DE3103110A1 - Triazinyl-containing compounds - Google Patents

Abstract

The invention concerns the compounds of the general formula I <IMAGE> where A is an optionally substituted alkylene radical, R<1> is hydrogen or optionally substituted alkyl, R<2> is hydrogen or optionally substituted alkyl, R<3> is hydrogen, methyl, ethyl, methoxy, acetylamino, chlorine or hydroxyl, R<4> is hydrogen, methyl, alkoxy or dialkylamino, X is for p = 1 fluorine, chlorine or bromine, optionally substituted alkoxy, alkylmercapto, amino or a radical of the general formulae <IMAGE> and for p = 2 a radical of the formula <IMAGE> Y is chlorine, optionally substituted amino, phenyl or a radical of the formula <IMAGE> where R<5> is hydrogen, optionally substituted alkyl or optionally substituted phenyl, R<6> is hydrogen, optionally substituted alkyl or optionally substituted phenyl, r is 0, 1 or a number > 1 W is <IMAGE> T is hydrogen, formyl or the complement to a cationic dye and the radicals A, R<1>, R<2>, R<3>, R<4>, T and Y, which can be present more than once, are mutually independent. The compounds of the invention are suitable in particular for dyeing paper stock.

Description

The invention relates to compounds of the general formula I.

I.

in the

A is an optionally substituted alkylene radical,

R [high] 1 hydrogen or optionally substituted alkyl,

R [high] 2 hydrogen or optionally substituted alkyl,

R [high] 3 hydrogen, methyl, ethyl, methoxy, acetylamino, chlorine or hydroxi,

R [high] 4 hydrogen, methyl, alkoxy, dialkylamino,

X for p = 1 fluorine, chlorine, bromine, optionally substituted alkoxy, alkyl mercapto, amino or a radical of the general formulas

or

and for p = 2 a radical of the formula

Y chlorine, optionally substituted amino, phenyl or a radical of the formula mean, where

R [high] 5 hydrogen, optionally substituted alkyl or optionally substituted phenyl,

R [high] 6 hydrogen, optionally substituted alkyl or optionally substituted phenyl,

r 0.1 or a number greater than 1,

w

T are hydrogen, formyl or the addition to a cationic dye and where the radicals A, R [high] 1, R [high] 2, R [high] 3, R [high] 4, T and Y are present several times can, are independent of each other.

Residues A are for example (CH [deep] 2) [deep] 2, (CH [deep] 2) [deep] 3, or (CH [deep] 2) [deep] 4.

B radicals preferably correspond to the general formulas

- (alkylene-W) [deep] r-alkylene-,

- (phenylene-W) [deep] r-alkylene- or

- (phenylene-W) [deep] r-phenylene-, in which r and W have the meaning given.

Optionally substituted alkyl radicals R [high] 1 are, for example, CH [low] 3, C [low] 2H [low] 5, -

Residues R [high] 2 are e.g. CH [low] 3, C [low] 2H [low] 5,

nC [low] 4H [low] 9 or

Optionally substituted alkoxy, alkyl mercapto or substituted amino radicals for X generally have 1 to 26 carbon atoms; in detail, for example, for p = 1:

OCH [deep] 3, OC [deep] 2H [deep] 5, OC [deep] 4H [deep] 9, SCH [deep] 3, SC [deep] 2H [deep] 5, SC [deep] 3H [deep] 7, -S-CH [deep] 2-CH [deep] 2-OH, -NH [deep] 2, -NHCH [deep] 3, NH-Et, NH-C [deep] 3H [deep] 7, N (CH [deep] 3) [deep] 2, N (Et) [deep] 2, N (nC [deep] 3H [deep] 7) [deep] 2, N (n-Bu) [deep] 2, N (C [deep] 13H [deep] 27) [deep] 2,

-CH [deep] 2-CH [deep] 2-OH, NH-CH [deep] 2-CH [deep] 2-NH [deep] 2, NH-

N [CH (CH [deep] 3) [deep] 2] [deep] 2, N (iC [deep] 4H [deep] 9) [deep] 2, N (C [deep] 6H [deep] 13) [ deep] 2, N (CH [deep] 2-CH [deep] 2-NH [deep] 2) [deep] 2,

For example, the following radicals are possible for p = 2:

-NH- (CH [deep] 2) [deep] 3-O- (CH [deep] 2) [deep] 2-O- (CH [deep] 2) [deep] 3-NH,

or

For Y, the same substituted amino radicals as for X come into consideration.

