DE3136259A1 - Methine dyes - Google Patents

Abstract

The invention relates to compounds of the general formula I <IMAGE> where the A radicals are identical or different aryl or hetaryl radicals, A<(-)> is an anion, B is a bridge member, B<1> is an alkylene radical, R is hydrogen, alkyl, aralkyl or acyl, and T is the radical of a quaternised heterocycle. The compounds of the invention are very highly suitable for dyeing/colouring paper stock.

Description

Methine dyes

The invention relates to compounds of the general formula I. in which A is identical or different aryl or hetaryl radicals, an anion, B is a bridge member, B1 is an alkylene radical, R is hydrogen, alkyl, aralkyl or acyl and T is the radical of a quaternized heterocycle.

A radicals are, for example, optionally replaced by fluorine, chlorine, bromine, Cyano, nitro, hydroxy, alkoxycarbonyl, optionally N-substituted carbamoyl, Alkyl, alkoxy, amino or substituted amino, substituted phenyl, optionally naphthyl substituted by alkyl, alkoxy, hydroxy, carboxy or substituted amino, Styryl, furyl, thienyl, pyridyl, indol.yl, benzofuryl, benzothienyl, pyrazolyl, Oxazolyl, thiazolyl, triazolyl, oxdiazolyl, thiadiazolyl, benzimidazolyl, indazolyl, Benzoxazolyl, benzthiazolyl, carbazolyl, phenthiazinyl or phenoxazinyl.

