DE318997C - Process for the production of leukotriarylmethanazo stain-coloring dyes - Google Patents

Description

Process for the production of stain-coloring leukotriarylethanazo dyes. It has been found that by coupling. development of the diazo compounds of such leukotriaryl methane derivatives, those in an aryl radical have a hydroxyl and an amino group in the o-position to one another contain, with suitable coupling components to new leukotriarylmethanazo dyes. can reach which have pronounced co-licensing properties and accordingly according to the production processes customary for mordant or post-chromium plating dyes real colorations on the animal fibers and also for transferring them to new ones valuable derivatives are suitable.

The leukotriarylmethane derivatives on which the process is based as starting materials, .the one in an Ar # Irest a hydroxyl and an amino group in o-position to each other contain, z. B. be produced by the following process: #. i. By Nitration and subsequent reduction of the aromatic condensation Oxyaldehydes or their substitution products with secondary or tertiary amines leucooxytriarylmethane, derivatives shown.

2. By condensation of such aromatic Amionoxyaldehydes or their substitution products in which the amino and hydroxyl groups are in the o-position stand to one another, with secondary or tertiary amines or by condensation of the corresponding nitrooxyaldehydes with secondary or tertiary amines and subsequent Reduction..

3. By condensation of the hydrols from secondary or tertiary amines with o-aminophenol derivatives. > The conversion of the o-aminooxyleukotriarylmethane derivatives obtained in the above or other ways into new ones. o-Oxyag.Ofarbstoffe is done by diazotization of the aminooxy compounds and coupling with suitable components according to known methods.

The leukotriaryl methanazo dyes prepared according to the method characterized above can be fixed to the animal fibers in the manner of acidic dyes will. The metallic lacquers of the dye e, in particular special, the chrome and copper lacquers that either by post-treatment of the acidic Colorations with, metal salts, in particular chromic acid salts or copper salts or by adding the substances mentioned to the dye bad can be generated on the fiber, are characterized by very pure tones and very good light, alkali; * Full and washable is from. .The * making a number of the new Leukotriaryl methane derivatives and leukotriaryl Methanazo dyes is, by the following Beie play egg-refined: Example, i.

112 g of the leukotriphenilmethane derivative represented by condensation of in-nitrobenzaldehyde with dimethylaniline, reduction of the nitro body obtained, diazotization, boiling and conversion of the oxy body formed into the disulfonic acid are dissolved with stirring in 5Ö0 9 sulfuric acid of 98 percent at about 20 to 30 ' and then at 0 to 5 '26 .5 9 mixed acid of 5o percent allowed to run in with stirring. The mixture is stirred for a further two hours at 20 'and the reaction mass is poured into ice water. Here, the body formed nitro I precipitates in crystalline; it can be separated out by filtering, washing and drying, or the well-washed paste can be subjected to reduction immediately. . The resulting nitro body forms a light greenish powder and, in the form of the free acid, is almost insoluble in water, slightly soluble in dilute soda solution and dilute sodium hydroxide with a green color with formation of the sodium salt. The green solution in caustic soda turns wine red when cooked; when oxidizing with lead peroxide, a strong blue-green dye is produced. To reduce the nitroleukotriphenyhnethanderi.vates obtained, 60 g of the nitro compound are suspended in 300 cc of water. The hot suspension is poured into a boiling mixture of 50 9 iron filings, 100 cc water and 25 9 40 percent acetic acid with stirring. . and boiling entered and after completing the entry, cooked for another half an hour. , Thereafter the iron is precipitated mitSoda, filtered off from Nied & shock, the filtrate is acidified with hydrochloric acid or sulfuric acid, and was completed by standing the crystallization of the obtained Aminooxyleukotriph # enylmethanderivafes. , The aminooxy compound is filtered, washed and dried. . . Example 2. Salicylaldehyde-5-sulfonic acid (see monthly books for chemistry iä [18971, page 132) is z. B. in concentrated sulfuric acid of the nitration untel-throws. The. 3-Nitrosalicvlaldehyde-5-sulphonic acid separated by known processes forms an almost colorless powder, which dissolves colorless in water, in dilute soda solution with a yellow-orange color; with aniline the sulphonic acid forms an egg-yellow benzylide compound, with phenylhydrazine an orange-colored hydrazone. 25 parts of the 3-nitrosalicylaldehyde-5-sulphonic acid thus prepared are mixed with 58 parts of ethylbenzylaniiinsulioic acid and igo, parts of water and heated in a boiling water bath for 24 hours with stirring. The resulting nitroleukotrilyhenylmethane body separates out in the form of a green resin, which solidifies when standing. The nitro body deposited in a known manner forms a light yellowish powder which dissolves in water with light green, in dilute soda solution with brown orange egg and in concentrated sulfuric acid with yellow color. To reduce the resulting Leukotriphenyhnethankörper is in 30o parts of water #md ii parts of sodium carbonate dissolved and after known methods, e.g., as with # 'iron and acetic acid, to, corresponding Aminokörper reduced. The filtered solution of the aminooxyleukotriphenylmethane derivative obtained after the iron has been precipitated with soda can be further processed immediately, or the aminooxyleukotriphenylmethane body can be separated from it by known methods.

