Dyeing or printing process with new and known cationic 4,5-dihydro-iH-1,2,3-triazolium compounds as dyestuffs and new cationic 4,5-dihydro-1H-1,2,3-triazolium compounds

Some triazolium compounds and their UV spectra and voltametric measurement are known from Chem. Ber. 112, 445 to 461 (1979) and Liebigs Ann. Chem. 1980, 285 to 290.

It has now been found a dyeing or printing process which comprises to dye or to print with one or more 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (I) ##STR2## in which R¹ and R² independently of one another denote C₆ -C₁₄ -aryl or a heterocyclic radical having up to 3 rings and up to 4 heteroatoms from the series consisting of O, S and N,

R³ and R⁴ independently of one another denote hydrogen, C₁ -C₁₂ -alkyl, C₂ -C₁₂ -alkenyl, C₄ -C₈ -cycloalkyl, C₇ -C₁₇ -aralkyl, C₆ -C₁₄ -aryl or nitrile or

R³ and R⁴ together denote a 2- to 5-membered C bridge, which can optionally be interrupted by up to two oxygen and/or nitrogen atoms, and

X^- denotes an anion,

wherein all the alkyl, alkenyl, cycloalkyl, aralkyl and aryl radicals and fused and heterocyclic radicals present can optionally be substituted by nonionic substituents, carboxyl groups, ammonium groups and/or pyridinium groups, can be used as dyestuffs.

Alkyl radicals, including those in alkoxy and aralkyl radicals, can be straight-chain or branched.

Nonionic substituents are, for example, the non-dissociating substituents customary in dyestuff chemistry, such as cyano, hydroxyl, halogen, nitro, C₁ -C₁₂ -alkyl, C₁ -C₁₂ -monoalkylamino, di-C₁ -C₁₂ -alkylamino, C₆ -C₁₂ -arylamino, C₇ -C₁₅ -aralkyl-amino, C₁ -C₁₂ -alkoxy, phenyl, C₁ -C₁₂ -acylamino, C₁ -C₁₂ -alkoxycarbonyl, C₁ -C₁₂ -alkoxycarbonyloxy, C₁ -C₁₂ -alkamidocarbonyl, C₁ -C₁₂ -alkylsulfonyl, C₆ -C₁₀ -arylazo, aminocarbonyl, phenylsulphonyl, sulphonamide, sulphonamyl and ureido, which in their turn can optionally be substituted by hydroxyl, halogen, cyano and/or C₁ -C₆ -alkoxy.

X^- preferably represents a colourless organic or inorganic anion, for example fluoride, chloride, bromide, iodide, perchlorate, tetrafluoroborate, hydroxide, hydrogen sulphate, sulphate, dihydrogen phosphate, hydrogen phosphate, phosphate, bicarbonate, carbonate, methyl-sulphate, ethyl-sulphate, cyanate, thiocyanate, tri- or tetrachlorozincate, tetrachloroferrate or hexafluorosilicate, or an anion of a saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic carboxylic or sulphonic acid, for example formate, acetate, hydroxyacetate, cyanoacetate, propionate, hydroxypropionate, oxalate, citrate, lactate, tartrate, the anion of cyclohexanecarboxylic acid, phenylacetate, benzoate, the anion of nicotinic acid, methanesulphonate, ethanesulphonate, benzenesulphonate, chlorobenzenesulphonate and toluenesulphonate.

If the anion is a polyvalent anion, for example sulphate or oxalate, X^- in formula (I) represents one equivalent of such a polyvalent anion.

According to the invention, 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (I) are preferred in which

R¹ and R² independently of one another denote phenyl, naphthyl, thienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, benzisothiazolyl, pyrazolyl, imidazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, indolyl or pyridyl, wherein these radicals can optionally be substituted by up to 5 radicals from the group consisting of C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, C₆ -C₁₀ -aryloxy, C₆ -C₁₀ -arylamino, C₇ -C₁₂ -aralkylamino, C₁ -C₈ -acylamino, C₁ -C₈ -acyloxy, C₁ -C₈ -monoalkylamino, di-C₁ -C₈ -alkylamino, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₁₂ -alkamidocarbonyl, C₁ -C₁₂ -alkylsulphonyl, C₆ -C₁₀ - arylazo, aminocarbonyl, halogen, cyano, hydroxyl, nitro, phenylsulphonyl, sulphonamide, sulphonamyl and ureido, which in their turn can optionally be substituted by hydroxyl, halogen, cyano and/or C₁ -C₄ -alkoxy,

R³ and R⁴ independently of one another in each case denote hydrogen, C₁ -C₈ -alkyl, allyl, cyclopentyl or cyclohexyl which are optionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, aminocarbonyl and/or C₁ -C₄ -alkoxycarbonyl, a benzyl, phenethyl, furyl, tetrahydrofurylmethyl, pyridyl, pyridylmethyl or pyridylethyl radical which are optionally substituted by halogen, cyano, C₁ -C₄ -alkyl and/or C₁ -C₄ -alkoxy, or a phenyl radical which is optionally substituted by halogen, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy or

R³ and R⁴, together with the two carbon atoms in between, form a cyclobutane, cyclopentane, cyclohexane or cycloheptane ring which is optionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy and/or aminocarbonyl and is optionally interrupted by a nitrogen atom, a tetrahydropyrrolidino or piperidino ring which is optionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy and/or aminocarbonyl and is optionally interrupted by an oxygen atom, or a tetrahydrofuryl or tetrahydropyranyl ring which is optionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy and/or aminocarbonyl and

X^- denotes an anion.