Individual residues A are, for example: chlorophenyl, bromophenyl, cyanophenyl, nitrophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, hydroxyphenyl, aminocarbonylphenyl, dimethylaminocarbonylphenyl, diethylaminocarbonylphenyl, methylphenyl, athylphenyl, cyclohexhenylamine, methylphenyl, cyclohexophenyl, ethylphenyl, cyclohexophenyl, ethylphenyl, cyclohexophenyl, methylphenyl, ethylphenyl, cyclohexylphenyl, methylphenyl, ethylphenyl, butophenylphenyl, methylphenyl, butophenylphenyl, butophenylphenyl, phenoxyphenyl, butophenylphenyl, butophenylphenyl, methylphenylphenyl, butophenylphenyl, butophenylphenyl. butylaminophenyl, phenylaminophenyl, cyanäthylaminophenyl, dimethylaminophenyl, Dimethylaminochlorphenyl, dimethylaminomethylphenyl, Dimethylaminomethoxyphenyl, Dimethylaminonitrophenyl, Dimethylaminocarbomethoxyphenyl, diethylaminophenyl, Äthoxydiäthylaminophenyl, dipropylaminophenyl, di-n-butylaminophenyl, dibenzylaminophenyl, di-ß-cyanäthylaminophenyl, di-ß-methoxyäthylaminophenyl, N-methyl-N- ethylaminophenyl, N-butyl-N-methylaminophenyl, N-methyl-N-benzylaminophenyl, N-ethyl-N-methoxybenzylaminophenyl, N-cyclohexyl-N-benzylaminophenyl, N-ß-cyanoethyl-N-benzylaminophenyl, N-ß-eth oxyethyl-N-benzylaminophenyl, N-j3-methoxycarbonylethyl-N-benzylaminophenyl, di-benzylaminochlorophenyl, dibenzylaminomethoxyphenyl, dibenzylaminomethylphenyl, N-methyl-N-ß-cyanoethylaminophenyl, N-ethyl-N-flaminophenyl-ND cyanoethylaminophenyl, N-butyl-ND-cyanoethylaminophenyl, N-methyl-N-ß-methoxycarbonyl-ethylaminophenyl, N-methyl-N-ß-ethoxycarbonyl-ethylaminophenyl, N-methyl-N-ß-carbamoyl-ethylaminophenyl, N-methyl-N-carbyl-ethyl-dimethyl Ethyl-N-ß-methoxycarbonyläthylaminophenyl, N-Äathyl-N-ß-ethoxycarbonyläthylaminophenyl, N-Äathyl-N-ß-carbamoyläthylaminophenyl, Piperidinophenyl, Pyrrolidinophenyl, Morpholinophenyl, N-Äathyl-N-Benzophenyl-phenyl, Niper-benzino-phenyl, piperino-phenyl, piperino-phenyl-benzino-phenyl, Niperino-phenyl, N-benzophenyl-phenyl, N-benzophenyl-phenyl, N-benzino-phenyl-phenyl-benzino-phenyl, N-ß-ß-ethoxycarbonyl-ethylaminophenyl, Methyl-N-phenylaminophenyl, N-cyanoethyl-N-phenylaminophenyl, diphenylaminophenyl, N-methyl-N-4-ethoxyphenylaminophenyl, N-methyl-N-4-methoxyphenylaminophenyl, N-methyl-N-4-methylphenylaminophenyl, N-ß- Methyl-N-2-methylphenylaminophenyl, N-methyl lN-cyanmethylaminophenyl, N-ethyl-N-cyanmethylaminophenyl, N-benzyl-N-cyanmethylaminophenyl, N-5-cyanoethyl-N-cyanmethylaminophenyl, N-methyl-Np-acetoxyethylaminophenyl, N-ethyl-N-ß-acetyloxyethyl Benzyl-Np-propoxyethylaminophenyl, N-Nthyl-ND-oxäthylaminophenyl, N-methyl-NB-oxäthylaminophenyl, dimethylaminohydroxyphenyl, diethylaminohydroxyphenyl, dibenzylaminohydroxyphenyl, dimethylaminoacetylaminophenyl, N-ethylaminoacetylaminophenyl, ethylaminoacetylaminophenyl, diethylaminophenyl, N-ethylaminophenyl, N-ethylaminophenyl, N-ethylaminophenyl, N-ethylaminophenyl, N-methyl-ethylaminophenyl, N-methyl-NB-oxäthylaminophenyl, N-methyl-NB-oxäthylaminophenyl, N-methyl-NB-oxäthylaminophenyl, N-methyl-Nb-oxäthylaminophenyl, N-methyl-Nb-oxäthylaminophenyl, N-methyl-Nb-oxäthylaminophenyl, N-methyl-Nb-oxäthylaminophenyl, dimethylaminoethylaminophenyl, N-benzyl-N-ß-dimethylaminoethylaminophenyl, N-ß-cyanoethyl-n-ß-dimethylaminoethylaminophenyl, N-ß-methoxycarbonylethyl-N-ß-dimethylaminoethylaminophenyl, N-ß-N-oxoethylaminophenyl, N-ß-N-oxoethylaminophenyl, N-ß-N-oxoethylaminophenyl, N-ß-N-oxoethylaminophenyl, N-ß-N-oxyethylaminophenyl ß-methoxyethyl-N-dimethylaminoethylaminophenyl, N-ethyl-ND-diethylaminoethylaminophenyl, N-ethyl-N-ß-dibenzylaminoethylaminophenyl, N-ethyl-N-ß-piperidinöthylaminophenyl, N-benzaminophenyl- -N-ß-trimethylammoniumethylaminophen ylchloride, N-methyl-N-ß-trimethylammoniumethylaminophenylchloride, N-methyl-N-ß-diethylbenzylammoniumethylaminophenylchloride, N-benzyl-N-ß-dimethylbenzylammoniumethylaminophenylchloride, N-ethyl-N-ß-pyramidylaminonylaminonylaminylaminylamino, tolaphylthylthylthylaminophenylchloride, dimaphthylaminoethylchloride, tolaphylthylaminophylchloride, tolaphthylthylaminylchloride, dimaphthylaminophylchloride, N-methyl-N-ß-diethylbenzylthylaminophenylchloride. Ethoxyphenylmethylaminonaphthyl, hydroxynaphthyl, hydroxymethoxycarbonylnaphthyl, methoxycarbonylmethoxynaphthyl, As bridge members B are z. B. to name the following residues: where R1 is hydrogen, optionally substituted C1- to C21-alkyl, cycloalkyl or aralkyl, optionally substituted by oxygen or sulfur, R2 optionally substituted alkyl, aralkyl or phenyl, X1 optionally by -COO-, Oxygen or sulfur-interrupted alkylene or diarylene alkylene and x2 optionally through or oxygen are interrupted alkylene or diarylene alkylene.

