JPS61152768A - Cationic pyrazole-azo compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel cationic pyrazole-azo compounds, processes for their preparation and for dyeing cationically dyeable materials, preferably materials made of polyacrylonitrile, acid-modified polyamides or acid-modified polyesters. Concerning its use as a dye.

Cationic pyrazole-azo compounds with unsubstituted or N-substituted anilines as coupling components are known from a large number of publications. Reference is made, for example, to: US Pat. No. 3,435,022;
British Patent Nos. 1404097 and 1438386, French Patent No. 1392581 and 1392
No. 645, USSR Patent No. 914603 (C, A, Vol.
97.11285).

The novel cationic pyrazole-azo compound according to the present invention is represented by the following general formula.

In the formula, RI H methyl, ethyl, hydroxyethyl or 2-
Hydroxypropyl.

R1 is C1-C6-alkyl, R11ltc, -C,-alkyl, hydroxyethyl or Fi2-hydroxypropyl, R4 is hydrogen, methyl or methoxy, each R3 is independently hydrogen, chlorine, methyl or methoxy, n is 1. 2 or 3, Aθ means an anion and the molecule contains at most one hydroxyalkyl group as mentioned above.

The alkyl groups R2 and R3 can be linear or branched,
Preferably, it is an isopropyl group or a dn-propyl group. n is preferably 1 or 2, particularly preferably 1
It is.

Ae can be any inorganic or organic anion, and this ion serves only as a counterion to the cation of the pyrazole nitrogen atom. This may be the same ion introduced during quaternization, or it may be another ion introduced later by ion exchange. Examples of anions Aθ that may be considered include: halide ions (e.g. chloride, bromide or iodine), boron tetrafluoride, rhodanide, sulfate, methyl sulfate. , ethyl sulfate ion, amino sulfate ion, perchlorate ion,
carbonate ion, bicarbonate ion, phosphate ion, phosphomolybdate ion, phosphotungstate ion,
Phosphorous tungsten molybdate ion, benzene sulfonate ion, naphthalene sulfonate ion, 4-
R-rolbenzene sulfonate ion, oxalate ion, maleate ion, formate ion, acetate ion, propionate ion, lactate ion, succinate ion, chloroacetate ion, tartrate ion, methanesulfonate ion - ions, benzoate ions, or complex anions such as zinc chloride double salt.

Preferred anions are halogen ions, sulfate ions,
Methyl sulfate ion, ethyl sulfate ion, phosphate ion, benzenesulfonate ion, 4-chlorobenzenesulfonate ion, oxalate ion, formate ion,
These are acetate ion, methanesulfonate ion, and the above complex ions.

It will be appreciated that the present invention encompasses all possible tautomers of compounds of formula (1).

For example, in the above formula, B is R4. Particularly recommended compounds of formula (1) are those in which R4 represents hydrogen and those in which R3 represents hydrogen.

Also preferred are compounds of formula (1) in which R8 means methyl or ethyl, especially methyl.

What is important in practice is that R7 and Rs are independently C
, -C, -alkyl group, in which KR and R1 have the same meaning and are preferably propyl.

The novel cationic pyrazole-azo compounds according to the invention are technically easy to prepare and can be prepared in a manner known per se, for example by the method described below.

The amine of formula is diazotized and coupled to the aniline of formula 1 and the resulting azo compound is quaternized with a compound of R1-A (41).

In addition, R,, R,, R,, R,, R6 and n of the above formula
has the meaning defined in formula (1), and means a group that can be converted into anion A during AU quaternization.

amines of formula (2) (see e.g. references cited above),
Anilines of formula (3) as well as quaternizing agents of formula (4) are known or can be easily obtained by methods known per se.

Diazotization of the amine of formula (2) is performed by a method known per se,
For example, it can be carried out under hydrochloric acid, sulfuric acid or phosphoric acid, in an aqueous medium, using sodium nitrite, and the like.

This diazotization can also be carried out using other diazotizing agents, such as nitrosylsulfuric acid.