Halogen preferably represents fluorine, chlorine and bromine.

According to the invention, 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (I) are particularly preferred in which

R¹ and R² independently of one another denote phenyl, naphthyl, thienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, benzisothiazolyl, imidazolyl, benzimidazolyl, benzoxazolyl, 1,2,4-triazolyl or pyridyl, wherein these radicals can optionally be substituted by up to 5 radicals from the group consisting of C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₆ -C₁₀ -aryloxy, C₆ -C₁₀ -arylamino, C₇ -C₁₂ -aralkylamino, C₁ -C₄ -acylamino, C₁ -C₄ -acyloxy, C₁ -C₄ -monoalkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxycarbonyloxy, C₁ -C₄ -alkamidocarbonyl, C₁ -C₄ -alkylsulphonyl, C₆ -arylazo, aminocarbonyl, halogen, cyano, hydroxyl, nitro, phenylsulphonyl, sulphonamide, sulphonylamyl and ureido, which in their turn can optionally be substituted by hydroxyl, halogen, cyano and/or C₁ -C₄ -alkoxy,

R³ and R⁴ independently of one another in each case denote hydrogen or a C₁ -C₄ -alkyl radical which is optionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, aminocarbonyl and/or C₁ -C₄ -alkoxycarbonyl or

R³ and R⁴, together with the two carbon atoms in between, denote a cyclopentane or cyclohexane ring which is optionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy and/or aminocarbonyl and

X^- denotes an anion.

According to the invention, 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (I) are especially preferred which correspond to the formula (II) ##STR3## in which R³ and R⁴ independently of one another in each case denote hydrogen or a C₁ -C₄ -alkyl radical which is optionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, aminocarbonyl and/or C₁ -C₄ -alkoxycarbonyl or

R³ and R⁴, together with the two carbon atoms in between, denote a cyclopentane or cyclohexane ring which is optionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy and/or aminocarbonyl,

R⁵ to R¹² independently of one another in each case denote hydrogen or a C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₆ -C₁₀ -aryloxy, C₆ -C₁₀ -arylamino, C₇ -C₁₂ -aralkylamino, C₁ -C₄ -acylamino, C₁ -C₄ -acyloxy, C₁ -C₄ -monoalkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxycarbonyloxy, C₁ -C₄ -alkamidocarbonyl, C₁ -C₄ -alkylsulphonyl or C₆ -arylazo radical which is optionally substituted by hydroxyl, halogen, cyano and/or C₁ -C₄ -alkoxy, aminocarbonyl, halogen, cyano, hydroxyl, nitro, phenylsulphonyl, sulphonamide, sulphonamyl or ureido and

X^- denotes an anion.

According to the invention, 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (II) are preferred in which

R³ and R⁴ independently of one another denote hydrogen or a C₁ -C₄ -alkyl radical,

R⁵ to R⁷ and R¹⁰ to R¹² independently of one another in each case denote hydrogen, a C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenoxy, phenylamino, phenyl-C₁ -C₄ -alkylamino, C₁ -C₄ -acylamino, C₁ -C₄ -acyloxy, C₁ -C₄ -monoalkyl-amino, di-C₁ -C₄ -dialkylamino, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxycarbonyloxy, C₁ -C₄ -alkamidocarbonyl, C₁ -C₄ -alkylsulphonyl or phenylazo radical, aminocarbonyl, halogen, cyano, hydroxyl, nitro, phenylsulphonyl, sulphonamide, sulphonamyl or ureido,

R⁸ and R⁹ independently of one another in each case denote hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, cyano or hydroxyl and

X^- denotes an anion.

According to the invention, 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (II) are particularly preferred in which

R³ and R⁴ independently of one another denote hydrogen or methyl,

R⁵ and R¹², R⁶ and R¹¹, R⁷ and R¹⁰, and R⁸ and R⁹, in each case as pairs, are identical and have one of the meanings given above as preferred in the case of formula (II) and

X^- denotes an anion.