Individual residues X2 are in addition to the z. E.g .: - (CH2) 2-, - (CH2) 3-, - (CH2) 4-, - (CH2) 6-, - (CH2) 3-O- (CH2) 2-O- (CH2) 3-, - (CH2) 3O (CH2) 4O (CH2) 3-, - (CH2) 3O (CH2) 2O (CH2) 2O (CH2) 3-, - (CH2) 3 [O (CH2) 4] 9O (CH2) 3-, - (Ch2) 2 -NH- (CH2) 2 -, - (CH2) 2NH- (CH2) 3-, - (CH2) 3-Nh- (CH2) 3-, - (CH2) 3-NH- (CH2) 2-NH (CH2) 3 Individual residues X1 are in addition to the z. B .; -CH2-CH2-, - (CH2) 4-, - (CH2) 5-, - (CH2) 2-O- (CH2) 2-, (CH2) 2-S- (CH2) 2-, - (CH2) 6-, - (CH2) 2O (CH2) 2O (CH2) 2-, - (CH2) 10-, -CH2-CH-CH-CH2-, -CH2-C = C-CH2-, For R2, for example, the following are to be mentioned in detail: CH3-, C2H5-, C3H7-, C4H9-, HO-Ch2-Ch2-, Individual radicals R1 are, for example: CH3-, C2H5-, C3H7-, (CH3) 2Ch-, $ C4H9-, (C2H5) - (CH3) CH-, (CH3) 2CH-CH2-, (CH3) 3C-, C5H11 -, (CH3) 2CH- (CH2) 2-, (CH3) 2CHCH-, CH3 CH3- (CH2) 5-, CH3 (CH2) 6-CH2-, C12H25CH2-, H3CO- (CH2) 2-, H5C2O- (CH2) 2-, H3CO- (CH2) 3-, H5C2O- (CH2) 3-, C13H27O (CH2) 3-, C18H37O (CH2) 3-, HO- (CH2) 2-, HO- (CH2) 2-O- (CH2) 2-, HO- (CH2) 2-NH- (CH2) 2-, HO- (CH2) 3-, (H3C) 2N- (CH2) 2-, (C2H5) 2N- (CH2) 2-, [(CH3) 2CH] 2N- (CH2) 2-, (C4H9) 2N- (CH2) 2-, (CH3) 2N (CH2) 3-, (C2H5) 2N (CH2) 3-, (C2H5) 2N (CH2) 4-, HOOC-CH2-, HO3S-CH2-, HSO2SO-CH2CH2-, Anions AO are e.g. B. organic or inorganic nature, in detail are, for. B. named: fluoride, chloride, bromide, iodide, perchlorate, hydrogen sulfate, sulfate, bisulfate, aminosulfate, nitrate, dihydrogen phosphate, hydrogen phosphate, phosphate, hydrogen carbonate, carbonate, ethosulfate, ethosulfate, cyanate, thiocyanate, tetrachlorozincate, borate, tetrafluorine Chloroacetate, cyanoacetate, hydroxyacetate, aminoacetate, methylaminoacetate, di- and trichloroacetate, 2-chloropropionate, 2-hydroxypropionate, glycolate, thioglycolate, thioacetate, phenoxyacetate, trimethylacetate, valerate, palmitate, acrylate, oxalate, citrone, malonate, crotonate , Ethylene bisiminoacetate, nitrilotriacetate, fumarate, maleate, benzoate, methyl benzoate, chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate, phthalate, terephthalate, indolylacetate, chlorobenzenesulfonate, benzenesulfonate, toluenesulfonate, biphenylsulfonate, and chlorobenzene sulfonate.

Alkylene radicals B1 are -CH2CH2 and preferably -CH for R are beside to name the preferred hydrogen in detail for example: CH3, C2H5, CH2C6H5, - CHO, CH3CO, C2H5CO, C6H5CO, COOCH3, COOC2H5, CH3NHCO, C2H5NHCO, C3 H7NHCO, C6H5NHCO, CH3NHCS, C2H5NHCS, C3H7NHCS, C6H5NHCS, CH2 -CH2-OH.

Residues T are e.g. B .: where R³ is hydrogen, methyl, ethyl, benzyl or phenyl and Y is hydrogen, chlorine, bromine, methyl, methoxy, ethoxy or nitro.

To prepare the compounds of the formula I, compounds of the formula II can be used with aldehydes of the formula III A-CHO III or derivatives thereof, e.g. B. Immonium salts, condense.

Compounds of the formula II are obtained, for. B. by reacting compounds of the formula T-CH3 with compounds of the formula where Hal is chlorine or bromine and Tos is tolylsulfonyl.

Details of the reactions can be found in the examples, which contain information about parts and percentages, unless otherwise stated refer to the weight.

The compounds of the formula I are particularly suitable for dyeing from paper stock, but also from anionically modified fibers, on paper yellow to bluish red dyeings with customary fastness properties. The new ones doubled Dyes are characterized by a high affinity for wood-containing and bleached ones Fabrics, d. H. most of the dye is absorbed onto the paper. the new compounds are therefore particularly environmentally friendly and economical in their Use.

Compounds of the formula I a are of particular importance in A1, N, N-disubstituted aminophenyl, indolyl or carbazolyl optionally substituted by chlorine, hydroxyl, methoxy, thoxy, methyl or ethyl, T1 is a radical of the formula R4 are hydrogen, formyl, acetyl or propionyl and B has the meaning given. Preferred radicals B are e.g. B .: EXAMPLE 1 18.2 parts of n-butylamine are slowly added dropwise with cooling to a mixture of 46.2 parts of epichlorohydrin and 3.7 parts of water so that a temperature of 30.degree.-35.degree. C. is not exceeded. After the addition has ended, the mixture is stirred for 5 hours at 30 ° C., then warmed to 95 ° C. and 42 parts of γ-picoline are added dropwise in such a way that the temperature does not exceed 110 ° C. and the mixture is stirred for a further 3 hours at the same temperature. Further quaternary compounds can be produced in a similar manner.

