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Publication numberUSRE35359 E
Publication typeGrant
Application numberUS 08/312,209
Publication dateOct 22, 1996
Filing dateSep 26, 1994
Priority dateMar 10, 1986
Also published asCA1277979C, DE3784362D1, EP0241413A2, EP0241413A3, EP0241413B1, US4992495, US5151505
Publication number08312209, 312209, US RE35359 E, US RE35359E, US-E-RE35359, USRE35359 E, USRE35359E
InventorsStefan Hari, Georg Cseh
Original AssigneeCiba-Geigy Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Amine salts of azo pigments based on pyrazolone derivatives
US RE35359 E
Abstract
Compounds of formula ##STR1## wherein a and b are each independently of the other halogen, --CH3, --C2 H5, --OC2 H5 or the group of formula --NHCO--C1 -C4 alkyl, c and d are each independently of the other hydrogen, halogen, --CH3, --C2 H5, --OCH3, --OC2 H5 or the group of formula --NHCO--C1 -C4 alkyl, and R1 is --CH3, phenyl, --COOCH3, --COOC2 H5, --NHCO--C1 --C4 alkyl or --CONH--C1 -C4 alkyl, and R2, R3, R4 and R5 are each independently hydrogen, C1 -C4 alkyl, unsubstituted or substituted by a chlorine atom or a --OH group, or are C7 -C9 aralkyl, C6 -C8 cycloalkyl, phenyl or phenyl which is substituted by 1 to 3 halogen atoms or methyl or methoxy groups, or is a heterocyclic radical of the benzimidazole, benzoxazole, benzthiazole or pyridine series, or R3 and R4, together with the linking nitrogen atom, are a pyrrolidine, imidazolidine, piperidine, piperazine or morpholine radical, or R3, R4 and R5, together with the linking nitrogen atom, are a pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline radical, are most suitable for coloring high molecular organic material.
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Claims(3)
What is claimed is:
1. A compound of formula I ##STR53## wherein .[.a and b are each --Cl,.]. .Iadd.a is --Cl and b is --Cl or --CH3, .Iaddend.
c and d are each independently of the hydrogen, --Cl or --CH3,
R1 is --CH3, and
R2, R3, R4 and R5 are each hydrogen.
2. A compound according to claim 1 wherein c and d are each hydrogen. .Iadd.3. A compound according to claim 2 wherein a is --Cl and b is --CH3. .Iaddend..Iadd.4. A compound according to claim 3 of the formula ##STR54##
.Iaddend. .Iadd.5. A compound according to claim 1, wherein a and b are each --Cl. .Iaddend.
Description

This is a divisional of application Ser. No. 207,414, filed on Jun. 16, 1988, now U.S. Pat. No. 4,992,495, issued on Feb. 12, 1991, which is in turn a continuation of application Ser. No. 020,059, filed on Feb. 27, 1987, now abandoned.

The present invention relates to novel amine salts of azo compounds, to the preparation thereof, and to the use thereof for colouring high molecular organic material.

Amine salts of azo compounds are known in the art. Thus, for example, ammonium salts of sulfonated azo dyes of the pyrazolone series are disclosed in European patent application 0 073 972. Such compounds are used as pigments for colouring plastics materials.

Specifically, the present invention relates to compounds of formula ##STR2## wherein a and b are each independently of the other halogen, --CH3, --C2 H5, --OCH3, --OC2 H5 or the group of formula --NHCO--C1 -C4 alkyl, c and d are each independently of the other hydrogen, halogen, --CH3, --C2 H5, --OCH3, --OC2 H5 or the group of formula --NHCO--C1 -C4 alkyl, and R1 is --CH3, phenyl, --COOCH3, --COOC2 5, --NHCO--C1 -C4 alkyl or --CONH--C1 -C4 alkyl, and R2, R3, R4 and R5 are each independently hydrogen, C1 -C4 alkyl, unsubstituted or substituted by a chlorine atom or a --OH group, or are C7 -C9 aralkyl, C5 -C8 cycloalkyl, phenyl or phenyl which is substituted by 1 to 3 halogen atoms or methyl or methoxy groups, or is a heterocyclic radical of the benzimidazole, benzoxazole, benzthiazole or pyridine series, or R3 and R4, together with the linking nitrogen atom, are a pyrrolidine, imidazolidine, piperidine, piperazine or morpholine radical, or R3, R4 and R5, together with the linking nitrogen atom, are a pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline radical.

