Monoazo dyestuffs

Abstract

Monoazo dyestuffs which, in the form of the free acid, correspond to the formula ##STR1## in which X.sub.1 and X.sub.2 denote chlorine, bromine or trifluoromethyl,R.sub.1 denotes hydrogen or C.sub.1 -C.sub.8 -alkyl, which can be substituted by hydroxyl,R.sub.2 denotes hydrogen, C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.13 -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl,R.sub.3 denotes a direct bond, methylene, ethylene, methyleneoxy, methyleneoxycarbonyl, methyleneoxycarbonylamino, --O--, --NH--, aminomethylene or aminoethylene,R.sub.4 denotes hydrogen, methyl, methoxy or ethoxy,R.sub.5 and R.sub.6 denote C.sub.1 -C.sub.4 -alkyl, which can be further substituted by cyano, chlorine, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkoxycarbonyloxy, C.sub.1 -C.sub.4 -alkylcarbonyloxy or phenylaminocarbonyloxy, benzyl or phenethyl,R.sub.7 denotes hydrogen or C.sub.1 -C.sub.4 -alkyl, andR.sub.8 and R.sub.9 denote hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or cyano,a process for their preparation and their use for dyeing natural and synthetic fibre materials.

Description

The invention relates to monoazo dyestuffs which, in the form of the free acid, correspond to the formula ##STR2## in which X.sub.1 and X.sub.2 denote chlorine, bromine or trifluoromethyl,

R.sub.1 denotes hydrogen or C.sub.1 -C.sub.8 -alkyl, which can be substituted by hydroxyl, R.sub.2 denotes hydrogen, C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.13 -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl, R.sub.3 denotes a direct bond, methylene, ethylene, methyleneoxy, methyleneoxycarbonyl, methyleneoxycarbonylamino, -O-, -NH-, aminomethylene or aminoethylene, R.sub.4 denotes hydrogen, methyl, methoxy or ethoxy, R.sub.5 and R.sub.6 denote C.sub.1 -C.sub.4 -alkyl, which can be further substituted by cyano, chlorine, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkoxycarbonyloxy, C.sub.1 -C.sub.4 -alkylcarbonyloxy or phenylaminocarbonyloxy, benzyl or phenethyl, R.sub.7 denotes hydrogen or C.sub.1 -C.sub.4 -alkyl, and R.sub.8 denote hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or cyano.

Preferred dyestuffs are those which, in the form of the free acid, correspond to the formula ##STR3## wherein R.sub.1 ' represents C.sub.1 -C.sub.4 -alkyl or hydrogen,

R.sub.2 ' represents C.sub.1 -C.sub.12 -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl, R.sub.5 ' represents methyl or ethyl, R.sub.6 ' represents methyl, ethyl or cyanoethyl, R.sub.8 ' represents hydrogen or chlorine, R.sub.9 ' represents hydrogen, chlorine, methyl, methoxy or ethoxy, and R.sub.3 ' represents a direct bond, ##STR4##

The new dyestuffs are prepared by diazotising an amine of the formula ##STR5## in which

X.sub.1, X.sub.2, R.sub.1 and R.sub.2 have the meaning indicated above, and coupling the diazotisation product to coupling components of the formula ##STR6## wherein R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 have the meaning indicated above.

The dyestuffs according to the invention are suitable for dyeing natural and synthetic fibre materials, in particular for dyeing polyamide fibres, in level, deep red shades, in particular yellowish-tinged red shades, of very good fastness to light and to wet processing. The new dyestuffs put an expert in the position of being able to produce interesting red shades by combination with, in particular, dyestuffs which dye in bluish-tinged red shades.

The new dyestuffs are already absorbed well onto polyamide fibres in a neutral to weakly acid dyebath. By polyamide fibers there are understood in this context, in particular, those of synthetic polyamides, such as .epsilon.-polycaprolactam or condensation products of adipic acids and hexamethylenediamine. The dyestuffs are used either in the form of the free acids or in the form of their salts, in particular their alkali metal salts, preferably the sodium salts or potassium salts, and their ammonium salts.

EXAMPLE 1

4.8 g of 3,4-dichloro-6-(N-methyl-N-phenyl-aminosulphonyl)-aniline are dissolved in 100 ml of glacial acetic acid and 30 ml of concentrated HCl. The solution is cooled to 0.degree. C. The amine is diazotised with 10 ml of a 10% strength NaNO.sub.2 solution and the mixture is subsequently stirred at 0.degree. C. for two hours.

3.6 g of 3-(2-chloro-4-sulphophenoxyacetylamino)-N,N-diethylaniline are introduced into 100 g of ice and 100 g of water. The diazonium salt solution described above is allowed to run into this suspension, and the pH is adjusted to about 4 with sodium acetate solution. The dyestuff of the formula ##STR7## which has precipitated is filtered off and dried at about 50.degree. C.

