GB2168713A - Cationic pyrazole-azo dyestuffs - Google Patents

Cationic pyrazole-azo dyestuffs Download PDF

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GB2168713A
GB2168713A GB08530952A GB8530952A GB2168713A GB 2168713 A GB2168713 A GB 2168713A GB 08530952 A GB08530952 A GB 08530952A GB 8530952 A GB8530952 A GB 8530952A GB 2168713 A GB2168713 A GB 2168713A
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cationic
methyl
azo compound
pyrazole
formula
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GB2168713B (en
GB8530952D0 (en
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Willy Stingelin
Peter Moser
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Novartis AG
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Ciba Geigy AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
    • D06P1/04—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal
    • D06P1/08—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal cationic azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C09B44/14—1,2-Diazoles or hydrogenated 1,2-diazoles ; Pyrazolium; Indazolium

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Novel cationic pyrazole-azo compounds (I) impart red shades to materials (esp. textiles) consisting of acrylonitrile polymers or acid-modified polyamides or polyesters, and also to gel fibres, tanned cellulose materials, paper and leather. <IMAGE> wherein R1 is methyl, ethyl, hydroxyethyl or 2-hydroxypropyl, R2 is C3-C6alkyl, R3 is C3-C6alkyl, hydroxyethyl or 2-hydroxypropyl, R4 is hydrogen, methyl or methoxy, and each R5 independently of the others is hydrogen, chlorine, methyl or methoxy, n is 1, 2 or 3, and A is an anion, with the proviso that at most one of said hydroxyalkyl groups is present in the molecule.

