DE1922901C3 - Azo dyes containing a sulfolanylpyrazole radical - Google Patents

Description

wherein R is hydrogen, phenyl, methoxy, ethoxy or methyl, Rj is hydrogen, methyl, hydroxy, methoxy, ethoxy, butoxy, acetoxy, propionyloxy, butyryloxy, ethoxycarbonyloxy, oj-melhoxycarbonyl-propionyloxy, benzoyloxy, m-methylbenzoyioxy, p-methoxybenzoyloxy , Nicotinoyioxy, thiophenecarbonyloxy, butylcarbamoyloxy. Phenylcarbamoyloxy, R _{2 is} hydrogen or methyl and D is optionally represented by halogen, methyl, methoxy, nitro, cyano. C ₁ -C ₂ -AIkOXycarbonyl, methylsulfonyl, trifluoromethyl, acetyl, Trimeinylammoniomethylcarbonyl, Triäthylammoniomelhylcarbonyl, Pyridiniomethylcarbonyl, Methyldiäthylammonioäthylaminocarbonyl, Dimethylhydraziniomethylcarbonyl, Trimethylammoniopropylaminosulfonyl, Butyldiäthylammonioäthylaminosulfonyl, Pyridinioäthoxy, amino to sulfonyl, Mcthylaminosulfonyl, N, N-dimethylaminosulphonyl, N, N-Diäthylaminosulfonyl, mono- or Di (bromine or chlorine) -s-triazinyl, mono- or dichloropyrimidyl, Mcno- or di (phcnylsulfonyl or alkanesulfonyl-pyrimidyl, y-halo-fi-hyüroxypropylamino, /; - haloethylsulfamoyl, / ι - haloethoxy. /; - haloethyl mercapto. 2-chlorobenzothiazolyl-6-azo.2-chlorobenzothiazolyl-6-amino, / -halogen-zf-hydroxypropylsulfamoyl, chloracelylamino, Λ, / ί-dibromopropionyl, 4 <> vinylsulfonyl or 2,3-epoxypropyl, chloracelyl, substituted phenyl Phenylazophenyl, optionally substituted by methyl, methoxy, chlorine, nitro or aminosulfonyl, a phenylazophenyl optionally substituted by cyano, Methyl, phenyl, chlorophenyl, nitrophenyl, ethyl, melhoxy, p-methoxyphenyl, ethoxycarbonyl or methylsulfonyl-substituted thiazole, pyridine, quinoline, pyrazole, indazole, benzthiazole, phthalimide, thiophene or isothiazole radical. where the nitrogen-containing heterocycles can also be quaternary.

2. Dyestuffs according to Claim I, characterized in that D is a radical of the general formula

where a is hydrogen. Halogen, methyl, methoxy. Nitro, cyano, carbo-C | -C ₂ -alkoxy or methylsulfonyl, b hydrogen, halogen, methyl, cyano or trifluoromethyl and c 'nitro. Are cyano, carbo-C, -C ₂ -alkoxy or methylsulfonyl. is.

wherein R is hydrogen, phenyl, methoxy, ethoxy or methyl, R, hydrogen, methyl, hydroxy, methoxy, ethoxy, butoxy, acetoxy, propionyloxy, butyryloxy, ethoxycarbonyloxy, o-melhoxycarbonyl-propionyI-oxy, benzoyloxy, m-methylbenzoyloxy, p -Methoxybenzoyloxy, phenacetyloxy, nicotinoyioxy, thiophencarbonyloxy, butylcarbamoyloxy, phenylcarbamoyloxy, R _{2 is} hydrogen or methyl and D is optionally substituted by halogen, methyl, methoxy, nitro, cyano, dC ₂ -alkoxycarbonyl, methylsulfonyl carbonyl, trimoonymethylaminoethyl carbonyl, trifluoromylammethyl, pyroonomylammonietyl, trifluoromylammylamethyl, methylsulfomethyl, carbonyl, trifluoromylammethyl, pyromethylammonethyl, trifluoromethyl, trimoonomylammonietyl, trifluoromylammethyl, methylsulfomethyl , Dimethylhydraziniomethylcarbonyl, Trimethylammoniopropylaminosulfonyl, Butyldiäthylammonioäthylaminosulfonyl, Pyridinioäthoxy,