According to the invention, 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (II) are especially preferred in which

R³ and R⁴ independently of one another denote hydrogen or methyl,

R⁶ denotes hydrogen, methyl, methoxy, ethoxy, phenoxy, acetylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, chlorine, cyano or nitro,

in the case where R³ and R⁴ in each case denote hydrogen,

R¹¹ denotes ethoxy, phenoxy, acetylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, chlorine, cyano or nitro,

and in the case where at least one of the radicals R³ and R⁴ is other than hydrogen

R¹¹ additionally can also denote hydrogen, methyl, methoxy or nitro,

R⁵ and R¹², and R⁷ and R¹⁰, in each case as pairs, are identical and denote hydrogen, methyl, methoxy, ethoxy, phenoxy, acetylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, chlorine, cyano or nitro,

R⁸ and R⁹ independently of one another in each case denote hydrogen, methyl or methoxy and

X^- denotes an anion.

4,5-Dihydro-1H-1,2,3-triazolium compounds of the formula (II) which are furthermore especially preferred are those in which

R³, R⁵, R⁸ R⁹ and R¹² in each case denote hydrogen,

R⁴ denotes hydrogen or methyl,

R⁶ denotes methyl, methoxy, ethoxy, phenoxy, acetylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl or aminocarbonyl,

in the case where R⁴ denotes hydrogen,

R¹¹ denotes ethoxy, phenoxy, acetylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl or aminocarbonyl,

and in the case where R⁴ denotes methyl,

R¹¹ additionally can also denote hydrogen, methyl, methoxy or nitro, R⁷ and R¹⁰ independently of one another in each case denote hydrogen, methyl or methoxy and

X^- denotes an anion.

New 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (Ia) ##STR4## in which the symbols used have the meaning given in the case of formula (I), but with the provisos that if R³ and R⁴ in each case denote hydrogen then in the case where R¹ =4-methylphenyl R² does not represent 4-nitrophenyl, 4-methoxyphenyl or phenyl and R¹ and R² do not both simultaneously represent 4-methylphenyl, 4-nitrophenyl, 4-methoxyphenyl or phenyl, have also been found.

The alkyl radicals, the nonionic substituents and the anion X^- can be of the same type as mentioned in the case of formula (I).

Preferred and particularly preferred 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (Ia) according to the invention are those in which the symbols used have the preferred and particularly preferred meaning mentioned in the case of formula (I), but in each case with the provisos that if R³ and R⁴ in each case denote hydrogen, in the case where R¹ =4-methylphenyl R² does not represent 4-nitrophenyl, 4-methoxyphenyl or phenyl and R¹ and R² do not both simultaneously represent 4-methylphenyl, 4-nitrophenyl, 4-methoxyphenyl or phenyl.

Especially preferred 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (Ia) according to the invention correspond to the formula (IIa) ##STR5## in which the symbols used have the meaning given in the case of formula (II), but with the proviso that if R³ and R⁴ in each case denote hydrogen, in the case where R⁶ =methyl R¹¹ does not represent nitro, methoxy or hydrogen and R⁶ and R¹¹ do not both simultaneously represent methyl, nitro, methoxy or hydrogen.

Preferred 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (IIa) according to the invention are those in which the symbols used have the meaning given as preferred in the case of formula (II), with the proviso that if R³ and R⁴ in each case denote hydrogen, in the case where R⁶ =methyl R¹¹ does not represent nitro, methoxy or hydrogen and R⁶ and R¹¹ do not both simultaneously represent methyl, nitro, methoxy or hydrogen.

Particularly and especially preferred 4,5-dihydro-1H-1,2,3 -triazolium compounds of the formula (IIa) according to the invention are those in which the symbols used have, without proviso, the meaning given as particularly preferred and especially preferred in the case of formula (II).

A process for the preparation of 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (I), is for example, that a diazo component of the formula (III).

R1 --NH2                                         (III),

in which

R¹ has the broadest meaning given in the case of formula (I),

to the secondary nitrogen atom of an activated coupling component of the formula (VI)

R2 --NH--CHR3 --CHR4 R13               (VI),

in which

R², R³ and R⁴ have the broadest meaning given in the case of formula (I) and

R¹³ denotes a leaving group,

and then cyclizating the triazenes formed, of the formula (VII)

R1 --N═N--N(--CHR3 --CHR4 R13)--R2(VII),

in which

R¹, R², R³, R⁴ and R¹³ have the abovementioned meaning,

to give 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (I).

The leaving group R¹³ can be, for example, methanesulphonate, chloride, bromide, benzenesulphonate, p-toluenesulphonate, trifluoroacetate, acetate or sulphate.

The activated coupling components of the formula (VI) are obtainable in a manner known per se, for example by reaction of compounds of the formula (IV)

R2 --NH--CHR3 --CHR4 --OH                   (IV),

in which

R², R³ and R⁴ have the broadest meaning given in the case of formula (I),

with an acid halide, an acid anhydride or a mineral acid, for example with methanesulphonyl chloride, benzenesulphonyl chloride, p-toluenesulphonyl chloride, trifluoroacetyl chloride, trifluoroacetic anhydride, acetic anhydride, acetyl chloride, hydrogen bromide, hydrogen chloride or sulphuric acid.