Description

SPECIFICATION Cationic pyrazole-azo compounds the present invention relates to novel pyrazole-azo compounds, to their preparation, and to the use thereof as dyes for dyeing or printing materials which are dyeable with cationic dyes, preferably those made of polyacrylonitrile, acid-modified polyamide or acid-modified polyester.
Cationic pyrazole-azo compounds carrying unsubstituted or N-substituted anilines as coupling component are disclosed in a host of publications (q.v. for example US patent 3 435 022, GB patents 1 404097 and 1 438 386, French patents 1 392 581 and 1 392 645, and SU patent 914603 (C.A. Vol. 97, 11285).
The novel cationic pyrazole-azo compounds of this invention are characterised by the formula
wherein R, is methyl, ethyl, hydroxyethyl or 2-hydroxypropyl, R2 is C3-C6aikyl, R3 is C3-C6alkyl, hydroxyethyl or 2-hydroxypropyl, R4 is hydrogen, methyl or methoxy, and each R5 independently of the others is hydrogen, chlorine, methyl or methoxy, n is 1, 2 or 3, and A is an anion, with the proviso that at most one of said hydroxyalkyl groups is present in the molecule.
An alkyl radical R2 or R3 may be straight chain or branched and is preferably the isopropyl or n-propyl radical. The index n is preferably 1 or 2 and, most preferably, 1.
The anion A" may be any inorganic or organic anion which acts solely as counterion for the positive charge at the pyrazole nitrogen atom. It may be identical to the anion introduced during the quaternisation, but can also be introduced subsequently in exchange for another anion.
Examples of possible anions A" are: halide (e.g. chloride, bromide or iodide) ions, boron tetrafluoride, thiocyanide, sulfate, methylsulfate, ethylsulfate, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, phosphoromolybdate, phosphorotungstate, phosphorotungstomolybdate, benzenesulfonate, naphthalenesulfonate, 4-Chlorobenzenesulfonate, oxalate, maleate, formate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or benzoate ions, or complex anions, for example those of chlorozinc double salts.
Preferred anions are halide, sulfate, methylsulfate, ethylsulfate, phosphate, benzenesulfonate, 4chlorobenzenesulfonate, oxalate, formate, acetate and methanesulfonate ions, as well as the cited complex anions.
It will be readily understood that the invention also encompasses all possible tautomeric forms of compounds of formula (1), e.g.:
In the above formulae, B is
Compounds meriting special mention within the scope of compounds of formula (1) are those wherein R4 is hydrogen, as well as those wherein R5 is hydrogen.
Preferred compounds of formula (1) are those wherein R1 is methyl or ethyl, preferably methyl.
Pyrazole-azo compounds of this invention which have a particularly interesting utility are those in which each of R2 and R3 independently of the other is C3-C6alkyl, especially those in which R2 and R3 are identical and are preferably propyl.
The novel cationic pyrazole-azo compounds are readily accessible and can be prepared by methods which are known per se. They can be obtained, for example, by diazotising an amine of formula
coupling the diazotised amine with an aniline of formula
and quaternising the resultant azo compound with a compound of formula R1-A (4) in which formulae above R1, R2, R3, R4, R5 and n are as defined in formula (1) and A is a radical which can be converted into the anion A in the quaternisation.
The amines of formula (2) (see e.g. the publications referred to at the outset), the anilines of formula (3) and the quaternising agent of formula (4) are known or can be readily prepared in a manner known per se.
The diazotisation of the amine of formula (2) is effected in a manner known per se, e.g. with sodium nitrite in acid aqueous medium, the acid employed being e.g. hydrochloric, sulfuric or phosphoric acid. However, the diazotisation can also be carried out with other diazotising agents, e.g. with nitrosylsulfuric acid. During diazotisation an additional acid may be present in the reaction medium, e.g. phosphoric acid, sulfuric acid, acetic acid, hydrochloric acid or a mixture of said acids, e.g. a mixture of phosphoric acid and acetic acid. The diazotisation is conveniently effected in the temperature range from - 100 to +30"C, e.g. from - 100 to room temperature.
The coupling of the diazotised amine of formula (2) to the coupling component of formula (3) is also carried out in known manner, e.g. in acid aqueous or aqueous-organic medium, with advantage in the temperature range from -10" to +30"C, preferably at below + 100C. The acid employed is suitably e.g. hydrochloric acid, acetic acid, sulfuric acid or phosphoric acid. Diazotisation and coupling can be carried out for example utilising a single reaction vessel for both steps without isolation of the intermediate, i.e. in the same reaction medium.