Aminosulfonyl, methylaminosulfonyl, N, N-dimethylaminosulfonyl, N, N-diethylaminosulfonyl, mono- or di (bromo or chloro) -s-iriazinyl. Mono or Dichloropyrimidyl, mono- or di (phenylsulfonyl or alkanesulfonyO-pyrimidyl, y-halogen-ZZ-hydroxypropylamino, / i-Halogenalhyisuifamoyl, / i-Haiugenethoxy. / y-Halogenäthylmercaplo, 2-chlorobenzothiazolyl-6-azo, 2-chlorobenzothiazolyl-6-amino. ;-Halogen-// - hydroxy - propylsulfamoyl, chloracctylamino, rt./i-dibromopropionyl, vinylsulfonyl or 2,3-epoxypropyl, Chloroacetyl, / i-chloroethylaminosulfonyl substituted phenyl, optionally by methyl, methoxy. Chlorine, nitro or aminosulfonyl substituted Phenylazophenyl, an optionally substituted by cyano, methyl, phenyl, chlorophenyl, nitrophenyl, Ethyl, methoxy, p-methoxyphenyl, ethoxycarbonyl or methylsulfonyl substituted thiazole, pyridine, Quinoline, pyrazole, indazole, benzthiazole, phthalimide, thiophene or isothiazole radicals, the nitrogen-containing Heterocycles can also be quaternized.

Preferred diazo components D - NH ₂ are those of the general formula

NH ₂

wherein a is hydrogen, halogen, methyl, methoxy, nitro, cyano, carbo-C, -C ₂ -alkoxy or methylsulfonyl, b is hydrogen, halogen, methyl, cyano or trifluoromethyl and c 'is nitro, cyano, carbo-C | -C ₂ -alkoxy or methylsulfonyl is.
Examples are:

