DE2509560A1 - PROCESS FOR PRODUCING AZO COMPOUNDS - Google Patents

Description

CIBA-GLIÖYAG, CH-4C02 Basal ν E ύ // ^

Dr. F. ZumslM fr. - Location. £ -.- r; nri Dr.Ri: - ^. »-.-.-- e - .Til.-Fr. .. ·. ■■■■ ^; : Dipl.-Kg. f ^r . · - ν- ß · - ¹ '· ¹ · = - = - t: inj

H. ■ Ιϊ! Ϊ́ 'a π. · ■ -3 t ρ 8 Munich 2, B.aufen .-. I-straGa 4

Cas e 3-9315-17 / +
GERMANY

Process for the preparation of azo compounds

In the DT-OS 2.139.311 there is a one-step procedure for Production of azo dyes described, according to which a diazo component with a coupling component from the Series of dialkylanilines is treated in an acidic liquid medium with a diazotizing agent. With this one known method is per mole of diazotizable amine at least 1 mole of an acid, preferably hydrochloric acid or acetic acid, as a diazotizing agent, preferably sodium nitrate and preferably water is used as the diluent.

The present invention relates to a one-step process for the preparation of azo compounds such as dyes, intermediates or pigments, which consists in adding an essentially anhydrous molar mixture of an amine which is free of sulfonic acid groups and an amine in o- or p-position to the amino groups -coupling tertiary aromatic amine or a coupled, at the hetero ring heterocyclic coupling component or a free carboxylic acid or of aromatic hydroxy compound Carbonsäureaniidgruppen ,, wherein the coupling groups free of diazotizable Aminogrupvien 'and

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Sulphonic acid groups can be found in an organic Diluent in the presence of less than the molar amount of a salt of a tertiary amine or that used Diazo component adds an ester of nitrous acid.

Both carbocyclic and heterocyclic aromatic amines are suitable as diazotizable amines. Of special The aminobenzenes, especially those of the formula, are of interest

wherein X and Y are H or halogen atoms, alkyl or alkoxy groups, Alkylsulfonyl or alkylsulfamoyl groups containing 1-4 carbon atoms, nitro, cyano, carbamoyl or trifluoromethyl groups, Containing alkoxycarbonyl, alkanoyl or alkylcarbamoyl groups 2-6 carbon atoms or optionally by halogen atoms, alkyl or alkoxy groups containing 1-4 substituted carbon atoms Phenoxy, phenalkoxy, phenylcarbamoyl, phenylsulfonyl, phenylsulfamoyl, Benzoyl or phenylazo groups and Z is H or Mean halogen atom or a trifluoromethyl group.

From the series of the heterocyclic diazo components are in particular 5-membered heterocyclic amines with 1-3 heteroatoms and optionally fused-on benzene nucleus, preferably those of the formula

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wherein X, an O or S atom or an imino group, X2 and X ~ H or halogen atoms, alkyl or alkoxy groups containing 1 to 4 C atoms, nitro, cyano, thiocyan or carbamoyl groups, Alkoxycarbonyl or alkylcarbamoyl groups containing 2-6 carbon atoms or alkylsulfonyl groups containing 1-4 carbon atoms.

The following amines may be mentioned as examples:

aniline

2-, 3- or 4-chloroaniline 2,4- or 2,5-dichloroaniline 2,4,6-trichloroaniline 2,4,6-tribromaniline 2-, 3- or 4-methylaniline 4-butyl aniline

4-dodecylaniline

4-aminodiphenyl

2-methyl-3-, -4-, -5- or 6-chloroanaline 2-, 3- or 4-methoxyaniline 2- or 4-phenoxyaniline 2,5-dimethoxyaniline 2,5-diethoxyaniline 2,5-dimethoxy-4-chloroaniline 2-methoxy-5-chloroaniline 2-ethoxy-5-chloroaniline 2-phenoxy-5-chloroaniline 2-, 3- or 4-nitroaniline 2,4-dinitroaniline 2,4-dinitro-6-chloroaniline 2,4-dinitro-6-bromaniline 2,5-dichloro-4-nitroaniline 2,6-dichloro-4-nitroaniline 2,6-dibromo-4-nitroaniline

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2-methoxy-4-nitroaniline 4-methoxy-2-nitroaniline 2-ethoxy-4-nitroaniline

4-ethoxy-2-nitroaniline 2-, 3- or 4-cyananiline.

2,4-dicyananiline 2-methyl-3-cyanoaniline 2-cyano-4-nitroaniline 2,6-dichloro-4-cyanoaniline 5-chloro-4-cyano-2-nitro-aniline 2,4-dinitro-6-cyano -aniline 3-tri fluorine thy lan il in 3,5-bis- (tri fluorine thy 1) -aniline 2-trifluoromethyl-4-chloro-aniline 2-trifluoromethyl 1-5-chloro-aniline 2-, 3- or 4 Methyl aminobenzoate, 2-, 3- or 4-aminobenzoic acid ethyl ester 2-, 3- or 4-aminobenzoic acid butyl ester 2-, 3- or 4-aminobenzoic acid phenyl ester 2- ", 3- or 4-aminobenzoic acid benzyl ester 2-amino-3- or -4 -chlorobenzoic acid methyl ester 2-amino-3,5-dichlorobenzoic acid methyl ester

4 ~ Amino-3 ~ bromobenzoic acid methyl ester 3-Amino-4-chlorobenzoic acid methyl ester 3-Amino-4-chlorobenzoic acid phenyl ester 3-Amino-4,6-dichlorobenzoic acid phenyl ester 2-, 3- or 4-amino-benzoic acid ~ 2 ', 4', 6'-trimethylphenyl ester 2-, 3- or 4-aminobenzoic acid amide 2-, 3- or 4-aminobenzoic acid monomethylamide 2-, 3- or 4-amino-benzoic acid-dimethylamide 2-, 3- or 4-amino-benzoic acid ethylene imide

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2-, 3- or 4-amino-benzoic acid-iso-propylamide 2-, 3- or 4-amino-benzoic acid-diethylamide 2-, 3- or 4-amino-benzoic acid-di-n-butylamide 2-, 3- or 4-amino-benzoic acid-morpholide 2-, 3- or 4-amino-benzoic acid-anilide 2-, 3- or 4-amino-benzoic acid-N-methylanilide 2-j 3- or 4-amino-benzoic acid-N, N-dimethylhydrazide 2-, 3- or 4-amino-benzoic acid- (7-diinethylamino-propylarai.d) 2-, 3- or 4-amino-benzoic acid-4'-tert-butylphenyl ester 2-, 3- or 4 -Amino-benzene-sulfonic acid methyl ester 2-, 3- or 4-amino-benzene-sulfonic acid ethyl ester 2-, 3- or 4-amino-benzene-sulfonic acid-ß-chloroethyl ester 2-, 3- or 4-amino-benzene-sulfonic acid butyl ester 2 -, 3- or 4-Amino-benzenesulfonic acid-n-hexyl ester 2-, 3- or 4-Amino-benzenesulfonic acid-phenyl ester 2-, 3- or 4-Amino-benzenesulfonic acid- (4'-methyl-phenyl ) -ester 2-, 3- or 4-aminobenzene-sulfonic acid- (4'-n-butyl-phenyl) -ester 2-, 3- or 4-aminobenzene-sulfonic acid- (4'-methoxyphenyl ) -ester 2-, 3- or 4-amino-benzene-sulfonic acid- (4'-n-butyl-phenyl) -ester 2-, 3- or 4-aminobenzenesulphonic acid amide 2-, 3- or 4-aminobenzenesulphonic acid monomethylamide 2-, 3- or 4-aminobenzenesulphonic acid-dimethylamide 2-, 3- or 4-amino -benzenesulfonic acid-ethylenimide 2-, 3- or 4-aminobenzenesulfonic acid-diethylamide 2-, 3- or 4-aminobenzenesulfonic acid-di-n-butylamide 2-, 3- or 4-aminobenzenesulfonic acid-morpholide 2-, 3- or 4-aminobenzenesulfonic acid-cyclohexylamide 2-, 3- or 4-aminobenzenesulfonic acid-anilide 2-, 3- or 4-aminobenzenesulfonic acid-N-methyl-anilide l-methyl-2-aminobenzene- 4-sulfonic acid amide 1-Methy1-2-amino-benzo1-4-sulfonic acid-η-hexylamide 1-methoxy-2 -amino-benzo 1-4-sulfonic acid amide 1-methoxy-2-amino-benzo1-4-sulfonic acid -dimethylamide

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l-Methoxy ^ -amino-benzene ^ -sulfonic acid-di-n-butylamide 1-methoxy-2-aminobenzene-4-sulfonic acid-N-methylanilide l-chloro ^ -amino-benzene ^ -sulphonic acid dimethylamide l-chloro ^ -amino-benzene-S-sulfonic acid-ß-ethoxy-ethylamide l-chloro-3-amino-benzene-4-sulfonic acid amide l-chloro-4-amino-benzene-2-sulfonic acid-dimethylamide 1-Nitro ^ -amino-benzene-S-sulfonic acid-cyclohexylamide l-Nitro ^ -amino-benzene-S-sulfonic acid-di-n-butylamide 2-, 3- or 4-aminoacetophenone 2-, 3- or 4-aminobenzophenone 4'-amino-2-chlorobenzophenone 4-amino-2 ', 4'-dichlorobenzophenone 2-Amino-4'-bromobenzophenone 3-Amino-3'-bromo-4'-methylbenzophenone 2-amino-2 ', 5'-dimethylbenzophenone

4-Amino-4'-ethylbenzophenone 2-Amino-4'-methoxybenzophenone 2-Araino-4 ^! methoxy-2 ', 5'-dimethylbenzophenone 3-amino-3', 4'-dimethoxybenzophenone 4-amino-5'-chloro-2'-methoxybenzophenone 4-amino-4'-methoxybenzophenone 3-amino-4'-methoxybenzophenone 2-Amino-2'-nitrobenzophenone 2-Amino-3'-nitrobenzophenone 4-Amino-4 '-nitrobenzophenone 4-Amino-2', 4'-dinitrobenzophenone 4-Amino-4'-methy1-3'-nitrobenzophenone 4- Amino-4'-butylbenzophenone 4-amino-4'-propoxybenzophenone 2-amino-4'-fluorobenzophenone 4-amino-2-propylbenzophenone 2-amino-4,5-dipropoxybenzophenone 2-amino-5-bromobenzophenone

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4-amino-3-chlorobenzophenone 2-amino-4,5-dichlorobenzophenone 4-amino-3,5-dibromobenzophenone 4-amino-2-methylbenzophenone 2-amino-5-methylbenzophenone 2-amino-4,5-dimethylbenzophenone 3-amino-2,4-dimethylbenzophenone 2-amino-4,5-dimethoxybenzophenone 2-amino-4-methoxybenzophenone 3-Amino-5-nitrobenzophenone 3-Amino-4-methyl-5-nitrobenzophenone 2-amino-6-methyl-3-nitrobenzophenone 2-amino-3,5-dinitrobenzophenone 2-Amino-4-methyl-3,5-dinitrobenzophenone 2-Amino-5-fluoro-benzophenone 2-methylsulfonyl-aniiine 4-methylsulfonyl aniline ^ • ~ Chlor-2-methyl-thy! Sulfonyl-aniline

2-chloro-4-methylsulfonyl aniline 2-phenylsulfonyl aniline 4-phenylsulfonyl-aniline 2-chloro-4-phenylsulfonyl-aniline 4-nitro-2,6-di (methylsulfonyl) aniline 4-chloro-2- (p-chlorophenylsulfonyl) aniline p- (p-Bromophenylsulfonyl) aniline 2-chloro-4- (phenylsulfonyl) aniline 2-chloro-6- (phenylsulfonyl) aniline 3-chloro-2- (phenylsulfonyl) aniline 3-chloro-4- (phenylsulfonyl) aniline 5-chloro-2- (phenylsulfonyl) aniline 4-chloro-3- (phenylsulfonyl) aniline 4-chloro-2- (phenylsulfonyl) aniline