The quaternisation is conveniently carried out in an inert organic solvent, e.g. in a hydrocarbon, chlorinated hydrocarbon or nitrateted hydrocarbon such as benzene, toluene, xylene, tetrachloroethane, chloroform, carbon tetrachloride, monochlorobenzene, dichlorobenzene or nitrobenzene, in an acid amide or acid anhydride such as dimethylformamide, N-methylacetamide or acetic anhydride, in dimethylsulfoxide, or in a ketone such as acetone or methyl ethyl ketone. An excess of the alkylating agent may also be used instead of an organic solvent. The quaternisation may also be effected in aqueous medium, e.g. in aqueous suspension, or in glacial acetic acid.It is advantageous to effect the quaternisation at elevated temperature, e.g. in the range from 30 to 200"C, in particular from 80 to 150"C, if appropriate with the addition of an acid acceptor such as an inorganic base, e.g. magnesium oxide, magnesium carbonate, sodium carbonate, calcium carbonate or sodium bicarbonate, under pressure or at normal pressure. The most favourable conditions can be each case easily be determined in a preliminary test.
Examples of preferred quaternising agents R,A are e.g. alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide or ethyl iodide, and, in particular, alkyl sulfates, e.g. dimethyl or diethyl sulfate, and alkyl esters of aromatic sulfonic acids, e.g.
methyl p-toluenesulfonate or methyl benzenesulfonate, as well as n-propyl benzenesulfonate, isopropylbenzenesulfonate as well as ethylene oxide or propylene oxide. Thus the radical A is e.g. halogen (preferably chlorine, bromine or iodine), CH3SO4-, C2H5SO4- or
(R6=hydrogen, halogen, methyl) After the quaternisation, the novel cationic pyrazole-azo compounds can be isolated from the reaction medium and dried or used direct as solution. If desired or necessary, it is possible to replace the anion A' by another anion. To facilitate isolation, the compounds of formula (1) can be precipitated from the reaction medium e.g. by converting them into a salt which is sparingly soluble therein, i.e. by appropriate exchange of the anion A'.This can be done e.g. by addition of a halide (conversion into a halide: A =Hal) or e.g. of ZnCl2 and NaCI (conversion into a chlorozinc double salt: A =ZnCI22'/2) ("salting out'').
The novel cationic pyrazole-azo compounds of formula (1) are used as dyes for dyeing and, with the addition of binding agents and solvents, for printing materials which can be dyed with cationic dyes, in particular textile fibre materials. These materials consist e.g. of homopolymers or copolymers of acrylonitrile (polyacrylonitrile) or synthetic polyamides or polyesters which are modified by acid groups. In addition, the novel cationic azo compounds are also used for dyeing gel fibres, plastics materials preferably consisting of the polymers indicated above, as well as tanned cellulosic materials, and leather and paper.The use of the azo compounds of the invention and a process for dyeing or printing the above-mentioned materials, which comprises applying to or incorporating one or more of the compounds of formula (1) in said materials likewise constitute objects of the present invention, as does the dyed material obtained by this dyeing process.
The cationic dyes of the general formula (1) are particularly suitable for dyeing flocks, fibres, filaments, ribbons, wovens or knits made of polyacrylonitrile or of copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazoie, vinyl alcohol, acrylates, methacrylates, acrylamides, methacrylamides and asymmetric dicyanoethylene, which copolymers contain at least 85% of acrylonitrile. Flocks, fibres, filaments, ribbons, wovens or knits made of acid modified synthetic materials, in particular acid modified aromatic polyesters and acid modified polyamide fibres can also be dyed.Examples of acid modified aromatic polyesters are the polycondensation products of sulfoterephthalic acid and ethylene glycol, i.e. polyethylene glycol terephthalates which contain sulfonic acid groups.
Dyeing is preferably carried out in aqueous neutral or acid medium by the exhaust process, with pressure or at normal pressure, or by the continuous process. In the dyeing process, the material to be dyed is e.g. put into the dye bath at a temperature in the range from about 40 to 60"C and then dyed at boiling point. It is also possible to carry out dyeing under pressure at a temperature above 100"C, e.g. in the range from 110 to 1300C, in a pressure dyeing apparatus. The textile material to be dyed may be in a multiplicity of forms, e.g. in the form of fibres, filaments, wovens, knits, piece goods or finished articles.
When applied to the above-mentioned materials, the pyrazole-azo compounds of formula (1) of the present invention give red dyeings or prints which have very good properties, in particular high pH stability and fastness to steam, and excellent lightfastness. The dyes of formula (1) have very good affinity for the substrates. Surprisingly, the dyeings exhibit no "first brake", i.e. no diminution of lightfastness after a brief exposure time, e.g. within the first 30 hours, as may frequently be observed in dyeings obtained with dyes of similar constitution.
