOLFF (Ber., 21, 123–126).—Aniline reacts with B-bromolævulinic acid, forming dimethylindole, CH11N. The vapour-density shows that this is the product of the reaction and not a compound of twice this molecular formula, as the author suggested in a former paper (Abstr., 1887, 464-465). This indole is identical in all respects with the 2.3' dimethylindole obtained by E. Fischer (Abstr., 1887, 149). J. W. L.

Isatoic Acid. By G. SCHMIDT and E. v. MEYER (J. pr. Chem., [2], 36, 370—389).-When isatoic acid is heated in closed tubes at 100° with excess of ethyl alcohol, hydrogen ethyl carboxylanthranilate, COOET CH, NH.COOH, is formed. It crystallises in thin, colourless needles, melts at 126°, and is soluble in boiling water. When heated with hydrochloric acid in closed tubes at 150,° this substance yields carbonic anhydride, ethyl chloride and anthranilic acid hydrochloride. The salts of this acid are crystalline; the silver salt,

COOEt CH, NH.COOAg,

forms white, microscopic needles or prisms, which are soluble in alcohol and sensitive to light.

When methyl alcohol is substituted for ethyl alcohol in the above reaction hydrogen methyl carboxyanthranilate, COOMe C ̧H, NH·COOH, is formed. This crystallises in minute needles, soluble in boiling water and melting at 176°. The silver salt forms small needles which are less stable than the ethyl compound. When heated with hydrochloric acid at 120°, the methyl compound dissolves, but on cooling crystallises out again unchanged. When heated at 200° with an indifferent substance, such as glycerol, carbonic anhydride is evolved, and methyl anthranilate is formed.

With phenol at 180°, isatoic acid yields phenyl anthranilate, NH2 C&H COOPh, but no carboxyl-derivative. The phenyl salt crystallises in colourless needles melting at 70°. It is easily soluble in alcohol and in ether, sparingly so in boiling water. It is slightly volatile in a current of steam.

When warmed with freshly precipitated ferrous hydrate in the presence of excess of soda, isatoic acid is reduced to anthranilic acid. With zinc-dust and acetic acid, isatoic acid yields anthranilcarboxylic ·COacid, <CHN.COOH.

When isatoic acid is heated with glacial acetic acid, carbonic anhydride is evolved, and a compound of the formula CзHN5O6 formed. This substance is almost insoluble in the usual solvents, and only melts at a very high temperature. At 150°, it is soluble in ammonia, but crystallises out again unchanged on cooling. With hydrochloric acid at 190°, it yields anthranilic acid hydrochloride. It dissolves in cold concentrated sulphuric acid with slight darkening, but is reprecipitated unchanged on the addition of water. 50 per

cent. sulphuric acid at 160° converts it into anthranilic acid. The compound is probably formed from 5 mols. of isatoic acid by the separation of 4 mols. of water. If acetic anhydride is used in place of acetic acid, carbonic anhydride is evolved, and acetylanthranilic acid is formed.

Meyer has already pointed out (Abstr., 1885, 666) that anthranilcarboxylic acid is formed from isatoic acid by oxidising as well as by reducing agents.

From a careful consideration of all the experimental results obtained, the authors conclude that isatoic acid is really identical and not isomeric with anthranilcarboxylic acid, and that the seeming differences of properties are due to the presence in isatoic acid of small quantities of a yellow-coloured impurity. This impurity, which modifies the properties of the acid, is not removed by the ordinary methods of purification, but is destroyed by strong oxidising or reducing agents.

Finally, the authors are inclined to think that the ethyl-compound described above is perhaps identical with that obtained by Weddige by the action of ethyl chlorocarbonate on anthranilic acid, in which case its constitution would be COOH-CH, NH-COOEt, and that of the methyl-compound analogous to it.

L. T. T.

Action of Glyoxal on Aromatic Amines. By O. HINSBERG (Ber., 21, 110-118).-It is easy to obtain reactions between aromatic monamines and glyoxal, if, instead of employing the latter in the free state, its compound with sodium hydrogen sulphite is used.