2-aminothiazole,
2-amino-5-methylsulfonyl-thiazole,

19th
3 is -Amino-4-chlorobenzene, 22nd 901
4th N ^ -chloroethyl-S-chloro-amino-benzenesulfamide —Ι I-amino-S-cyanthiazole, ί -Amino-4-bromobenzene, 4'-chloro-4-aminoazo benzene, (Hydrochloric!), - H -R ₁ 2-amino-4-methylthiazole, ! I-amino-4-methylbenzene, 2'- or 3'-chloro-4-aminoazobenzene, N./f-Chloräthyl^-aminobenzol-sulfamid UP / 2-amino-4-phenylthiazole, ϊ I-amino-4-nitrobenzene, 3-Mitro-4-amino-2 ', 4'-dichlorazobenzene and (Hydrochloric!), ■ • 2 ¹ - \ / 2-Amino-4- (4'-chloro) -pheny] lhiazole, j -Amino-4-cyanobenzoI, 4-Am; noazobenzene-4'-sulfonic acid amide. S-bromine ^ -amino-fij-chloracetophenon, 2-Amino-4- (4'-nitro) -phenylthiazoI, -Amino-2,5-dicyanobenzene, 5 N ^ -Chlor-Zi-hydroxypropyl ^ -aminobenzene- 3-aminopyridine, j -Amino-4-methylsulfonylbenzene, Instead of the above, from ionogenic, water sulfamid and wherein R, Rj and R _{2 are} the same as above. 3-aminoquinoline, I. -Amino-2,4-dichlorobenzene, solubilizing groups free diazo components N, / i-chloroethyl-1-amino-3,5-dichloro-benzene- couples and, if necessary, if the remainder D quater- 3-aminopyrazole, I. -Amino-2,4-dibromobenzene, can also be used, which the sulfamide. Has nizable nitrogen atoms, quaternized. 3-amino-1-phenylpyrazole, -Amino-2-methyl-4-chloi benzene, fiber-reactive groups mentioned in claim I. These clutch components are new, and man 3-aminoindazole, -Amino-2-trinuomethyl-4-chlorobenzene. 10 contain: You can get to the new dyes if you it is advantageously obtained by condensation of a 3-hy- 3-amino-1- (4'-methoxyphenyl) -pyrazole, -Amino-2-cyano-4-chlorobenzene, I mole of a diazonium compound of an amine drazino-sulfolans with a compound of the formula 2-aminobenzothiazole, -Amino ^ -carbomethoxy ^ -chlorobenzene, 5 »-halogen- / i-hydroxy-propyIsulfamoylreste, general formula D — NH ₂ , where D is the above N = C-CH ₂ -COR, where R is a hydrogen atom, 2-amino-6-methylbenzothiazole, -Amino ^ -carbomelhoxy ^ -nitrobenzene, Chloroacetylamino groups, has mentioned meaning with a clutch com Is methyl, phenyl, methoxy or ethoxy and 2-amino-6-methoxybenzthiazole, -Amino ^ -chloM-eyanbenzol, «, // - dibromopropionyl groups, component of the general formula Ring closure and cyclization in the presence of a 2-amino-6-cyanobenzothiazole, -Amino-2-chloro-4-nitrobenzene, ! 5 Vinylsulfonyl groups or Mineral acid. 2-amino-6-carhnäίhoxybenzthiazol, -Amino-2-bromo-4-nitrobenzene, 2,3-epoxypropyl groups. HC C-R The diazotization is carried out in a manner known per se 2-amine- (4- or 6 -) - methyIsulfonylbenzthiazol, -Amino ^ -ehloM-carbethoxybenzene, Il Il made, for example in niineralsaurer. water 2-amino-3,5-bis (methylsulfonyI) -thiophene, -Amino-2-chloro-4-methylsulfonylbenzo]. Suitable fiber-reactive diazo components are Η, Ν — C N riger solution with alkali salts of nitrous acid S-amino ^ -methyl-isothiazole, -Amino-2-methylsιιlfonyl-4-chlorobenzene, e.g. \ / or in conc. Sulfuric acid with nitrosylsulfuric acid. 2-amino ~ 4-cyano-pyrazol, -Amino ^ -methylsulfonyM-nitrobenzene, 20th \ /
N The coupling can also be known per se 2- (4'-nitrophenyI) -3-amino-4-cyanopyrazoI, -Amino-2,4-dinitrobenzene, Way, e.g. B. in neutral to acidic means given 3- or 4-aminophthalimide, -Amino-Z ^ -dicyanbenzene, if in the presence of sodium acetate or the like. Aminobenzene, -Amino-2-cyano-4-methylsulfonylbenzene. R ₂ - the coupling speed influencing buffer -Amino-2,6-dichloro-4-cyanobenzene, substances or catalysts, such as. B. pyridine. -Amino ^ ö-dichloM-nilrobenzol, 25th resp. its salts, are made. I l-Amino-2,4-dicyano-6-chlorobenzene I I -amino-2,4-dinitro-6-chlorobenzene \ and in particular fs l-Amino ^ -cyan ^ -nilrobenzoI, also I 2-nitro-4-amino-l, l'-azobenzene, JO III-aminobenzene-2-, -3- or -4-sulfonic acid amide % and l-amino-4-chlorobenzene-2-sulfonic acid amide <i and their N-methyl or Ν, Ν-dimethyl or I -diethylamide, I <u-Trimethylainmonium-p-amino-acetophenon- Ji I salt. ■ - 4-aminoazobenzene, ¹ 3,2'-dimethyl-4-aminoazobenzene, ■}, 2-! VIethyl-5-methoxy-4-aminoazobenzene. § 4-Amino-2-nitroazobenzene, 40 ξ 2,5-dimethoxy-4-aminoazobenzene, . ^ 4'-Melhoxy-4-aminoazobenzene, V ₁ 2-methyl-4'-niethoxy-4-aminoazobenzene, ] 1 3,6,4'-trimeihoxy-4-aminoazobenzene, 4) > 0 55 W) h5

After the coupling reaction has taken place, the non-quaternized dyes formed from the coupling mixture, e.g. B. separated by filtration as they are practically insoluble in water.

Instead of a single diazo component, a mixture of two or more of the Diazo components according to the invention and instead of a single coupling component a mixture use two or more of the coupling components according to the invention.

The new dyes can also be used, for example, by coupling with a reactive coupling component, such as l, N- (4'-Hydroxy-sulfolan-3'-yI) -3-methyl-5-aminopyrazole and subsequent acylation with carboxylic acid halides, chloroformic acid derivatives or isocyanates.

Compared to the known from US-PS 29 57 8f 3 analogous dyes of the pyrazo ion series, the dyes according to the invention have significantly better sublimation fastness, better resistance to over-dyeing compared to polyamide and significantly better resistance to alkali.

Even if the radical D of the diazo component contains a quaternizable nitrogen atom, such as. B. the abovementioned heterocyclic amines of the formula D - NH2, the dyes can be quaternized which is preferably done as the last stage.