The C1 -C4 alkyl moiety of --NHCO--C1 -C4 alkyl and --CONH--C1 -C4 alkyl radicals may be methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl, with methyl being preferred.

Halogen by itself as a, b, c and d and as substituent R2, R3, R4 and R5 of phenyl is fluorine, chlorine, bromine or iodine, with chlorine or bromine being preferred and chlorine most preferred.

R2, R3, R4 and R5 as C1 -C4 alkyl may be methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.

C1 -C4 Alkyl substituted by a chlorine atom or a --OH group may be β-chloroethyl or 2-hydroxyethyl.

R2, R3, R4 and R5 as C7 -C9 aralkyl may be benzyl or ethylphenyl.

C5 -C8 Cycloalkyl may be cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Heterocyclic radicals of the benzimidazole, benzoxazole, benzthiazole and pyridine series are e.g. radicals derived from 5-amino-benzimidazole, 5-amino-2-methylbenzimidazole, 5-aminobenzoxazole, 5-aminobenzthiazole, 2-amino-6-ethoxybenzthiazole, 2-aminobenzimidazole, and 2-, 3- or 4-aminopyridine.

Particularly preferred compounds of formula I are those wherein a and b are each independently of the other --Cl, --Br, --CH3 or --OCH3, c and d are each independently of the other hydrogen, --Cl, --Br, --CH3 or --OCH3, R1 is --CH3, --COOC2 H5, --CONHCH3 or --NHCOCH3, and R2, R3, R4 and R5 are each independently hydrogen or --CH3.

The most preferred compounds of formula I are those wherein a and b are each independently of the other --Cl or --CH3, c and d are each independently of the other hydrogen, --Cl or --CH3, R1 is --CH3 and R2, R3, R4 and R5 are hydrogen.

The compounds of formula I are prepared, for example, by reacting a diazo compound of an amine of formula II ##STR3## with a coupling component of formula III ##STR4## under reactions which are known per se, and subsequently treating the reaction product, which is preferably in the form of the free disulfonic acid, with a compound of formula IV

N.sup.⊕ (R2)(R3)(R4)(R5)           (IV)

in the form of its chloride or sulfate, in which formulae II, III and IV above a, b, c, d, R1 and R2 to R5 are as defined above.

Instead of the chloride or sulfate of this compound, it is also possible to use the free compound.

A variant of the process comprises carrying out the diazotisation and coupling steps without using an inorganic acid by mixing the amine of formula II and the coupling component of formula III, in water or in an organic solvent, with the stoichiometric amount of a nitrite, e.g. NaNO2, and converting the resultant azo compound into the compound of formula I by conventional methods. Examples of amines of formula II are: 2-amino-3-methyl-5-chlorobenzenesulfonic acid, 2-amino-3,4-dichlorobenzenesulfonic acid, 2-amino-3,5-dichlorobenzenesulfonic acid, 2-amino-3,5-dimethylbenzenesulfonic acid, 2-amino-4,5-dimethylbenzenesulfonic acid, 2-amino-4-chloro-5-acetylaminobenzenesulfonic acid, 2-amino-4-methoxy-5-acetylaminobenzenesulfonic acid, 2-amino-4-chloro-5-methylbenzenesulfonic acid, 2-amino-4-methyl-5-chlorobenzenesulfonic acid, 2-amino-4,5-dichlorobenzenesulfonic acid, 2-amino-4-chloro-5-methoxybenzenesulfonic acid.

Examples of coupling components of formula III are:

1-(2'-sulfophenyl)-3-methyl-5-pyrazolone;

1-(4',5'-dichloro-2'-sulfophenyl)-3-methyl-5-pyrazolone,

1-(3'-sulfophenyl)-3-methyl-5-pyrazolone,

1-(6'-chloro-3'-sulfophenyl)-3-methyl-5-pyrazolone,

1-(4'-sulfophenyl-3-methyl-5-pyrazolone,

1-(2'-chloro-6'-methyl-4'-sulfophenyl)-3-methyl-5-pyrazolone,

1-(2'-methyl-4'-sulfophenyl)-3-methylpyrazolone,

1-(2',5'-dichloro-4'-sulfophenyl)-3-methylpyrazolone,

1-(3'-sulfophenyl)-3-carbomethoxy-5-pyrazolone,

1-(2',5'-dichloro-4'-sulfophenyl)-3-carbomethoxy-5-pyrazolone,

1-(3'-sulfophenyl)-3-carboethoxy-5-pyrazolone,

1-(2',5'-dichloro-4'-sulfophenyl)-3-carboethoxy-5-pyrazolone,

1-(3'-sulfophenyl)-3-(N-methylcarbamyl)-5-pyrazolone,

1-(3'-sulfophenyl)-3-acetylamino-5-pyrazolone,

1-(2',5'-dichloro-4'-sulfophenyl)-3-acetylamino-5-pyrazolone.