A process for the preparation of 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (Ia) is, for example, that a diazo component of the formula (IIIa)

R2 --NH2                                         (IIIa),

in which

R¹ has the broadest meaning given in the case of formula (Ia),

coupling the diazotization product to the secondary nitrogen atom of a coupling component of the formula (IVa)

R2 --NH--CHR3 --CHR4 --OH                   (IVa),

in which

R², R³ and R⁴ have the broadest meaning given in the case of formula (Ia),

and then cyclizating the triazenes formed, of the formula (V)

R1 --N═N--N(--CHR3 --CHR4 13 OH)--R2(V),

in which

R¹, R², R³ and R⁴ have the broadest meaning given in the case of formula (Ia),

intramolecularly by activation of the hydroxyl group to give 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (Ia).

The aromatic and heterocyclic diazo components of the formulae (III) and (IIIa) and aromatic and heterocyclic coupling components of the formulae (IV) and (IVa) are known, for example from Houben-Weyl, Methoden der Organischen Chemie Methods of Organic Chemistry!, Volume XI/1, pages 3 to 262 and 341 to 1025, or are obtainable analogously thereto.

The activation of the hydroxyl group can be carried out in a manner known per se, for example by reaction of the hydroxyl group with an acid halide or anhydride, for example with methanesulphonyl chloride, benzenesulphonyl chloride, p-toluenesulphonyl chloride, trifluoroacetyl chloride, trifluoroacetic anhydride, acetic anhydride or acetyl chloride.

Another process for the preparation of 4,5-dihydro-1H-1,2,3-triazolium compounds of the formula (I) is for example, that a diazo component of the formula (III), is diazotized, the diazotization product is coupled to the nitrogen atom of a coupling component of the formula (VIII)

R2 --NH2                                         (VIII),

in which

R² has the broadest meaning given in the case of formula (I), and

reacting the triazene formed, of the formula (IX)

R1 --N═N--NH--R2                             (IX),

in which

R¹ and R² have the abovementioned meaning,

with compounds of the formula (X)

R15 --CHR3 --CHR4 R14                  (X),

in which

R³ and R⁴ have the broadest meaning given in the case of formula (I),

R¹⁴ represents a leaving group to be replaced nucleophilically and

R¹⁵ represents hydroxyl or a leaving group,

and then cyclizating the products in the case where R¹⁵ =hydroxyl after prior activation, as described above.

R¹⁴ and R¹⁵, the latter where it denotes a leaving group, can be, for example, of the same nature as mentioned for R¹³.

The diazotizations mentioned can be carried out in a manner known per se, for example in accordance with Houben-Weyl, Methoden der Organischen Chemie Methods of Organic Chemistry!, Volume X/3, pages 1 to 112 and E16a, pages 1052 to 1087. For these reactions it is possible to use, for example, sodium nitrite in aqueous mineral acid, for example hydrochloric acid or sulphuric acid or nitrosylsulphuric acid in 80 to 90% strength by weight phosphoric acid or in mixtures of such phosphoric acids with acetic acid, propionic acid and/or sulphuric acid.

The couplings mentioned to give the triazenes of the formulae (V), (VII) and (IX) can likewise be carried out in a manner known per se, for example in accordance with Houben-Weyl, Methoden der Organischen Chemie Methods of Organic Chemistry!, Volume X/3, pages 695 to 723 and E16a, pages 1186 to 1220.

The diazotizations and couplings can also be carried out simultaneously by other processes known per se, for example by reacting compounds of the formulae (III) and (IIIa) and compounds of the formulae (IV) or (IVa) together in an acid medium with, for example, sodium nitrite. Suitable acid media are, for example, aqueous mineral acids or organic acids or mixtures thereof, possible aqueous mineral acids being, for example, aqueous hydrochloric acid, sulphuric acid or phosphoric acid and possible organic acids being, for example, formic acid, acetic acid or propionic acid. Carbon dioxide liquefied under pressure can also serve as the acid medium.

The compounds of the formula (I) or (Ia) formed precipitate directly out of the solutions and can be isolated, for example, by filtration. They can be obtained as solid products which can be filtered off, if water-miscible solvents are used, by dilution with water and addition of water-soluble salts, such as sodium chloride or potassium chloride, if appropriate in the presence of zinc chloride. Highly pure compounds can be obtained, for example, by purification by chromatography over silica gel.

Preferred processes for dyeing and printing with 4,5-dihydro-1H-1,2,3-triazolium compounds of the formulae (I) and (Ia) according to the present invention are processes for dyeing and printing cationically dyeable fibres, preferably polymers and copolymers of acrylonitrile and dicyanoethylene, and acid-modified fibres of polyamide and polyester, fast colour shades being obtained. These triazolium compounds can also be used for dyeing and printing tannin-treated cellulose materials, paper, silk and leather. They are furthermore suitable for the preparation of writing liquids, stamping liquids, ball-point pen pastes and ink-jet inks and can also be used in flexographic printing.