Qualernization takes place through treatment with esters of strong mineral acids or organic ones Sulfonic acids, such as. B. dimethyl sulfate, diethyl sulfate. Alkyl halides, such as methyl chloride, bromide or iodide, aralkyl halides such as benzyl chloride. Esters of low molecular weight alkanesulfonic acids. such as B. the methyl ester of methane, ethane or butanesulfonic acid and the alkyl esters of (4-methyl-, 4-chloro- or 3- or 4-nitro) -benzenesulfonic acid. those as anions halogen, sulfuric acid half ester. Alkane or form benzenesulfonic acid anions, preferably with heating in inert organic solvents, for example xylene. Carbon tetrachloride. o-dichlorobenzene and nitrobeiizole. It can, however also solvents such as acetic anhydride. Dimethylformamide, acetonitrile or dimethyl sulfoxide are used will. The quaternized dyes preferably contain the remainder of one as anion Y ″ strong acid, such as sulfuric acid or its half-ester, or a halide ion. but they can also as double salts, e.g. B. with zinc chloride, or as free bases can be used.

The dyes described above do not contain any acidic water-solubilizing groups, in particular no sulfonic acid groups and are therefore sparingly or insoluble in water. Contain them quaternized nitrogen atoms, on the other hand, they are soluble in water.

The new dyes, their mixtures with one another and their mixtures with other Azofarbs'offen are suitable excellent for dyeing and printing synthetic fibers such as acrylic or Acrylonitrile fibers, polyacrylonitrile fibers and copolymers made from acrylonitrile and other vinyl compounds, like acrylics, acrylamides. Vinyl pyridine. Vinyl chloride or vinylidene chloride. Mixed polymers Dicyanäthylcn and vinyl acetate, as well as from acrylonitrile block copolymers, Polyurethane fibers. Polyolefins. Cellulose tri- and 2 '/ 2-acetate, polyamides, like nylon-6. Nylon-6,6 or nylon-12, and in particular Fibers from aromatic polyesters. such as those made from terephthalic acid and ethylene glycol or 1,4-dimethylolcyclohexane, and copolymers from

Terephthalic and isophthalic acid and ethylene glycol.

Deep dyeings of good lightfastness are obtained

and excellent fastness to sublimation.

For dyeing fibers containing ester groups, in particular polyester fibers, the

non-quaternized new dyes, expediently in finely divided form and dyes with the addition of Dispersants such as soap, sulfite cellulose liquor or synthetic detergents, or a combination various wetting and dispersing agents. As a rule, it is useful to add the dyes before Dyeing in a dye preparation that has a dispersant and finely divided dye in such Form contains that when the dye preparations are diluted with water, a fine dispersion is formed. Such dye preparations can be used in a known manner, for. B. by reprecipitation of the dye from sulfuric acid and grinding the slurry thus obtained with sulphite waste liquor, optionally also by grinding of the dye in highly effective grinding devices in dry or wet form with or without The addition of dispersants during the grinding process will be required.

The new water-insoluble dyes are particularly suitable for dyeing thanks to their alkali fastness after the so-called thermosetting process, after which the fabric to be dyed with an aqueous Dispersion of the dye, which is advantageously 1 to 50% urea and a thickener, in particular Sodium alginate, preferably impregnated at temperatures of at most 60 C and is squeezed as usual. It is advisable to squeeze in such a way that the impregnated goods are 50 to 100% retains its initial weight of dye liquid.

To fix the dye, the fabric impregnated in this way is expediently dried after prior drying, z. B. in a warm air stream, at temperatures of over 100 C. for example between 180 heated to 220 C.

Due to the high fastness to sublimation of the new water-insoluble dyes are suitable with them Dyed textile articles also for subsequent "permanent press" finishing using heat-curing Resins, which after dyeing are applied to the articles together with latent hardeners and in corresponding molds are cured hot.

The heat setting process just mentioned is of particular interest for dyeing blended fabrics made of polyester fibers and cellulose fibers, especially cotton. In this case, the padding liquid contains in addition to the dispersed dyes according to the invention, they are also suitable for dyeing cotton Dyes, especially vat dyes, or reactive dyes, d. H. Dyes on the cellulose fiber can be fixed with the formation of a chemical bond, for example containing dyes a chlorotriazine or chlordiazine residue. in the

In the last case, it proves to be useful to use the padding solution an acid binding agent, for example an alkali carbonate, or alkali phosphal, alkali borate or perborate or mixtures thereof. When using vat dyes, there is a treatment of the padded fabric after heat treatment with an aqueous alkaline solution of a in the Küpeüfäi'befci usual reducing agent necessary. The colorations obtained are expedient

subjected to an aftertreatment, for example by heating with an aqueous solution of a ion-free detergent.

Thanks to their good wool reserve the rfindungsgcuiiißen water-insoluble dyes are also> excellent for dyeing blended fabrics made of polyester fibers and wool.

