MONOAZO DYE AND PROCESS OF MAKING SAME.

Thilo Kröber, of Basel, Switzerland, assignor to the firm of Society of Chemical Industry in Basle. Patent No. 805,918, dated November 28, 1905.

The invention relates to the manufacture of new monoazo dyestuff's derived from 1-amido-2-acidyloxynaphthalenesulphonic acids and sulphonic acids of 1-8-dioxynaphthalene, according to the process, which consists in acetylizing 1-2-amidonaphtholsulfonic acids in the hydroxyl group, then diazotizing the so-obtained l-amido-2acetyloxynaphthalenesulphonic acids and combining the resulting diazo compounds with sulphonic acids of 1-8-dioxynaphthalene.

These new monoazo dyestuffs dissolve in water with violet-blue to blue coloration, in concentrated sulfuric acid with greenishto blue coloration, in concentrated sulphonic acid with greenishwhich become bluish green on treatment with chromium compounds-as, for instance, potassium bichromate.

NAPHTHALENE DYE AND PROCESS OF MAKING SAME.

René Bohn, of Mannheim, Germany, assignor to Badische Anilin und Soda Fabrik. Patent No. 806,053, dated November 28, 1905.

This invention consists in the manufacture and production of a new coloring-matter from naphthazarin. It has been found that when one molecular proportion of naphthazarin is heated in aqueous solution with more than two molecular proportions of caustic soda, preferably while passing air through the mixture, the solution which is at first of a corn-flower-blue color changes gradually into a fuchsin-red and contains a new coloring-matter, and by the addition of acid to the said solution this new coloringmatter is precipitated as a brown crystalline precipitate. If less than two molecular proportions of caustic soda be employed, different color changes are observed, and the result is not that contemplated according to this invention.

The new coloring-matter dyes wool, from an acetic-acid bath,

orange-red shades, which upon treatment with a bichromate are converted into reddish-black shades. When the new coloringmatter is printed with chromium acetate on cotton, a very fast full black is obtained of greater beauty than the shades obtained similarly with naphthazarin.

BLUE AZO DYE AND PROCESS OF MAKING SAME. Thilo Kroeber, of Basel, Switzerland, assignor to the firm of Society of Chemical Industry in Basel. Patent No. 806,415, dated December 5, 1905.

The invention relates to the manufacture of new monoazo dyestuff's derived from 1-amido-2-acidyloxynaphthalenesulphonic acids and naphtholsulphonic acids, according to the general process, which consists in acetylizing sulphonic acids of 1-2-amidonaphthol in the hydroxyl group, then diazotizing the so-obtained 1-amido2-acetoxynaphthalenesulfonic acids and combining the resulting diazo compounds with naphtholsulfonic acids.

The claims specify the monoazo dyestuff, derived from 1-2amidonaphthol-4-sulphonic acid and 1-5-naphtholsulphonic acid, which yields blue solutions in water and in concentrated sulfuric acid and dyes unmordanted wool in bordeaux shades becoming blue on treatment with chromium compounds.

RED AZO DYE AND PROCESS OF MAKING SAME.

Felix Klingemann and Georg Kalischer, of Frankfort-on-theMain, Germany, assignors to Cassella Color Company, of New York, N. Y. Patent No. 807,119, dated December 12, 1905.

This invention is based upon the discovery that the monoazo dyes formed by combining the diazo compounds of aromatic amidoaldehydes with the sulpho acids of alpha and beta naphthol can be condensed in acid solution with the 1-2-diamido-naphthalene5-hydroxy-7. sulphonic acid in the proportion of two molecules to one to form the diazo coloring-matters of the following constitution:

in which X represents a mono- or disulphonic acid of alpha- or beta-naphthol. These diazo coloring-matters which in themselves are of no great value can be transformed into highly valuable products by combining them in alkaline solution with one molecule of an aromatic diazo compound. The new azo coloring-matters thus obtained are of a brilliant red color, the shade of which varies from a yellowish red to a bluish red, according to the naphtholsulphonic acid and to the diazo compound used in the preparation of the dyestuff. They have a strong affinity for cotton. The dyes obtained with them are of great fastness to washing and to acids.