Rather than by condensation of the # -l # itrosalicvlaldehyd-5-sulfonic acid with Äthylb.enzylanillinsulfosäure and därauffolge'nde reduction may be the Aminooxytriphenylmethankörper, even by condensation of the corresponding 3-aminosalicylaldehyde-5-sulfonic acid are represented by Athylbenzylanilinsulfosäute.

Example 3.

27 parts of tetramethyldiaminobenzhydrol and ig parts of 2-amino-i-oxyberiz01-4-sulfonic acid are added with stirring to 250 parts of sulfuric acid * of 98 percent at about 25 ' and then heated on a water bath, the hydrol nicely after a short time has disappeared; it is allowed to cool, the reaction mass is poured into water and neutralized, the leuco compound formed precipitating, which is filtered, washed and dried.

. The properties of the products that can be prepared according to Examples 1 to 3 are given in the table below. When solving Product appearance solution in acidic the in l # onzeii- organic D ' trated Lb 'over- Witsser water, r, * ", n sulfur in oleum 1 solution bond Iaz Solution re ni ttel to light gray, greenish brown, reddish brown, yellowish, insoluble, slightly Example i powder brown 'soluble (Na salt) to green-gray yellow-green brown brown brown insoluble easily Example 2, powder soluble (Na-Salz) i iach dark- dirty- red-brown red-colored green- insoluble easily Example 3 gray, brown, brown, soluble (Na-Salt) Pulvei brown Example 4.

Fa 'rbstoff from the diazo compound of Aminooxyleukotriphenvimethanderivates according Beispief i and beta-naphthol.

57 parts of the amino body shown in Example i are dissolved in about 250 parts of water in 40 'and 25 parts of 3o' percent sodium hydroxide solution, 7 parts of sodium nitrite are added to the solution and the solution is acidified at 0 ' with 40 parts of concentrated hydrochloric acid all at once. The diazo solution obtained is allowed to run into a solution, which is as concentrated as possible, of 14 parts of p-naphthol, 13 parts of 30 percent sodium hydroxide solution and 50 g of soda. After several days of stirring or standing, the coupling is what. going very slowly, ends. The dye is deposited by salting out. It forms a blue powder, which, with blue, dissolves in water in concentrated sulfuric acid with brown-violet color; He dyes wool from an acid bath in green-blue tones, which change to a wash- and light-fast green-blue when re-chroming, when re-coppering or when dyeing with the addition of copper salts to the bath, turn into a pure wash- and light-fast blue. Example 5.

Dye from the diazo compound of the aminooxyleukotriphenvimethane derivative according to Example i and i-PhenY1-3-methyl-5-pyrazolone. The diazo compound prepared according to Example 4 consists of 57 parts of the aminooxyleukotriphenylmethane derivative. according to example: c is added to a concentrated soda-potash with stirring. Solution of 17.5 parts of i-phenyl-3-methyl-5-pyrazolone. The resulting dye is deposited after coupling is complete by adding sodium chloride., It forms a brown-yellow powder that dissolves in water with yellow, in concentrated sulfuric acid with orange-yellow dye and dyes wool from acidic bath in green tones. A washable and lightfast blue-green is obtained when the acidic dyeings are re-chromed, a washable and lightfast pure green when re-coppering, a pure green when re-treating with iron salts or when dyeing with the addition of iron salts to the bath. Example 6.

Dye from the diamo compound of the aminooxyleukotriphenylmethane derivative according to example. i and aceto-acetic anilide.

The diazo compound of 57 parts of the aminoxy compound is added with stirring to the solution of 18 parts of aceto-aceticanilide, 13 parts of 30 percent sodium hydroxide solution and 40 parts of soda in 300 cc of water. After standing for a long time, the dye is salted out with common salt and deposited in the usual way. It dissolves in water with a greenish-yellow color, in concentrated sulfuric acid with an orange-yellow color and produces green dyes on wool from acid baths, which turn into a washable and lightfast blue-green when re-chromed, when re-coppered or when dyed with the addition of copper salts for bathing in a wash - and pass over light-fast green of excellent purity, Example 7.