In this case additional acids can be present in the reaction medium, for example phosphoric acid, sulfuric acid, acetic acid, hydrochloric acid or mixtures of these acids, for example mixtures of phosphoric acid and acetic acid. Diazotization is suitably carried out at temperatures ranging from -10 to 30°C, for example -10°C to room temperature.

The coupling of the diazotized amine of formula (2) to the coupling component of formula (3) is likewise carried out by known methods, for example in an acidic, aqueous or organic aqueous medium, preferably from -10°C to 30°C. It is particularly preferably carried out at temperatures below 10°C. As acid, for example, hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid is used.

Diazotization and coupling can be carried out, for example, in a 1" membrane and without isolation of the intermediate, both steps can be carried out using a single reactor, ie in the same reaction medium.

It is convenient to carry out the quaternization in an organic solvent that does not take part in the reaction. For example, in hydrocarbons, chlorinated or nitrated hydrocarbons such as benzene, xylene, toluene, tetrachloroethane, chloroform, carbon tetrachloride, mono- or di-chlorobenzene or nitrobenzene, or in dimethylformamide, N- % in acid amides or acid anhydrides such as methylacetamide or acetic anhydride or in dimethyl sulfoxide or ketones.

For example, it is carried out in acetone or methyl ethyl ketone. However, an excess of alkylating agent may also be used instead of the organic solvent. Alternatively, it can also be carried out in an aqueous medium, for example in an aqueous suspension or in glacial acetic acid. Preferably the quaternization is carried out at an elevated temperature,
For example, 30 to 200℃, especially 80 to 150℃
The process is optionally carried out with the addition of an acid binder such as an inorganic base, eg magnesium oxide, magnesium carbonate, sodium carbonate, calcium carbonate or sodium bicarbonate, and optionally under pressure. The optimum conditions at that time can be easily determined through preliminary experiments.

Examples of suitable quaternizing agents R+-A are as follows. Halogen full kill, e.g.

Methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide, particularly preferably alkyl sulfates, such as dimethyl or diethyl sulfate, or alkyl esters of aromatic sulfonic acids, such as.

Methyl-p-toluenesulfonate or methylbenzenesulfonate, n-furobylbenzenesulfonate, isopropylbenzenesulfonate, and also ethylene oxide or propylene oxide. That is, the group A
is, for example, a halogen (especially chlorine, bromine or iodine), CH,SO,-, C,H,80,- or after quaternization, the novel cationic pyrazole-azo compounds of the invention are separated from the reaction medium. death.

It can be dried or alternatively used directly as a solution. If desired or necessary, the expression (
It is also possible to exchange the anion Aθ of the compound of 1) with another anion. To facilitate isolation, the compound of formula (1) can be precipitated, for example, by conversion from the reaction medium into a salt that is sparingly soluble in that medium, ie by appropriate exchange of the anion Aθ. This is carried out, for example, by addition of a halide (in the case of conversion to a halide: Aθ=Yakuchi) or by addition of Muα2 or Naα (in the case of conversion to a zinc chloride double salt; A0=Muα429/2). (salting out).

Novel cationic pyrazole of formula (1) according to the present invention -
Azo compounds can be used for dyeing materials dyeable with cationic dyes, in particular textile materials, and with the addition of binders and solvents for printing. The materials to be dyed or printed are, for example, materials consisting of homopolymers or copolymers of acrylonitrile (polyacrylonitrile) or synthetic polyamides or polyesters (modified with acid groups). Furthermore, the novel cationic azo compounds according to the invention are preferably used for the dyeing of wet-spun lines of the above-mentioned polymers (dying of fibers in the gel state), for the dyeing of synthetic material melt raw materials, and also for the dyeing of tannin-treated raw materials. It can also be used for dyeing cellulosic materials, leather and paper.

The azo compounds according to the invention are used for dyeing or printing the above-mentioned materials and one or more compounds of formula (1) are applied onto the above-mentioned materials. Also included within the subject matter of the present invention are dyeing or printing processes that do not require dyeing or incorporation into the material, and also dyed products obtained by this process.