Residues T are in addition to hydrogen and formyl z. E.g. those of the formulas -N = NK [high] plus in a circle, -CH = K [high] 1 plus in a circle or where K [high] plus in a circle is a remainder of the pyrazole, thiazole, triazole, benzthiazole or indazole series,

K [high] 1 plus in the circle a remainder of the pyridine, indolenine, quinoline, benzoquinoline, cyanoacetic ester, pyrrolidinobenzimidazole, dihydropyrimodone, benzthiazole, benzimidazole or 2-methylquinoxalone series,

Ar optionally substituted phenylene and B [high] 1 and B [high] 2 denote hydrogen or optionally substituted alkyl.

Individual remainders K [high] plus in a circle are e.g.

For K [high] 1 plus in the circle, for example, the following are to be mentioned in detail: n

Remnants of the formula contain for example as:

B [high] 1: CH [low] 3, Et, CH [low] 2- or CH [deep] 2-Clow2-CN

B [high] 2: H, CH [low] 3 or Et

Ar:

Examples of anions for the compounds of the formula I are: chloride, bromide, tetrachlorozincate, phosphate, hydrogen phosphate, acetate, propionate, succinate, hydroxiacetate, chloroacetate, dichloroacetate, tartrate, benzenesulfonate, toluenesulfonate, lactate, sulfate, carbonate, hydrogen sulfate, hydrogen carbonate or methyl sulfate.

To prepare the compounds of the formula I with T = H, cyanuric halides or phenylcyanuric halides can be used with compounds of the formula

React in a molar ratio of 1: 1 or 1: 2 and, if appropriate, introduce other substituents X and / or Y by methods known per se.

The compounds with T = CHO are obtained from the products obtained by formylation, and those with T = N = N-K [high] plus in a circle by azo coupling and subsequent quaternization.

Compounds with T = CH = K [high] 1 plus in the circle are accessible through condensation of the formyl compounds with methylene-active compounds HK [high] 1 or H [low] 2K [high] 1 plus in the circle and the compounds with is obtained from the compounds with T = H z. B. by reaction with 4,4'-diaminoarylmethane bases, for example by the method of catalytic oxidation described in US Pat. No. 3,828,071.

Details of the preparation can be found in the examples, in which data on parts and percentages relate to weight, unless otherwise stated.

Of particular industrial importance are compounds of the formula I in which T is a radical of the benzothiazolazo series or a radical of the formula means.

Further are preferred for

A: (CH [deep] 2 ([deep] 3

R [high] 1: H

R [high] 2: H, CH [low] 3, Et

R [high] 3: H, CH [low] 3

R [high] 4: H

X for p = 1 Cl, NH [deep] 2, substituted amino

for p = 2 -

Y: or NH- (CH [deep] 2) [deep] 3-

The compounds of the formula I are yellow to blue, depending on the chromophore, and are preferably suitable for dyeing paper stock.

example 1

500 parts of water, 1 part of tetra-n-butylammonium chloride and then 82 parts of N-methyl-N-aminopropylaniline are added dropwise at 20 ° C. to a solution of 92 parts of cyanuric chloride in 520 parts of xyol.

The pH is kept at about 8 by adding 50% NaOH dropwise. After the addition has ended, the temperature is increased to 60 ° C. and a further 82 parts of the amine are added under the same conditions. Stirring for two hours at 60 ° C. gives, according to TLC, complete conversion.

It is allowed to cool, suctioned off and washed with ethanol. 193 parts (88% of theory) of a crystalline product of the structure are obtained in this way with a melting point of 143-145 ° C.

Calculated for C [deep] 23H [deep] 30N [deep] 7Cl: C = 62.78%; H = 6.87%; N = 22.28%

found: C = 62.7; H = 6.8; N = 21.1%

Example 2

1000 parts of water and 5 g of tetra-n-butylammonium chloride are added at 20 ° C. to a solution of 342 parts of phenyl-dichloro-1,3,5-triazine in 1250 parts of ethylene chloride and then 248 parts of N-methyl-N- aminopropylaniline was added dropwise. The pH is kept at around 8 by adding 50% NaOH dropwise, the temperature rising to 50.degree. The mixture is stirred for one hour at 20 ° C., the greasy precipitate is filtered off with suction, washed with methanol and dried. 370 parts of product were thus obtained.