Dye from the Diäzcverbindungen des Arnine, -, oxytripbenylmethankkörpers # 3r # s iidth Example 2 and . P-naphtol.

81 parts of the aminooxyleukotriphenylmethanesulfonic acid shown in Example? Are diazotized in the usual way and then added to a solution full of 14.5 parts of # -naphthol, 13.5 parts of 30 percent sodium hydroxide solution and 40 parts of soda at about 15 'with stirring. After, completed coupling . the dye is deposited by salting out. It dyes wool from an acidic bath in red-brown tones, which when chrome-plating turn into a wash-, light- and potting-fast green-blue, when re-coppering or when dyeing with the addition of copper salts for bathing, it turns into a red-violet with good wash- and lightfastness. . Example 8.

Dye off. the diazo compound of, Aminooxyleukotriphenylmethans.ulfosäure, according to Example 3 and P-naphtol.

The diazo compound, prepared in a known manner from 44 parts of the condensation product of tetramethyldiaminobenzhydrol and 2-Aüiino-i-oxybenzene-4-sulfoic acid, is allowed to run into a concentrated alkaline solution of 14.3 parts of 14.3 parts of Ci-naphthol and 13 parts of 30% sodium hydroxide solution with stirring. When the coupling is complete, the dye is deposited by adding sodium chloride. It is in the dry state one, brown powder is, 'which is sparingly soluble in water and dilute sodium carbonate solution in red blue with a violet color, in concentrated sulfuric acid dissolves color. Wool is dyed from an acid bath in brown tones, which change to black-blue when chromium-plating and bordeaux when re-coppering. The aftertreated dyeings are very washable and lightfast.

Example g.

Dye # from the diazo compound of aminooxyleukotriphenylmethanesulfonic acid according to Example 3 and i-amino-8-oxynaphthalene-3,6-disulfonic acid.

The diazo compound from 44 parts of the condensation product of tetramethyldiaininobenzhydrol and 2-amino-i-oxybenz01-4-sulf0-acid is introduced into a concentrated soda-alkaline solution of 32 parts of i-amino-8-oxynaphthalene-3,6-disulfonic acid with stirring. The dye formation is possible only after prolonged stirring or standing ended. The dye is deposited in a known manner from the reaction mass by adding sodium chloride. It is in the dry state is a black powder, which dissolves in water with blue violet, in concentrated sulfuric acid with a red color and stains from wool acid bath in violet shades. After treatment with bichromate, green-blue dyeings of good wash and lightfastness are obtained when after-treatment with copper salts or when dyeing with the addition of copper salts to the bath. Example: io.

Dye from the diazo compound of the aminooxyleukotriphenylmethane derivative according to example i and i- (4'-oxy-3'-carboxyphenyl) -3-methY1-5epyrazolone. 57 parts DES according to Example i representable Aminokörpers be in i "twa 2oo parts of water vo n 70 0: dissolved z5 parts of sodium hydroxide solution of 30 percent, the solution after completion cooling on o 'with 7 parts Natriuninitrit added and Init # 45 parts acidified concentrated hydrochloric acid all at once The diazo solution obtained is allowed to run in with stirring "in a solution of 2,3,4 parts. l- (4'-oxy-3 '-' carboxYPbe-ny1) -3-methY1-5-pyrazolo -Ion in 200 parts of water, 40 g of calcined Socla and: 25 parts of 30 percent sodium hydroxide solution. After the coupling has ended, the mixture is neutralized in the warm with hydrochloric acid and the dye is > deposited with common salt, filtered, pressed and dried. It gives green dyeings on wool.

1- (4'-OxY-3'-caibäxyphenyl) -3-methyl-5-pyrazolone is obtained by the fact that mani-Ox #, -2-carboxY-4-hydrazinobenzene (Bei 1 st a, 11th, Supplement, p. goo) condensed in the usual way with acetoacetic ester. The almost colorless pyrazolone is insoluble in water and easily soluble in alkalis with a brownish color. It is easily soluble in alcohol and very sparingly soluble in benzoil. It dissolves brownish in concentrated sulfuric acid and precipitates from the solution on the addition of ice in brown flakes.

Claims (1)

PATENT CLAIM 'Process for the production of stain-coloring leukotriarylmethanazo dyes, characterized in that o-, Aminooxyleukotriarvlmethaiid' derivatives are diazotized and with azo dye components. clutch,