Патент USA US2405816код для вставки
Patented Aug. 13, 1946 2,405,816 UNITEDTSTATES PATENT OFFICE 2,405,816 O:O’-DIHYDROXY AZO DYE'STUFFS AND A PROCESS FOR THEIR MANUFACTURE Achille Conzetti, Basel, Switzerland, assignor to . J. R. Geigy A. G., Basel, Switzerland, a Swiss company . No Drawing. Application September 21, 1942, I Serial No. 459,172. In Switzerland November 4, 1941 4 Claims. (01. 260-163) 1 It has been found that dyestu?s of very good dyeing properties are obtained by coupling diazo tised 6-nitro-2-amino-4-alkylpheno1s, the alkyl group of which contains at least 3 C-atoms, with azo components containing'at least one water solubilizing group and having an OH-group in the 2-position to the coupling place. With regard to known dyestu?s possessing, instead of the above mentioned alkyl groups, alkyl groups with less than 3 C-atoms the new dyestuffs are im proved with respect to the fastness properties. They are distinguished in the most cases espe 2 shows a better drawing power according to the one-bath chroming process. If, instead of the above. azo component, there are used 1,-(3’-sulfo)- or 1-(2'-sulfo)-phenyl-3 methyl-5-pyrazolone and their methyl or halogen substitution products, dy'estu?s of similar prop erties are obtained. Example 2 22.4 parts of 6-nitro-2-amino-4-amylphenol are diazotised as indicated in Example 1. The diazo suspension is caused to flow into a solution of 22.5 parts of Z-hydroxy-naphthalene-4-sul they possess improved wetting properties and are ionic, acid, made weakly alkaline to litmus, to by far more suitable for the one-bath chroming 15 which solution there has still been added 15 parts process. According to the azo component used of calcinated sodium carbonate and 20 parts of they dye wool, when after-chromed, with purer technical pyridine. On the following day, the shades than the known comparable products. mixture is salted out by means of 60 parts of The production of the claimed alkyl phenols sodium chloride, ?ltered and dried. is carried out vaccording to known methods by 20 The new dyestu? dyes, when after-chromed, nuclear alkylation of a phenol with the corre with reddish blue shades. Also in this case some sponding alcohol or by conversion of an acylated properties are improved when compared with the phenol into a C-acyl phenol and reduction of the dyestu? from the 4-methyl derivative, but espe latter. cially to a great extent the drawing power ac While the diazotisation takes place in the nor 25 cording to the one-bath chroming process is mal manner it is advantageous, but not absolutely highly improved. ' cially by an improved light-fastness. Moreover, necessary, to add an auxiliary agent, such as for example pyridine, during the coupling. The present invention is illustrated, but not limited by the following examples, the parts being by weight, unless otherwise stated. Example 1 22.4 parts of 6-nitro-2-amino-4-amylphenol of . 100% strength are introduced in form of the 1‘ chlorhydrate into 160 parts of water and, after addition of 14 parts by volume of concentrated hydrochloric acid, diazotised at 0°-5° C. by means of 6.9 parts of nitrite. The yellow diazo suspension is allowed to run at 0° C. into a solution of 29.06 parts of 1-(4' sulfo) -pheny1 - 3 - methyl - 5 — pyrazolone in 150 Example 3 22,4 parts of 6enitro=2~amino-4-amy1phenol are diazotised as stated in Example 1. The diazo suspension is caused to ?ow into an ice-cold solu tion of 31.2 parts of 2-carbomethoxy-amino-6 hydroxy-naphthalene-8-sulfonic acid which has been dissolved in 200 parts'of water, made alka line to litmus by means of sodium carbonate and then treated with 20 parts of calcinated sodium carbonate. On the next morning, the dyestu?