The water-insoluble dyes can also be applied by printing. To this Purpose one uses z. B. a printing ink, which in addition to the usual aids in printing, such as NUz- and thickeners, the finely dispersed dye, optionally in a mixture with one of the above cotton dyes mentioned, optionally in the presence of urea and / or an acid-binding agent. You can also use the dyes also use in the form of solutions in organic media for dyeing and printing.

The new water-soluble quaternized dyes or dye salts are suitable for dyeing and printing a wide variety of fully synthetic fibers, such as. B. of polyvinyl chloride, polyamide, polyurethane and especially polyacrylic fibers. Some of them are extremely soluble in water or polar solvents. The dyeing with the 2 ^r > quaternized water-soluble dyes is generally carried out in an aqueous, neutral or acidic medium, at boiling temperatures under atmospheric pressure or in a closed vessel at elevated temperature and pressure. The commercially available leveling agents can be added.

The new water-insoluble dyes are also suitable for the mass coloring of polymerization products of acrylonitrile, of polyolefins, as well as other plastic masses, furthermore for the Coloring of oil paints and varnishes. They can also be used in the form of solutions in organic Use media for coloring and printing, ζ. Β in a mixture of 90% perchlorethylene and 10% Dimethylacetamide for padding polyester or nylon fabric and then fixing it in place dry heat or steam.

The water-insoluble fiber-reactive dyes are mainly used for dyeing nylon or Basically modified polyester, acrylic or polypropylene fibers, with an acid-binding agent added before, during or after dyeing to chemically fix the dye on the fiber to reach.

Some of the new, water-insoluble, non-quaternized dyes are also valuable pigments which are suitable for a wide variety of pigment applications can be used e.g. B. in finely divided form for dyeing rayon and rayon or Cellulose ethers and esters, for the production of inks, in particular ballpoint pen inks, and for the production of colored lacquers or lacquer formers, solutions and products made from acetylcellulose, Nitrocellulose, natural resins or synthetic resins such as polymerization resins or condensation resins, z. B. aminoplasts, alkyd resins, phenoplasts, polyolefins, such as polystyrene, polyvinyl chloride, Polyethylene, polypropylene, polyacrylonitrile, rubber, casein, silicone and silicone resins.

In the following example, unless otherwise specified, the parts are parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

B e i s ρ i e I!

1.52 parts of sodium nitrite are dissolved in 28 parts of sulfuric acid monohydral. 3.26 parts of 2-amino-5-nitrobenzonitrile willow registered at about IO and the mixture stirred for two hours at 20 to 25 and held in 120 parts of F.iswassei. The thus obtained Diazo solution is added at 0 to 5 'to a solution of 4.3 parts of l [3'-sulfolane] 3-methyl-5-aminopyrazole in added to a mixture of 4 parts of hydrochloric acid and 50 parts of water. The mixture is during Stirred for 10 hours. The precipitated dye is filtered off and washed with water until the Wash water reacts neutrally. The obtained dye of the formula

CN

N = NC-
Il / Il
H, N-C
\ /
N
I. \ I.
CH
\ / \ /
CH,
I. O, S - -C-CH,
Μ Il
, ^N CH,
I. I.
CH,

dyes polyester fibers in orange shades with excellent fastness properties.

The coupling components are obtained as follows: 9 parts of diacetonitrile are used in 15 parts of hydrochloric acid and 75 parts of water dissolved. The solution becomes a solution of 18.65 parts of 3-hydrazinosulfolane hydrochloride added in 50 parts of water. The mixture is heated to 90 ° and for 3 hours stirred. After adding blood charcoal, the reaction mixture is clarified by filtration and treated with sodium hydroxide solution adjusted to pH 8. Stirring is continued for 1 hour at 90-95 ". After cooling the precipitated product is filtered off and washed with water. The l- (3'-sulfolanyl) -3-methyl-5-aminopyrazole thus obtained melts at 211 after recrystallization from methyl alcohol.

1- (3'-SulfoIanyl) -3-phenyI-5-aminopyrazole can be prepared in an analogous manner produce if, instead of diacetonitrile, an equimolar amount of benzoylacetonitrile used.

Manufacture of the
1- (3'-Sulfolanyl) -3-methoxy-5-aminopyrazole

21.7 parts of cyanoacetic acid (3-sulfolanyl) hydrazide are dissolved in 1500 parts of methyl alcohol and hydrochloric acid gas is passed in at 20-30 ° until saturated. That The reaction vessel is closed and left to stand for 4 days. Methanolic hydrochloric acid is in vacuo evaporated at a maximum of 30 °. The residue is suspended in water and washed with sodium hydroxide solution made alkaline. The alkaline solution is extracted with chloroform. The chloroform extracts are washed with a little water, dried and evaporated. The residue is H3'-sulfolanyl) -3-methoxy-5-aminopyrazole obtain.

