DE3434923A1 - Salts of sulpho group-containing heterocyclic monoazo compounds - Google Patents

Abstract

Salts of sulpho group-containing heterocyclic monoazo compounds correspond in one of the possible tautomeric forms to the formula I <IMAGE> in which the radicals R1 to R4, Q1, Q2, X, Y, Z and n are as defined in Claim 1 and at least one sulpho group is present as Q1 or Q2 as a quaternary ammonium salt. These salts are obtained as ready-to-use dyeing preparations; they are used for the dyeing or printing of organic substrates containing hydroxy groups or nitrogen, such as cellulose-containing textiles, leather and in particular paper.

Description

Salts of heterocyclic monoazo compounds containing suifo groups

The present invention relates to heterocyclic sulfo groups Monoazo compounds in a certain salt form, process for production and their use as dyes and coloring preparations thereof. The invention therefore relates to compounds in one of the possible tautomeric forms of the formula I.

correspond to where

Rl and R2, independently of one another, hydrogen, Ci_4Alkyl, Ci_4Alkoxy or COOM,

η 0 or 1,

Ql hydrogen or SO3M1,

Q2 means hydrogen or SO3M2,

with the proviso that at least one of the two radicals Qi and Q _{2 is} the sulfo group,

Mi and M ₂ , independently of one another, mean any non-chromophoric cation with the proviso that at least one of the cations Mi and M _{2 stands} for an ammonium ion which is derived from a quaternary ammonium compound, stands for any non-chromophoric cation, where M with Mi and / or M _{2 can be} identical or different;

X for 0 or NH,

for OH, NH ₂ , methyl or ethyl,
for 0, S or N-Yi,

for H, CN, CONH ₂ , Ci_4Alkyl; Ci_4Alkyl substituted by OH, CN, halogen or Ci-4alkoxy; optionally substituted phenyl or 1- or 2-naphthyl; Phenyl-Ci ^ alkyl, the phenyl radical of which can be further substituted; Ci_6Alkylen-S03M, Ci> 6Alkylen-0S03M or Ci_6-Alkylen-COOM,

- 5 - Case 150-4933

R3 and R4, independently of one another, represent hydrogen, Ci_4alkyl, phenyl-Ci_4alky1 or phenyl, where the phenyl radical can in each case be further substituted, or , if Y represents N-Yi with Yi as hydrogen, one of the two radicals R3 and R4 also one which can have additional meanings for Yi.

The remainder Qi preferably stands for SO3M1, which is more preferably in position 7,
η preferably means 0.

A radical Ri is preferably, independently of one another, Ri _a as hydrogen, Ci_4alkyl, methoxy or ethoxy; more preferably than hydrogen, methyl, methoxy or ethoxy; more preferably for Rlc as hydrogen or methyl; Ri particularly preferably represents hydrogen.

The radical R2 preferably stands for R £ _a as Ci_4alkyl, C ^ alkoxy or COOM; more preferably for R2 _D as methyl, methoxy, ethoxy or COOM; R2 particularly preferably represents methyl.

0.2 in the meaning of SO3M2 is preferably located on a to Azo group in the ortho position C atom.

X preferably means 0.

Z preferably denotes Z _a as OH or NH2.

A substituted 1- or 2-naphthyl radical defined for Yi is preferably by 1 or 2 substituents from the series OH, NH2, acetyl amino, Benzoylamino, methoxy, ethoxy, SO3M, COOM and chlorine substituted.

A substituted phenyl or phenyl alkyl radical defined for Yi is in the phenyl ring preferably by 1 or 2 substituents from the series Chlorine, Ci_4Alkyl, Ci_4Alkoxy, Acetyl amino, COOM and SO3M substituted; more preferably the phenyl ring is made up of 1 or 2 substituents of the series chlorine, methyl, methoxy, COOM and SO3M.