The cationic dyes of the general formula (1) are particularly suitable for dyeing materials such as: polyacrylonitrile % or acrylonitrile in which the proportion of acrylonitrile is at least 85% and other vinyl compounds, such as vinyl chloride, chloride vinylidene,
Flock products, fibers, filaments, ribbons, woven or knitted fabrics made of copolymers with vinyl fluoride, vinyl acetate, vinylpyridine, vinylimidazole, vinyl alcohol, acrylates, methacrylates, acrylamide, methacrylamide, asymmetric dicyanoethylene. It is likewise suitable for dyeing flock products, fibres, filaments, ribbons, woven or knitted fabrics made of acid-modified synthetic materials, in particular acid-modified aromatic polyester and acid-modified polyamide fibers. An example of an acid-modified aromatic polyester is a polycondensation product of sulfoterephthalic acid and ethylene glycol, ie polyethylene glycol terephthalate containing sulfonic acid groups.

The dyeing is preferably carried out from a neutral or acidic aqueous medium, optionally under pressure, by the exhaust method or by the continuous method.

For example, the material to be dyed is immersed in a dye bath at a temperature of 40 to 60° C. and dyeing is carried out at boiling temperature. Alternatively, dyeing can be carried out under pressure at a temperature of 100° C. or more, for example from 110 to 130° C., using a pressure dyeing device.

If the material to be dyed is a fibrous material, it can be of various shapes. For example, fiber.

It can be a filament, a woven fabric, a knitted fabric, a semi-finished product or a finished product.

Application of the pyrazole-azo compounds according to the invention of formula (1) to materials such as those described above gives red dyeings or prints. This dyeing has very good properties. In particular, it has high pIII stability, high vapor fastness, very good adsorption, and excellent light fastness. The dyeings obtained do not suffer from a first brake', i.e. short, e.g. after the first 30 hours of exposure, a decrease in light fastness, as is often observed in dyeings with dyes of similar chemical structure. No problems at all.

The compounds of the formula (1) according to the invention can be used individually or in combination with at least two compounds of the formula (1) as dyes for the above-mentioned purposes.
It can be used as a mixture containing the following compounds.

Examples for explaining the present invention will be described below. Parts and percentages in the examples are by weight unless otherwise specified. Furthermore, melting points are uncorrected.

Example 1! L) 43.2 parts of 1-phenyl-3-methyl-5-7 minopyrazole was added to 203 parts of 68 ton of sulfuric acid at 50 to 55°C.
Dissolve at 4°C and cool to -10°C.
79.4 parts of nitrosyl sulfuric acid was added dropwise over 30 minutes to effect diazotization. After stirring for another hour at the same temperature, the diazo solution was added with 10 ml of glacial acetic acid at -5°C to -10°C.
A solution of 44.2 parts of N,N-dipropylaniline in a mixture of 0 parts and 50 parts of propionic acid is added dropwise.

After stirring for a further 2 hours at the same temperature, the reaction mixture is added dropwise at 0 to 5° C. to a mixture of ice and 750 parts of sphagnum moss. At this time, 15 tons of sodium hydroxide and 1164 parts of sodium hydroxide were simultaneously added dropwise to maintain a constant pit value of 2 to 2.5. The azo compound is extracted from the resulting suspension with 1300 parts of methylene chloride and the extract is dried over sodium sulfate. After distilling off the solvent, 84 parts of an azo compound of the following formula are obtained.

Melting point: 90-93°C b) 52% azo compound of formula (100) 24.3 parts of magnesium oxide and 650 parts of ethylene chloride are heated to 75-80°C. 72 parts of dimethyl sulfate are added dropwise to this over a period of 60 minutes, and the mixture is stirred for a further 3 hours at the above temperature.

The solvent is distilled off and the remaining reaction product is dissolved in 1 soo part of water, heated to 70°C and clarified by filtration. The pli of this solution is adjusted to 4 with 2-N hydrochloric acid at room temperature, and the reaction product is salted out by adding 215 parts of sodium chloride and 14 parts of zinc chloride. The precipitated product is filtered off and dried. Thus, 53 parts of a quaternized azo compound of the following formula is obtained.