Färv-j-s

1 part of the dye obtained above is mixed with 2 parts of a 50% strength aqueous solution of the sodium salt the dinaphthylmethanedisulphonic acid wet-ground and dried.

This dye preparation is with 40 parts of an IO% aqueous solution of the sodium salt of N - benzyl - »- heptadecyl - benzimidazole disulfonic acid and 4 parts of a 40% acetic acid solution admitted. A dye bath of 4000 parts is prepared from it by diluting it with water.

100 parts of a cleaned polyester fiber material are added to this bath at 50 and the temperature is increased within half an hour to 120 to 130 and stains an hour in a closed vessel this temperature. Then it is rinsed well.

Example 2

3.26 parts of 2-amino-5-nitrobenzonitrile are diazotized as indicated in Example 1. The thus obtained Diazo solution becomes a solution of 4.62 parts of 1- (4'-hydroxy-3'-sulfolanyl) -3-methyl-5-aminopyrazole at 0-5 added in a mixture of 4 parts of hydrochloric acid and 50 parts of water. The mixture is stirred for a further 10 hours. The precipitated dye is filtered off and washed with water until the wash water is neutral reacted. The obtained dye of the form!

CN

O, N

CH

CH ₂

O, S

CHOH

-CH ₁

dyes polyester fibers in orange shades with excellent fastness properties.

The aminosulfolane pyrazole compounds mentioned below are also prepared in an analogous manner.

If the diazo component indicated in column I is diazotized as above and with the in Coupling the coupling component indicated in column 11, dyes are obtained that contain polyester fibers color the shades given in column III.

Ill

1 2,4-dinitroaniline T 2-chloro-4-nilroaniline 3 2-nitroaniline 4th 4-cyananiline 5 2-chloro-4-methylsulfony! Aniline 6th 2,6-dichloro-4-nitroaniline 7th 2-carbomethoxy-4-nitroaniline 8th 2-trifluoromethyl-4-nitroaniline 9 2-cyano-4-nitroaniline 10 2,4-dinitroaniline 11th 2-Bromo-4-nitro-6-chloroaniline 12th 2-nitro-4-methylaniline 13th 2-amino-5-cyanthiazole 14th 2-amino-6-cyanobenzothiazole 15th 2-methoxy-4-nitroaniline 16 2-cyano-4-nitroaniline 17th 2,4-dinitroaniline 18th 4-dimethylaminosulfonylanilir 19th 2-bromo-4-nitroaniline 20th 4-carboethoxyaniline 21 2-trifluoromethyl-4-chloroaniline 22nd 2,4-dinitro-6-chloroaniline 23 2-cyano-4-chloroaniline 24 4-amine o-azobenzene 25th 2-cyano-4-nitroaniline 26th 4-acetyl aniline

1- [3'-sulfolanevl] -3-methyl-5-aminopyrazole red orange | orange the same golden yellow I the same yellow § Red orange the same yellow 'S yellow the same yellow I. golden yellow the same golden yellow I yellow the same golden yellow 1 yellow the same goldgeib | orange l- [3'-methyl-3'-sulfolanyl] -3-methyl- orange 1 5-aminopyrazole I. yellow the same red orange 1 the same golden yellow I golden yellow the same yellow I. orange the same Scarlet fever 1 yellow the same orange 1 l- [3 ', 5'-dimethyl-3'-sulfolanyl] -3-methyl- golden yellow I 5-aminopyrazole I. l- [4'-methoxy-3'-sulfolanyl] -3-methyl- 5-aminopyrazole the same the same the same l- [4'-ethoxy-3'-suIfolanyl] -3-methyl- the same l- [4'-n-Butoxy-3'-sulfoIanyl] -3-methyl- 5-aminopyrazoI 1 - [4'-Hydroxy-3 '-sulfolanyl] -3-methy 1- 5-aminopyrazole the same 1- [3'-Sulfolanyl] -3-methoxy-5-aminopyrazole the same

continuation

111

27 4-bromoaniline

28 2-cyano-4-nitroaniline

29 4-nitroaniline

- [? -Methyl-3'-sulfolanyl] -3-methoxy- yellow

5-aminopyrazole

! - ["! 'Sulfolanyl] -5-aminopyra7ol orange

1- [3'-Sulfolany!] - 3-phenyl-5-aminopyrazole yellow

Example 3

4.05 parts of the dye obtained in Example 2 are mixed and cooled to 500 parts of water are dissolved hot in 50 parts of glacial acetic acid. 15 parts i> carried out. The precipitated dye is filtered off,