‘ is ?ltered. It dyes, when after-chromed on wool, with grey shades of a high light-fastness. According to the one-bath chroming process the new dyestuff draws much better than the dyestuff from parts of water and 20 parts of calcinated sodium 6-nitro-2-amino-4-methyl phenol; the dyeings carbonate. On the next morning, the Whole mixture is ?ltered. The after-chromed wool dye 45 thus obtained are faster to potting. ing, a clear yellowish red, shows better fastness Example 4 properties to light and potting and purer shades than the dyeings obtained with the dyestu? from 21 parts of 6-nitro-4-butyl-2-aminophenol are 6-nitro-2-amino-4-methylphenol and the same dissolved in 200 parts of alcohol, then 30 parts azo component. Moreover, the new dyestu? 50 of concentrated hydrochloric acid are added 1 7 2,405,816 3 4 thereto and the whole is diazotised at 0° C. with azotised 6-nitro-2-amino-4-amplypheno1 with a pyrazolone sulfonic acid. 2. Process for the manufacture of o:0'-dihy droxy azo dyestuffs which comprises coupling di azotised 6-nitro-2-amin0-4-amy1phen0l with l (4’-sulfo) -phenyl-3-methyl-5-pyrazolone, 3. Dyestuffs of the formula a solution of 6.9 parts of sodium nitrite in 10 ‘parts of water. The diazo solution is then caused to flow into a solution of 25.4 parts of p-sulfo phenyl methyl pyrazolone in 300 parts of water and 22 parts of sodium carbonate as acid binding agent. The dyestu? precipitates out in a crys talline form. After completion of the coupling it is ?ltered off and dried. 1O Example 5 NO: ‘26.6 parts of 6-nitro-4-diisobutyl-2-aminophe_ nol are dissolved in 400 parts of alcohol, then treated with 30 parts of concentrated hydro chloric acid and diazotised at 0f’ C. with asolution of 6.9 parts of sodium nitrite in 10 parts of water. The diazo solution is caused to ?ow into an am moniacal solution of 22.4 parts of 2-.naphthol-4 sulfonic acid in 200 parts of water, to which solu SQaH tion 10 parts of pyridine has been added. When the coupling is completed, the alcohol is evapo» possessing valuable properties, being very suit rated, the dyestu? salted out with sodium chlo- ' ride, ?ltered o? and dried. . .7 Example 6 r r . a ,_ able for the one-bath chroming process and show ing; when after chromed, excellent fastness prop - erties to light. V 19.6 parts of 6-nitro-4.-isopropyl-2-aminophe " 4. The dyestu? of the formula 25 no-l are dissolved in 200 parts of alcohol; then 30 parts of concentrated hydrochloric acid are’ added thereto and the solution ‘is diazotised with a solu tion of 6.9 parts of sodium nitrite in 10 parts of water; A neutral solution of 32parts of chromo 30 tropic acid in 1000 parts of waterv is‘then caused N0: HnCt —OH to ?ow into this solution. As acid binding agent lime milk is added.‘ After completion of the cou-. pling the whole is heated up ‘to 80f’ C, and the excess slaked lime is ?ltered oil. The d'yestu? is as now salted out by‘ means of sodium chloride, ?lt ered o? and dried ’ 1 _ v In the following table still some further dye 803E stu?s are enumerated which are obtainedwith 40 a diazotised 6-nitro-2-amino-alkylphenol.1 dyeing wool according to the one-bath chroming , Color of the Diazo component Azo component " 6-nitro-2-amino-4‘amylphenol ____ ._ _Do .... ___ _____________________ __ ->6-n1tro-2-am1no-4-amylphenoL. Do __________ _; ............. _;-. _Do.____; ___________________ ._ ?-nrtro-Z-amrnM-hutylphenol ____ __ ' - 5 . ' After-chromed dyeing lz8idihydroxynaphthalene3z?-disulfonic acid __________ __ Violet-blu Blue. l-(3'-carboxyphenyl)-5-pyrazolone-3-carboxylic acid l-hydroxynaphthalene-‘l-sulfonic acid ____________ __ Brown__ Dull viol Clear yellowish red. Pure reddish violet. l-phenylamino-8-hydroxynaphthalene-ll-sulionic acid____ 1-benzoylamHi08-hydrqxynaphthalene-4sr?fonic acid- _. Dull violet-grey. ._ Red-violet ........ __ Pure bluish green. Bluish-grey. z-naphthol-‘i-suliomc acid___ Violet Grey‘blue. Orange __ Red, process with very pure red shadesof very good f, 1_. Process for the manufacture of o:o’-dihy.. _ __ 6~mtro-2~ammo-4-rsooctylphenol-___ p-suliophenylmetliylpyramlons WhatIclaimis: Acid dyeing [fastness to light and potting. droxy azo dyestuffs which comprises coupling di- 55 > ACHILLE CONZETTI.