EXAMPLE 2

5 g of 3,4-dichloro-6-(diisobutylaminosulphonyl)-aniline are diazotised with 10 ml of a 10% strength NaNO.sub.2 solution in 100 ml of glacial acetic acid and 30 ml of concentrated hydrochloric acid at 0.degree. C. The mixture is subsequently stirred at 0.degree. C. for 2 hours.

2.7 g of 3-(sulphophenylacetylamino)-diethyl-aniline are dissolved in 30 ml of 1 N sodium hydroxide solution and the solution is introduced into 100 g of ice and 100 g of H.sub.2 O. The diazonium salt solution described above is allowed to run into this mixture at 0.degree. C. The pH value is then adjusted to about 4 with sodium acetate solution. The dyestuff of the formula ##STR8## which has precipitated is filtered off and dried at 50.degree. C.

DYEING EXAMPLE

0.1 g of the dyestuff from Example 1 is dissolved hot in 100 ml of water, 5 ml of 10% strength ammonium acetate solution are added and the mixture is diluted to a volume of 500 ml with H.sub.2 O. 10 g of polyamide fibres are introduced into the dyebath, the dyebath is brought to the boiling point in the course of 20 minutes, 4 ml of 10% strength acetic acid are added and the bath is boiled for one hour. The fibres are then rinsed and dried at 70.degree. to 80.degree. C. A dyeing is obtained with a yellowish-tinged red shade and with good fastness properties in use, in particular with very good fastness to wet processing.

If the procedure followed is as in Example 1 and 2, using the appropriate diazo components and coupling components, further dyestuffs of the general formula ##STR9## are obtained.

__________________________________________________________________________Example Colour shade onNo. R.sub.1 R.sub.2 R.sub.3 Substituent in B polyamide__________________________________________________________________________3 Ethyl Phenyl --CH.sub.2 --O-- 2-Chloro-4-sulpho yellowish-tinged red4 Methyl Benzyl " " "5 iso-Butyl iso-Butyl " " "6 H Hexyl " " "7 H Hexyl " 2,4-Dichloro-X- " sulpho8 H Cyclohexyl " 2,4-Dichloro-X- " sulpho9 Methyl Phenyl " 2,4-Dichloro-X- " sulpho10 Ethyl Phenyl " 2,4-Dichloro-X- " sulpho11 Methyl Cyclohexyl " 2,4-Dichloro-X- " sulpho12 Methyl Benzyl " 2,4-Dichloro-X- " sulpho13 Ethyl Ethyl " 2,4-Dichloro-X- " sulpho14 Butyl Butyl " 2,4-Dichloro-X- " sulpho15 Butyl Butyl " 2-Methyl-4-chloro- " X-sulpho16 Methyl Benzyl " 2-Methyl-4-chloro- " X-sulpho17 Methyl Cyclohexyl " 2-Methyl-4-chloro- " X-sulpho18 H Butoxypropyl " 4-Sulpho "19 Ethyl Phenyl " " "20 Methyl Benzyl " " "21 Ethyl Ethyl " " "22 iso-Butyl iso-Butyl " " "23 Methyl Cyclohexyl " " "24 Methyl Octyl " " "25 Ethyl Phenyl " 4-Methyl-X-sulpho "26 Methyl Phenylethyl " " "27 H Phenylethyl " " "28 Methyl 2-Chlorophenyl " " "29 H Hexyl " " "30 Methyl 4-Methoxyphenyl " " "31 Ethyl Ethyl " " "32 Ethyl Phenyl -- 4-Methoxy-3-sulpho red33 Methyl " -- " "34 Methyl Cyclohexyl -- " "35 Methyl Benzyl -- " "36 Methyl Benzyl -- 3-Sulpho yellowish-tinged red37 Methyl Cyclohexyl -- " "38 Methyl Phenyl -- " "39 Ethyl " -- " "40 H Cyclohexyl -- " "41 H Octyl -- " "42 Methyl Phenyl -- 2-Sulpho scarlet43 Ethyl Phenyl -- " "44 Methyl Benzyl -- " "45 " Cyclohexyl -- " "46 " 4-Methylphenyl -- " "47 " 2-Methoxyphenyl -- " "48 " Phenyl --NH-- 4-Sulpho red49 " Cyclohexyl " " "50 " 4-Methylphenyl " 4-Methoxy-3-sulpho "51 Butyl 3-Chlorophenyl " 4-Chloro-4-sulpho "52 .beta.-Hydroxy- 4-Ethylphenyl " 2-Methyl-4-sulpho " ethyl53 Ethyl Phenyl --O-- 4-Sulpho yellowish-tinged__________________________________________________________________________ red

The following table lists examples of other dyestuffs which can be obtained by coupling a diazotised amine of the formula ##STR10## in which

R.sub.1 and R.sub.2 have the meaning indicated in the table, to the coupling components also indicated.