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2-Bromo-4- (phenylsulfonyl) aniline ρ- (2,4-dichlorophenylsulfonyl) aniline ρ- (2,5-dibromophenylsulfonyl) aniline ρ- (3,4-dichlorophenylsulfonyl) aniline 5-chloro-2- (p-tolylsulfonyl) aniline p- (p-tolylsulfonyl) aniline p- (p-Propylphenylsulfonyl) -aniline p- (p-Fluorophenylsulfonyl) -aniline p- (3-Chloro-4-methoxyphenylsulfonyl) -aniline p- (2,4-Dimethoxyphenylsulfonyl) -aniline p- (3,5-dimethoxyphenylsulfonyl) aniline p- (p-Methoxyphenylsulfonyl) aniline p- (p-Ethoxyphenylsulfonyl) -aniline p- (2-Methoxy-4-nitrophenylsulfonyl) -aniline o- (p-Methox3'pheny lsulfonyl) aniline p- (o-methoxyphenylsulfonyl) aniline p- (p-Nitrophenylsulfonyl) aniline 2-nitro-3- (phenylsulfonyl) -aniline 2-nitro-5- (phenylsulfonyl) -aniline 2,4-Dinitro-5- (phenylsulfonyl) -aniline 2-Nitro-4- (p-nitrophenylsulfonyl) -aniline 2-nitro-4- (ra-nitrophenylsulfonyl) aniline o- (o-Nitrophenylsulfonyl) aniline 2-nitro-4- (phenylsulfonyl) aniline

2-nitro-4- (p-tolylsulfonyl) aniline 2,6-Dinitro-4- (p-tolylsulfonyl) aniline 4- (p-Butoxyphenylsulfonyl) -3-ethylaniline p- (2,5-xylylsulfonyl) aniline p- (2,4-xylylsulfonyl) aniline p- (2,4-Dinitrophenylsulfonyl) aniline 2,4-dichloro-5-phenylsulfonyl-aniline 2,3-diethyl-4-phenylsulfonyl-aniline 2,5-dimethoxy-4-phenylsulfonyl aniline

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4-acetylamino-aniline 4-propionylamino-aniline 4-amino-azobenzene 4-amino-2 ', 3'-methyl-azobenzene 4-amino-2-methyl-5-methoxy-azobenzene 1-aminonaphtha1ine 1-Amino-8-chloro-naphthalene 2-Amino-naphthalene-6-sulfonic acid dimethylamide 1-aminoanthraquinone l-amino-S-chloroanthraquinone.

From the heterocyclic series are in particular those optionally in the benzene ring of the halogen atoms, alkyl and Alkoxy groups containing 1-4 carbon atoms called substituted benzothiazoles and the aminopyridines. As examples are mentioned:

2-aminothiazole 2-Amino-5-nitrothiazole 2-amino-5-methylsulfonyl-thiazole 2-Amino-5-cyanthiazole 2-Amino-4-methyl-5-nitrothiazole 2-amino-4-iaethyl thiazo 2-amino-4-phenylthiazole 2-amino-4- (4'-chloro-phenyl) thiazole 2-Amino-4- (4'-nitro-phenyl) thiazole 2-aminopyridine 3-aminopyrid in 4-aminopyridine 3-aminoquinoline 3-aminopyrazole 3-amino-2-phenylpyrazole 3-aminoindazole 2-aminobenzothiazole

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2-Amino-4-chlorobenzothiazole 2-Amino-4-bromobenzothiazole 2-amino-4-nitrobenzothiazole · 2-amino-4-cyanobenzothiazole · 2-amino-6-bromobenzothiazole 2-amino-6-cyanobenzothiazole · 2-amino-6-nitrobenzothiazole 2-Amino-6-trifluoromethyl-benzothiazole 6-Acetyl-2-aminobenzothiazole 2-Araino-6-trifluoroacetyl-benzothiazole 2-Amino-6-valeroylbenzothiazole · 2-Amino-6- (ß-hydroxypropionyl ·) -benzothiazole 2-Amino-6-cyclohexylcarbonyl-benznthiazole 2 -Amino-6- (p-toluoyl) -benzothiazole 2-amino-6- (o-chlorobenzoyl) -benzothiazole 2-Amino-6- (p-bromobenzoyl) -benzothiazole 2-Amino-6- (m-nitrobenzoyl) -benzothiazole 2-Amino-6-methylsulfonyl-benzothiazole 2-Amino-6 - ^ '- hydroxyethylsulfonyl) benzothiazole 2-amino-6-propylsulfonyl-benzothiazole.

2-Amino-6-cyclohexylsulfonyl-benzothiazole 2-Amino-6-phenylsulfonyl-benzothiazole 2-amino-6- (o-tolylsulfonyl) benzothiazole 2-Amino-6- (m-chlorophenylsulfonyl) -benzothiazole 2-amino-6- (p-bromophenylsulfonyl) benzothiazole 2-Amino-6- (m-nitrophenylsulfonyl) -benzothiazole 2-Amino-6-ethoxycarbony1-benzothiazole 2-Amino ~ 6-butoxycarbonyl-benzothiazole 2-Amino-6-trifluoromethylsulfonylbenzothiazole 2-Amino-4-bromo-6-nitrobenzothiazole 2-Amino-4,6-dinitrobenzothiazole 2-Amino-4,6-dicyanobenzothiazole 2-Amino-6-bromo-4-methyibenzothiazole

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2-Amino-4-methoxy-6-nitrobenzot: hiazole 2-Amino-6-bromo-4-propoxybenzothiazole 2-Amino-4-cyano-6-nitrobenzothiazole 2-Amino-6-chloro-4-cyanobenzothiazole 2-Amino-6-chloro-4-nitrobenzothiazole 2-Amino-6-bromo-4-cyanobenzoi: h.iazol 2-Amino-6-cyano-4-methylbenzothiazole 2-Amino-6-meth.yl-4-nitrobenzothiazole 2-Amino-6-methoxy-4-nitrobenzothiazole 2-Amino-6-butoxy-4-chlorobenzothiazole 2-Amino-4-cb.lor-6-methoxybenzothiazole 2-Amino-4-bromo-6-methoxybenzothiazole 2-Amino-4,6-dichlorobenzothiazole 2-Amino-4,6-dibromobenzothiazole 2-Amino-4-methyl-6-trifluoromethylbenzothiazole 2-Amino-4-methyl-6-propionyrbenzothiazole 2-Amino-4-chloro-6-methylulionylben2othia2ol 2-Aiiiino-6_methylsulfamo3'-l-4-nitroben2rothia2ol 2 «Amino-4-chloro_cyclohexylsulfonyl» benzothiazole 2-Amino-4-bromine-6 ".ätl ^ .ylsulfonyl-bellzothiazole 2-Amino-N, N-dimethyl-4-nitro-6-benzothiazolesulfonamide 2-Amino -N-benzy 1-4-chloro -N- thy 1-6-berizothiazolesulfonamide 2-Amino-4-bromo- ■ N-ethyl-6-benzothiazolesulfonanilide 2-amino-N, N-dipropyl-4-methyl-6-benzothiazole sulfonamide 2-Amino-4-chloro-6-methoxycarbonyl ^ benzothiazate) l 2-Amino-4-bromo-6-butoxycarbonyl-benzothiazole 2-Amino-6-benzoylbenzothiazole 2-Amino-6-acetylbenzothiazole 2-Amino-N, N-dibutyl ~ 6-benzothiazolesulfonamide 2-Amino-N-ethyl-6-benzothiazolesulfonamide 2-Amino-N-butyl-N-methyl-6-benzothiazolesulfonamide 2-Amino-N-benzyl-N-ethyl-6-benzoth-lazolesulfonamLd

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2-Amino-N-benzy1-6-benzothiazole sulfonamide 2-amino-N-isopropyl-N-methyl 1-6-benzothiazolesulfonamide 2-amino-N-isobuty1-6-benzothiazole sulfonamide 2-amino-N, N-diethyl-6-benzothiazolesulfonamide 2-Amino-N-sec-butyl-6-benzothiazolesulfonamide 2-Amino-N, N-dimethyl-6-benzothiazolesulfonamide 2-amino-N, N-dipropy1-6-benzothiazole sulfonamide

5-methylsulfonyl-2-aminothiazole 5-benzoyl-2-aminothiazole 2-aminoimidazole 4,5-dicyano-2-aminoimidazole 4,5-diphen) '-1-2-aminothiazole 2-aminopyridine-N-oxide 2-aminothiophene 2-amino-3j4-thiadiazole 2-amino-3,5-thiadiazole 2-aminobenzimidazole 3-aminobenzisothiazole 3-amino-5-chlorobenzisothiazole 3-Amino-5-nitro-benzisothiazole 3-Amino-5-nitro-7-bromo-benzisothiazole

3-Amino-5,7-dichlorobenzisothiazole 3-Amino-5-chloro-7-bromo-benzisothiazole 3-Amino-5,7-dibromo-benzisothiazole 3-Amino-6-methyl-benzisothiazole 3-Amino-5-methyl-sulfonylbenzisothiazole 2-Amino-3,4-oxadiazole 2-Amino-3-cyano-tetrahydrobeiizthiophene 3-aminocarbazole and especially 3-amino-1,2,4-triazole.

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The coupling components are preferably those from the series the dialkylanilines and in particular those of the formula

^X l

into consideration, in which R and R 2 denote alkyl radicals, which may or may not be by halogen atoms, hydroxy, cyano or carbamoyl groups, alkoxy groups containing 1-4 C atoms, alkoxycarbonyl or Alkoxycarbonyloxy groups containing 2-6 C atoms, dialkylamino groups with 1-4 carbon atoms in the alkyl radicals or optionally with halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms substituted phenoxycarbonyl, phenoxycarbonyloxy, phenyl or phenoxy groups, can be substituted, X, an H atom, an alkyl or an alkoxy group containing 1 - 4 carbon atoms, Yi contains a Η atom, an alkyl or alkoxy group 1-4 carbon atoms, a phenoxy optionally substituted by halogen atoms, alkyl or alkoxy groups containing 1-4 carbon atoms or benzoylamino group, a formylamino group, an alkanoylamino group, containing 2-6 carbon atoms or an alkyl sulfonylamido group, containing 1-6 carbon atoms.