Examples of free compounds of formula IV are: ammonia, methylamine, ethylamine, n-propylamine, n-butylamine, cyclohexylamine, benzylamine, aniline, 2-chloroaniline, 2-, 3- or 4-methylaniline, 2,4-dimethylaniline, 2,4,6-trimethylamine, dimethylamine, trimethylamine, tetramethylamine, 2-, 3- or 4-aminopyridine, morpholine, piperidine, 2-, 3- or 4-picoline as well as pyridine.

The compounds of formula I can be used as pigments for colouring high molecular organic material. They can normally be used direct in the form in which they are obtained in their synthesis. Depending on the envisaged utility, the compounds of formula I can be converted into a more opaque or more transparent form.

If it is desired to obtain a more opaque pigment form, then it is usually expedient to effect a thermal aftertreatment in water or an organic solvent, under normal or elevated pressure. It is preferred to use organic solvents such as benzenes which are substituted by halogen atoms, alkyl or nitro groups, for example xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene, as well as pyridine bases such as pyridine, picoline or quinoline, and also ketones such as cyclohexanone, alcohols such as isopropanol, butanols or pentanols, ethers such as ethylene glycol monomethyl or monoethyl ether, amides such as dimethylformamide or N-methylpyrrolidone, as well as dimethylsulfoxide or sulfolane. The aftertreatment can also be carried out in water, under normal or elevated pressure, in the presence of organic solvents and/or with the addition of surfactants.

Examples of high molecular organic materials which may be coloured with the compounds of formula I are cellulose ethers and esters such as ethyl cellulose, nitrocellulose, cellulose acetate, cellulose butyrate, natural resins or synthetic resins such as polymerisation resins or condensation resins, for example aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyesters, rubber, casein, silicone and silicone resins, singly or in mixtures.

The compounds of formula I are particularly suitable for colouring polyvinyl chloride and polyolefins such as polyethylene and polypropylene.

The above high molecular organic compounds may be singly or as mixtures in the form of plastics, metals or of spinning solutions, varnishes, paints or printing inks. Depending on the utility, it is advantageous to use the compounds of formula I as toners or in the form of preparations.

The compounds of formula I are preferably employed in an amount of 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on the high molecular organic material to be pigmented.

The pigmenting of the high molecular organic compounds with the compounds of formula I is carried out for example by incorporating such a compound, optionally in the form of a masterbatch, into the substrates using roll mills, mixing or grinding machines. The pigmented material is then brought into the desired final form by methods which are known per se, for example calendering, moulding, extruding, coating, spinning, casting or by injection moulding. It is often desirable to incorporate plasticisers into the high molecular compounds before processing in order to produce nonbrittle mouldings or to diminish their brittleness. Suitable plasticisers are for example esters of phosphoric acid, phthalic acid or sebacic acid. The plasticisers may be incorporated before or after working the compound of formula I into the polymers. To obtain different shades, it is also possible to add fillers or other chromophoric components such as white, coloured or black pigments, in any amount, to the high molecular organic compounds, in addition to the compounds of formula I.

For pigmenting varnishes and printing ink, the high molecular organic materials and the compounds of formula I, together with optional additives such as fillers, other pigments, siccatives or plasticisers, are finely dispersed or dissolved in a common organic solvent or mixture of solvents. The procedure may be such that the individual components by themselves, or also several jointly, are dispersed or dissolved in the solvent and subsequently all the components are mixed.

The colourations obtained, for example, in polyvinyl chloride or polyolefins with the compounds of formula I, have a good allround fastness properties such as good dispersibility, high tinting strength and purity, good fastness to migration, heat, light, and weathering, as well as good hiding power.

In the following Examples, parts and percentages are by weight.