It is diluted with 150 parts of glycol, treated with 74 parts of p-dimethylaminobenzaldehyde and 2 parts of pyrrolidine and then boiled for 5 hours at 130.degree. After cooling, an approximately 50% solution of the dye of the following structure is obtained: which colors wood-containing and wood-free fabrics in brilliant orange tones with low wastewater pollution.

In the same way as the process described above, other dyes can be produced, the structures of which and their color tone in the case of paper coloring are shown in the table below. Example BR B1 TAA # Farhton No. C2H5 2 CH3- (CH2) 3-NB CH2 -N- # # -N- Cl # brilliant red C2H5 C2H5 3 """"# -N- "orange C2H4-Cl C2H5 4 """"# -N- CH3 "" C2H4-N- CH3 5 """"# -N - # - O "" CH3 6 -N - # - N- """#-N-" brilliant orange CH3 C2H5 7 """"# -N- "brilliant red C2H5 C2H5 8 """"# -N- "orange C2H4-Cl Example BR B1 TAA # Farhton No. CH3 9 -N - # - N- H CH2 -N - # - # -N- Cl # orange CH2- # C2H5 10 """"# -N- "" CH2- # CH2- # 11 """"# -N- "" CH2- # 12 """"# -N- # O "brilliant orange CH3 13 # -N- """#-N-" brilliant red CH3 C2H5 14 """"# -N- "" C2H5 C2H5 15 H3CO-CH2-CH2-N """#-N-" red C2H5

Example 17 In a mixture of 78 parts of 3-chloro-1,2-dihydroxypropane and 1.8 parts of conc. H2SO4 are added dropwise at 95-100 ° C within 2 1/2 hours 64.8 parts of epichlorohydrin. The mixture is stirred for 3 hours at 95-100 ° C., the acid is destroyed by adding sodium carbonate and 150.2 parts of t-picoline are added; then it is held at 110 ° C. for 1 hour, any excess t-picoline is drawn off under vacuum, 100 parts of glycol and 210 parts of p-dimethylaminobenzaldehyde and 10 parts of pyrrolidine are added and the mixture is heated at 110 ° C. for 4 hours. This gives a solution of a dye of the following structure, which colors wood-containing and wood-free paper pulp in brilliant red tones with little or moderate wastewater contamination.

Example 18 If, instead of p-dimethylaminobenzaldehyde, N-methyl, N-benzyl-p-aminobenzaldehyde is used, a solution of a dye of the following structure is obtained: which has similar application properties as that described in Example 12.

Example 19 To a mixture of 41.7 parts of Epicote 828 Zu (German Shell Chemie Gesellschaft m.b.H.) and 23 parts * -Picolin are added to 11.5 parts of formic acid and heated to 47 OC.

The reaction takes place isothermally without further heating and is after finished about 1 hour. The mixture is stirred for 4 hours, the excess picolin is drawn off under vacuum, sets 37 parts of p-dimethylaminobenzaldehyde, 60 parts of glycol as well 2 parts of pyrrolidine are added and the mixture is stirred at 130.degree. C. for 5 hours.

This gives the solution of a dye of the following structure: which colors wood-containing and wood-free paper pulp in brilliant red tones with low or moderate wastewater pollution. The following dyes are obtained in an analogous manner, Example BR B1 TAA # Farhton No. CH3 CH3 20 -O - # - C - # - O- H CH2 # N- # -N- HCOO # red CH3 CH2- # CH3 21 -O- (CH2) 4-O- """#-N-" brilliant red CH3 C2H5 22 """"# -N- "orange CH2- # C2H5 23 """"# -N- CH3 "brilliant orange C2H4-N- CH3 C2H5 24 """"# -N- CH3 "" C2H4-N-CH3 CH3 C2H5 25 """"# -N- CH3 "" C2H4-N-CH3 # -CH2 Cl

Claims (2)

Claims 1. Compounds of the general formula I in which A is identical or different aryl or hetaryl radicals, A e is an anion, B is a bridge member, B1 is an alkylene radical, R is hydrogen, alkyl, aralkyl or acyl and T is the radical of a quaternized heterocycle. 2. Use of the dyestuffs according to Claim 1 for coloring paper stocks.