Tetramethyldiamidothiobenzophenone. By O. BAITHER (Ber., 20, 3289-3298).-The author is inclined to think that this substance, which he previously described (Abstr., 1887, 816), is really a thioketone, and identical with the compound obtained by Fehrmann (this vol., p. 156) from auramine. He believes the differences of properties and melting points are due to want of purity and difficulty in exactly determining the melting point. He now gives the melting point as 193-194°.

With

When the ketone is heated with benzoic chloride in carbon bisulphide solution, a dichloro-derivative, CCl2(CH, NMe2)2, is formed, which is soluble in alcohol and glacial acetic acids, sparingly so in benzene and chloroform, and when heated decomposes. water, it yields Michler's ketone, CO(CH, NMе2)2, and is probably the compound prepared from the latter in the manufacture of auramine colouring matters.

With benzoic chloride, the thioketone forms an additive derivative, CS(CH, NMе2)2, COPhCl. This substance is crystalline and melts below 200°, but was not obtained quite pure. It is soluble in acetic acid and in benzene. Alcohol and chloroform .also dissolve it, but at the same time decompose it into its two constituents. Acetic chloride yields a similar derivative, CS(C,H, NMe2)2, COMeCl, which is crystalline and begins to decompose at 160°. It is soluble in alcohol, acetic acid, chloroform, and benzene.

When the thioketone is heated with acetic anhydride and sodium acetate, it yields a compound, C38H.NO,S, of which the constitution is probably S[C(CH1·ÑMe2)2·OAc]. It forms a green powder which begins to decompose at 120°.

When heated with aniline, the thioketone appears to yield chiefly Michler's ketone, but with aniline hydrochloride it yields phenylauramine. The author found the melting point of the latter to be 170-171°. Phenylhydrazine appears to convert the thioketone into the corresponding oxy- (Michler's) ketone.

In his previous communication, the author described the product of the action of nitric acid on the thioketone as trinitrodimethylaniline. He now finds, however, that it is the same compound,

CO[C&H2(NO2)2 N Me NO2]2,

obtained from Michler's ketone. With hydroxylamine, this compound yields van Romburgh's compound, CO[CH2(NO2)2 NHMe]2. It is probable that an oxime is first formed and is subsequently decomposed. L. T. T.

Ring-formation with Elimination of Hydrogen Bromide or Nitrous Acid. By E. LELLMANN and O. SCHMIDT (Ber., 20, 3154— 3157). When B-naphthylamine is treated with glycerol, orthonitrophenol, and sulphuric acid, it yields B-naphthaquinoline in which the condensation has occurred at the 1: 2 position; it was thought that by starting from a-bromo-ẞ-naphthylamine, in which the 1 position is occupied, the condensation would occur at the 2:3 positions. a-Bromo-3-naphthylamine [Br: NH2-1: 2] was obtained by brominating B-acetonaphthalide; it was then treated with glycerol, orthonitrophenol, and sulphuric acid, and the product of the reaction crystallised

from light petroleum; it melted at 93.5°, and on examination it was found that B-naphthaquinoline had been formed with elimination of hydrogen bromide. a-Nitro-3-naphthylamine when treated in a similar manner yields the same compound with elimination of nitrous acid. The conclusion drawn is that the B'-carbon-atom is far less prone to ring-formation than the a-carbon-atom. The nitrophenol takes no part in the reaction, the result being the same whether it is present or not. F. S. K.

Isomeric Naphthylaminesulphonic Acids. By G. SCHULTZ (Ber., 20, 3158-3162).-Bayer and Duisberg (this vol., p. 732) have stated that when B-naphthylamine is sulphonated, a mixture of sulpho-acids is obtained from which a hitherto unknown B-naphthylamine-o-monosulphonic acid can be isolated; this compound yields a B-naphthol-6-sulphonic acid which is identical with Casella and Co.'s naphtholsulphonic acid F; conversely, by heating this acid with ammonia, Bayer and Duisberg obtained a compound identical with B-naphthylamine-6-sulphonic acid. Weinberg and Lange (this vol., p. 160) throw doubt on the identity of the acid which they themselves obtained from naphtholsulphonic acid F and that prepared by Bayer and Duisberg from B-naphthylamine. The author concludes that Weinberg obtained an impure product only, and gives proofs of the identity of the acids in question.

F. S. K.

Intramolecular Migration in B-Naphthylaminesulphonic Acids. By A. WEINBERG (Ber., 20, 3353-3355).-When ẞ-napthylamine-a- and 7-sulphonic acids are added to sulphuric acid (3 parts) previously heated at 160°, and the whole kept at this temperature for 1 hours, they both yield as chief product the 2: 2' acid together with the 2: 3' acid. The same product is formed by sulphonating B-naphthylamine sulphate. It is possible that Bayer and Duisberg's -acid (Abstr., 1887, 732) really consisted of this mixture. (Compare Schultz, preceding Abstract.)