YELLOW-GREEN DYE AND PROCESS OF MAKING SAME.

Charles Oswald, Hermann Lorétan, and Charles de la Harpe, of Basel, Switzerland, assignors to dyeworks, formerly L. Durand Huguenin & Co. Patent No. 807,181, dated December 12, 1905.

Formaldehyde reacts with dyestuffs of the gallocyanin series either singly in aqueous solution or in aqueous solution in presence of acids or alkalies. This reaction is facilitated by a rise of temperature or by the presence of acids. For example, the reaction occurs very rapidly and at ordinary temperature in presence of strong sulphonic acid. The proportions of formaldehyde employed may be varied. The products obtained are dyestuffs dyeing with chromium mordanted fibres yellowish green. Their solutions in concentrated sulphuric acid are green blue and turn to reddish by addition of water. Their solutions in acid

ulated water are rose-colored and turn to intense fuchsin red by addition of sodium nitrite. Their aqueous solutions give by addition of sodium acetate a green precipitate and by addition of alkalies a brownish precipitate. When these new yellowish-green dyestuffs are heated with water alone or with acidulated water either for a long time at 100° or for a shorter time at a higher temperature and under pressure or with aqueous solutions of certain salts—as calcium chlorid, zinc sulphate, ammonium hydrochlorid, anilin hydrochlorid-they are modified, become more easily soluble in water, and yield on with chromium mordanted fibres blue tints.

GREEN DYE AND PROCESS OF MAKING SAME.

Charles Oswald, Hermann Lorétan, and Charles de la Harpe, of Basel, Switzerland, assignors to dyeworks, formerly L. Durand Huguenin & Co. Patent No. 807,182, dated December 12, 1905.

The inventors have found that by heating the yellowish-green dyestuffs described in U. S. Patent No. 807,181 by the action of formaldehyde on gallocyanin dyestuffs with neutral, acid, or alkaline reducing agents-as, for instance, stannous chlorid, zinc, aluminium, hydrosulphites, and their compounds with aldehydes, alkali sulfids, hydrogen sulphide, titanium chlorid, glucose, &c.—in a convenient medium the said dyestuffs are modified and become more soluble in water. An excess of the reducing agent does no harm. The yellowish aqueous solutions of the modified dyestuffs give by addition of sodium acetate a yellow precipitate, and these dyestuffs dye with chromium mordanted fibres vivid green tints which are a little bluer and more intense than the tints obtained with the dyestuffs which are employed as parent materials.

BROWN AZO DYE AND PROCESS OF MAKING SAME. Thilo Kroeber, of Basel, Switzerland, assignor to Society of Chemical Industry in Basel. Patent No. 807,289, dated December 12, 1905.

According to the present invention the derivatives of triamidobenzene corresponding to the general formula

X

R-N-H-C6-H2-NH2

NH2

(wherein R is a radical of the benzene or naphthalene series and X hydrogen, SO,H, or COOH) are combined with orthodiazophenol derivatives for the manufacture of brown dyestuffs, which when developed by chroming are faster to copper and copper salts than are the analogous products from diamins. The triamido deriva

tives in question are easily obtained by condensing, for example, 1:3:4-dinitrochlorobenzene, its sulphonic acid, (NO2:NO2:C1: SO2H =1:3:4:5.) or dinitrochlorobenzenesulphonic acid, (NO2:NO2: Cl :SO,H=2:6:1:4,) or either of the two corresponding dinitrochlorobenzoic acids, with bases of the benzene and naphthalene series, their sulphonic and carboxylic acids, and reducing the condensation products thus formed. The combination of the diazo derivatives with the triamidobenzene derivatives occurs in part, even in mineral acid solution, better in acetic acid or sodium carbonate solution. The new dyestuffs thus obtained correspond to the general formula

(wherein X signifies hydrogen, SO,H, or COOH, R an aromatic radical, and R, the radical of an orthodiazophenol), and dissolve in water with yellow-brown to violet-brown coloration and give on wool in acid-bath brown tints, which become by chroming fast to light and fast to fulling.