Acetic anhydride are added and the mixture is ^{stirred at 100 J} until no starting product is visible in the thin-layer chromatogram. The GE-

washed with water and dried. The received Dye of the formula

CN

O ₂ N

= N-C

Il

H ₂ NC

C-CH,

N I CH

H ₂ C

I as

CHOCOCH ₃
-CH,

dyes polyester fibers in orange shades with very good fastness properties.

Example 4

4.05 parts of the dye obtained in Example 2 ίο stirred. The mixture is cooled and reduced to 200 parts are dissolved in 15 parts of pyridine. 2.8 parts of benzoyl water discharged. The precipitated dye will chloride are added dropwise at 0-5 °. The reaction mixture is heated to 80 ° and 3 hours after

filtered off, washed with water and dried. The obtained dye of the formula

CN

O ₂ N

N = N-C-

-C-CH ₃

H, N-C N

, CH

H ₂ C CHOC

Q ₂ S

-CH,

dyes polyester fibers in orange shades with very good fastness properties.

Example 5

4.05 parts of the dye 65 obtained in Example 4 were stirred until no in the thin layer chromatogram

are dissolved in 40 parts of dimethylformamide. 1 part of the starting product is visible. The mixture will

Pyridine and 2 parts of n-butyl isocyanate are cooled in a draw and poured onto 500 parts of water,

give. The mixture is heated to 120 ° and the precipitated dye is filtered off with water

washed and dried. The obtained dye of the formula

CN

N = N-C C-CH,

Il Il

H ₂ NC N

CH
H ₂ C CHOCONHC ₄ H ₉

O ₂ S CH;

dyes polyester fibers in orange tones of very created product with the in column I

good lights. given acylating agent aeylated, one obtains

If one uses the diazo dyes indicated in column I, the polyester fibers in column IV

koniponenten diazoticrt, color with the shades given in column II, given coupling components and that

I. II Example 6 111 IV I. 2,6-dichloro-4-nitroaniline l- [4'-hydroxy-3'-sulfo- Acetic anhydride golden yellow lanyl] -3-methyl-5-amino- pyrazole 2 4-methylsulfonyl aniline the same Propionic anhydride yellow 3 2,4-dinitroaniline the same Succinic acid methyl ester Red orange chloride 4th 2-methoxy-4-nitroaniline the same 3-methyl-benzoyl chloride golden yellow 5 2-trifluoromethyl-4-nitro-
aniline the same 4-methoxybenzoyl chloride golden yellow 6th 4-amino-azobenzene the same Nicotinic acid chloride golden yellow 7th Carbethoxyaniline the same Thiophene carboxylic acid yellow chloride 8th 2-carbomethoxy-4-nitro- the same Butyl isocyanate golden yellow aniline 9 4-acetylaniline the same Phenyl isocyanate yellow

5.38 parts of ^ -amino-S-chloro-benzenesulfo-ß-chlorithylamide are concentrated with 8 parts by volume. Triturated hydrochloric acid and diluted with 80 parts of water. the Solution is obtained at 0-5 ° by adding 5 parts by volume 4N sodium nitrite solution diazotized. The diazo solution becomes a solution of 4.3 parts at 0-5 ° l- [3'-Sulfolanyl] -3-methyl-5-aminopyrazole in a Mi-

Schung of 4 parts of hydrochloric acid and 50 parts of water were added. The coupling mixture is made by adding Congoneutral made by sodium acetate solution. After the coupling has ended, the dye is filtered off, washed with water and dried. The obtained dye of the formula

ClCH ₂ CH ₂ HNO ₂ S - \ ~~ \ - N = NC C- CH ₃

H ₂ NC N

CH

/ \
H ₂ C CH ₂

O ₂ S CH ₂

dyes polyamide fibers after alkaline or heat fixation in yellow shades with very good fastness properties.

If 4-aminomochloroacetophenone is used as the diazo component, this gives a dye with similar properties.