The compounds of formula (1) can be used as dyes for the above described utilities as single compounds or also in mixtures which contain at least two compounds of formula (1).
The invention is further illustrated by the following Examples, in which parts and percentages are by weight unless otherwise stated. Melting points are uncorrected.
Example 1: a) 43.2 parts of 1-phenyl-3-methyl-5-aminopyrazole are dissolved at 50"-550C in 203 parts of 68% sulfuric acid. The solution is cooled to 5 to - 100C and diazotised over 30 minutes by the dropwise additionof 79.4 parts of 40% nitrosylsulfuric acid.The diazo solution is stirred for 1 hour at the same temperature and then a solution of 44.2 parts of N,N-dipropylaniline in 100 parts of glacial acetic acid and 50 parts of propionic acid is added dropwise at --5" to -10"C. After stirring for 2 hours at the same temperature, the reaction mixture is added dropwise at 0"-5"C to a mixture of 750 parts of ice and 750 parts of water, while keeping the pH constant at 2-2.5 by the simultaneous dropwise addition of 1164 parts of 15% sodium hydroxide solution. The azo compound is extracted from the resultant suspension with 1300 parts of methylene chloride and the extract is dried over sodium sulfate. The solvent is then distilled off, affording 84 parts of the azo compound of the formula
with a melting point of 90"-93"C.
b) 52 parts of the azo compound of formula (100), 24.3 parts of magnesium oxide and 650 parts of ethylene chloride are heated to 75"-80"C. Then 72 parts of dimethyl sulfate are added dropwise over 60 minutes and the mixture is stirred for 3 hours at the indicated temperature.
The solvent is distilled off and the residual reaction product is dissolved in 1500 parts of water.
The solution is heated to 70"C and clarified by filtration, adjusted to pH 4 at room temperature with 2N hydrochloric acid, and the reaction product is salted with with 215 parts of sodium chloride and 14 parts of zinc chloride. The precipitated product is isolated by filtration and dried, affording 53 parts of the quaternised azo compound of formula
with a melting point of 162"-172"C.
Example 2: The procedure of Example 1 is repeated, using 1 is repeated, using 1-phenyl-3-methyl-5aminopyrazole as diazo component, a suitably substituted aniline as coupling component, and a suitable quaternising agent that introduces the radical R1, to give the quaternised azo compounds of the formula
listed in the following table. Table
Shade on Compound R1 R2 R3 R4 A# polyacrylonitrile 201 CH3 n-C4H9 n-C4H9 H ZnCl42# red 202 C2H4OH *) n-C3H7 n-C3H7 H ZnCl42# red 203 CH3 n-C3H7 C2H4OH H ZnCl42# red 204 CH3 n-C3H7 n-C3H7 OCH3 ZnCl42# red 205 CH3 n-C3H7 n-C3H7 CH3 ZnCl42# red 206 CH3CH(OH)CH2 **) n-C3H7 n-C3H7 H ZnCl42# red 207 CH3 n-C4H9 C2H4OH H ZnCl42# red 208 CH3 n-C5H11 C2H4OH H ZnCl42# red 209 CH3CH(OH)CH2 n-C4H9 n-C4H9 H ZnCl42# red Table (continuation)
Shade on Compound R1 R2 R3 R4 A# polyacrylonitrile 210 CH3 n-C6H13 n-C6H13 H ZnCl42# red 211 C2H4OH *) n-C6H13 n-C6H13 H ZnCl42# red 212 C2H4OH *) n-C6H13 n-C6H13 CH3 ZnCl42# red 213 CH3 n-C4H9 n-C4H9 CH3 ZnCl42# red *) The quaternisation is carried out with ethylene oxide.
**) The quaternisation is carried out with propylene oxide.
The compounds (101) and (201)-(213) can also be isolated with another anion AO, for example as chloride, iodide, bromide or acetate, if they are salted out of the reaction mixture with a suitable salt, e.g. NaCI, KBr, KI, sodium acetate and the like. However, they can also be isolated direct, e.g. as methosulfate (Ae=CH3SO43) [compounds (201), (203)-(205), (207), (208), (210) and (213)], which can be quaternised with dimethyl sulfate.
Example 3: A polyacrylonitrile fabric is put at 600C into an aqueous bath (goods to liquor ratio 1:80) which contains, per litre, 0.125 g of glacial acetic acid, 0.375 g of sodium acetate and 0.075 g of the dye of formula (101) (or the corresponding amount of a solid or liquid formulation of said dye). The bath is heated over 20 to 30 minutes to the boil and then kept for 90 minutes at this temperature. After rinsing, a brilliant red dyeing of very good fastness properties is obtained.
Example 4: An acid modified polyester fabric is put at 200C into an aqueous bath (goods to liquor ratio 1:30) which contains, per litre, 6 g of sodium sulfate, 2 g of ammonium sulfate and 0.15 g of the dye of formula (101) (or the corresponding amount of a solid or liquid formulation of said dye). The bath is adjusted with formic acid to pH 5.5. The dyeing is carried out in a closed vessel by heating over 45 minutes to 120"C and maintaining this temperature, with shaking, for 60 minutes. After rinsing and drying, a brillant red dyeing of very good fastness properties is obtained.
If a compound of formulae (201) to (213) is used instead of the compound of formula (101) in Examples 3 and 4, red dyeings of comparably good fastness properties are also obtained on the fabrics employed.