Melting point: 162-172°C Example 2 The same procedure as in Example 1 was carried out. 1-phenyl-3-methyl-5-amino-pyrazole was used as the diazo component, an appropriately substituted aniline was used as the coupling component, and a quaternizing agent for introducing a group R2 was used.

A quaternized azo compound shown in the table of the following formula was obtained.

Bone) Quaternization is carried out with ethylene oxide.

4I4) Quaternization is carried out with propylene oxide.

Compounds (101) and (201) to (213) can also be isolated with other anions, Ae.
Ru. For example, the corresponding salts, Naα, KBr%KJ,
Chloride, iodide, bromide, acetate ions, etc. can also be isolated if they can be salted out from the reaction solution, such as with sodium acetate. But also, for example, metoftc III salt (Ae= CHs S
O4) can also be isolated (compound (20
1), (203) - (205), (207), (20
8), <210), (213).

These are quaternized with dimethyl sulfate).

Example 3 A polyacrylonitrile cloth is placed in an aqueous bath at a temperature of 60° C. at a bath ratio of 1:80. This bath is 0.125.9 per 1
of glacial acetic acid, 0.375 g of sodium acetate and 0.0
75! A dye of formula (101) of I (or a corresponding amount of a solid or liquid preparation of this dye). 2o to 3
Heat to boiling temperature in 0 minutes and bring the bath to this temperature for 90 minutes.
Hold for a minute. After washing, a bright red dyed fabric was obtained. This dyed product has excellent color fastness.

Example 4 A cloth made of modified polyester is placed in an aqueous bath at a temperature of 20° C. at a bath ratio of 1:30. This bath was a hit! I sodium sulfate, 2 g ammonium sulfate and 0.15.9
(or a corresponding amount of a solid or liquid formulation of this dye). Add this to 1 with formic acid.
) III Adjust to 5.5. Heat to 120°C in a closed container for 45 minutes and hold at this temperature for 60 minutes or more while shaking. After washing and drying, a bright red dyed fabric is obtained. This dyed product has excellent color fastness.

Claims (1)

[Claims] 1. Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is methyl, ethyl, hydroxyethyl or 2-
hydroxypropyl, R_3 is C_3-C_6-alkyl, R_3 is C_3-C_6-alkyl, hydroxyethyl or 2-hydroxypropyl, R_4 is hydrogen, methyl or methoxy each R_5 is independently hydrogen, chlorine, methyl or methoxy, n Cationic pyrazole-azo compounds of 1, 2 or 3, A♦ means an anion and the molecule contains at most one hydroxyalkyl group as defined above. 2. The cationic pyrazole-azo compound according to claim 1, wherein n is 1. 3. The cationic pyrazole-azo compound according to claim 1 or 2, wherein R_4 and R_5 represent hydrogen. 4. A cationic pyrazole-azo compound according to any one of claims 1 to 3, in which R_1 means methyl or ethyl, in particular methyl. 5. R_2 and R_3 independently form C_3-C_5
The cationic pyrazole-azo compound according to any one of claims 1 to 4, which means -alkyl. 6. Cationic pyrazole-azo compounds according to claim 5, in which R_2 and R_3 are the same and mean propyl. 7. In the method for producing a cationic pyrazole-azo compound according to claim 1, an amine of the formula ▲ has a mathematical formula, a chemical formula, a table, etc. is diazotized, and the amine of the formula ▲ has a mathematical formula, a chemical formula, a table, etc. A method characterized by coupling with aniline of and n have the meaning stated in claim 1,
and A means a group that is converted into an anion A■ upon quaternization). 8. A method for dyeing or printing a cationically dyeable material, characterized in that one or more compounds according to claim 1 are applied to the material or incorporated into the material. How to do it. 9. Cation dyeable material is polyacrylonitrile,
The method according to claim 8, characterized in that the material is made of acid-modified polyamide or acid-modified polyester. 10. Process according to claim 9, characterized in that the cationically dyeable material is a fiber material, preferably a fiber material made of polyacrylonitrile. 11. A material dyed or printed by the method according to any one of claims 8 to 10. 12. A polyacrylonitrile fiber material dyed or printed by the method set forth in claim 10.