Example 7

4.57 parts of 4-aminophenacyltrimethylammonium chloride are dissolved in 20 parts of water and 8 parts by volume of Jconz. Hydrochloric acid added. The solution at 0-5 "by adding 5 parts by volume of 4N sodium nitrite solution diazotized. The diazo solution becomes a solution of 4.3 parts of 1- [3'-SuIfO-lanyl] -3-methyl-5-aminopyrazole at 0-5 ' added in a mixture of 4 parts of hydrochloric acid and 50 parts of water. The coupling mixture is made by adding Congoneutral made by sodium acetate solution. When the coupling is complete, the dye is added precipitated by salt. The dye is bottled off, redissolved in hot water and, after filtering the solution, salted out from the filtrate. Of the

unusual dye of the formula

(CH ₃ ) JNCH ₂ CO

10

N = N-C CCi

Il Il

Η, Ν-C N

CH

/ \ H, C CH ₂

-CH,

O ₂ S

is filtered off and dried. It dyes polyacrylonitrile fibers in yellow shades with excellent fastness properties.

If you diazotized the diazo components indicated in column I and with the in column II Coupling specified coupling components, one obtains dyes, the polyacrylonitrile fibers in the in Color column III indicated colors.

(CH ₃ ) ₃ NCH ₂ CO
Cl

(CHj) ₃ NCH ₂ CO
Cl

(C ₂ H ₅ ) JNCH ₂ CO-

Cl
the same

NC H ₂ CO
Cl

SO ₄ CH ₃

(C ₂ H ₅ ) ₂ N ⁺ (CH ₂ ) ₂ I INCO
CH ₃

P "

(CH ₃ ) ₂ N-C

NH ₂
the same

SO ₄ CH,

NH,

Br

NH,

NH ₂ 1- [3'-methyl-3'-sulfolanyl] -3-methyl-5-aminopyrazole

the same

the same

1 - [4'-Methoxy-3'-sulfolanyl] -3-methyl-5-aminopyrazole

1 - [3'-Sulfolanyl] -3-methoxy-5-aminopyrazole

NH ₂ 1- [3; 5'-dimethyl-3'-sulfolanyl] -3-methyl-5-aminopyrazole

1 - [3'-Sulfolanyl] -3-methyl-5-aminopyrazole

1 - [3'-methyl-3'-sulfolanyl] -3-methyl-5-aminopyrazole

V-NH- rlespj.

III

yellow

golden yellow

yellow

yellow yellow

yellow

yellow yellow

yellow

909 618/54

ϊ8

continuation

I. Br the same Example 8 > —NH ₂ II III 10 SO ₄ CH,
(CH,), N (CH,)., ENT, S - ' (C ₂ H ₅ ) ₂ N (CH ₂ ), HNO, S-
C ₄ H ₉ 1 - [3'-SulfoIany!] - 3-methyl-
5-aminopyrazole yellow π the same O ₂ N - (^) - NH ₂ Cl l- [4'-methoxy-3'-sulfolanyl] -
3-methyl-5-aminopyrazole yellow OC ₂ H ₄ N J> ^ V- NH ₂ 12th SO ₁ C ₇ H ₇ 1 - [3'-sulfolanyl] -3-methyl-
5-aminopyrazole yellow 13th the same orange 14th l-r3 ^f -methyl-3'-sulfolanyl] -
3-methyl-5-aminopyrazole orange dissolved in hot water and after Filtering the

1.88 parts of 3-aminopyridine are mixed with 8 parts by volume conc. Dissolved hydrochloric acid and 40 parts of water. the Solution is at 0-5 "by adding 5 parts by volume 4N sodium nitrite solution diazotized. The diazo solution becomes a solution of 4.3 parts at 0.5 " 1- [3'-Sulfolanyl] -3-methyl-5-aminopyrazole in a mixture of 4 parts of hydrochloric acid and 50 parts Water added. After the coupling has ended, the coupling mixture is made by adding sodium hydroxide solution adjusted to pH 7-8. The dye is filtered off, washed with water and dried.

3.2 parts of the dye obtained above are dissolved in 150 parts of hot chlorobenzene. 1.9 parts of dimethyl sulfate, dissolved in 10 parts of chlorobenzene, are added dropwise and the reaction mixture is stirred for a further 3 hours at 95-100 ". After cooling, the solution is nitrated. The filter residue becomes g
Dye of the formula

NI CH ₃

-N = N-C-

I!

Η, Ν - C

-C-CH,

Il

CHjSO ₄

CH

/ \ H ₂ C CH ₂

O, S CH,

is filtered off and dried. It dyes polyacrylonitrile fibers in yellow tones with very good fastness properties.

Claims (1)

Patent claims: 1. Azo dyes of the general formula
DN = NC CR The present invention relates to new valuable azo dyes of the general formula IO