Claims (16)

1. A cationic pyrazole-azo compound of formula
wherein R1 is methyl, ethyl, hydroxyethyl or 2-hydroxypropyl, R2 is C3-C6alkyl, R3 is C3-C6alkyl, hydroxyethyl or 2-hydroxypropyl, R4 is hydrogen, methyl or methoxy, and each R5 independently of the others is hydrogen, chlorine, methyl or methoxy, n is 1, 2 or 3, and AO is an anion, with the proviso that at most one of said hydroxyalkyl groups is present in the molecule.
2. A cationic pyrazole-azo compound according to claim 1, wherein n is 1.
3. A cationic pyrazole-azo compound according to either claim 1 or claim 2, wherein R4 and R5 are hydrogen.
4. A cationic pyrazole-azo compound according to any one of claims 1 to 3, wherein R, is methyl or ethyl.
5. A cationic pyrazole-azo compound according to claim 4 wherein R1 is methyl.
6. A cationic pyrazole-azo compound according to any one of claims 1 to 5, wherein each of R2 and R3 independently of the other is C3-C6 alkyl.
7. A cationic pyrazole-azo compound according to claim 6, wherein R2 and R3 are the same and are propyl.
8. A process for the preparation of a cationic pyrazole-azo compound as defined in claim 1, which comprises diazotising an amine of formula
coupling the diazotised amine with an aniline of formula
and quaternising the resultant azo compound with a compound of formula R,-A in which formulae above R1, R2, Rt, R4, Rs and n are as defined in claim 1 and A is a radical which can be converted into the anion A in the quaternisation.
9. A process for dyeing or printing material which is dyeable cationic dyes, which comprises applying to, or incorporating in, said material one or more compounds as defined in claim 1.
10. A process according to claim 9, wherein the material which is dyeable with cationic dyes consists of acid-modified polyamide or acid-modified polyester.
11. A process according to claim 9, wherein the material which is dyeable with cationic dyes is textile material.
12. A process according to claim 11 wherein the textile material is polyacrylonitrile.
13. The material dyed or printed by a process as claimed in any one of claims 9 to 12.
14. Polyacrylonitrile textile material which is dyed or printed by a process as claimed in claim 12.
15. A cationic pyrazole-azo compound according to claim 1 substantially as hereinbefore described with reference to Example 1 or 2.
16. A process according to claim 9 substantially as hereinbefore described with reference to Example 3 or 4.
GB08530952A 1984-12-20 1985-12-16 Cationic pyrazole-azo compounds Expired GB2168713B (en)

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CH605284A CH661739A5 (en) 1984-12-20 1984-12-20 CATIONIC PYRAZOLE AZO COMPOUNDS.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6489452B1 (en) 2000-03-22 2002-12-03 Fuji Photo Film Co., Ltd. Azo dyes, process for making the same, ink-jet printing ink, ink-jet recording method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1086994A (en) * 1964-07-10 1967-10-11 Geigy Ag J R Monazo heterocyclic dyes, cationic derivatives thereof, and their use

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Publication number Priority date Publication date Assignee Title
US3515715A (en) * 1967-01-23 1970-06-02 Eastman Kodak Co Quaternized pyrazolylazo dyes
BE795903A (en) * 1972-02-24 1973-08-23 Ugine Kuhlmann NEW AZO-PYRAZOLIUM COLORS
CH578029A5 (en) * 1972-07-13 1976-07-30 Basf Ag
FR2240269B1 (en) * 1973-08-08 1978-11-10 Ugine Kuhlmann
DE2553508A1 (en) * 1975-11-28 1977-06-02 Hoechst Ag AZO BASIC DYES, METHOD FOR THEIR MANUFACTURING AND USE
US4382801A (en) * 1980-12-24 1983-05-10 Ciba-Geigy Corporation Process for spin dyeing polymers or copolymers of acrylonitrile with quaternized heterocyclic diazo dye and tetrafluoro-borate anion

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
GB1086994A (en) * 1964-07-10 1967-10-11 Geigy Ag J R Monazo heterocyclic dyes, cationic derivatives thereof, and their use

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6489452B1 (en) 2000-03-22 2002-12-03 Fuji Photo Film Co., Ltd. Azo dyes, process for making the same, ink-jet printing ink, ink-jet recording method
US6613888B2 (en) 2000-03-22 2003-09-02 Fuji Photo Film Co., Ltd. Azo dyes, process for making the same, ink-jet printing ink, ink-jet recording method

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DE3544574A1 (en) 1986-07-10
FR2575169A1 (en) 1986-06-27
GB2168713B (en) 1988-07-06
GB8530952D0 (en) 1986-01-29
FR2575169B1 (en) 1988-11-10
JPS61152768A (en) 1986-07-11
CH661739A5 (en) 1987-08-14

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