The following coupling components are listed as examples:

Dimethylani1ine

Dimethyl 1-m-toluidine

Diethyl-m-toluidine

Di- (n-propyl) -o-toluidine

N-methyl-N- (/ 3-cyanoethyl) aniline

N-Ethyl-N-cyanoethyl-aniline

N, N-bis (ß-cyanoethyl) aniline

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N-methyl-N- (7-cyanopropyl) -m-toluidine N-cyanoethy1-N- (ß-acetoxyethyl) -aniline Ν, Ν-bis- (ß-acetoxyethyl) -aniline Ν, Ν-bis- (7- butyryloxypropyl) -m-toluidine Ν, Ν-bis- (ß-benzoyloxyethyl) -m-toluidine Ν, Ν-bis- (ß-polyoxyethyl) rm-toluidine N- (ß-cyanoethyl) -N- (ß-benzoyloxyethyl) -aniline N-ethyl-N- (ß-cyanäthy1) -aniline N-ethyl-N- (/ 3-cyanoethyl) -m-toluidine N- (ß-cyanoethyl) -N- (ß-hydroxyethyl) -aniline Ν, Ν-bis- (2-hydroxyethyl) -aniline Ν, Ν-bis- (ß-hydroxyethyl) -m-toluidine, N- (ß-cyanoethyl) -N- (/ 3-mesitoy loxyäthyl) -aniline Ν, Ν- Bis- (/ 3-pivaloyloxyethyl) -aniline in-chlorine dime thy laniline Ν, Ν-bis- (/ 3-carbamoylethyl) -aniline N-ethyl-N-benzyl ~ 2-methoxy ~ 5 ~ acetylamino-aniline N-methy 1-N-ß-phenylethyl-3-methyl-aniline NjN-dibenzyl-Z-methoxy-S-acetylamino-aniline N-benzyl-N-cyanoethy1-3-acetylamino-aniline N-ethyl1-N-ß- (pyridyl- 1) -ethyl-aniline N-ethyl-N-ß- (pyridyl-1) -ethyl-3-acetylamino-aniline Ν, Ν-bis- (2'-acetoxyethyl) -5-benzoylamino-aniline Ν, Ν-bis - (2 ¹ -benzoyloxyethyl) -5-benzoylamino 2-methoxy-5-benzoylamino-N, N-diet hylaniline Ν, Ν-bis- (2 ¹ -benzo yloxyäthy1) -5-methanesulfonylaminoaniline N, N-bis- (2'-benzoyloxyethyl) -5-toluenesulfonylaminoaniline Ν, Ν-bis- (2'-acetoxyethyl) -3-methanesulfonylamino -aniline N, N-dimethyl-2-methoxy-5-methylaniline Ν, Ν-bis (2 ¹ -hydroxyethyl) -2-methoxy-5-chloroaniline N, N-dimethyl-2,5-dimethoxyaniline N-methyl- N- (2 ¹ , 3'-dihydroxypropyl) -2-chloro-5-methylaniline, N- (2'-methoxyphenyl) morpholine

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N-methyldiphenylamine

N, N- (2 ^r -hydroxyethyl) -2-chloro-5- (p-nitrobenzoylamino) -aniline N-ethy 1- 2- chloro- 5- (2 ', 4' - dimethoxybenzoylamino) - aniline N- ( 2'-cyanoethyl) -2,5-dimethoxyaniline N-ethyl-N- (ß-cyanoethyl) -cresidin

N, N-bis (ß-cyanoethyl) -m-anisidine

N, N-dimethyl-5- (o-anisoylamino) -aniline N-methyl-N- (2 ^! , 3'-dihydroxypropyl) -m-toluidine N- (2'-cyanoethyl) -N- (benzoyloxyethyl) -aniline N, N-diethy1-3-propionylamino-aniline

As heterocyclic coupling components are in particular 5- or 6-membered heterocyclic compounds containing 1-2 heteroatoms, especially N atoms, and preferably an enolized or enolizable keto group on the ring, mentioned, for example pyrazolones, pynridones, quinolones, isoquinolones, Pyrimidones, pyridazones, coumarins or indoles.

From the series of the pyrazolones are in particular those of the formula

called, wherein R-, containing one optionally by alkoxy groups 1-4 carbon atoms, cyano or phenyl groups substituted alkyl group or an optionally substituted by halogen atoms, alkyl or alkoxy groups, alkylsulfonyl or alkylsulfamoyl groups containing 1-4 carbon atoms of substituted phenyl or phenylsulfonyl radical and R ~ the methyl or carbamoyl group or an alkoxycarbonyl, mono- or dialkylcarbamoyl group containing 2 - S mean C atoms.

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From the series of the pyridones are in particular those of the formula

mentioned, in which R ^ is an optionally substituted by alkoxy groups, containing 1-4 carbon atoms, substituted cyano or phenyl groups Alkyl radical or a halogen atom, if appropriate, Alkyl or alkoxy groups containing 1-4 carbon atoms denotes a substituted phenyl radical, Q denotes an H atom, containing an alkyl group 1-6 C atoms, a cycloalkyl group containing 5-6 C atoms or an optionally substituted by halogen atoms, alkyl or alkoxy groups containing 1-4 carbon atoms, a substituted phenyl group, a cyano group or an alkoxycarbonyl group 2-6 C atoms, or a group of the formula -CONR ^ R, wherein R ^ is an H atom, an alkyl group containing 1-4 C atoms or a phenyl radical which is optionally substituted by halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms and R, an H atom or an alkyl group containing 1-4 C atoms, V an H or halogen atom, a cyano group, an alkyl group optionally substituted by phenyl radicals containing 1-6 Carbon atoms, a cycloalkyl group containing 5-6 carbon atoms, an alkanoyl group containing 2-4 carbon atoms, an alkylsulfonyl group, containing 1-4 C atoms, a benzoyl or phenylsulfonyl group or a group of the formula -CONR ^ R, or SC wherein R ~ and R ^ have the meaning given above.

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_ 17 -

From the series of Chiiiolones and Isoquinolones are in particular those of the formulas

OH

mentioned, in which Ro has the meaning given above, Z-, and Z _? H or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms.

From the series of the pyrimidones, in particular, the barbituric acid derivatives are the formula

X. O

^Y l

called,

wherein Ro has the meaning given above, the radicals R- also can be different among themselves, X, an O atom or a Imino group and Y, an O or S atom or an imino group.

From the series of the indoles, in particular those of the formula

mentioned, wherein R- has the meaning given above and R, -eine Denotes an alkyl group containing 1-4 carbon atoms or a phenyl radical.

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The following coupling components may be mentioned as examples: a) Pyr azolones

1,3-Dimethylpyrazolone-5 l-cyanoethyl-S-methyl-pyrazolone-S l-methyl-S-methoxycarbonyl-pyrazolone-S l-methyl-S-ethoxycarbonyl-pyrazolone-S l-phenyl-S-methylpyrazolone-S l - (2'-3'- or 4 '"chlorophenyl) -3-methylpyrazolone-5 l- (2'-3'- or 4'-methylphenyl) -3-methylpyrazolone-5 l- (2 ^! -3'- or 4 '~ methoxyphenyl) -3-methylpyrazolone 1- (2 *, 5'-dichlorophenyl) -3-methylpyrazolone-5 1- (4 <-Methylsulfonylphenyl) -3-methylpyrazolone-5 1- (4'-nitrophenyl) - 3-methylpyrazolone-5 1- (3'-dimethylsulfamoylphenyl) -3-methylpyrazolone-5 l-benzyl-3-methylpyrazolone-5 l-phenylsulfonyl-S-methylpyrazolone-S

b) pyridones

6-Hydroxypyridon-2 4-Methyl-6-hydroxypyridon-2 4 ~ phenyl-6-hydroxy-pyridon-2 4- (p-Methoxyphenyl) -6-hydroxypyridon-2 4-cyano-6-hydroxypyridone-2 4-methoxycarbony 1-6-hydroxypyridon-4-phenoxycarbonyl-6-hydroxypyridon-2 4-diethylcarbaxiioyl-6-hydroxypyridon-2 1-methyl-6-hydroxypyridone-2 1-Ethylene-6-hydroxy-pyridon-2 1,4-dimethyl-6-hydroxypyridon-2 1-Ethyl-4-methyl-6-hydroxypyridon-2 1-isopropyl-4-methyl-6-hydroxypyridon-2

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1-phenyl-4-methyl-6-hydroxypyridone-2, 1-cyanoethy1-4-methyl-6-hydroxypyridone-2, 1-methyl-3-cyano-6-hydroxypyridone-2, 1-phenyl-3 -cyan-6-hydroxy-pyridon-2 1,4-Dimethy1-3-cyano-6-hydroxypyridon-2 1-Aethy1-3-cyano-4-methyl-6-hydroxypyridon-2 1-n- Butyl- 3 - cyano- 4-raethy I- 6-lrydroxy- pyridon-1-benzy 1- 3- cyano- 4-methyl 1-6 -hydroxy- pyridon-3-cyano-4-inethy 1- 6- hydroxypyridon-2 1-methyl-3-acetyl-6-hydroxypyridon-2 1-ethy1-3-acetyl-6-hydroxypyridon-2 1-phenyl-3-acetyl-6-hydroxypyridon-2 1-Benzy1-3-acetyl-6-hydroxypyridone-2 1,4-dimethyl-3-acetyl-6-hydroxyridone-2 1-phenyl-4-methy1-3-acetyl-6-hydroxypyridone- 2 1-methyl-3-benzoyl-6-hydroxypyridone-2 1-pheny1-3-benzoy1-6-hydroxypyridone-2 1,4-dimethy1-3-benzoyl-6-hydroxypyridone-2 1- Methyl-3-methoxycarbonyl-6-hydroxypyridon-2 l-ethyl-3-methoxycarbonyl-6-hydroxypyridon-2 1,4-dimethyl 1-3-methoxycarbonyl-6-hydroxypyridon-2 1-methyl 1-3-dimethyl-carbamo 3 * 1- 6-hydroxypyridone-1-pheny 1-3-dimethyl-carbamo3 ⁷ I-6-hydroxypyrido n-1,4-Dimethy 1-3- dime thy 1-carbamoyl-6-lrydroxy- pyridon-1-Methy 1-3-pheny lcarbamoy 1-6-hydroxypyridon-2 1-phenyl-3-phenylcarbamoy1- 6-hydroxypyridone-2 1,4-dimethyl-3-pheny lcarbamoy 1- 6-trydroxypyridonl-methyl-3-methylsulfonyl-6-hydroxypyridone-1,4-dimethyl-3-methylsulfonyl-6- hydroxypyridon-2 1-methyl-3-pheny-sulfonyl-6-hydroxypyridon-2 l-phenyl-3-phenylsulfonyl-6-li3 ^T drox3'-pyridon-1,4-dimethy 1-3-pheny ! sulfonyl-6-lrydroxy-p3 ^T Ridon-2

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I-methyl-3-diinethylsulfamoyl-6-hydroxypyridon-2 1-Phenyl-3-diiaethylsulfyl-6-hydroxypyridon-2 1,4-Dimethyl-3-diinethylsulfamoyl-6-hydroxypyridon-2

e) quinolones and isoquinolones

2,5-dihydroxyquinoline 2,3-dihydroxyisoquinoline 1-methy 1-4-hydroxy-quino lon-

1-ethyl-4-hydroxy-chir.olon-2 l-n-butyl-4-hydroxy - quinolone ~ 2 1- (β-methoxyethyl) ^ -hydroxy-cbinolone ^ 1- (β-cyano-ethyl) -4-hydroxy-quinone-2-methy1-3-hydroxy-quinoline

d) pyrimidones

Tetrahydro-pyrimidone-2 barbituric acid

N, N ¹ -Dime thy lbarbi Tür sä'ur e N, N-Diphenylbarbituräure N-Meth ^ '- lN-Phenylbarbituräure N-Methy IK- (3 "-chlorphenyl) -barbitursMure N- (ß-Methoxyäthyl) -If-phenylbarbituric acid N, N-dibenzylbarbituric acid 2,4-dihydroxy-dihydro-pyriraidine 2,4-diimino -H- oxo-hexahydro-pyrimidine 2-imino-4,6-dioxo-hexahydro-pyrimidine 2-thio-4,6-dioxo-hexahydro-pyrimidine

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e) indoles

2-methyl-indole, 2-methyl-5- or -6-chloroindole 2-methyl-5-nitro-indole 2-methyl-5-methoxycarbonyl-indole 2,4-dimethyl-7-methoxy-indole 2-ethyl-indole 2-phenyl-indole 2-phenyl-5-ethoxy-indole 2-hydroxyindole 1,2-dimethyl indole l-methyl-2-phenyl-indole 1- (ß-methoxyethyl) -2-phenyl-indole 1- (/ 3-cyanoethyl) -2-phenyl-indole Indoxyl

5-chloro-indoxyl

5-bromo-indoxyl 2,5-dichloroindoxyl 2,5-dibromoindoxyl

£) Uob i-ige

Pyridazon-3 4,5-dichloropyridazon-3 4-methyl-imidazole 4-phenyl-imidazo!