- 6 - Case 150-4933

The radical Yi preferably represents Yj ^ as H, CN, CONH ₂ ; Methyl, ethyl; C2-4alkyl monosubstituted by OH, CN, Cl or OCH3; Phenyl or phenyl ~ Ci_2a1ky1, the phenyl radicals of which can be substituted by 1 or 2 substituents from the group consisting of chlorine, methyl, methoxy, COOM and SO3M; C2-4alkylene-SO3M, C2-4alkylene-0S03M or C2-4alkylene-C00M; more preferred for Yib as H, CN, CONH2; Methyl, ethyl, 2-hydroxyethyl; Phenyl, phenyl-Ci_2alkyl, C2_4alkylen-SO3M or C ₂ -4alkylen-COOM; more preferably for Yi _c as H, CN or CONH ₂ ; more preferably for Yid as H or CN; very particularly preferably Υχ stands for hydrogen "

Y preferably represents Y _a as 0 or N-Yi _a ; more preferably for Yj ₃ as 0 or N-Yi ₀ ; more preferably for Y _c as 0 or N-Yi _c ; more preferably for Yd as 0 or N-Yi ^; particularly preferred for Y _e as 0 or

NH. ~ ·

The radicals R3 and R4 are preferably, independently of one another, for and R4 _a as hydrogen, methyl, ethyl, phenyl-chalky! or phenyl, where the phenyl radicals can in each case be substituted by 1 or 2 substituents from the series chlorine, methyl, methoxy, COOM and SO3M, ' or one of the radicals R3 _a and R ^ ₃ in the event that Y is N-Yi with Yi as hydrogen also has one of the meanings additionally given _{for Yi a;} more preferably, the radicals R3 and R4, independently of one another, stand for R3 _D and R4b as hydrogen, methyl, ethyl, phenyl or benzyl, or one of the radicals R3b and R4b in the event that Y stands for N-Yi with Yi as hydrogen , also has one of the additional meanings listed _{for Yu 5;} R3 and R4 are particularly preferably hydrogen.

A quaternary ammonium ion present in a compound of the formula I is derived from ammonium compounds, which preferably contain 1 or 2 quaternary ammonium ions; are to be mentioned by way of example Tetramethyl, tetraethyl, ethyltrimethyl, benzyldiethylmethyl, Trimethylphenyl, trimethyl benzyl, triethylcyclohexyl, trimethylhydroxyethyl, Tetrahydroxyethyl ammonium hydroxide and N, N-dimethylpiperidinium hydroxide, or also compounds of the formula

- 7 - Case 150-4933

^R 5 ^R 5

H3C - N - X - (S - CH3

C ¹ H ₃ (Ih ₃ 20H3

wherein R5 is methyl, ethyl, hydroxyethyl, 2- or 3-hydroxypropyl and X is Ci_4alkylene or -CHgCH ₂ NCH ₂ CH ₂ -.

CH ₃

In addition to a sulfo group in the form of the quaternary ammonium salt can further anionic groups also in the form of the free acid, as alkali metal salt or present as any ammonium salt, with ammonium or substituted ammonium as cations in Which are derived from a primary, secondary or tertiary amine come into consideration. For example, the following amines can be mentioned: Mono-, di- or tri-methyl-, -ethyl-, -propyl- or -butyl-amine; Mono-, di- or tri-ethanol, propanol or isopropanolamine; N-methyl-N-hydroxyethylamine, N-methyl-N, N-di (hydroxyethyl) amine, N-ethyl-N-hydroxyethoxyethylamine, morpholine, piperidine, piperazine, Hydroxyethylmorpholine, hydroxyethylpiperazine, aminoethylpiperazine; Ethylenediamine, hexamethylenediamine; Dimethyl aminopropylamine, diethylaminopropylamine, Diethylene glycol amine, diglycol amine and 3-methoxypropyl amine.

As amines, polyglycolamines are also suitable, for example by Reaction of ammonia, alkyl or hydroxyalkylamine with alkylene oxides can be obtained.

Preferred compounds of the formula I correspond to one of the possible tautomeric forms of the formula Ia,

Yes

with the proviso that at least one of the cations M ^ and M _{2 stands} for an ammonium ion which is derived from an ammonium compound which contains one or two quaternary ammonium ions.

Case 150-4933

Compounds of the formula Ia in which

(1) Rib is Ric;

(2) Rib is hydrogen and R £ b is methyl;

(3) Y _{b is} Y _c ;

(4) those of (1) to (3) wherein RSSB and R4b is hydrogen and Yb, or Y stand for _c Y (j;

(5) those of (4) wherein Yj is Y _e .

The compounds of the formula I or mixtures thereof are prepared by the diazonium salt of one or more amines of the formula II,

II

where Ri, R2, Qi, Q2 and η are as defined above, with a compound in one of the possible tautomeric forms of the formula III

III

corresponds to, wherein X, Y, Z, R3 and R4 are as defined above, or with a mixture of compounds of the formula III in the presence of at least equimolar amounts of a quaternary ammonium compound which is suitable for the salt formation of at least one sulfo group as Qi or Q2 is required are, couples.

