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orthonitrocumenylacrylic acid, orthamidocumeny lacrylic acid, and propylhydrocarbostyril. The author considers that the so-called "cumenylpropionic acid" contains normal propyl, and that it is parapropylhydrocinnamic acid. The propionic radicle, therefore, as well as the methyl and acrylic acid radicles, influences a propyl-group in the para-position, causing the formation of normal propyl. N. H. M.

Reciprocal Transformations of Cymene- and Cumenederivatives. By O. WIDMAN (Ber., 19, 2781-2785). With regard to the change of cumene- into cymene-derivatives, the author objects to Fileti's suggested law (this vol., p. 36) on the ground that the nature of the group has not been determined in any of the compounds containing these elements or groups (Cl, Br, Cy, COOH, &c.), and mentions experiments previously described by him (Abstr., 1886, 464) which show Fileti's view to be quite incorrect. N. H. M.

Octylbenzene. By F. AHRENS (Ber., 19, 2717-2725).-Octylbenzene (v. Schweinitz, Abstr., 1886, 540) boils at 262-264° (uncorr.), sp. gr. 0·852 at 14°. It solidifies at -7° to a crystalline mass, is insoluble in water, miscible with alcohol, ether, and benzene. Chloroctylbenzene, CH,Cl-C,H17, is prepared by the action of chlorine in presence of iodine on the hydrocarbon. It is a yellowish oil, almost without odour, readily soluble in alcohol and ether; it boils at 270-275°. Bromoctylbenzene, C.H.Br.C.H17, boils at 285-287°. The moniodo-derivative is prepared by the action of iodine and mercury oxide on octylbenzene diluted with light petroleum. It is a yellow oil, insoluble in water, soluble in alcohol and ether. It solidifies at -4°, and does not distil without decomposition. It is very susceptible towards light and heat. Metanitro-octylbenzene, NO2 CHCH1, is formed by the action of fuming nitric acid on octylbenzene in the cold. It crystallises in long needles insoluble in water and ether; sparingly soluble in alcohol and chloroform; it melts at 123-124°, and sublimes unchanged at a high temperature. When oxidised with potassium permanganate, it yields metanitrobenzoic acid. Orthonitro-octylbenzene is obtained, together with the para-derivative, by heating the mother-liquor from the preparation of the meta-compound. The heavy oil so formed is washed with hot water. It is a thick, yellow oil with a peculiar aromatic odour. It begins to decompose at 100°, and cannot be distilled; at 130° it suddenly carbonises. Paranitro-octylbenzene is obtained by first nitrating octylbenzene in the cold, separating the liquid from the crystals of metanitro-octylbenzene, and heating for 12 hours. It is then filtered and again heated, and this is repeated until all the hydrocarbon has dissolved. The crystalline substance is gently heated to sublime any metanitro-derivative present, and then strongly heated, when the para-compound sublimes. It forms small, yellowish, lustrous needles, having a slight odour of benzaldehyde; it melts at 204°, is insoluble in water, soluble in alcohol and ether. Dinitro-octylbenzene,

CH, (NO2)2 C8H17,

was formed when crystals of metranitro-octylbenzene containing

fuming nitric acid were washed with ether. Water was poured on to stop the violent reaction which at once took place. It melts at 226°, and sublimes below this temperature in transparent crystals with a vitreous lustre, soluble in ether and alcohol, insoluble in water; its constitution was not determined. Orthamido-octylbenzene hydrochloride, NH, CH, CH17, HCl, is prepared by reducing the nitro-compound with tin and hydrochloric acid; it forms small, lustrous, white plates; when heated, it becomes red. N. H. M.

A Fourth Monobromophenol, and a Second Monobromobenzene. By F. FITTICA (Ber., 19, 2632-2634). In this communication, the author still maintains the existence of the fourth monobromophenol described by him in a former work, the conclusions from which were subsequently shown by Hand to be erroneous (Abstr., 1886, 1017). The preparation of a second monobromobenzene is also described, but it was not obtained of constant boiling point (60-66°), and the analytical results are far from satisfactory. V. H. V.

Constitution of Nitranilic Acid. By R. NIETZKI (Ber., 19, 2727). When diamidotetrahydroxybenzene (obtained by reducing nitranilic acid) is distilled with zinc-dust, paraphenylenediamine is formed. This is fresh evidence that nitranilic acid is paradinitrodihydroxyquinone (compare Hantzch, Abstr., 1886, 1021).

N. H. M.

Aniline and its Homologues. By L. LEWY (Ber, 19, 27282729; compare Abstr., 1886, 872).-When paratoluidine is boiled with water, splendid crystals of the hydrate separate on cooling; when exposed to air they effloresce.

The xylidines and cumidines behave towards phosphoric acid as orthotoluidine does, and yield only primary phosphates.