4,5-diphenyl-imida oil 4-hydroxycurnarin thioindoxyl-S-dioxide as well as the compound of the formula

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OH

CH ₃

Coupling components from the series of aromatic hydroxy compounds are in particular those of the formula

> H

mentions j in which V, an H atom or a hydroxyl or alkoxy group containing. 1-4 C atoms, Q an H or halogen atom or an alkyl group containing 1-4 C atoms, R an H or halogen atom, an alkyl or alkoxy group containing 1 - 12 carbon atoms, a cycloalkyl group containing 5-6 carbon atoms, a cyanoalkyl or alkoxycarbonylalky! group containing 3-6 carbon atoms, a Phenyl group, containing an alkanoyl or alkanoylamino group

2-6 carbon atoms, a sulfonic acid alkyl ester or alkyl sulfonyl group, an alkyl or dialkylsulfamoyl group containing 1-8 carbon atoms, a sulfonic acid phenyl ester, phenylsulfonyl, Phenylsulfamoyl or benzoyl group or in which the Pv.es te Q and R form a fused benzene, alicyclic or heterocyclic 5- or 6-membered ring.

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Examples are:

phenol

3- or 4-chlorophenol 2-, 3- or 4-methylphenol 4-tert-butylphenol 4-tert-octylphenol 4-nonylphenol 4-decylphenol 4-dodecyl phenol 4-cyclohexyl phenol 3,4-dimethylphenol 2,4-dimethylphenol 4-methyl-2-butylphenol 4-β-cyanoethylphenol 2-methyl-4- / 3-cyanoethylphenol 2-methyl-4-ß-methoxycarbonylethyl-phenol 3- or 4-hydroxydiphenyl 4-methoxypheηο1 4-butoxyphenol 4-octyloxyphenol 4-acetylaminophenol 4-methoxycarbonylaminophenol 4-methyl-2-acetylaminophenol 4-propionylarainophenol 3-diethylaminophenol Resorcinol

4-Benzoylresorcinol Resorcinol monomethyl or monoethyl ether N-methyl-3-hydroxy-diphenylamine N-butyl-3-hydroxydiphenylamine

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1-naphthol

5-chloro-1-naphthol

5,8-dichloro-1-naphthol

4-methyl-1-naphthol

4-methoxy-1-naphthol

5-acetylamino-1-naphthol

5-benzoylamino-1-naphthol

5-benzoylsulfonylamino-1-naphthol 1-hydroxynaphthalene-4-sulfonic acid diinethylamide 1-Hydroxynaphthalene-4-sulfonic acid phenylamide 1-Hydroxynaphthalene-5-sulfonic acid dimethylamide 1-hydroxynaphthalene-5-sulfonic acid phenylamide 1-hydroxynaphthalene-3-sulfonic acid dimethylamide 1-hydroxynaphthalene-3-sulfonic acid phenylamide 1-hydroxynaphthalene-4-sulfonic acid phenyl ester 3,4- or 5-methylsulfonyl-l-naphtho!

2-. Naphthol

6-chloro-2-naphthol

6-bromo-2-naphthol

2,6- and 2, 7-dihydroxynaphthalene, 1, 3- and 1, 5-dihydroxynaphthalene 6-methyl-6-cyano-2-naphthol

8-acetylamino-2-naphthol

8-benzoylamino-2-naphthol

8-Methoxycarbonylamino-2-naphthol "8-Methane sulfony! Amino-2-naphthol 8-benzenesulfonylamino-2-naphthol 5-acetylamino-2-naphthol

2-hydroxynaphthalene-6-sulfonic acid dimethylamide 2-hydroxynaphthalene-6-sulfonic acid (N-methyl-N- / 3-hydroxyethylamide 2-hydroxynaphthalene-6-sulfonic acid- (N-methyl-N-ß-acetoxyethylamide ^ 2-hydroxynaphthalene-7-sulfonic acid dimethylamide 2-hydroxynaphthalene-6-sulfonic acid phenyl ester 2-hydroxynaphthalene-7-sulfonic acid phenyl ester

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8-hydroxyquinoline
S-chloro-S-hydroxyquinoline
6,8-dihydroxyquinoline
2-hydroxy diphenylene oxide
4-hydroxy-acenaphthene
3-hydroxy-fluorene
5-hydroxy indane

Nitrous acid esters, in particular of primary or secondary monohydric and dihydric aliphatic alcohols having 1 to 6 carbon atoms, are used as diazotizing agents. Examples of such esters are the liquid nitrites of butyl, pentyl or isopentyl, alcohol, but then also the nitrous acid esters of heptyl and decyl alcohol, propylene glycol, glycol, glycol monoalkyl ethers with alkyl radicals containing 1-5 carbon atoms and benzyl alcohol with a boiling point above 50 ⁰ C; advantageous to use the esters with alcohols containing 1-3 carbon atoms, ie methyl, ethyl, propyl or isopropyl esters which have a boiling point below 50 ⁰ C and gaseous or very volatile liquids. The esters can be added to the reaction mixture in liquid form or dissolved in a solvent, for example in the same in which the reaction takes place; the low boiling points can also be introduced in a gaseous state.

Organic or inorganic salts are used as catalysts Acids with tertiary amines or the diazo component used.

Examples of inorganic acids are hydrochloric acid and hydrogen bromide acid, sulfuric acid or the various phosphoric acids called.

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From the series of organic acids come both the carboxylic acids as well as the sulfonic acids, for example formic acid, aliphatic mono- and dicarboxylic acids such as acetic acid, Propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, oc-halogenated aliphatic carboxylic acids with 2-6 C atoms, such as chloroacetic acid, α-chloropropionic acid, α-chlorobutyric acid, oc-chloroisovaleric acid and the corresponding bromine-containing Acids, polyhalogenated carboxylic acids such as dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid and perfluorobutyric acid, also cyanoacetic acid. From the E. series of aromatic carboxylic acids be benzoic acids and their ring-substituted derivatives, such as 2-, 3- or 4-chlorobenzoic acid, 2,4- or 2,5-dichlorobenzoic acid, alkylated benzoic acids, such as 2-, 3- or 4-methylbenzoic acid, Nitrobenzoic acids or phthalic acid, also called phenylacetic acid.

Examples of organic sulfonic acids are aliphatic sulfonic acids, such as methane or ethanesulphonic acid, but especially aromatic sulphonic acids such as benzene or naphthalenesulphonic acids called.

Instead of acids, acidic salts such as zinc chloride, iron chloride or aluminum chloride or acidic ion exchangers can also be used.

It has proven to be particularly advantageous to use the salts of the acids mentioned with the diazo or coupling component as catalysts to use. This can be accomplished in a practically expedient manner by adding the acids to the reaction mixture.

The salts of the acids mentioned with other tertiary amines, for example pyridine bases or trialkylamines, can also be used. preferably those whose alkyl radicals have 1-6 carbon atoms, such as Use triethylamine or triethylamine.

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The amount of the catalyst to be used is appropriate 0.0001-0.5, preferably 0.001-0.1 mol per mole of diazo component The optimal amount of catalyst is different for each acid and depends heavily on its dissociation constant.

The reaction takes place in an organic diluent.

These include water-miscible (hydrophilic) organic solvents, for example aliphatic alcohols such as methanol. Ethanol, isopropanol, ketones such as acetone, methyl ethyl ketone, or Cyclohexanone, ethers such as ethylene glycol monomethyl or ethyl ether, Tetrahydrofuran or dioxane, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or tetramethylurea, or also dimethyl sulfoxide and suIfolan. But also with water immiscible solvents, preferably aliphatic and

aromatic halogenated hydrocarbons are found to be suitable. For example, methylene chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloropropane , 1,3-dichloropropane, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene or mixtures thereof. As mixtures of those are preferred which consist of a low boiling point, having a boiling point below 90 ⁰ C and a high-boiling, a boiling point above 130 ⁰ C-containing solvents such as mixtures of l, l, l ~ trichloroethane and chlorobenzene or 1,2-dichloroethane and o-dichlorobenzene or chloroform and 1,2,4-trichloroethane. Other suitable solvents are hydrocarbons which are liquid at room temperature, such as benzene, toluene, xylene, cyclohexane, tetralin and decalin, and also petroleum fractions.

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The amount of the solvent used becomes appropriately such dimensioned so that a readily miscible reaction mixture is formed. When using liquid coupling components, the latter can at the same time serve as a diluent, so that only small additional amounts of an organic solvent are required are.

The diluent used should have the ability to provide sufficient To dissolve amounts of both the diazo and coupling components and the catalyst, so that the azo dye formation can progress at reasonable speeds.

The reaction may be at a temperature of 0-80 ⁰ C, preferably from 0-50 ⁰ C.

As a result of the practically simultaneous, accelerated by the amine salt Diazotization and coupling, the reaction proceeds very quickly. The one obtained in good yield and purity Azo dye can be obtained by simply filtering it and, if necessary, subsequently washing the filter residue with an organic Solvent to be isolated.

The azo dyes obtainable according to the process can be used for A wide variety of purposes are used, preferably for dyeing hydrophobic, synthetic textile fibers from aqueous Dispersion, for example for dyeing cellulose to triacetate, but especially for dyeing high molecular weight esters of aromatic polycarboxylic acids with polyfunctional alcohols, for example of polyalkylene glycol terephthalates. The dyes but can also be used to dye synthetic polyamide fibers.

The coloring takes place according to the usual procedures.

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Instead of isolating the dyes, secondary reactions can then take place in the reaction mixture with the dye obtained be carried out, such as acylations, alkylations or aminations. So can dyes containing tertiary Amino groups, for example, with an alkyl halide, a dialkyl sulfate or alkylene oxide with a benzenesulfonic acid ester Quaternized, or dyes containing exchangeable halogen atoms can also be used with tertiary amines quaternary ammonium salts are implemented. In this way, cationic dyes are obtained, which are particularly suitable for Dyeing polyacrylonitrile fibers are suitable.

In the following examples, unless otherwise stated, parts are parts by weight and percentages Weight percentages, and temperatures are in degrees Celsius specified.

example 1

It is a mixture of 17.26 parts of 2-chloro ~ 4-nitro-aniline, 21.22 parts of N-ethyl-N-cyanoethyl-aniline, 0.24 parts of pyridine trichloroacetate and 50 parts of xylene mixture. At 20-25 °, 16.85 parts of isopentyl nitrite are left within Add dropwise for 1 1/2 hours. After 3 hours of removal at 20 refluxed for another 1/2 hour. The reaction mixture is slowly cooled to 0 °, the precipitated dye filtered and washed four times with 5 parts each of a mixture of cyclchexane and isoamyl alcohol 7: 3 and dried in vacuo at 60-70 °. This gives 27.6 parts (77.1%) of the red azo dye of the formula

Cl

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Example 2

The procedure is as in Example 1, but used instead of 0.24 part of pyridine trichloroacetate 0.26 part of triethylamine trichloroacetate. The yield of azo dye is 27.3 parts (76.3%).

Example 3

The procedure is as in Example 1, but instead of 0.24 part of pyridine trichloroacetate, 0.39 part of 1,8-bis (dimethylsiiiino) is used -naphthalene trichloroacetate. The yield at Azo dye is 25.9 parts (72.4%).