Dyeing of, for example, polymers and copolymers of acrylonitrile can be carried out, for example, from a weakly acid liquor, the goods preferably being introduced into the dyebath at 40° to 60° C. and dyeing then being carried out at the boiling point. Dyeing can also be carried out under pressure at temperatures above 100° C. Furthermore, the compounds of the formulae (I) and (Ia) can be introduced into spinning solutions for the production of dyed fibres.

Dyeings with compounds of the formulae (I) and (Ia) on materials of polyacrylonitrile are distinguished by very good fastnesses to light, wet processing and rubbing and by a high affinity for the fibre.

Compounds of the formulae (I) and (Ia) can be used individually, as mixtures with one another or as mixtures with other dyestuffs.

Finally, the present invention relates to cationically dyeable fibres, tannin-treated cellulose materials, paper, silk, leather, writing liquids, stamping liquids, ball-point pen pastes and ink-jet inks, which are characterized in that they comprise at least one 4,5-dihydro-1H-1,2,3-triazolium compound of the formula (I) or (Ia).

Those compounds of the formulae (I) and (Ia) which are preferably, particularly preferably and especially preferably prepared and used for dyeing are those which are described as such in the description of the compounds.

EXAMPLES

Example 1

2.3 g of 3,4-dimethoxyaniline were diazotized in a mixture of 22 ml of water and 3.75 ml of concentrated hydrochloric acid at 0° to 5° C. by dropwise addition of 1.1 g of sodium nitrite, dissolved in 4 ml of water. The diazonium salt solution was added dropwise to a solution of 2.29 g of the coupling component of the formula (IV) where R² =p-phenoxyphenyl and R³ ═R⁴ =hydrogen in 50 ml of methanol, 50 ml of ice/water and 9 g of sodium bicarbonate at 0° to 50° C. in the course of 15 minutes. When the addition had taken place, the mixture was subsequently stirred for 10 minutes and extracted immediately with methylene chloride. The organic phase was dried with sodium sulphate. The triazene of the formula (V) where R¹ =3,4-dimethoxyphenyl, R² =p-phenoxyphenyl and R³ ═R⁴ =hydrogen contained in the organic phase was then cyclized directly with methanesulphonic acid. For this, 1.68 g of diazabicyclononane (DABCO) were added to the organic phase and 1.16 ml of methanesulphonyl chloride, dissolved in 3 ml of methylene chloride, were slowly added dropwise at -10° C. After a reaction time of 60 minutes, the solution was concentrated. After purification by chromatography over silica gel using the mobile phase mixture of methylene chloride:methanol 4:1, 2.1 g (52%) of an orange-yellow powder were obtained. The product of the formula (II) where R³, R⁴, R⁵, R⁷, R⁸, R⁹ and R¹² =hydrogen, R⁶ =phenoxy, R¹⁰ ═R¹¹ =methoxy and X═Cl gave a λ_max of 431 nm in methanol.

FAB-MS: 376 (M⁺).

¹ H-NMR (CD₃ OD): 2.69, 3.92, 3.97, 5.03, 7.08, 7.15, 7.18, 7.22, 7.28, 7.38, 7.43 and 7.78 ppm.

Example 2

2.25 g of p-aminoacetanilide were diazotized in a mixture of 22 ml of water and 3.75 ml of concentrated hydrochloric acid at 0° to 5° C. by dropwise addition of 1.1 g of sodium nitrite, dissolved in 4 ml of water. The diazonium salt solution was added dropwise to a solution of 1.67 g of the coupling component of the formula (IV) where R² =p-methoxy and R³ ═R⁴ =hydrogen in 50 ml of methanol, 50 ml of ice/water and 9 g of sodium bicarbonate at 0° to 5° C. in the course of 15 minutes. When the addition was complete, the mixture was subsequently stirred for 10 minutes and then filtered with suction. The triazene of the formula (V) isolated, where R¹ =p-acetaminophenyl, R² =p-methoxyphenyl and R³ ═R⁴ =hydrogen, was then dissolved in acetonitrile and cyclized analogously to Example 1. The precipitate which had separated out was filtered off with suction. After purification by chromatography over silica gel using the mobile phase mixture of methylene chloride:methanol 4:1, 2.4 g (69%) of an orange powder were obtained. The product of the formula (II) where R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰ and R¹² =hydrogen, R⁶ =methoxy, R¹¹ =acetamino and X═Cl gave a λ_max of 426 nm in methanol.

FAB-MS: 311 (M⁺).

¹ H-NMR (CD₃ OD): 2.16, 2.69, 3.90, 5.01, 7.17 and 7.70 ppm.