N. H. M.

Conversion of Naphthylaminesulphonic Acid into Dichloronaphthalene. By H. ERDMANN (Ber., 20, 3185-3187).-When Witt's naphthalenedisulphonic acid (Abstr., 1886, 554) is diazotised, the product warmed with phosphorus pentachloride, and then distilled, dichloronaphthalene [14] melting at 107° is obtained, together with some a-monochloronaphthalene. The yield of dichloronaphthalene is 30 to 40 per cent. of the theoretical. N. H. M.

Action of Bromine on Diamido-x-naphthol. By T. ZINCKE and C. GERLAND (Ber., 20, 3216-3231; compare Abstr., 1887, 838). -When bromine acts on bromamido-z-naphthaquinonimide or bromohydroxynaphthaquinonimide, the main products are the tribromide, C10H BraNO3, and the dibromide, C,H,Br.O,; the latter melts at 176°, which is rather higher than the figure given by Kronfeld. In the second case, a small quantity of a third bromide melting at 130° is also formed.

By the bromination of bromamidonaphthaquinone or of bromohydroxynaphthaquinone, four brominated compounds are obtained, of which three are formed in very small quantity. Two of these are not yet worked out, the other is identified as the dibromide C,H,Br2O2. The main product is a dibromo-compound, CH,Br2O,, dibromotriketoCO-C(OH); this crystallises in CO-CBr;

hydronaphthalene hydrate, CH,</ matted needles, melts at 114-115° with decomposition, is readily soluble in alcohol, chloroform, and benzene, less readily in light petroleum, and is soluble in alkalis with yellow coloration. It is readily converted into bromoxy-a-naphthaquinone and hypobromous acid, either when heated alone or when boiled with benzene, toluene, dilute alcohol, or dilute acetic acid. When boiled with water, carbonic anhydride is evolved and a mixture of bromoxynaphthaquinone and the dibromide C,H,Br2O, separates. When dissolved in ethyl or methyl alcohol and treated with hydrogen chloride, chlorohydroxy-anaphthaquinone is formed. When boiled with aqueous potash, it yields a monobromo-compound, crystallising in small, nearly colourless plates and needles, and melting at 118-119°, and probably of the constitution C.H.C(OH) CBr or C.H.<CO>CHBr, probably due C(OH)(COOH), first

CO

to the decomposition of an acid, CH< -CO·CBr2

formed, and for whose existence some evidence is adduced.

, pre

The corresponding dichloro-compound, CHCOCCI CO-C(OH) pared in similar manner, crystallises in thick, white needles, melts at 105° without decomposition, and is far more stable than the dibromocompound. When treated with alkalis, it is converted into a crystalline compound melting at 128-129°, and if the alkaline solution is oxidised, small lustrous plates melting at 124-125°. The authors regard these substances as having the formula C.H.<C(OH)(COOH).

CO

--CCI2

A chlorobromo-compound, CoH CIBRO, was also prepared; it is less stable than the dichloro-compound, crystallises in white needles, melts at 104-105°, and when oxidised in alkaline solution yields plates of a substance melting at 141°.

When the dibromide C,H,Br2O, is treated with aqueous soda, it yields bromoform, phthalic acid, and the monobromo-compound C,H,BrO, described above. A. J. G.

Synthesis of Anthracoumarins from Cinnamic and Metahydroxybenzoic Acids. By S. v. KOSTANECKI (Ber., 20, 31373145). When a mixture of cinnamic acid and metahydroxybenzoic acid, or any hydroxy-derivative of the latter, is heated with concentrated sulphuric acid, condensation products are formed.

From metahydroxybenzoic acid, anthracoumarin, CH,O3, is obtained as a yellow, crystalline compound melting at 260°; it dissolves readily in hot glacial acetic acid, benzene, concentrated sulphuric acid,

and hot baryta-water, sparingly in alcohol; with boiling alkalis, it forms a yellow solution of green fluorescence which probably contains a salt of the corresponding coumaric acid. It is not dissolved by alkalis in the cold, whilst the compounds obtained from dihydroxybenzoic or gallic acid are readily soluble.

This fact shows that the hydroxyl-group has taken part in the condensation, and from the great similarity between these compounds and anthraquinone-derivatives the constitution of anthracoumarin is CH.CO•O、

CH2.

In like manner metahydroxyanthracoumarin, CH,O,, is obtained from symmetrical dihydroxybenzoic acid. By sublimation or crystallisation from acetic acid, yellow needles are formed which melt at 325° and are only sparingly soluble in any ordinary solvent; they dissolve, however, in alkalis and sulphuric acid. When boiled with barytawater, the coumarin-ring is probably split, an insoluble barium salt. being precipitated. The yellow crystalline monacetyl-derivative, CH,O,Ac, melts at 255°.