Example 4

28 parts of 1-amino-2-cyclohexylsulfamoylbenzene, 16 parts, are dissolved N-Methy1-N (2'-cyanoethyl) aniline and 1.6 parts of trichloroacetic acid in 40 parts of dichloromethane and conducts 8.3 parts at 0-10 °

Ethyl nitrite as a gas. It is allowed to react for 3 hours and then replaces the dichloromethane with 40 parts, an alcohol / water device. The failed dye is filtered off, washed and dried. 38 parts of the dye of the formula are obtained

N = N

ENT ₂ sj

which dyes cellulose acetate fibers in reddish yellow tones

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Example 5

32.9 parts of 1-amino-4-nitro-6-cyclohexylsulfamic benzene are suspended, 26.5 parts of N-bis (2'-acetoxyethyl) aniline and 3.3 Parts of trichloroacetic acid in 100 parts of dichlorine than and introduces 8.3 parts of ethyl nitrite as a gas at 0-10 °. One lets 12 React for hours and replace dichloromethane with 100 parts of an alcohol / water mixture. The precipitated dye will filtered off j washed and dried. 50 parts of the dye of the formula are obtained

H V-HNO ₂ S

which dyes acetate silk fibers in bluish red tones. Example 6

36.2 parts of 1-amino-4-nitro-6-N, N-dibutylsulfa; r.oy are suspended benzene, 19.9 parts of N-bis (/ 3-cyanoethyl) aniline and 3.3 parts of trichloroacetic acid in 100 parts of dichloromethane and introduces 8.3 parts of ethyl nitrite as a gas at 0 ~ 10 °. Leave for 12 hours react completely and replace dichloromethane with 100 parts of an alcohol / water mixture. The precipitated dye is filtered off, washed and dried. 48 parts of the dye of the formula are obtained

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NO ₂

which dyes acetate silk fibers in orange tones.

Example 7

8.4 g of 3-amino-l, 2,4-triazole, 14.9 g of Ν, Ν-diaethylaniline, 50 mg of trichloroacetic acid and 3 ml of isopropanol are presented and stirred well. Then cool down to 0 ° and leave at one At a temperature of 0 - 10 ° 12 g of isopropyl nitrite are added dropwise. at a temperature of 0-10 ° is stirred overnight, then the resulting 3- (4'-N, N-Diaethylaminophenylazo -) - l, 2,4-triazole is filtered off and dried in vacuo at 60 °. The dye dyes polyester fibers in orange tones.

Example 8

If the procedure is as in Example 7, but replaces the 50 mg of trichloroacetic acid by 1/1000 mole of triethylamine trichloroacetate, the same product is obtained.

Example 9

If the procedure is as in Example 7, but replaces the 50 mg trichloa-acetic acid by 1/1000 mol of pyridine trichloroacetate, the same product is obtained.

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Example 10

If the procedure is as in Example 7, but replaces the 50 mg of trichloroacetic acid by 1/1000 mol of pyridine hydrochloride, the same product is obtained.

Example 11

If the procedure is as in Example 7, but replaces the 50 mg of trichloroacetic acid by 1/1000 mole of Diaethylanilintrichloracetat and used instead of 14.9 g 14.75 g Ν, Ν-Diaethylanilin so obtained one the same product.

O-

Example 12

If the procedure is as in Example 7, but replaces the 50 mg of trichloroacetic acid by 1/1000 mole of 3-amino-1,2,4-triazole-trichloroacetate and the 8.4 g of 3-amino-1,2,4-triazole by 8.32 g of 3-amino-1,2,4-triazole, so you get the same product.

Example 33

If the procedure is as in Example 7, but the 50 mg of trichloroacetic acid is replaced by 1/1000 mol of dichloroacetic acid one the same product.

Beis piel 14

If the procedure is as in Example 7, but replaces the 50 mg of trichloroacetic acid by 1/1000 mol of chloroacetic acid, iv.nn the same product.

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_ 34 -

Example 15

If the procedure is as in Example 7, but replaces the 50 mg of trichloroacetic acid 1/100 mol of glacial acetic acid gives the same product.

Example 1 6

If the procedure is as in Example 7, but replaces the 50 mg of trichloroacetic acid 1/1000 mol of sulfuric acid gives the same product.

Example 17

If the procedure is as in Example 7, but replaces the 50 mg of trichloroacetic acid with 50 mg of zinc chloride, the same product is obtained.

Example 18

Proceed as in Example 7, but replace the 3 ml isopropanol by 3 ml of methyl ethyl ketone, the same product is obtained.

Example 19

If you proceed as in Example'7, but replace the 3 ml isopropanol by 3 ml of methanol, the same product is obtained.

Example 2 0

The procedure is as in Example 7, but replaces the 3 ml of isopropar.ol with 3 ml of amyl alcohol, the same product is obtained.

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Example 21

The procedure is as in Example 7, but replaces the 12 g of isopropyl nitrite 0.14 mol of methyl nitrite gives the same product.

Example 22

The procedure is as in Example 7, but replaces the 12 g of isopropyl nitrite by 15.5 g of amyl nitrite, the same is obtained Product.

Example 23

The procedure is as in Example 7, but replaces the 3 ml of isopropanol by 3 ml of ethanol and the 12 g of isopropyl nitrite by 10 g of ethyl nitrite, the same product is obtained.

Example 24

If the procedure is as in Example 7, but replaces the 50 mg of trichloroacetic acid with the appropriate amount of an acidic ion exchanger, the same product is obtained.

To determine the acidity of the reaction mixture, 8.4 g of 3-amino-1,2,4-triazole, 14.9 g of N, N-diethylaniline, 0.5 g Trichloroacetic acid and 3 ml of isopropanol mixed intensively for 10 minutes, 6.5 g of water, corresponding to 25% of the volume of the reaction mixture, added and mixed intensively for another 10 minutes. After separating the layers, the pH is determined the aqueous phase and the organic phase saturated with water are measured. In both cases pH 5.9 is measured.

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Example 25

To a mixture of 19.7 g of N-methyl-N-benzylaniline, 8.7 g of 3-aminotriazole-1,2,4 and 10 ml of methanol, 0.26 g of triethylamine trichloroacetate are added as a catalyst and 13.4 g of isopropyl nitrite are added dropwise to. The mixture is stirred at room temperature until the reaction has ended and filtered. After washing with ethanol and drying in vacuo, crystals of a yellow dye are obtained, which corresponds to the following constitution:

Further proportions of the dye can be isolated from the filtrate and wash liquor.

Example 26

A dye of the same constitution is obtained when the catalyst from Example 25 is replaced by 0.24 g of pyridine trichloroacetate.

Example 27

The same dye is obtained if, instead of the catalyst from Example 25 0.12 g of pyridine hydrochloride used as a catalyst.

Example 28

If the catalyst from Example 25 is replaced by 0.17 g of trichloroacetic acid, this also gives the same dye.

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Example 29

If one passes into the reaction mixture, according to Example 25, the none Contains catalyst, HCl gas in, the same dye is again obtained after the reaction has ended.

Example 30

In example 29, if the HCl gas is replaced by aqueous, concentrated gas Hydrochloric acid, the reaction also leads to the dye with the constitution given in Example 25.

Example 31

18 g of 2-amino-6-methoxy-benzothiazole, 16.5 g of N-ethyl-N-β-hydroxyethyl-aniline, 500 mg of trichloroacetic acid and 30 ml of ethanol are initially charged and stirred well. 12 g of isopropyl nitrite are added dropwise at room temperature and the mixture is stirred overnight. Subsequently, the resulting 2- [4 ¹ - (N-ethyl-N-.beta.-hydroxyethylamino) (phenylazo)] 6-methoxy-benzthiazoi filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in bluish red tones.

Example 32

18 g of 2-amino-6-methoxy-benzothiazole, 12.1 g of N, N-dimethyl aniline, 3 g of trichloroacetic acid and 30 ml of butanol are initially charged and stirred well. At a temperature of 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 2- [4 '- (N ₅ N-dimethylamino) phenylazo -] - 6-methoxy-benzothiazole was filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in bluish red tones.

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Example 33

15 g of 3-amino-benzisothiazole, 12, Ig Ν, Ν-dimethylaniline, 3 g of trichloroacetic acid and 50 ml of ethanol are introduced and stirred well. At a temperature of 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. The 3- [4 '- (N _s N-dimethylamino) -phenylazo] -benzisothiazole formed is then filtered off and dried at 60 ° C. in vacuo. The dye dyes polyester fibers in purple tones.

Example 34

15 g of 3-amino-benzisothiazole, 26.5 g of Ν, Ν-bis-ß-acetoxyethylaniline, 3 g of trichloroacetic acid and 30 ml of ethanol are introduced and stirred well. At a temperature of 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 3- [4 '- (N, N-bis-.beta.-acetoxyäthylamino) phenylazo] -benzisothiazol filtered off and dried in vacuo at 6O ⁰ C. The dye dyes polyester fibers in purple tones.

Example 35

15 g of 3-amino-benzisothiazole, 21.3 g of N, N-bis-ß-cyanoethyl-3-methyl-aniline, 3 g of trichloroacetic acid and 50 ml of ethanol are introduced and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. The 3 ~ [4 '- (N, N-bis-ß-cyanoethylamino) -3'-methyl-phenylazo] -benzisothiazole formed is then filtered off and dried at 60 ° C. in vacuo. The dye dyes polyester fibers in blue-red tones.

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Example 36

15 g of 3-amino-benzisothiazole, 39.8 g of N ~ ethyl ~ N-ß-pyridJ.niumäthyl-anilin-tosylat, 3 g of trichloroacetic acid and 25 ml of ethanol are introduced and stirred well. Up to 0-5 ⁰ G, 12 g of isopropyl nitrite are added dropwise and the mixture is stirred overnight. Subsequently, the resulting 3- [4 '- (N-Aethy1-N- {3-pyridiniumäthylamino) phenylazo] -benzisothiazol-tosylate is filtered off and dried in vacuo at 60 ⁰ C. The dye dyes acrylic fibers in blue-red tones.

Example 37

19.5 g of 3-amino-5-nitro-benzisothiazole, 26.5 g of N / N-bis-ßacetoxyäthy1-aniline, 3 g of trichloroacetic acid and 30 ml of ethanol are placed in a vessel and stirred well. At 0-5 ° C., 12 g of isopropyl nitrite are added dropwise and the mixture is stirred overnight. Subsequently, the enstandene 3- [4 '~ (N, N' Bisß-acetoxyäthylamino) phenylazo] -5-nitro-benzisothiazol filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in reddish blue tones.

Example 38

19.5 g of S-amino-S-nitro-benzisothiazole, 21.3 g of N, N-bis-f3-cyanoethyl-3-methyl-aniline, 3 g of trichloroacetic acid and 80 ml of ethanol are introduced and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 3- [4 ^f - (N, N-bis-.beta.-cyanäthylamino) -3'-methyl-phenylazo] -5-nitro-benzisothiazol filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in purple tones.

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Example 39

17.7 g of 5-amino-3-phenyl-1,2,4-thiadiazole, 21.3 g of N, N ~ bis-cyanethyl-3-methyl-aniline, 3 g of trichloroacetic acid and 50 ml of ethanol are initially introduced and stirred well . At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 5- [4 '- (N, N-bis-.beta.-cyanäthylamino) -3 ^{1-methyl-phenylazo]} -3-phenyl-1,2, 4-thiadiazole was filtered off and dried in vacuo at 60 ⁰ C .. The dye dyes polyester fibers in yellowish red tones.

Example 4 0

19.4 g of 2-amino-6-ethoxy-benzothiazole, 19 g of N-ß-cyanoethyl-N-ß-hydroxyethyl aniline, 3 g of trichloroacetic acid and 30 ml of ethanol are introduced and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 2- [4 '- (N-.beta.-cyanoethyl-N-.beta.-hydroxyethyl-amino) phenylazo] -6-ethoxy-benzothiazole filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in red tones.

Example 41

19.4 g of 2-amino-6-ethoxy-benzothiazole, 21.3 g of N, N-bis-ß-cyanoethylaniline, 3 g of trichloroacetic acid and 80 ml of ethanol are introduced and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 2- [4 '- (N, N-bis-.beta.-cyanäthylamino) phenylazo] -6-ethoxy-benzothiazole filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in yellowish red tones.

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Example 42

13.3 g of 2-amino-4,5-dicyanimidazole, 12.1 g of Ν, Ν-dimethylaniline, 3 g of trichloroacetic acid and 40 ml of isopropanol are initially charged and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Finally presented the resulting 2- [4 * - (N, N-dimethylamino) phenylazo] -4,5-dicyanoimidazole is filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester in reddish yellow tones.