The starting compounds of formula II, diazo components of 2-Phenyl-benzothiazole series are either known or can be analogous to methods known per se, for example according to M. Schubert, Annalen 558, 10 (1947).

- 9 - Case 150-4933

The coupling components, compounds of formula III, are also known or can be prepared by methods known per se. Such manufacturing processes are described, for example in: The Chemistry of Heterocyclic Compounds, The Pyrimidines, Interscience Publishers 1962; also in numerous patents such as US-PS 2,673,204 or DE-PS 134,984; 158,591; 165.692; 186,456 et al.

Diazotization and coupling reactions are known per se Methods carried out. For the diazotization, the amines or amine mixtures are advantageously dissolved or suspended in aqueous alkali and mixed with a 5-10% molar excess of sodium nitrite. The diazotization is expediently carried out in mineral acidic, preferably hydrochloric acid medium at 0-20 ° C. The coupling is expediently carried out at pH 3-10, preferably at pH 4-8 with the addition of a Quaternary ammonium compound in at least equimolar amounts is sufficient for the neutralization of a sulfo group. The resulting compound of formula I can be obtained in the form of Solution to be used per se; however, the solution can also be converted into the solid by spray drying.

The compounds according to the invention in the form of their water-soluble ones Salts are used for dyeing or printing hydroxyl group or nitrogen-containing organic substrates. They are used, for example, for dyeing or printing fibers, threads or made from them Textiles made of cellulose material, e.g. cotton or contain these, according to methods known per se; Cotton is preferably dyed using the exhaust process, for example from long or short liquor and at room to cooking temperature. Printing is carried out by impregnating with a printing paste, which is compiled according to a method known per se. In particular, however, the compounds of formula I are suitable for Coloring or printing of paper, e.g. for the production of mass-colored, sized or unsized paper. But you can can also be used for dyeing paper by the dipping process. The dyeing and printing of paper is carried out using known methods. The new dyes can also be used for dyeing or printing

- 10 - Case 150-4933

Leather, preferably of chrome-tanned types of leather, according to known ones Methods are used.

The dyeings and prints obtained in each case (especially those on paper) show good fastness to use.

It is of particular advantage that the compounds of the formula I are due to their preparation occur as concentrated solutions, which are very suitable as ready-to-use staining preparations. These preparations are storage-stable, fluid even after prolonged standing, which plays an important role in the metering of the dye, and with Water miscible in any ratio. The dye solutions obtained can optionally also contain other, for example hydrotropic, auxiliaries can be added.

Suitable hydrotropic auxiliaries are, for example, low molecular weight Amides, lactones, alcohols, glycols or polyols, low molecular weight Ethers or oxyalkylation products as well as nitriles or esters; in Methanol, ethanol, propanol are preferred; Ethylene, propylene, diethylene, thiodiethylene and dipropylene glycol; Butanediol; ß-hydroxypropionitrile, pentamethylene glycol, ethylene glycol monoethyl and propyl ether, ethylene diglycol monoethyl ether, triethylene glycol monobutyl ether, Butyl polyglycol, formamide, dimethylformamide, Pyrrolidone, N-methylpyrrolidone, glycol acetate, butyrolactone, urea and £ -caprοlactam.

Hydrotropic compounds are described, for example, by H. Rath and S. Müller, MeIliand Texti reports 40, 787 (1959) or by E.H. Daruwalla in K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. VIII, pp. 86-92 (1974).

The dye salts of the formula I have, depending on the present Cation or cation mixture good solubility properties and are characterized in particular by good cold water solubility. In addition, they practically do not stain the waste water at all or only slightly during the production of both sized and unsized paper. They do not blur on paper, are largely insensitive to filler and pH fluctuations and have little tendency to be colored Paper two-sidedness. The dyeings on paper show good lightfastness; after prolonged exposure the shade changes tone-on-tone. the

- 11 - Case 150-4933

Dyed papers are very good wetfast not only to water, but also to milk, fruit juices and sweetened mineral water, and also have good alcohol fastness. The dyes have high substantivity, i.e. they draw up and show practically quantitatively at the same time a good build-up ability; they can be added to the paper pulp directly, i.e. without prior dissolving, as dry powder or granules without a reduction in the brilliance or a reduction in the color yield occurring. However, such are advantageous Real solutions of the dyes as mentioned above are used, which are stable, of low viscosity and therefore very easy to dose. Fibers containing wood pulp are dyed with the dyes of the present invention to a good and level quality. The colored papers can be bleached both oxidatively and reductively, which means that scrap and waste paper can be reused Importance is.