Orthodihydroxyanthracoumarin, CHO, has already been obtained by Jacobsen and Julius (this vol., p. 56), who gave to it the name "styrogaliol;" this compound and also its diacetyl-derivative were prepared, the latter melts at 260°, and its formation lends support to the constitution assigned to the anthracoumarins. Orthodihydroxyanthracoumarin can be fixed by a mordant, a fact which is in accordance with a theory put forward by the author (see this vol., p. 274).

F. S. K.

Purpurogallin. By S. C. HOOKER (Ber., 20, 3259-3260).—The author recommends the following method of preparing purpurogallin: -20 grams of pyrogallol is dissolved in 330 c.c. of cold water and treated with a solution of 87 grams of potassium ferricyanide in 330 c.c. of water. Gas is evolved, the solution loses its deep red colour, and purpurogallin separates; in about hour the oxidation is complete. The yield is 13 to 14 per cent. of the pyrogallol employed. Purpurogallin is formed in the oxidation of an aqueous solution of gallic acid by sodium nitrite.

Purpurogallin dissolved in sulphuric acid gives an intense, but fugitive, violet coloration when a trace of nitrous acid or a nitrite is added. The reaction is very characteristic and delicate.

A. J. G.

Hydrogenation of Aromatic Hydrocarbons. By E. BAMBERGER and W. LODTER (Ber., 20, 3073-3078).-The hydrocarbons are boiled with amyl alcohol and sodium, the whole poured into water, and the upper layer dried with sodium carbonate and distilled. yield varies with different hydrocarbons from 50 to 80 per cent. of the theoretical.

The

Tetrahydroretene, CH22, forms a clear viscous oil which when kept from air remains liquid; in open vessels it solidifies, probably becoming oxidised to retene. It boils at 280° under 50 mm. pressure.

Tetrahydro-acenaphthene, C12H, is a clear, colourless, viscous oil of

a slightly aromatic odour, boiling at 249-5° (corr.) under 719 mm. pressure.

149

Tetrahydrodiphenyl, C12H, is a clear, colourless, viscous oil having a slight odour of diphenyl. It boils at 244-8° under 716 mm. pressure.

Dihydronaphthalene, dihydroanthracene (m. p. 108.5°), and tetrahydrophenanthrene were also prepared. N. H. M.

Sulphocamphylic Acid. By A. DAMSKY (Ber., 20, 2959-2967). -When ammonium sulphocamphylate is distilled with atamonium chloride, a yellowish-brown oil of peculiar turpentine-like odour is obtained, which, on fractionation, can be separated into two portions, one boiling at 108-110° and the second at 195—196°. These were

separately examined.

The fraction boiling at 108-110° is a colourless, mobile liquid, having the odour of the crude product, and a sp. gr. = 0·7949 at 11.5°. It has the composition CH, and is a non-aromatic hydrocarbon, possibly identical with that obtained by Moitessier by distilling copper camphorate (Jahresb., 1866, 410). On treatment with concentrated nitric acid, it is violently attacked and completely resinified, but when dissolved in acetic acid and treated with an acetic acid solution of nitric acid, no action occurs. Oxidation with chromic acid mixture does not convert it into an aromatic acid, and with permanganate it yields only oily fatty acids; whilst, contrary to the behaviour of aromatic hydrocarbons, it does not form an acid amide on treatment with amidoformic chloride. Bromine reacts with it readily, yielding an unstable, crystalline compound, C.H2Br2, and subsequently liquid higher substitution-products, whilst the unstable, crystalline additive-compounds, C,H,HCl and C,H,HBr, are formed when it is treated with hydrogen chloride and hydrogen bromide respectively.

The fraction boiling at 195-196° undergoes slight decomposition at each distillation, and is a colourless liquid, having an odour similar to that of the lower fraction. It has probably the composition CHO, and forms oily compounds with hydroxylamine hydrochloride and phenylhydrazine hydrochloride; the oxime having probably the formula C1H, N.OH.

When potassium sulphocamphylate is fused with twice its weight of potassium hydroxide and the melt extracted with ether, a brown, resinous mass is obtained, which, on distillation in a vacuum, yields a pale-yellow, readily crystallisable oil. The crystals have the composition C9H12O2, are readily soluble in alcohol and ether, very sparingly soluble in hot water and melt at 99°. The compound, although prepared by Kachler's method (Abstr., 1874, 154), and having the same composition, differs from the substance prepared by him in its lower melting point and marked acid character. The silver salt, C,HO2Ag, is soluble in hot water; the calcium salt, (C,H1О2)¿Ca + 2H2O, forms yellowish crystals, soluble in hot water; the barium salt, (C9H1O2)2Ba + 2H2O, is crystalline and soluble in hot water; the methyl salt was also prepared and is crystalline. Treated with bromine, the acid yields a crystalline compound with the evolution of