As paratoluidine forms a secondary phosphate, and orthotoluidine a primary phosphate, the para-compound behaves like an element having the atomic weight 214, whilst the ortho-compound behaves like an element having the atomic weight 107. In estimating the phosphoric acid in a mixture of the two phosphates, the relative amounts of paratoluidine and orthotoluidine can therefore be determined. N. H. M.

Alkyl-derivatives of Aniline. By A. CLAUS and H. HIRZEL (Ber., 19, 2785-2791).-Methylpropylaniline, NPhMePr, is prepared by heating methylaniline and propyl iodide for eight hours in a waterbath. The product is dissolved in water, extracted with ether, and treated with alkali. It is a yellowish oil, boiling at 212° (uncorr.). The hydrochloride melts at 106° (uncorr.); it is very hygroscopic. The ethiodide, NPhMePr, EtI, is a viscous substance readily soluble in water. When boiled with concentrated aqueous potash, methylethylaniline is formed.

Ethylpropylaniline, NPhEtPr, is obtained by the action of propylaniline (Claus and Roques, Ber., 16, 909) on ethyl bromide, or from ethylaniline and propyl bromide. It is a bright yellow oil boiling at

216° (uncorr.). The hydrochloride is a crystalline substance, and melts at 131° (uncorr.). The methiodide is a syrup having all the properties of methylpropylaniline ethiodide.

Methylethylaniline was prepared by the method of Claus and Howitz (Abstr., 1884, 1005); it was obtained in the crystalline state. The hydrochloride melts at 114°. The propiodide is identical with the iodide mentioned above. When the aqueous solution of the iodide is heated, or kept in contact with ether, decomposition takes place, with formation of propyl alcohol and methylethylaniline hydriodide. Ń. H. M.

Action of Ethyl Imidocarbonate on Aromatic Ortho-compounds. By T. SANDMEYER (Ber., 19, 2650-2657).-In continuation of former experiments on the reactions between ethyl imidocarbonate and the amines of the aromatic series (Abstr., 1886, 611), the prepation and properties of various derivatives of phenylene and toluylene diamines are described.



Ethoxymethenyltoluylenediamine, C,H,<H>C-OEt, prepared from toluylenediamine hydrochloride and ethyl imidocarbonate, crystallises in golden needles which melt at 163°, insoluble in cold, sparingly soluble in hot water, moderately soluble in alcohol. Its aqueous solution gives a voluminous, white precipitate with mercuric chloride. With acids, it forms very soluble salts.



When heated with hydrochloric acid, it yields hydroxymethenyltoluylenediamine, C,H,<>COH. This substance crystallises in small needles, melts at 290°, and is sparingly soluble in boiling alcohol, readily in water. From its formation, it would seem to contain the hydroxyl-group, but it is also identical with a compound obtained directly from carbamide and toluylenediamine, which would contain the carbonyl-group; the atomic transformation of the -N-COHgroup into NH-C: O is however of frequent occurrence.



Ethoxymethenylphenylenediamine, C.H.<H>C·OEt, prepared in like manner from phenylenediamine, crystallises in reddish glistening leaflets which melt at 160°. In its solubility and physical properties, it resembles its homologue. With hydrochloric acid, it yields hydroxymethenylphenylenediamine, C.H.<H>COH, which crystallises in leaflets, and is identical with phenylenecarbamide obtained directly from orthonitrophenylurethane.


Ethoxymethenylamidophenol, C.H.<>COEt, prepared from amidophenol and ethyl imidocarbonate, is a colourless oil, boiling at 225230°, of peculiar odour. It is converted by hydrochloric acid into hydroxymethenylamidophenol, CH,<>COH, crystallising in red prisms, which lose their colour on exposure or when separating slowly from solution.

The reaction of the amido-acids on ethyl imidocarbonate differs

from those of the amines and the amidophenols; thus with anthranilic acid an amidine of the composition


is formed. This crystallises in white needles, melts at 223°, and is sparingly soluble in boiling water, soluble in hot alcohol. It would appear from its formation that this substance should be a bibasic acid, yet its silver salt contains only one atom of the metal in the molecule. V. H. V.

Decomposition of Diazo-compounds by Alcohol: Paradiazotolueneorthosulphonic Acid. By I. REMSEN and A. G. PALMER (Amer. Chem. J., 8, 243–251).-The authors expected to be able to prepare benzoic sulphinide by the oxidation of orthotoluenesulphonamide, itself prepared from the orthotoluenesulphonic acid obtained by boiling the diazo-compound of paramidotolueneorthosulphonic acid with alcohol. This method seemed all the more promising, as Jensen and Ascher have described the actual elimination of the diazo-group in the above compound.