The following examples serve to illustrate the invention, without limiting them. In the examples, parts mean weight or weight. Parts by volume and percentages percentages by weight; the temperatures are given in degrees Celsius.

example 1

32 parts of 2- (4'-aminophenyl) -6-methyl-benzthiazole-7-sulfonic acid become Stirred in 300 parts of water and then with 11 parts of 30% Hydrochloric acid added. 27 parts of 4N sodium nitrite solution are slowly added dropwise and the temperature is kept at 15-20 °. After stirring for 2 hours, the Excess nitrite destroyed with sulfamic acid. The diazo suspension is then in a template consisting of 13 parts of 2,4-diamino-6-hydroxypyrimidine and 125 parts of 24.5% tetramethylammonium hydroxide solution dripped. The clutch works immediately. After the coupling has ended, the mixture is clarified by filtration, and a storage-stable, Ready-to-use dye preparation containing the dye as a tetramethylammonium salt according to the formula

- 12 - Case 150-4933

NH ^H

N (CH,)

3 ^; 4th

contains. The preparation colors paper in brilliant, neutral yellow tones, the dyeings show very good sewage and wet fastness properties. The A measured in distilled water is 412 nm.

Example 2

Instead of the 13 parts of 2,4-diamino-6-hydroxypyrimidine, 13.2 Parts of barbituric acid are used. If the procedure is otherwise as indicated for Example 1, a storage-stable dye preparation is obtained, which is the dye salt according to the formula

and dyes paper in yellow tones with high fastness properties.

In Examples 1 and 2, instead of tetramethylammonium hydroxide, other quaternary ammonium hydroxides can also be used, such as tetraethylammonium, ethyltrimethylammonium, butyl trimethylammonium, benzyldiethylmethylammonium, trimethylphenylammonium, triethylcyclohexylammonium, triethylcyclohexylammonium, triethylcyclohexylammonium, triethylcyclohexyletrutylammonium, triethylcyclohexylammonium, triethylcyclohexylammonium, triethylcyclohexylammonium, triethylcyclohexylammonium N, N-dimethyl piperidinium, Ν, Ν-dimethylmorpholinium, N-methyl-N-hydroxyäthylpiperidinium-, N-methyl-N-hydroxyäthylmorpholinium-, Ν, Ν-dimethyl-N ¹ -hydroxyäthylpiperazinium-, Ν, Ν, Ν 'Ν'-Tetramethylpiperazinium-, N, N-dimethyl-N'-methyl-N'-aminoäthylpiperazinium-; Tetrahydroxyethyl

Case 150-4933

ammonium-, methyl-tris (hydroxyethyl) ammonium-, dimethyl-bis (hydroxyethyl) ammonium, triethyl-hydroxyäthylammonium- or triethyl-2-hydroxypropylammoni um-hydroxi d.

If the method according to Example 1 is followed, then also Storage-stable dye preparations are obtained with good dyeing properties.

Example 3

In Example 1, instead of the tetramethylammonium hydroxide solution 33 parts of the bisquaternary ammonium hydroxide of the formula

OH XH ₂ CHCH ₃

OH
XH ₂ CHCH ₃

H ₃ C- NCH ₂ CH ₂ NCH ₂ CH ₂ - NCH ₃ CH ₃ CH ₃ CH ₃

20ΗΘ

(produced by the addition of propylene oxide onto (CH ₃ ) ₂ NCH ₂ CH ₂ NCH ₂ CH ₂ N (CH ₃ ) ₂ ) CH ₃

a, a yellow, storage-stable liquid preparation is obtained which the dye of the formula

N = Ν - V> =

OH

XH ₀ CHCH ₀ 9i 2

OH XH ₂ CHCH ₃

H ₃ C- NCH ₂ CH ₂ NCH ₂ CH ₂ CH ₂ -N-CH ₃

CH ₃

C ¹ H ₃ CH ₃

contains. The solution is very good because of its thin liquid dosable, it colors paper in brilliant, neutral yellow tones.