Example 3

9 g of p-anisidine were diazotized in a mixture of 50 ml of water and 20 ml of concentrated hydrochloric acid at 0° to 5° C. by dropwise addition of 18 ml of 30% strength by weight sodium nitrite solution. This diazonium salt solution was added dropwise to a solution of 20.4 g of the hydrobromide of the activated coupling component of the formula (VI) where R² =phenyl, R³ =R⁴ =hydrogen and R¹³ =bromine in 125 ml of methanol, 125 ml of water and 46 g of sodium bicarbonate at 0° to 5° C. in the course of 30 minutes. After the mixture had been stirred overnight at room temperature, it was filtered with suction and the residue was washed with 200 ml of water. 60 ml of 2 molar aqueous zinc chloride solution were added to the yellow mother liquor and the precipitate was filtered off with suction and dried. 7.4 g (24% of theory) of powder of the formula (II) where R⁶ =methoxy, R³ to R⁵ and R⁷ to R¹² =hydrogen and X^- ═ZnCl₃ ^- were obtained. A λ_max of 407.5 nm resulted in ethanol/glacial acetic acid.

¹ H-NMR (CD₃ OD): 3.90, 5.09, 7.08, 7.52, 7.63 and 7.77 ppm.

The activated coupling component of the formula (VI) was prepared as follows:

310 ml of 48% strength by weight hydrobromic acid were added dropwise to 100 g of N-(2-hydroxyethyl)-aniline at 0° C. The mixture was then heated to the boiling point and distilled over a packed column until the temperature at which the distillate passed over had reached 125° C. At this temperature at which the distillate passed over, a total of 347 g of distillate had been distilled off. The distillate was then cooled to room temperature, diluted with 500 ml of acetone and filtered with suction. After drying, 103 g (50% of theory) of the hydrobromide of the activated coupling component of the formula (VI) wherein the radicals had the meaning mentioned above for the active coupling component were obtained as colourless crystals of melting point 135° to 137° C.

Example 4

The procedure was as in Example 3, but 17.9 g of the activated coupling component of the formula (VI) where R² =4-methoxyphenyl, R³ ═R⁴ =hydrogen and R¹³ =═O--SO₂ --OH were employed. 13.2 g (40% of theory) of yellow powder of the formula (II) where R⁶ ═R¹¹ =methoxy, R³ to R⁵, R⁷ to R¹⁰ and R¹² =hydrogen and X^- ═ZnCl₃ ^- were obtained. A λ_max of 423 nm resulted in methanol.

FAB-MS: 284 (M⁺).

¹ H-NMR (CD₃ OD): 2.69, 3.90, 4.99, 7.17 and 7.72 ppm.

The activated coupling component of the formula (VI) was prepared as follows:

4.5 g of N-(2-hydroxyethyl)-4-methoxyaniline were introduced into 8ml of concentrated sulphuric acid at 0° C. for 24 hours and then discharged onto 150 g of ice. The solution was brought to pH=4.5 with 8 ml of 45% strength by weight aqueous sodium hydroxide solution. After the mixture had been stirred overnight, it was filtered with suction. 4.4 g (66% of theory) of the activated coupling component of the formula (VI) wherein the radicals had the meaning given above for the active coupling component were obtained as colourless crystals. The mass of 247 is found in the mass spectrum (FAB).

Example 5

61.6 g of p-anisidine were initially introduced into 170 g of ice and 250 ml of water, and 76.5 g of concentrated hydrochloric acid were added. A solution of 17.4 g of sodium nitrite in 42 ml of water was added dropwise at 0° to 5° C. in the course of 15 minutes. A further solution of 70.5 g of sodium acetate in 135 ml of water was added dropwise in the course of 10 minutes. After the mixture had been stirred at room temperature for 2 hours, it was filtered with suction and the residue was washed with ice-water. After drying, 50.4 g (78%) of yellow powder of the triazene of the formula (IX) where R¹ ═R² =p-methoxyphenyl remained.

2.6 g of triazene of the formula (IX) where R¹ ═R² =p-methoxyphenyl were heated under reflux in 25 ml of tert-butanol with 2.3 g of potassium tert-butylate for 15 minutes. After dropwise addition of 1.6 g of chloroethanol, the mixture was heated for a further two hours. After cooling to 10° C., 3.5 g of benzenesulphonyl chloride and 2.8 ml of triethylamine were added dropwise in succession and the mixture was stirred at room temperature for 2 hours. After filtration with suction and drying, 2.8 g (63%) of yellow-orange powder of the formula (II) where R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰ and R¹² =hydrogen, R⁶ ═R¹¹ =methoxy and X=benzenesulphonate were obtained from the orange-coloured suspension.

The analytical data correspond to those given in Example 4.

Examples 6 to 97

The procedure was analogous to Examples 1 to 5 and produced the following dyestuffs of the formula (I) wherein R³ and R⁴, unless stated otherwise, denote hydrogen and X^-, unless stated otherwise, denotes chloride.