Another 97 parts of product of the structure could be obtained from the methanol mother liquor isolate. Yield 467 g = 88% of theory Th. Mp. 128-130 ° C.

Calculated for C [deep] 19H [deep] 20N [deep] 5Cl

C = 64.49% H = 5.69% N = 19.79% Cl = 10.02%

found: C = 64.3% H = 5.6% N = 19.5% Cl = 10.3%

Example 3

300 parts of water, 1 part of tetra-n-butylammonium chloride and then 86 parts of N-ethyl-N-aminopropyl-m-toluidine are added dropwise at RT to a solution of 46 parts of cyanuric chloride in 375 parts of ethylene chloride. The pH is kept at around 8 by adding 50% NaOH dropwise, the temperature rising to 55 ° C. The mixture is stirred for a further ½ h at 60 ° C., allowed to cool, the ethylene chloride phase is separated off and concentrated.

The solid residue is rubbed with ethanol, filtered off with suction and dried. 66 g (53% of theory) of a product of the structure are obtained with a m.p. 104-105 ° C.

Calculated for C [deep] 27H [deep] 38ClN [deep] 7

C = 65.4% H = 7.7% Cl = 7.1% N = 19.8%

found: C = 65.1% H = 7.5% Cl = 7.2% N = 19.9%

Example 4

To a solution of 115 parts of phenyl-dichloro-1,3,5-triazine in 375 parts of ethylene chloride, 700 parts of water and 5 parts of tetra-n-butylammonium chloride are added at 20 ° C. and then 100 parts of N-ethyl-N- aminopropyl-m-toluidine was added dropwise. The pH is kept at around 8 by adding 50% NaOH dropwise. The temperature rises to 75 ° C. during this process. The mixture is stirred for a further 1 h at 60 ° C., allowed to cool, the ethylene chloride phase is separated off, concentrated, rubbed with methanol, filtered off with suction and dried.

127 parts (66% of theory) of a crystalline product of the structure are obtained in this way with a melting point of 95-96 ° C.

Calculated for C [deep] 21H [deep] 24ClN [deep] 5

C = 66.14% H = 6.29%, Cl = 9.31% N = 18.37%

found: C = 66.3% H = 6.3% Cl = 8.8% N = 18.4%

Example 5

88 parts of the product described in Example 1, 10 parts of piperazine and 40 parts of soda are refluxed in 500 parts of xylene for 4-5 hours. It is allowed to cool, filtered and concentrated. The residue consists of 85 parts of a non-crystalline mass of the structure.

Example 6

160 parts of the product described in Example 2 were dissolved in 375 parts of ethylene chloride and 700 parts of water. 5 parts of tetra-n-butylammonium chloride are added and, with stirring at 80 ° C., 80 parts of N-methyl-N-aminopropylaniline are added. During the addition, the pH is kept at 10 by continuously adding 50% strength NaOH. The mixture is refluxed for 6 hours, allowed to cool, the organic phase is separated off and concentrated. This gives 209 parts of a non-crystalline mass of the structure

Example 7

14.5 parts of nitrosylsulfuric acid are added dropwise at -5 to 0 ° C. to a solution of 39 parts of 75% strength sulfuric acid in 6.5 parts of water. The mixture is stirred for 1 h at 0 ° C. and then a solution of 4 parts of conc. Sulfuric acid, 10.5 parts of water and 7.2 parts of 5-methoxy-2-aminobenz-thiazole. The mixture is stirred for 2 hours at -5 to 0 ° C., a solution of 8.8 parts of the product described in Example 1, dissolved in 30 parts of dilute hydrochloric acid, is then added dropwise and the mixture is stirred for 2 hours. It is then poured onto ice water, the pH is adjusted to 3-4 with 50% NaOH, the precipitate is filtered off with suction, washed and dried. 17 g of a crystalline compound of the structure are obtained

5 parts of this compound are refluxed in 50 parts of ethylene chloride in the presence of one part of MgO with the addition of 5 parts of dimethyl sulfate. The ethylene chloride is then distilled off and at the same time 50 parts of hydrochloric acid are added dropwise. It is allowed to cool, the dye is precipitated with conc. ZnCl [deep] 2 solution, sucks off and dries. 5 parts of a cationic dye are obtained which dye wood pulp blue without pollution of the wastewater and pulp with a small amount of dye in the wastewater in a brilliant blue shade. The lightfastness of the dye on cellulose is good. The dye on the fiber can be completely bleached with sodium dithionite. Benzthiazolanzo dyes with various coupling components were obtained analogously to the above procedure. These blue dyes had similar properties and are listed in the table below.