Example 43

18 g of 2-amino-6-niethoxy-benzothiazoi, 16.5 g of N-ethyl-N-ß-hydroxyethyl-aniline, 500 mg of trichioracetic acid and 25 ml of ijopropanol are introduced and stirred well. At room temperature, 12 g of isopropyl nitrite are added dropwise and the mixture is stirred overnight. Finally presented is the resulting 2- [4 '- (N-ethyl ~ N-ß-hydroxyethylamino) (phenylazo)] - 6-methoxy-benz thiazol äbfiltriert and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in bluish red tones.

Example 44

18 g of 2-amino-6-methoxy-benzothiazole, 12.1 g of Ν, Ν-dimethylaniline, 3 g of trichioracetic acid and 15 ml of isopropanol are initially charged and stirred well. At a temperature of 0-5 ° C., 12 g of isopropyl nitrite are added dropwise and the mixture is stirred overnight. Finally presented is the resulting 2- [4 '- (N, N-dimethylamino) -phenylazo] -6-methoxy-benzothiazole abf iltrierl: and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in bluish red tones.

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Example 45

15 g of 3-amino-benzisothiazole, 12.1 g of N, N-dimethyl aniline, 3 g of trichloroacetic acid and 45 ml of isopropanol are initially charged and stirred well. At a temperature of 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 3- [4 ¹ ~ (N, N-dimethylamino) -phenylazo] -benzisothiazol is filtered and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in purple tones.

Example 46

15 g of 3-am: \ no-benzisothiazole, 26.5 g of N, N-bis-ß-acetoxyethyl aniline, 3 g of trichloroacetic acid and 20 ml of isopropanol are initially charged and stirred well. At a temperature of 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the enstandene 3- [4 '- (N ₅ N-bis-.beta.-acetoxyäthylamino) phenylazo] -benzisothiazol is filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in purple tones.

Example 47

15 g of 3-amino-benzisothiazole, 21.3 g of N, N-bis-ß-cyanoethyl-3-methyl-aniline, 3 g of trichloroacetic acid and 40 ml of isopropanol are initially charged and stirred well. At 0-5 ° C., 12 g of isopropyl nitrite are added dropwise and the mixture is stirred overnight. The 3- [4 ¹ - (N ₃ N-bis ~ ß-cyanoethylamino) -3'-methyl-phenylazo] -benzisothiazole formed is then filtered off and dried at 60 ° C. in vacuo. The dye dyes polyester fibers in blue-red tones.

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Example 48

15 g of 3-amino-benzisothiazole, 39.8 g of N-ethyl-N-ß-pyridiniumethyl-aniline tosylate, 3 g of trichloroacetic acid and 20 ml of isopropanol are introduced and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 3- [4 '- (N-ethyl-N-ß-pyridiniuniäthylamino) phenylazo] -bensisothiazol tosylate filtered off and dried in vacuo at 60 ⁰ C. The dye dyes acrylic fibers in blue-red tones.

Example 49

19.5 g of 3-amino-5-nitro-benzisothiciZol, 26.5 g of N, N-bis-ßacetoxyethyl-aniline, 3 g of trichloroacetic acid and 20 ml of isopropanol are introduced and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. The 3- [4 '- (N, N-bis-acetoxyethylamino) -phenylazo] -5-nitro-benzisothiazole formed is then filtered off and dried at 60 ° C. in vacuo. The dye dyes polyester fibers in reddish blue tones

Example 50

19.5 g of S-amino-S-nitro-benzisothiazole, 21.3 g of N, N-bis-ßcyanäthyl-3-methyl-aniline, 3 g of trichloroacetic acid and 60 ml of isopropanol are introduced and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 3- [4 '- (N, N-bis-.beta.-cyanäthylamino) -3'-methyl-phenylazo] -5-nitrobenzisothiazole filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in purple tones.

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Example 51

17.7 g of S-amino-S-phenyl-l ^ jA-thiadiazole, 21.3 g of N, N-bis-ßcyanäthyl-3-methyl-aniline, 3 g of trichloroacetic acid and 40 ml of isopropanol are introduced and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. The 5- [4 '- (N, N-bis-ß-cyanoethylamino) -3'-methyl-phenylazo] -3-phenyl-1,2,4-thiadiazole formed is then filtered off and dried at 60 ° C. in vacuo . The dye dyes polyester fibers in yellowish red tones.

Example 52

19.4 g of 2-amino-6-ethoxy-benzothiazole, 19 g of N-ß-cyanoethyl-N-ß-hydroxyethyl aniline, 3 g of trichloroacetic acid and 20 ml of isopropanol are initially charged and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 2- [4 '- (N ~ ß-cyanoethyl-N-.beta.-hydroxyethyl-araino) phenylazo] -6-äthoxybenzthiazol filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in red tones.

Example 53

19.4 g of 2-amino-6-ethoxy-benzothiazole, 21.3 g of N, N-bis-β-cyanoethylaniline, 3 g of trichloroacetic acid and 60 ml of isopropanol are initially charged and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. Subsequently, the resulting 2- [4 '- (N, N ~ ice ~ ß-cyanäthylamino) phenylazo] -6-ethoxy-benzothiazole filtered off and dried in vacuo at 60 ⁰ C. The dye dyes polyester fibers in yellowish red tones.

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Example 54

13.3 g of 2-amino-4,5-dicyanimidazole, 12.1 g of N, N-dimethyl aniline, 3 g of trichloroacetic acid and 50 ml of ethanol are initially charged and stirred well. At 0-5 ⁰ C 12 g of isopropyl nitrite are added dropwise and the mixture stirred overnight. The 2- [4 '- (N, N-diethylamino) phenylazo] -4,5-dicyanimidazole formed is then filtered off and dried at 60 ° C. in vacuo. The dye dyes polyester in reddish yellow tones.

Example 55

If 20 ml of ethanol are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 56

If 20 ml of methanol are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 5 7

If 20 ml of amyl alcohol are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 58

If 20 ml of petroleum ether are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 59

If 20 ml of diethyl ether are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

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Example 60

If 20 ml of tetrahydrofuran are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 61

If 20 ml of benzene are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 62

If 20 ml of xylene are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 63

If 20 ml of toluene are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 64

If 20 ml of chloroform are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 65

If 20 ml of methylene chloride are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 66

If, instead of 15 ml of isopropanol, 20 ml of clilobenzene are used in Example 44, the same dye is obtained.

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Example 67

If 30 ml of sulfolane are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 68

If 30 ml of hexamethylphosphoric triamide are used instead of 15 ml of isopropanol in Example 44, the same is obtained Dye.

Example 69

If 30 ml of nitromethane are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 70

If 20 ml of dimethylformamide are used instead of 15 ml of isopropanol in Example 44, the same dye is obtained.

Example 71

If, instead of 15 ml of isopropanol, 30 ml of nitrobenzol are used in Example 44, the same dye is obtained.

Example 72

If 15 ml of isopropanol is used in Example 44 20 ml of η-hexane this gives the same dye.

Example 73

Isopropanol is used instead of 15 ml in Example 44 20 ml of tetramethylurea so one obtains the same dye.

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Example 74

9j4 g of 3 ~ amino ~ pyridine, 12.1 g of Ν, Ν-bimethylaniline, 1 g of tri ~ chloroacetic acid and 20 ml of benzene are presented and good stirred. At a temperature of 20-25 ° G, 12 g of isopropyl nitrite are obtained added dropwise and the mixture stirred overnight. The resulting 3- [4 '- (Ν, Ν-dimethylamino) phenylazo)] - pyridine is then used isolated. The dye dyes polyester fibers in reddish yellow tones.

Example 7 5

15.9 g of 2-phenyl-3-aminopyrazole, 1.5 g of trichloroacetic acid and 20 ml of benzene are initially charged and stirred well. At a At a temperature of 20-25 ° C., 6 g of isopropyl nitrite are obtained. added dropwise and the mixture, stirred overnight. Then it will 3'-amino-2,2'-diphenyl-3,4'-azo-pyrazole formed was isolated. The dye stains polyester fibers in yellow tones.

Example 76

15.9 g of 2-phenyl-3-aminopyrazole, 1.5 g of trichloroacetic acid, 12.1 g of Ν, Ν-dimethylaniline and 20 ml of benzene are presented and mixed well. At a temperature of 20-25 ° C., 12 g of isopropyl nitrite are added dropwise and the mixture is overnight stirred. The resulting 2-phenyl-3- (ρ-N, N-dimethylaminophenylazo) pyrazole is then used isolated and cleaned. The dye dyes polyester fibers in a reddish yellow Tones.

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Example 77

A mixture of 3 9.6 parts of 4-amino-azobenzene, 43.1 parts of N-bis-oxyethyl-3-chloro-aniline, 0.5 parts of trichloroacetic acid and 500 parts of a xylene mixture is prepared. At 0-10 ° C, 17 parts of methyl nitrite are introduced and ausgerlihrt the mixture for several hours at 10-20 ⁰ C. The xylene is then removed by steam distillation, and 100 parts of methanol are added to the residue. 70 parts of the yellow azo dye of the formula crystallize from the methanol

Example 78

There is a mixture of 39.5 parts of 4-amino-azobenzene, 39.85 parts of N-bis-cyanoethyl-aniline, 0.33 parts of trichloroacetic acid and 80 parts of o-xylene prepared. To this end, 24 parts of isopropyl nitrite are added dropwise at 20-25 ° C., the mixture Stirred for 18 hours at 20-25 ° G, then on for a short time 60 ° C heated. On cooling, 41.3 parts of the azo dye crystallize

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Example 79

A mixture of 17.3 parts of 2-chloro-4-nitroaniline is obtained and 21.6 parts of N-bis-oxyäthyl.-3-chloro-aniline, 0.5 parts Trichioracetic acid and 250 parts of o-xylene produced. In addition 6.5 parts of methyl nitrite are introduced at 5-10 ° G and the Mixture stirred for 5 hours. The xylene is then removed by steam distillation, leaving 37 parts of the azo dye

Cl

lag behind.

Example 80

A mixture of 19.8 parts of 4-aminoazobenzene, 38.9 parts of 2- (bis-cyanoethoxyethyl) amine-4-propionylaminoanisole. 5 parts of chloroacetic acid and 300 parts of xylene prepared. For this purpose, 9 parts of methyl nitrite are introduced at 5-10 ° C and the mixture was stirred for 22 hours. Remain after removing the xylene by steam distillation 44.5 parts of the azo dye

2 ^H 4- ° - ^C 2 ^H 4 ^CT) 2

HH-C OCLH- ^ 5

return.

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Example 81

A mixture of 17.3 parts of 2-chloro-4-nitroaniline, 38.9 parts of 2 (bis ~ cyanoethoxyethyl) amino-4-propionylaminoanisole, 0.5 part of trichloroacetic acid and 300 parts of xylene is prepared. For this purpose, 9 parts of methyl nitrite are passed in at 5-10 ^° C. and the mixture is stirred for a further 22 hours. After the xylene has been removed by steam distillation, 50 parts of the azo dye remain

° 2 ^Ν ~ <Ρχ- ^Ν = ^Ν - \ Ο> - ^ΙΤ ( ^G 2 ^H 4 ^0C 2 ^H 4 ^GN) :

^η 3
return.