__________________________________________________________________________Ex- Analogously                  FAB-ample    to Example                λmax                            MSNo. No.   R1    R2  (nm)                            (M+)__________________________________________________________________________ 6  1     4-Nitrophenyl                4-Chlorophenyl                         397                            304 7  1     4-Methoxyphenyl                4-Cyanophenyl                         420                            279 8  1     3,4-Dichlorophenyl                4-Phenoxyphenyl                         410                            385 9  1     3,5-Dimethoxyphenyl                3,4-Dichlorophenyl                         395                            35310  1     4-Phenoxyphenyl                4-Chlorophenyl                         409                            35111  1     4-Phenoxyphenyl                4-Tolyl  408                            33112  1     4-Methoxyphenyl                4-Chlorophenyl                         415                            28813  1     4-Phenoxyphenyl                4-Chlorophenyl                         409                            35114  1     4-Nitrophenyl                4-Methoxyphenyl                         426                            29915  1     4-Nitrophenyl                4-Phenoxyphenyl                         418                            36116  1     2,4-Dimethoxyphenyl                4-Cyanophenyl                         415                            30917  1     4-Cyanophenyl                4-Tolyl  397                            26318  1     4-Phenoxyphenyl                4-Cyanophenyl                         412                            34119  1     2,4-Dimethoxyphenyl                3,4-Dichlorophenyl                         409                            35320  1     3,4-Dichlorophenyl                4-Methoxyphenyl                         416                            32321  1     2,4-Dichlorophenyl                4-Tolyl  397                            30722  1     2,4-Dimethoxyphenyl                2-Methyl-4-                         403                            343                nitrophenyl23  1     2-Methyl-4-nitrophenyl                4-Methoxyphenyl                         409                            31324  1     2-Methyl-4-nitrophenyl                4-Tolyl  388                            29725  1     2-(5-Diisopropylamino-                4-Methoxyphenyl                         474                            364     1,3,4-thiadiazolyl)26  1     as for Example 25                4-Tolyl  467                            34827  1     as for Example 25                2,4-Dimethoxy-                         462                            390                phenyl28  1     as for Example 25                4-Phenoxyphenyl                         474                            42429  1     2,4,6-Trimethylphenyl                (5-Diisopropyl-                         432                            374                amino-1,3,4-                thiadiazol)-2-yl30  1     2,4-Dimethoxyphenyl                4-Methoxyphenyl                         406                            31431  1     4-Methoxyphenyl                4-Methoxyphenyl                         424                            28432  1     2,4-Dimethoxyphenyl                4-Nitrophenyl                         422                            32933  1     2,4-Dimethoxyphenyl                4-Chlorophenyl                         403                            31934  1     R1 and R2 as for Example                R3 = Methyl                         406                            333     3335  1     3,4-Dichlorophenyl                4-Phenoxyphenyl                         410                            38536  1     R1 = 3,4-Dichlorophenyl                R2 = 4-Tolyl, R3 =                         391                            321                Methyl37  1     1- 4-(4'-Chlorophenyl)-                4-Phenoxyphenyl                         415                            493     naphthyl!38  1     as for Example 37                4-Tolyl  394                            41539  1     1-(4-Nitronaphthyl)                2,4-Dimethoxy-                         405                            379                phenyl40  1     2-Methoxyphenyl                4-Methoxyphenyl                         398                            28441  1     3-Methoxyphenyl                4-Methoxyphenyl                         413                            28442  1     3,4-Dimethoxyphenyl                4-Methoxyphenyl                         433                            31443  1     2-Methyl-4-methoxy-                4-Methoxyphenyl                         398                            334     phenyl44  1     3-Methoxy-4-methyl-                4-Methoxyphenyl                         420                            334     phenyl45  1     3,5-Dimethoxyphenyl                4-Methoxyphenyl                         412                            31446  1     4-Phenoxyphenyl                4-Methoxyphenyl                         420                            34647  1     3-Tolyl    4-Methoxyphenyl                         407                            26848  1     3,4-Dimethoxyphenyl                4-Phenoxyphenyl                         431                            37649  1     3-Methoxy-4-methyl-                4-Phenoxyphenyl                         421                            360     phenyl50  1     3-Methoxy-4-methyl-                3,4-Dimethoxy-                         412                            328     phenyl     phenyl51  1     3,4-Dimethoxyphenyl                4-Tolyl  424                            33452  1     3-Methoxy-4-methyl-                4-Tolyl  408                            318     phenyl53  1     4-Methoxyphenyl                4-Tolyl  412                            26854  1     4-Tolyl    4-Tolyl  398                            25255  1     3,4-Dimethylphenyl                4-Tolyl  389                            26656  1     4-Ethoxycarbonylphenyl                4-Tolyl  398                            31057  2     4-Acetamidophenyl                4-Tolyl  415                            25558  2     4-Acetamidophenyl                4-Methoxyphenyl                         426                            31159  1     4-Ethoxycarbonylphenyl                4-Methoxyphenyl                         415                            32660  1     2,4-Dimethylphenyl                4-Methoxyphenyl                         399                            28261  2     3,4-Dimethoxyphenyl                4-Acetamidophenyl                         436                            30662  2     4-Phenoxyphenyl                4-Acetamidophenyl                         420                            37363  2     2-Methoxyphenyl                4-Acetamidophenyl                         415                            31164  2     2,4-Dimethylphenyl                4-Acetamidophenyl                         395                            30965  2     3,5-Dimethoxyphenyl                4-Acetamidophenyl                         415                            34166  2     4-Acetamidophenyl                4-Acetamidophenyl                         432                            33867  1     4-Phenoxyphenyl                4-Phenoxyphenyl                         417                            40868  1     4-Ethoxycarbonylphenyl                4-Phenoxyphenyl                         410                            38869  2     4-Phenoxyphenyl                4-Acetamidophenyl                         423                            373 70*    1     4-Phenoxyphenyl                4-Phenoxyphenyl                         416                            40871  2     3-Methoxy-4-acetamido-                4-Phenoxyphenyl                         433                            403     phenyl72  2     3,4-Diacetamidophenyl                4-Phenoxyphenyl                         419                            43073  2     2,5-Dimethyl-4-                4-Phenoxyphenyl                         394                            401     acetamidophenyl74  2     2,4-Dimethoxyphenyl                3,4-Diacetamido-                         410                            398                phenyl75  2     2,4-Diacetamidophenyl                4-Acetamidophenyl                         408                            36876  1     R1 = 3,4-Dimethoxyphenyl, R2 = 4-Phenoxy-                         422                            390     phenyl, R3 = Methyl77  1     R1 = 3,4-Dimethoxyphenyl, R2 = 4-Methoxy-                         425                            328     phenyl, R3 = Methyl78  1     R1 = R2 = 4-Methoxyphenyl, R3 = Methyl                         414                            28979  1     4-Methoxyphenyl                4-Methoxyphenyl                         423                            28480  1     4-Ethoxyphenyl                4-Ethoxyphenyl                         425                            34881  1     4-Ethoxyphenyl                4-Methoxyphenyl                         423                            33482  5     4-Nitrophenyl                4-Nitrophenyl                         395                            31483  1     4-Nitrophenyl                4-Tolyl  404                            28384  1     4-Nitrophenyl                4-Dimethylamino                         529                            31285  2     3,4-Diacetamidophenyl                4-Methoxyphenyl                         425                            36886  2     2,5-Dimethyl-4-acet-                4-Methoxyphenyl                         399                            339     amidophenyl87  2     2-Methoxy-5-acetamido-                4-Methoxyphenyl                         406                            341     phenyl88  2     3-Methoxy-4-acetamido-                4-Methoxyphenyl                         434                            341     phenyl89  2     2-Methyl-4-acetamido-                4-Methoxyphenyl                         402                            325     phenyl90  2     2-Methyl-4-acetamido-                4-Phenoxyphenyl                         400                            387     phenyl91  2     3-Methoxy-4-acetamido-                3-Methoxy-4-                         419                            371     phenyl     phenoxyphenyl92  2     3-Methoxy-4-acetamido-                4-Acetamidophenyl                         419                            368     phenyl93  2     3,4-Diacetamidophenyl                4-Acetamidophenyl                         427                            39594  2     2,5-Dimethyl-4-                4-Acetamidophenyl                         419                            366     acetamidophenyl95  1     R1 = 3,4-Dimethoxyphenyl, R2 = 4-Methoxy-                         425                            328     phenyl, R3 = Methyl96  5     Phenyl     Phenyl   385                            22497  5     Phenyl     4-Methoxyphenyl                         400                            254__________________________________________________________________________ *in Example 70, X- was a tosylate anion.