EXAMPLE 1

5.2 g of the azo compound of formula ##STR5## (obtainable by known methods) are dissolved at room temperature in a mixture of 50 ml of acetic acid and 50 ml of deionised water. To the clear, dark red solution is added, over 2 minutes, a solution of 2.6 g of aniline hydrochloride in 10 ml of distilled water. The resultant orange yellow suspension is stirred for 3 hours at room temperature and filtered. The filter residue is washed with 100 ml of deionised water and vacuum dried at 60 C., affording 5.1 g of a deep orange powder of formula ##STR6##

Analysis: theory (in %): C 48.49, H 3.78; Cl 10.22; N 12.11; S 9.24; found (in %): C 48.32; H 3.87; Cl 10.46; N 12.20; S 8.90.

This compound colours polyvinyl chloride and polyethylene in strong, fast yellow shades.

Instead of using aniline hydrochloride, it is possible to use other amine hydrochlorides listed in the following table to give the compounds of formula ##STR7## in accordance with the process conditions described in this Example.

__________________________________________________________________________                                      Shade in soft PVCExampleAmine hydrochloride   A               (0.2% of pigment)__________________________________________________________________________2    ammonium chloride                       ##STR8##       yellow3    methylamine hydrochloride                       ##STR9##       orange yellow4    benzylamine hydrochloride                       ##STR10##      yellow5    trimethylamine hydrochloride                       ##STR11##      yellow6    tetramethylammonium chloride                       ##STR12##      greenish yellow7    2,5-dimethylaniline hydrochloride                       ##STR13##      yellow8    pyridine hydrochloride                       ##STR14##      yellow9    2-hydroxyethyl hydrochloride                       ##STR15##      yellow10   cyclohexylamine hydrochloride                       ##STR16##      yellow11   morpholine hydrochloride                       ##STR17##      yellow12   2-aminopyridine hydrochloride                       ##STR18##      yellow13   6-amino-benzthiazole hydrochloride                       ##STR19##      yellow14   5-amino-2-methylbenzimidazole hydrochloride                       ##STR20##      yellow__________________________________________________________________________
EXAMPLE 15

15.4 g of 36% disodium salt of the azo compound used in Example 1 and 4.4 g of ammonium chloride are heated to 80 C. in 100 ml of deionised water. The deep yellow suspension is stirred for 4 hours at this temperature, cooled to room temperature and filtered. The filter residue is washed with a small amount of deionised water and vacuum dried at 60 C., affording 5.1 g (94.2% of theory) of a product that is identical structurally and in all properties with the pigment obtained in Example 2. In analogues manner, further compounds of formula I can be prepared starting from an amine of formula II, a coupling component of formula III and an amine of formula IV, as listed in the following table.

__________________________________________________________________________             Coupling component                            Amine of                                  Shade in soft PVCExampleAmine of formula II             of formula III formula IV                                  (0.2% of pigment)__________________________________________________________________________16 ##STR21##              ##STR22##     NH3                                  yellowish orange17 ##STR23##              ##STR24##     CH3 NH2                                  yellowish orange18 ##STR25##              ##STR26##     NH3                                  yellow19 ##STR27##              ##STR28##     CH3 NH2                                  yellow20 ##STR29##              ##STR30##     NH3                                  orange yellow21 ##STR31##              ##STR32##     NH3                                  orange yellow22 ##STR33##              ##STR34##     NH3                                  orange23 ##STR35##              ##STR36##     NH3                                  yellow24 ##STR37##              ##STR38##     NH3                                  greenish yellow25 ##STR39##              ##STR40##     NH3                                  greenish yellow26 ##STR41##              ##STR42##     NH3                                  greenish yellow27 ##STR43##              ##STR44##     NH3                                  greenish yellow28 ##STR45##              ##STR46##     NH3                                  greenish yellow29 ##STR47##              ##STR48##     NH3                                  yellow30 ##STR49##              ##STR50##     CH3 NH2                                  orange31 ##STR51##              ##STR52##     NH3                                  yellow__________________________________________________________________________
EXAMPLE 32

13 g of 93% 2-amino-4,5-dichlorobenzenesulfonic acid are dissolved in 90 ml of deionised water and 5.7 ml of 25% ammonia solution. Then 27.5 ml of 23.5% hydrochloric acid are added to the clear, reddish violet solution. The resultant thick, white suspension is cooled to 5 C. and 12.5 ml of 4N sodium nitrite solutions are then added over 5 minutes. Then 15.5 g of 90.1% 1-(3'-sulfophenyl)-3-methyl-5-pyrazolone in the form of a fine suspension in 100 ml of deionised water are added dropwise over 5 minutes to the slightly beige-coloured suspension. The pH of the resultant pale yellow suspension is adjusted to 6.5 with 15.5 ml of 25% ammonia solution. The now orange-coloured suspension is stirred for 3 hours, during which time the temperature of the suspension rises from 5 to 22 C. When coupling is complete, this suspension is heated to 80 C., stirred for 6 hours at this temperature, then cooled to room temperature and filtered. The filter residue is washed with a small amount of deionised water and vacuum dried at 60 C., affording 26.9 g (99.5% of theory) of a product which is identical with that of Example 2.