Anilidoacetanilide, NHPh-CH, CO NHPh, is prepared by heating aniline and glyoxal sodium hydrogen sulphite with dilute alcohol in the water-bath for 20 to 30 hours. The melting point, 112-113°, is found to be rather higher than has previously been stated. Under like conditions, paratoluidine gives paratoluidoacetotoluide.

When B-naphthylamine is heated with glyoxal sodium hydrogen sulphite in alcoholic solution, the reaction takes another course and the sodium salt of B-naphthoxindolesulphonic acid separates. The free acid could not be obtained. The potassium salt, C12H,N-SO,K, crystallises in white plates, and when heated with aqueous hydrochloric or sulphuric acid at 80-90° yields B-naphthoxindole whilst much sulphurous anhydride is evolved.

NH

B-Naphthoxindole, C1H<CH2>CO, crystallises in pale green needles, melts at 234°, and is sparingly soluble in water, readily in alcohol, ether, and glacial acetic acid. It dissolves in potash without decomposition, and is insoluble in mineral acids, but with concentrated sulphuric acid it gives a bluish-green coloration which disappears on NH COdilution. The isonitroso-compound, CH<C(NOH), prepared by the action of nitrous acid, forms slender, reddish-yellow needles, and

melts at 240°.

NH.

B-Naphthisatin, CH.<>CO, is prepared by reducing isonitroso-ß-naphthoxindole in dilute alcoholic solution by zinc and

hydrochloric acid, and treating the colourless liquid so obtained with ferric chloride. It forms slender, red needles, melts at 248°, is moderately soluble in the ordinary solvents, and resembles isatin in its chemical behaviour.

From a-naphthylamine, the corresponding a-compounds were ob tained in similar manner. The sodium and silver salts of a-naphthindolesulphonic acid were prepared, but the free acid could not be obtained.

a-Naphthoxindole crystallises in colourless needles, melts at 245°, is insoluble in aqueous soda, and gives a greenish-black coloration with ferric chloride and hydrochloric acid. The isonitroso-compound forms yellowish-red needles, sinters, and turns black at 230°, and is completely fused at 260°.

a-Naphthisatin forms red needles, melts at 255°; the phenylhydrazide melts at 268-270°. Neither of the naphthisatins give the blue coloration with sulphuric acid and benzene containing thiophen. A. J. G.

Condensation-compounds of Metanitrobenzaldehyde with Benzene and Toluene. By O. TSCHACHER (Ber., 21, 188-191).— Metanitrotriphenylmethane, CHPh2 CH, NO2, is formed when a solution of metanitrobenzaldehyde in benzene is shaken with half its volume of sulphuric acid; it crystallises from light petroleum in colourless crystals, and melts at 90°. When reduced in acetic acid solution with zinc-dust, it yields the amido-derivative, which crystallises from ether in short needles, melts at 120°, and forms a hydrochloride,

C19H15 NH2,HCI.

The acetyl-derivative, C19H15 NHAC crystallises in colourless, nacreous scales, melts at 115°, and is soluble in alcohol.

When metanitrotriphenylmethane in carbon bisulphide solution is treated with the calculated quantity of bromine and exposed to sunlight, an oil, probably C19H,BrNO2, is obtained which on treatment with potassium acetate in acetic acid solution, and subsequent hydrolysis with aqueous potash, yields metanitrotriphenyl carbinol,

14

NO2 C19H14 OH.

This crystallises from light petroleum in colourless crystals, and melts at 75°; when reduced, it is converted into the amido-derivative, which crystallises from ether in colourless, stellate forms, melts at 155°, and yields an acetyl-derivative, OH C19H NHAc, crystallising in colourless, nacreous scales and melting at 164°.

Metanitrophenylditolylmethane, CH(C,H,Me)2 C2H, NO2, is obtained by treating a solution of metanitrobenzaldehyde in toluene with sulphuric acid in the cold. It crystallises from light petroleum in colourless forms, and melts at 85°. W. P. W.

Action of Dichlorether on Phenol. By J. WISLICENUS and H. REINHARDT (Annalen, 243, 151–165).-Dichlorether acts on phenol,