Example 98

Dyeing process for polyacrylonitrile

0.1 g of the dyestuff obtained according to Example 2 was made into a paste with 2 ml of water with the addition of a little acetic acid and dissolved with 50 ml of hot water. 1.2 g of a condensation product of naphthalenesulphonic acid and formaldehyde were then added and the mixture was topped up to 500 ml with cold water.

The pH of this dye liquor was brought to pH=4.5 to 5 with acetic acid and sodium acetate. 10 g of polyacrylonitrile fibres (piece goods) were agitated constantly in this dye liquor, while the temperature was increased to 100° C. in the course of 30 minutes. Dyeing was carried out at the boiling point for 60 minutes and the material was then rinsed with cold water and dried at 60° to 70° C. The material was dyed an intensive reddish-tinged yellow.

Example 99

Dyeing process for paper containing mechanical wood pulp

Dry pulp comprising 60% mechanical wood pulp and 40% non-bleached sulphite cellulose was beaten in a beater and refined to a degree of freeness of 40° SR with water in an amount such that the dry content was somewhat above 2.5%. A dry content of the thick pulp of exactly 2.5% was then established with water. 5 g of a 0.5% strength by weight aqueous solution of the dyestuff obtained according to Example 4 were added to 200 g of this thick pulp, the mixture was stirred for 5 minutes, 2% of resin size and 4% of alum, based on the dry pulp, were added and the mixture was again stirred homogeneously for a few minutes. The pulp was then diluted to 700 ml with water and sheets of paper were produced from this in a manner known per se by filtration with suction over a sheet former. The sheets showed an intensive yellow dyeing.

Example 100

Results analogous to those in Examples 98 and 99 were obtained using dyestuffs according to Examples 1, 3 and 5 to 97.