Further cationic azo dyes based on 2-amino-1,3,5-triazole, 3-amino-indazole, 5-amino-1-benzyl-pyrazole and 2-aminothiazole were synthesized by known methods. Examples are given in the table below.

Example 33

15.5 parts of phosphorus oxychloride are added dropwise to 143 parts of DMF at 0 ° C. The mixture is allowed to warm to 20 ° C. and stirred for a further 1 h. Then 22 parts of the product described in Example 1 are introduced with stirring at 20 ° C. and stirred for 30 minutes. The mixture is slowly heated to 80 ° C. until TLC shows complete conversion. It is then poured onto ice water and adjusted to pH 6 with sodium acetate. This gives 30 parts of a product of the structure

Example 34

176 parts of the product described in Example 2 are dissolved in 715 parts of DMF and 134 parts of POCl [deep] 3 are added dropwise at 60 ° C. and the mixture is heated to 80 ° C. for 2½ hours.

It is allowed to cool, poured onto ice and a pH of 8 is set with sodium hydroxide solution. The solid product is filtered off with suction and recrystallized from ethanol. This gives 146 parts (75% of theory) of a crystalline product with the following structure:

with a melting point of 176-177 ° C.

Example 35

8 parts of the product described in Example 34 are added to a solution of 3.5 parts of tribase in 21 parts of glacial acetic acid and refluxed for 3 h. It is allowed to cool and a brilliant red dye is precipitated with ZnCl [deep] 2 solution. After drying in air, 14 g of solid of the structure are obtained

The chlorine analysis showed 12.9%.

The dye turns wood pulp containing paper red.

Example 36

7.6 parts of the reaction product of cyanoacetic acid, acetic anhydride and chlorine chloride are mixed with 17 parts of the product described in Example 34 and 52 parts of glacial acetic acid and heated to 80 ° C. for 2 hours. It is allowed to cool and 5 parts of a solid of the structure are precipitated with NaCl / ZnCl [deep] 2 solution

The dye turns wood pulp containing paper yellow.

Styryl dyes

Example 59

22 parts of the product described in Example 1, 25.4 parts of 4,4'-bis-dimethylaminodiphenylmethane, 0.5 part of Fe-TAA- * complex and 0.5 part of chloranil are added to 180 ml of glacial acetic acid at 40-43 ° C gassed with intense stirring with oxygen. The oxidation is complete after 2.5 hours and the solution prepared in this way is used directly as a liquid formulation for coloring the paper pulp. 60/40 fabric (containing wood pulp) is dyed without, 70/30 fabric (pure cellulose) with low wastewater pollution. The resistance to bleeding to water (sandwich test) is very good. In the following table, dyes which were produced by analogous processes are presented; these have properties similar to those described above. 4,4'-bis-dimethylaminodiphenylmethane were used for all dyes, ie:

* Fe-TAA = iron tetraazaannulene

Claims (2)

1. Compounds of the general formula containing triazine groups I. in the A is an optionally substituted alkylene radical, R [high] 1 hydrogen or optionally substituted alkyl, R [high] 2 hydrogen or optionally substituted alkyl, R [high] 3 hydrogen, methyl, ethyl, methoxy, acetylamino, chlorine or hydroxi, R [high] 4 hydrogen, methyl, alkoxy, dialkylamino, X for p = 1 fluorine, chlorine, bromine, optionally substituted alkoxy, alkyl mercapto, amino or a radical of the general formulas , or and for p = 2 a radical of the formula and Y chlorine, optionally substituted amino, phenyl or a radical of the formula mean, where R [high] 5 hydrogen, optionally substituted alkyl or optionally substituted phenyl, R [high] 6 hydrogen, optionally substituted alkyl or optionally substituted phenyl, r 0.1 or a number greater than 1, W. T are hydrogen, formyl or the addition to a cationic dye and where the radicals A, R [high] 1, R [high] 2, R [high] 3, R [high] 4, T and Y are present several times can, are independent of each other. 2. Use of the compounds according to Claim 1 for dyeing paper stocks.