Example 82

A mixture of 19.8 parts of 4-aminoazobenzene, 42.8 parts of N-bis-acetoxyethyl-aniline, 10 parts of trichloroacetic acid and 300 parts of xylene is prepared. For this purpose, 9 parts of methyl nitrite are introduced at 0-10 ⁰ C and the mixture stirred for 22 hours. After removing the xylene by steam distillation, the dye is filtered, washed neutral and dried. Yield: 43 g of dye of the following formula

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Example 83

There is a mixture of 17.3 parts of 2-chloro-4-nitroaniline, 21.3 parts of N-bis-cyanoethyl-m-toluidine, 0.33 parts Trichloroacetic acid and 100 parts of xylene prepared. For this purpose, 9 parts of methyl nitrite are introduced at 20-25 ° G. To The xylene is distilled off briefly, with 38.8 parts of the following azo dye

Cl

lag behind. -

Example 84

A mixture of 22.7 parts of 4-aminobenzoic acid benzyl ester, 17.55 parts of 3-methyl-1-phenyl-5-pyrazolone, 0.39 parts of 4-aminobenzoic acid benzyl ester trichloroacetate and 50 15.4 parts of isopentyl nitrite are added dropwise over the course of 1 1/4 hours at 25-30 ° C. After stirring for about 30 minutes, the mixture becomes thick and a further 70 parts of xylene must be added. Mach 2 % Hour stirring and \ hour refluxing is cooled to 0 °, the dye obtained

of the formula _n

H ₃ C

? / ^ Vi

"CH ₂ -OCQ ^ H = N - ^ ₀

filtered off, washed with 4x5 parts of xylene and am Vacuum dried at 60 - 70 °.

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85

A mixture of 22.7 parts of 4-aminobenzoic acid benzyl ester, 17.55 parts of 3-methyl-1-phenyl-5-pyrazolone, 0.39 part of 4-arenobenzoic acid benzyl ester trichloroacetate and 25 parts is obtained Methylethy! Ketone submitted. While stirring, 15.4 parts of isopentyl nitrite are added dropwise within 1% hour at 25-30 ° . After about 1 hour of dropping, the mixture becomes thick and a further 20 parts of methyl ethyl ketone have to be added. Is After stirring for 2% hours from \ Std boiled at reflux, then cooled to 0 °, the resulting dye abfiitriert with 4x5 parts of methyl ethyl ketone, and washed on Yakuui7i at 60 -.. Dried 70 °.

Example 86

A mixture of 12.3 parts of p-anisidine, 17.55 parts of 3-methyl-1-phenyl-5-pyrazolone, 0.21 part of p-anisicline cyanoacetate and 25 parts of isophenyl alcohol is presented. With stirring, 15.4 parts of isopentyl nitrite are added dropwise over the course of 1 \ hour at 25-30 °. When the dropwise addition is complete, the mixture becomes thick and a further 10 parts of isopentyl alcohol are added. After 2 \ hours, stirring and \ Std. Refluxing is cooled to 0 °, the dye of formula obtained

filtered off, washed with 4x5 parts of isopentyl alcohol and am Vacuum dried at 60 - 70 °.

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Example 87

A mixture of 10.7 parts of p-toluidine, 17.55 parts of 3-methyl-1-phenyl-5-pyrazolone, 0.14 part of p-toluidine hydrochloride and 25 parts of isopentyl alcohol is presented. With stirring, 15.4 parts of isopentyl nitrite are added dropwise over the course of 1% hour at 25-30 °. After 2% hours. Trituration and \ Std. Refluxing is cooled to 0 °, the dye of formula obtained

H ~ C
\

.Filtered off, washed with 4x5 parts of isopentyl alcohol and on Vacuum dried at 60 - 70 °.

Example 88

A mixture of 16.8 parts of 2-nitro-4-methoxy-aniline, 28.0 parts of N- (m-chlorophenyI) -N ¹ -methyl-barbitaric acid, 0.33 parts of trichlcressetic acid and 20 parts of methyl ethyl ketone is presented. 17.0 parts of isopentyl nitrite are added dropwise over the course of 1 hour at 20.degree.-25.degree. After about 10 minutes the mixture becomes thick, which is why 60 parts of cyclohexane are added. After stirring for 3 hours and cooling to 0 °, the dye obtained is of the formula

CH "

filtered off, washed with 15 parts of cyclohexane and dried in vacuo at 60-70 °.

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Example 89

26 parts of 2-aminobenzene-1-cyclohexylsulfamide, 17.4 parts of 1-phenyl-3-methylpyrazolone (5) and 1.6 parts of trichloroacetic acid are dissolved in 100 parts of dichloromethane and passed in about 20 minutes at 0-10 ° 9, 1 part of ethyl nitrite as a gas. The reaction is allowed to complete for three hours and then dichloromethane is replaced by 100 parts of an alcohol / water mixture. The precipitated dye is filtered off, washed and dried. 44 parts of dye of the formula are obtained

SO ₂ NH-ZhS

Example 90

26 parts of 2-amixiobenzene-1-cyclohexylsulfamide, 19.5 parts of 2-phenylindole and 1.6 parts of trichloroacetic acid are suspended in parts of dichloromethane and 9.1 parts of ethyl nitrite are passed in at 0-10 ° in about 20 minutes. The mixture is stirred for 3 hours at 10-2U °, dichloromethane is distilled off and stirred with 200 parts of ethanol / water mixture. The precipitated dye is filtered off, washed and dried. 49 parts of a brown dye of the formula are obtained

SO ₂ NH- (H.

which also dissolves in methylene chloride with a scarlet color.

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Example 91

26 parts of 2-aminobenzene-1-cyclohexylsulfainide are suspended, Parts of 3-cyano-4-methyl-6-hydroxypyridone (2) and 2.4 parts. Pyridinium trichloroacetate in 200 parts of dichloromethane and passes in 9.1 parts of ethyl nitrite as a gas at 0-10 ° in 1 hour. The initially yellow-green suspension turns dark green after stirring for 12 hours. Dichloromethane is distilled off and replaced by 100 parts Aethano1 / water mixture. The dye is filtered off and washed and dried. 32 parts of a light green dye of the formula are obtained

OH
which dissolves in dichloromethane with a green-yellow color.

Example 92

26 parts of 2-aminobenzo1-1-eyelohexylsulfamide are suspended, 19.5 parts of 1-ethyl-4-methyl-3-carboxamid-6-hydroxypyridone (2) and 1 part of cyanoacetic acid in 200 parts of dichloromethane and conducts at 0-10 ° in about 1 hour 9.1 parts of ethyl nitrite as a gas. The mixture is stirred for 3 hours at 10-15 °, dichloromethane is distilled off and stirred with 100 parts of ethanol / water mixture. The dye is filtered off, washed and dried. Man contains 25 parts of the dye of the formula

3 C0NH _?

HO. .

which dissolves in ethyl acetate A _H with a yellow color.

2 5

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Example 93

ps becomes a mixture of 29.88 parts p-aminoazobenzene, 15.53 Parts of phenol, 0.54 parts of p-aminoazobenzene trichloroacetate and 50 parts of xylene mixture prepared. At 50 - 55 ° one leaves 25.3 parts of isopentyl nitrite are added dropwise over the course of 1 1/2 hours. After stirring overnight at 50-55 °, the mixture is refluxed for 1/2 hour cooked. The reaction mixture is slowly cooled to 0 °, filtered, the dye with four times 5 parts of cyclohexane-isoamyl alcohol 7: 3 washed and dried in vacuo at 60-70 °. This gives 36.2 parts of the dye of the formula

-N = K-OJ) -N = N - <U

corresponding to a yield of 79.1% of theory.

Beis piel 94

The procedure is as in Example 93, but instead of 0.54 part of p-x ^ minoazobenzene-trichioracetate 0.36 part is used Pyridine trichloroacetate. Yield: 33.9 parts of dye, corresponding to 74.1% of theory.

Example 95

The procedure is as in Example 93, except that 0.40 part is used instead of 0.54 part of p-aminoazobenzene trichloroacetate Triethylamine trichloroacetate. Yield: 37.7 parts of dye, corresponding to 82.3% of theory.

Example 96

The procedure is as in Example 93, except that p-aminoazobenzene-trichloroacetate is used instead of 0.54 part

0.58 parts 1,8-bis (dimethylamino) naphthalene trichloroacetate. Yield: 37.1 parts of dye, corresponding to 81.0% of theory.

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Example 97

A mixture of 24.7 parts of p-anisidine, 61.8 parts of 2-hydroxynaphthalene 6- sulfonic acid (N-methy 1-N-β-hydroxy'ethyl) amide, 0.17 Parts of cyanoacetic acid and 120 parts of ligroin are presented. While stirring, 20.7 parts of isopropyl nitrite, dissolved in 30 parts of ligroin, added dropwise over the course of 11/2 hours. After stirring at room temperature for 16 hours, it is increased Chilled 0-5 °, the dye of the formula

SO ₉ -N

filtered off, with a mixture of 5 parts of isopropanol and Washed parts of ligroin and dried in vacuo at 60 °.

Example 98

A mixture of 10.7 parts of p-toluidine, 28.1 parts of 2-hyd ^ oxynaphthalene-6-sulfonic acid (N-methyl 1-N-β-hydroxy ethyl) amide, 0.085 Parts of cyanoacetic acid and 25 parts of dioxane are presented. With stirring, 15.4 parts of isopentyl nitrite are added at 25-30 ° added dropwise from 1 1/2 hours. After stirring at room temperature for 20 hours is refluxed for 1/2 hour and then cooled to 0 °. The dye of the formula

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SO ₉ -N ^ό

CH ₉ CH ₉ OH

is filtered off, washed with 3 χ 10 parts of dioxane and on Vacuum dried at 60-70 ° C.

Example 99

If 0.085 part of cyanoacetic acid is replaced by 0.19 part of p-toluidine cyanoacetate in Example 98, the same is obtained Dye.

Example 100

The same dye is obtained if, in Example 98, 0.085 part of cyanoacetic acid is replaced by 0.12 part of pyridine hydrochloride replaced.

Example 101

A mixture of 2.0 parts of p-amino-azobenzene, 2.8 parts 2-Hydroxy-naphthalene-6-sulfonic acid (N-methyl-N-ß-hydroxyethyl) amide, 0.1 part of trichloroacetic acid and 16 parts of isopentyl alcohol is presented. While stirring, 5 parts of isopenty-initrite are added dropwise at 55-60 ° over the course of 20 minutes. After stirring at 55 ° -60 ° for 2 1/2 hours, the dye of the formula is cooled to room temperature

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N = N

SO ₉ -N ^Z

filtered off, washed with 20 parts of isoamyl alcohol and dried in vacuo at 70-80 °.

Example 102

8.9 g of aniline and 11.0 g of resorcinol are dissolved in 200 ml of dichloroethane at 80 ⁰ C. After cooling to 30 ⁰ C are added 1.26 g Anilxniumtrichloracetat and forwards within 20 minutes, about 6.1 g of a methyl nitrite, which is released from a mixture of methanol, sodium nitrite and water with hydrochloric acid. The temperature is maintained between 30 and 35 ⁰ C. Then allowed to 1 hour at 30 ⁰ C and concentrated to react the reaction solution at Rotavan. Subsequently, the residue obtained is taken up in a solution of 16.1 g of 30% sodium hydroxide solution and 70 ml of water, the mixture was dissolved at about 50 ⁰ C and for the purpose of precipitation in an ice-cold mixture of 24.5 g of 307c-hydrochloric acid and 300 ml of ice water slowly run in. The orange-brown precipitate is immediately filtered and washed with about 300 ml of ice-cold water. After drying in vacuo at 70-80 ⁰ C is obtained 19.7 g of dye, corresponding to a yield of the theoretical of 96%.

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25Ü9560

Example 103

14.4 g of 1-naphthol and 8.9 g of aniline are introduced into 200 ml of cyclohexane. After briefly heating to about 70 ⁰ C, a solution being obtained, one klihlt the mixture to 30 ° C zurlick, ftigfc 0.55 g Aniliniumchloracetat at and passes within 15 minutes under vigorous stirring, about 6.1 g of a methyl nitrite. Which

forming dye precipitates out continuously, the temperature rises to about 40 ⁰ C. The suspension is then cooled to 30 ⁰ C a short time by stirring at room temperature, filtered and washed with about 20 ml of cold cyclohexane carefully. The dried dye is 18.4 g, ie about 78% of theory; At least 1.5 g of dye can still be obtained from the mother liquor, which corresponds to a total yield of 84% of theory.