__________________________________________________________________________ Coupling Colour shade onExample R.sub.1 R.sub.2 component polyamide__________________________________________________________________________54 CH.sub.3 C.sub.3 H.sub.6OC.sub.4 H.sub.9 ##STR11## yellowish-tinged red55 C.sub.4 H.sub.9 C.sub.4 H.sub.9 ##STR12## "56 CH.sub.3 ##STR13## ##STR14## "57 C.sub.2 H.sub.5 ##STR15## ##STR16## "58 CH.sub.3 ##STR17## ##STR18## "59 H ##STR19## ##STR20## "60 CH.sub.3 ##STR21## ##STR22## "61 C.sub.2 H.sub.4OH ##STR23## ##STR24## "62 CH.sub.3 ##STR25## ##STR26## "63 C.sub.3 H.sub.7 ##STR27## ##STR28## scarlet64 C.sub.2 H.sub.5 C.sub.4 H.sub.9 ##STR29## yellowish-tinged red65 H H.sub.3 C(CH.sub.2).sub.12 ##STR30## "66 C.sub.2 H.sub.5 ##STR31## ##STR32## red67 H ##STR33## ##STR34## yellowish-tinged__________________________________________________________________________ red

Other preferred dyestuffs can be obtained by diazotising amines of the formula ##STR35## wherein X.sub.1, X.sub.2, R.sub.1 and R.sub.2 have the meanings indicated in the table which follows,

and coupling the diazotisation products to the coupling components likewise listed in the table. __________________________________________________________________________ Colour shade onExample X.sub.1 X.sub.2 R.sub.1 R.sub.2 Coupling component polyamide__________________________________________________________________________68 Cl CF.sub.3 CH.sub.3 ##STR36## ##STR37## yellowish-tinged red69 Cl CF.sub.3 CH.sub.3 ##STR38## ##STR39## yellowish-tinged red70 Cl CF.sub.3 CH.sub.3 ##STR40## " yellowish-tinged red71 Cl CF.sub.3 CH.sub.3 ##STR41## ##STR42## red72 Cl CF.sub.3 H ##STR43## ##STR44## yellowish-tinged red73 Cl Br C.sub.4 H.sub.9 C.sub.4 H.sub.9 " yellowish-tinged red74 CF.sub.3 Br CH.sub.3 ##STR45## ##STR46## yellowish-tinged red75 CF.sub.3 Br CH.sub.3 ##STR47## ##STR48## red76 CF.sub.3 Cl H ##STR49## ##STR50## yellowish-tinged red77 Cl Cl CH.sub.3 ##STR51## ##STR52## yellowish-tinged red__________________________________________________________________________

Claims

1. Monoazo dyestuffs which, in the form of the free acid, correspond to the formula ##STR53## in which X.sub.1 and X.sub.2 denote chlorine, bromine or trifluoromethyl,

R.sub.1 denotes hydrogen or C.sub.1 -C.sub.8 -alkyl, which can be substituted by hydroxyl,

R.sub.2 denotes hydrogen, C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.13 -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl,

R.sub.3 denotes a direct bond, methylene, ethylene, methyleneoxy, methyleneoxycarbonyl, methyleneoxycarbonylamino, aminomethylene or aminoethylene,

R.sub.4 denotes hydrogen, methyl, methoxy or ethoxy,

R.sub.5 and R.sub.6 denote C.sub.1 -C.sub.4 -alkyl, which can be further substituted by cyano, chlorine, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkoxycarbonyloxy, C.sub.1 -C.sub.4 -alkylcarbonyloxy or phenylaminocarbonyloxy, benzyl or phenethyl,

R.sub.7 denotes hydrogen or C.sub.1 -C.sub.4 -alkyl, and R.sub.8 and R.sub.9 denote hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or cyano.

2. Monoazo dyestuffs according to claim 1, which, in the form of the free acid, correspond to the formula ##STR54## wherein R.sub.1 ' represents C.sub.1 -C.sub.4 -alkyl or hydrogen,

R.sub.2 ' represents C.sub.1 -C.sub.12 -alkyl, phenyl which is optionally substituted by methyl, ethyl, chlorine, methoxy or ethoxy, benzyl, phenethyl, cyclohexyl or methylcyclohexyl,

R.sub.5 ' represents methyl or ethyl,

R.sub.6 ' represents methyl, ethyl or cyanoethyl,

R.sub.8 ' represents hydrogen or chlorine,

R.sub.9 ' represents hydrogen, chlorine, methyl, methoxy or ethoxy, and

R.sub.3 ' represents a direct bond, --CH.sub.2 -- or --CH.sub.2 --O--.