EXAMPLE 33

5.2 g of the azo compound used in Example 1 (disulfonic acid) are dissolved at 70 C. in 150 ml of deionised water. Then 1.85 g of aniline are added to the clear, red solution. The resultant orange suspension is stirred for 2 hours without heating and then filtered. The residue is washed with 100 ml of deionised water and vacuum dried at 60 C., affording 5.6 g (80.8% of theory) of an orange product that is identical in structure and all properties with the pigment obtained in Example 1.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US839605 *Feb 28, 1906Dec 25, 1906Hoechst AgYellow azo dye.
US901675 *Jun 11, 1908Oct 20, 1908Corp Of Chemical Works Formerly SandozYellow azo dye and process of making same.
US2490703 *May 1, 1946Dec 6, 1949Gen Aniline & Film CorpSalts of organic dyestuffs
US2842537 *Dec 30, 1953Jul 8, 1958Gen Aniline & Film CorpPyrazolone dyestuffs
US3671254 *Sep 4, 1970Jun 20, 1972Eastman Kodak CoRadiographic elements,compounds and processes
US3770638 *Nov 3, 1971Nov 6, 1973Eastman Kodak CoLiquid developers containing metal salts of acid dyes
US3802836 *Oct 30, 1972Apr 9, 1974Du PontAqueous dye baths containing mixtures of acidic dyes for deep-dyeing nylon yarns
US4388115 *Jun 15, 1981Jun 14, 1983Fuji Photo Film Co., Ltd.Aqueous ink composition
US4594411 *Jun 6, 1984Jun 10, 1986Basf AktiengesellschaftSulfonated monoazo colorant lake obtained by di-azo coupling of 5-acetylamino-2-aminobenzene-1-sulfonic acid with 1-(3'-sulfophenyl)-3-methylphyrazol-5-one
US4992495 *Jun 16, 1988Feb 12, 1991Ciba-Geigy CorporationProcess for coloring high-molecular weight organic material using amine salts of azo pigments based on pyrazolone derivatives
DE2616981A1 *Apr 17, 1976Oct 27, 1977Basf AgPyrazolon-azofarbstoffe
EP0225553A2 *Nov 27, 1986Jun 16, 1987Bayer AgAzo dye lacquer
GB763555A * Title not available
GB1286770A * Title not available
GB1410862A * Title not available
GB1490139A * Title not available
Classifications
U.S. Classification534/728, 534/784, 534/793
International ClassificationC08L101/00, C08K5/42, C08K5/34, C08K5/3442, C09B69/04, C08K5/41, C08K5/3445, C09B29/46, C09B29/01, C09B29/50
Cooperative ClassificationC09B29/0007, C09B29/366, C09B69/045
European ClassificationC09B69/04B, C09B29/00B1, C09B29/36B6B4
Legal Events
DateCodeEventDescription
Mar 27, 1998ASAssignment
Owner name: CIBA SPECIALTY CHEMICALS CORP., NEW YORK
Free format text: "RERECORD TO CORRECT ERRONEOUSLY STATED PROPERTY NUMBER 035706. PREVIOUSLY RECORDED AT REEL 8753, FRAME 0646.;ASSIGNOR:NOVARTIS CORPORATION;REEL/FRAME:009178/0934
Effective date: 19970818
Oct 1, 1997ASAssignment
Owner name: CIBA SPECIALTY CHEMICALS CORPORATION, NEW YORK
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NOVARTIS CORPORATION;REEL/FRAME:008753/0646
Effective date: 19970818
Sep 8, 1997ASAssignment
Owner name: NOVARTIS CORPORATION, NEW JERSEY
Free format text: CHANGE OF NAME;ASSIGNOR:CIBA-GEIGY CORPORATION;REEL/FRAME:008698/0892
Effective date: 19970811