The authors find no difficulty in the conversion of paranitrotoluene into paradiazotolueneorthosulphonic acid; but this, when boiled with alcohol under pressure, yields, contrary to the statements of Jensen and Ascher, not tolueneorthosulphonic acid as the principal product, but ethoxytolueneorthosulphonic acid. The reaction will not proceed without the application of pressure; it commences at 90 mm., and the two compounds are then formed in equal quantities, but the yield is very bad, the reaction slow, and the product is black with tarry matters. At 150 mm. thrice as much of the ethoxy-compound as of the toluenesulphonic acid is formed, and at 500 mm. the ethoxy-compound is formed almost alone; the reaction takes only a few minutes, and the product is far purer. The acid product of the reaction cannot be purified by means of the barium salts, but has to be converted into the acid amide, and it is to be noted that ethoxytoluenesulphamide, OEt C,H,Me SO,NH, [4: 1: 2], melts at 143-144', and not at 136°, as described by Heffter.

This action has not been satisfactorily explained. It is at present assumed by all writers that the normal reaction of the diazo-compounds when boiled with alcohol is that which results in the displacement of the diazo-group by hydrogen; it is, however, certain that the reaction frequently takes place in such a way as to form phenetoïls: thus the sulphate or nitrate of diazobenzene yields benzene in extremely small quantity, but phenetoïl in very considerable quantity, and it appears probable that the normal reaction is the one that gives the phenetoïl. A list of 15 similar cases is cited in illustration. The action in the above case is therefore represented not by the equation generally given, but by



+ EtOHOEt C,H,Me SOзH + N2.

H. B.

Diazo- and Diazoamido-compounds. By O. WALLACH (Annalen, 235, 233-255).-Some of the diazo-compounds of the monacetic derivatives of the diamines (Abstr., 1883, 584) are quite stable in the dry state, and their hydrobromides can be obtained in a pure state owing to their relatively slight solubility in water and alcohol. Acetic anhydride decomposes the dry diazo-compounds, yielding the acetic derivative of a phenol, thus acetoparatoluidine orthodiazobromide yields diacetamidocresol, OAc C,H,Me-NHAC. The diazo-compounds unite with nitro-ethane to form the mixed azo-compounds discovered by V. Meyer (this Journal, 1875, 1202, and 1876, ii, 93), and they also combine with secondary amines, forming diazoamidocompounds. The latter substances are decomposed by boiling with strong hydrochloric, hydrobromic, and hydriodic acids according to the equation RNN·NR" + 2HCl = RC1 + N2+ NHR", HCl. Phenols are the chief products of the action of dilute sulphuric acid on the mixed diazoamido-compounds.

Benzene diazopiperidide, C,NH10 N2 Ph, first described by Baeyer and Jaeger (this Journal, 1876, i, 273), can be readily prepared by pouring a dilute ice-cold solution of diazobenzene chloride (from 100 parts of aniline) into a dilute cold aqueous solution of piperidine, 100 parts by weight mixed with 60 of potassium hydroxide. Every precaution must be taken to prevent the temperature of the mixture rising above 0°. The piperidide melts at 43°. It is decomposed by warm hydrochloric, hydrobromic, and hydriodic acids, yielding chloro-, bromo-, or iodo-benzene respectively, and piperidine.

Toluene paradiazopiperidide, CH,Me N2C,NH10, crystallises in colourless prisms. It is soluble in alcohol, light petroleum, and ether, and melts at 41°. It unites with 2 mols. HCl to form an unstable compound. Toluene orthodiazopiperidide and orthonitrotoluene paradiazopiperidide are oily liquids. Paranitrotoluene orthodiazopiperidide melts at 50-51°, and is decomposed by hydrobromic acid, yielding bromonitrotoluene, C,H,MeBr-NO, [1:2:4]. Nitrobenzene metadiazopiperidide and benzene diazoconine and toluene paradiazoconine are oily liquids.

By the action of sodium nitrite on a solution of acetotoluylenediamine in hydrobromic acid, the diazobromide,

NHACCH Me•N,Br [Me:N,Br:NHA = 1:2:4]

is obtained as a yellow precipitate. In the dry state, this diazobromide is remarkably stable. It acts on an alcoholic solution of nitroethane and sodium ethoxide, yielding a red precipitate of acetoparatoluidine orthodiazonitroethane,

NHAC.C,H,Me N, CHMe NO, [Me: N2C2H,NO2: NHAC 1:2:4]. The precipitate dissolves in alkalis, and is reprecipitated by acids. It is deposited from an ethereal alcoholic solution in red needles melting at 143°.

Acetoparatoluidine orthodiazodiethylamide, NHACC1H,Me N2 NEt2, is deposited in colourless prisms when acetoparatoluidine orthodiazobromide is added to a cold solution of diethylamine. It melts at 108°.

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