Example 1 04

8.0 g of 1,3-dihydroxynaphthalene and 6.9 g of m-nitroaniline are placed in 100 ml of benzene, the suspension is briefly refluxed and then cooled ^{to 20 ° C. again.} After adding 436 mg of pyridinium trichloroacetate, the mixture is passed within about 1 hour

6.1 g of methyl nitrite, which is released from a mixture of methanol, sodium nitrite and water with hydrochloric acid. The brown suspension is stirred for 1 hour at room temperature, ^{cooled to 0 ° C. and kept at 0 °} C. for a further 1 hour. Subsequently, the suspension is filtered, the filtercake is washed first with 20 ml of benzene and then 70 ϊΛ cyclohexane and drying the dye obtained in a vacuum oven at 70 ⁰ C. It will be 12.3 g of uniform dye, ie, 80% yield based on the amount diazo component, obtain.

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25U9560

Example 1 05

16.0 g of 1,5-dihydroxynaphthalene are refluxed for 10 minutes in 200 ml of 1,1,2-trichloroethane. The suspension is then ^{cooled to 60 °} C. and 15.1 g of ethyl anthranilate are added. The mixture is cooled to 10 ° C. and 487 mg of pyrazinium trichloroacetate are added. At a reaction ^{temperature of 10 °} C. and with vigorous stirring, about 6.1 g of freshly prepared methyl nitrite are introduced within about 110 minutes. The reaction mixture is then allowed to warm to room temperature, diluted with 50 ml of trichloroethane, cooled to 0 ^° C. and kept at this temperature for at least 30 minutes. The product is filtered off, washed with 20 ml of cold trichloroethane and then with a further 80 ml of petroleum ether and dried in a vacuum oven. About 22.8 g of dye are isolated by filtration. There is still an additional amount in the trichloroethane mother liquor. The yield is 71% of theory.

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- ⁶³ - 25U9560

Example 106

To a mixture of 127.7 parts of N-cyanoethyl-N-cyanoethoxyethyl-aniline, 86.3 parts of 2-chloro-4-nitro-aniline and 180 parts of cyclohexane are given as a catalyst of 0.5 part Trichloroacetic acid and 70.9 parts of isopentyl nitrite are added dropwise at 45 ° with stirring. It is then slowly cooled to 10 ° and 2 hours at this temperature. The precipitated dye is filtered and mixed with a mixture of 50 parts Cyclohexane and 10 parts of isopentyl alcohol. After drying in vacuo at 80-90 °, 190 parts of one are obtained red pigment of the constitution

/ CH GH OCH CH CN N) H CH CN

which corresponds to a yield of 89% of theory. Example 107

To a mixture of 104.3 parts of N-hydroxyethyl-N-cyanoethylaniline, 86.3 parts of 2-chloro-4-nitro-aniline and 120 parts of cyclohexane are given as a catalyst to 0.82 parts of trichloroacetic acid and 74 parts of isopentyl nitrite are added dropwise at 45 ° with stirring. The mixture is left to stir for 2 hours at 45 °, then cooled slowly down to 10 ° and stirred for 1 hour at 10 °. The precipitated dye is filtered and washed with a mixture of Washed 30 parts of cyclohexane and 30 parts of isopentyl alcohol. After drying in vacuo at 80-90 °, 169 parts are obtained red dye of the consitution

which corresponds to a yield of 88% of theory.

509837/0990

Claims (31)

"64-25U9560 claims 1. Process for manufacturing i: ^ vovi Azo connections, thereby marked that one eu onea. essentially anhydrous molar mixture of a sulfonic acid group free diazotizable amine and one in o- or p-position for Amino group coupling tertiary aromatic amine or a on the heterocyclic coupling component coupling to the hetero ring or one of carboxylic acid or carboxamide groups free aromatic HyarorryyerbiauiiTig, ~ 7 with the coupling components free of diazotizable ^ miiiogruppen and sulfonic acid groups Must be in an organic diluent in the presence of less than the molar. Amount of one Salt of a tertiary amine or the 5inestablished diazo component adding an ester of nitrous acid. 2. The method according to claim I _5, characterized in that one of a diazotizable amine of the formula Y- <O rs starts, in which X and Y H or halogen atoms, alkyl or alkoxy groups, alkylsulfonyl or alkylsulfamoyl groups, containing 1-4 C atoms, cycloalkylsulfamoyl groups containing 5-6 C atoms, nitro, cyano, carbamoyl or trifluoromethyl groups, Alkoxycarbonyl, alkanoyl or alkylcarbamoyl groups containing 2-6 carbon atoms or optionally through Halogen atoms, alkyl or alkoxy groups containing 1-4 carbon atoms, substituted phenoxy, phenalkoxy, phenylcarbamoyl, Phenylsulfonyl, phenylsulfamoyl, benzoyl or phenylazo groups and Z represents an H or halogen atom or a trifluoromethyl group. 509837/0990 25U9560 3. The method according to claim 2, characterized in that one of an aminobenzene with at most 2 electronegative
Starting out substituents. 4. The method according to claim 3, characterized in that one of an aminobenzene with 2 identical electronegative
Starting out substituents. 5. The method according to claim 3, characterized in that one of an aminobenzene with 2 different electronegati / s Going out of substituents. 6. The method according to claim 2 ₃ Iadu: -: ch characterized that one of an aminobenzene with only one alektronegative
Starting out substituents. 7. The method according to claim I _3, characterized in that one starts from a heterocyclic diazo component with at most 2 electronegative substituents. 8. The method according to claim 7, characterized in that one of a heterocyclic diazo component with 2 equal enters into electronegative substituents. 9. The method according to claim 7, characterized in that one starts from a heterocyclic diazo component with 2 different electronegative substituents. 10. The method according to claim 7, characterized in that one starts from a heterocyclic diazo component free of electronegative substituents. 509837/0990 25U956.Q 11. The method according to claim 1, characterized in that one of a diazotizable amine of the formula X ₁ going out j where Xi is an 0 or S atom or an imino group, X «and X« Containing H or halogen atoms, alkyl or alkoxy groups 1-4 carbon atoms, nitro, cyano, thiocyan or carbamoyl groups, Alkoxycarbonyl or alkylcarbamoyl groups containing 2-6 carbon atoms or alkylsulfonyl groups containing 1-4 carbon atoms, mean. 12. The method according to claim 11, characterized in that that one in the benzene ring optionally by halogen atoms, alkyl or alkoxy groups containing 1-4 carbon atoms substituted 2-aminobenzothiazole starts. 13. The method according to claim 1, characterized in that that 3-amino-1,2,4-triazole is used as the diazo component. 14. The method according to claim 1, characterized in that an aminopyridine is used as the diazo component. 15. Process according to Claims 1-14, characterized in that the coupling component used is an amine of the formula used. 509837/0990 57 - 25U9560 16. The method according to claims 1-14, characterized in that that the coupling component is a pyrazolone of the formula used, wherein R _{1 is} optionally through alkoxy groups. containing 1-4 carbon atoms, cyano or phenyl groups or an alkyl group optionally substituted by halogen atoms, alkyl or alkoxy groups, alkyl sulfonyl, odor alkyl.su If an.oylgrappen ₅ containing 1-4 carbon atoms substituted phenyl οαει phenylsulfonyl and Rr denotes the methyl or carbamcyl group or an alkoxycarbonyl, mono- or di-alkylcarbamoyl group containing 2-8 carbon atoms. 17. The method according to claims 1-14, characterized in that that the coupling component is a pyridone of the formula used, in which Ro is an optionally substituted by alkoxy groups, containing 1-4 carbon atoms, cyano or phenyl groups, substituted alkyl radicals or one optionally substituted by halogen atoms, Denotes alkyl or alkoxy groups containing 1-4 carbon atoms substituted phenyl radical. Q a. Η atom, one Alkyl group containing 1-6 carbon atoms, a cycloalkyl group, containing 5-6 carbon atoms or optionally containing halogen atoms, alkyl or alkoxy groups 509831/0990 " ⁶⁸ " 25U9560 1-4 carbon atoms substituted phenyl radical. a Gyan group or an alkoxycarbony group containing 2-6 C atoms, a group of the formula -COlTIUR ,,., wherein R- is an H atom, an alkyl group containing 1-4 C atoms, or an optionally by Halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms substituted phenyl radicals and R ₇ denotes a Η atom or an alkyl group containing 1-4 C atoms, V denotes an H or halogen atom, a cyano group, one optionally substituted by phenyl radicals substituted alkyl or cycloalkyl group containing 1-6 carbon atoms, an alkanoyl group containing 2-4 carbon atoms, an alkylsulfonyl group containing 1-4 carbon atoms, a benzoyl or phenylsulfonyl group, a group dtr formula -CQNR-R ^ , or SO ^ NR ^ R ,, where R, and R ^ have the meaning given above, 18. The method according to claims l-14 _5, characterized in that the coupling component is a quinolone of the formula used, wherein R- has the meaning given in claim 17 and Z-, and Z ₉ mean H or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms. 19. The method according to claims 1-14, characterized in that that the coupling component is a pyrimidone of the formula γ * 'Ii
^Y l 509837/0990 - ⁶⁹ "2bU9560 used, wherein R ₃ cii-s has the meaning given in claim 17, where the radicals Ro can also be different from each other, X, an O atom, or an imino group and Y, an O or S atom or an imino group . 20. The method according to claims 1-14, characterized in that that the coupling component is an indole of the formula used, wherein R ~ has the meaning given in claim 17 and R, is an alkyl group containing 1-4 carbon atoms or a phenyl radical. 21. The method according to claims 1-14, characterized in that that you have a coupling component of the formula OH CT used, wherein V is a Η atom, a hydroxyl or an alkoxy group containing 1-4 G atoms, Q is an H or halogen atom or an alkyl group containing 1-4 C atoms, R containing an H or halogen atom, an alkyl or alkoxy group 1-12 carbon atoms, a cycloalkyl group containing 5-6 carbon atoms, a cyanoalkyl or alkoxycarbonylalkyl group containing 3-6 carbon atoms, a phenyl group, an alkanoyl or alkanoylamino group, containing 2-6 carbon atoms, an alkyl sulfonate or alkylsulfonyl group, an alkyl or dialkyl group 509837/0990 2 b U 9 5 6 0 sulfamoy! group, containing 1-8 carbon atoms, a sulfonic acid phenyl ester, Phenylsulfonyl, phenylsulfamoy1 or benzoyl group or in which the radicals Q and R are a fused benzene, alicyclic or heterocyclic 5- or 6-membered ring form. 22. The method according to claims 1-21, characterized in that that the amine is used as a salt of the diazo component. 23. The method according to claims 1-2!, Characterized in that that a salt of a heterocyclic tertiary base is used as the amine salt. 24. The method according to claims 1-21, characterized in that that the amine salt is a salt of the coupling components used. 25. The method according to claims 1-24, characterized in that that 0.0001-0.1 mol of amine salt is used per mol of diazo component. 26. The method according to claim 25, characterized in that one mole of the diazo component 0.01-0.1 mole of amine salt used. 27. The method according to claims 1-26, characterized in that the amine salt is prepared in the reaction mixture will. • 509837/0990 25U9560 28. The method according to claims 1-27, characterized in, that the diazotization agent is an ester of the nitrous Acid with an aliphatic alcohol containing 1-6 C-Aton-e used. 29. The method according to claims 1-27, characterized in that that the reaction is carried out in the presence of a hydrophilic organic solvent « 30. Process according to claims 1-27, characterized in that the reaction is carried out in the presence of a hydrocarbon or halogen hydrocarbon which is liquid at room temperature , 31. The azo compounds obtained according to claims 1-30.