- 14 - Case 150-4933

The corresponding ammonium salt for the dye can be used in an analogous manner from Example 2 can be prepared.

Possible applications of the dye preparations according to the invention are illustrated in the following regulations.

Dyeing instruction A

70 parts of chemically bleached sulphite cellulose are made in a Dutch oven made of softwood and 30 parts of chemically bleached sulfite cellulose Birch wood ground in 2000 parts of water. 1.0 part of the liquid preparation according to example 1, 2 or 3 is added to this mass Minutes of mixing time is used to make paper. The absorbent paper obtained in this way is colored yellow. The sewage is practical colorless.

Dyeing instruction B

1.0 parts of the dye preparation according to Example 1, 2 or 3 become 100 parts of chemically bleached sulfite cellulose, which was ground with 2000 parts of water in a hollander, was added. After 15 minutes Mixing is done in the usual way with resin glue and aluminum sulfate. Paper made from this material shows one yellow shade and has good sewage and wet fastness properties.

Dyeing instruction C

An absorbent paper web made of unsized paper is at 40-50 °

drawn through a dye solution of the following composition:

0.5 part of the liquid preparation from Example 1, 2 or 3
0.5 parts starch and
99.0 parts of water.

The excess dye solution is squeezed out through two rollers. The dried paper web is colored yellow.

Claims (10)

Claims 1. Compounds in one of the possible tautomeric forms of the formula I correspond to where Rl and R2, independently of one another, hydrogen, C ^. ^ Alkyl, C or COOM, η 0 or 1, Ql hydrogen or SO3M1,
Q2 means hydrogen or SO3M2, with the proviso that at least one of the two radicals Qi and Q2 is the sulfo group,
Mi and M2, independently of one another, mean any non-chromophoric cation with the proviso that at least one of the cations Mi and M2 stands for an ammonium ion that is different from a quaternary ammonium compound, M stands for any non-chromophoric cation, where M with Mi and / or M2 can be the same or different; X for 0 or NH, Z for OH, NH ₂ , methyl or ethyl,
Y for 0, S or N-Yi, Case 150-4933 Yl for H, CN, CONH2, C] __ 4 alkyl; by OH, CN, halogen or Ci_4Alkoxy substituted C 1-4 alkyl; optionally substituted phenyl or 1- or 2-naphthyl; Phenyl-C ^ alkyl, the phenyl radical of which is further substituted can be; Ci_sAlkylen-S03M, Ci_6Alkylen-0S03M or Ci_6-Alkylen-COOM, R3 and R4, independently of one another, represent hydrogen, Ci_4alkyl, phenyl-Ci_4alkyl or phenyl, where the phenyl radical can in each case be further substituted, or , if Y represents N-Yi with Υχ as hydrogen, one of the two radicals R3 and R4 also one which can have additional meanings for Yi. 2. Process for the preparation of compounds of the formula I or Mixtures thereof, characterized in that the oiazonium salt one or more amines of the formula II, II wherein Ri, R2, Qi, Q2 ^unc · ⁿ wi ^e are defined in claim 1, with a compound which is in one of the possible tautomeric forms of the formula III III corresponds to, wherein X, Y, Z, R3 and R4 are as defined in claim 1, or with a mixture of compounds of the formula III in the presence of at least equimolar amounts of a quaternary ammonium compound, for the salt formation at least one sulfo group as Qi or Q2 are required couples. - 3 - Case 150-4933 3. Containing storage-stable, liquid-aqueous dye preparation a compound of the formula I as defined in claim 1 which contains at least one quaternary ammonium ion. 4. Use of a compound of formula I defined in claim 1 or a preparation according to claim 3 for dyeing or Printing on organic substrates containing hydroxyl groups or nitrogen. 5. Use according to claim 4 for dyeing or printing textiles consisting of or containing cellulose or of Leather. 6. Use according to claim 4 for dyeing or printing Paper. 7. A method for dyeing or printing hydroxyl-containing or nitrogen-containing organic substrates, characterized in that that a compound of the formula I is defined in claim 1 or dyed or printed with a preparation according to claim 3. 8. The method according to claim 7 for dyeing or printing textiles consisting of or containing cellulose or of Leather. 9. The method according to claim 7 for dyeing or printing paper. 10. The substrates dyed or printed according to the method of claim 7, 8 or 9.