| United States Patent | RE35,359 |
| Hari , et al. | October 22, 1996 |
Amine salts of azo pigments based on pyrazolone derivatives
Abstract
Compounds of formula ##STR1## wherein a and b are each independently of the other halogen, --CH.sub.3, --C.sub.2 H.sub.5, --OC.sub.2 H.sub.5 or the group of formula --NHCO--C.sub.1 -C.sub.4 alkyl, c and d are each independently of the other hydrogen, halogen, --CH.sub.3, --C.sub.2 H.sub.5, --OCH.sub.3, --OC.sub.2 H.sub.5 or the group of formula --NHCO--C.sub.1 -C.sub.4 alkyl, and R.sup.1 is --CH.sub.3, phenyl, --COOCH.sub.3, --COOC.sub.2 H.sub.5, --NHCO--C.sub.1 --C.sub.4 alkyl or --CONH--C.sub.1 -C.sub.4 alkyl, and R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each independently hydrogen, C.sub.1 -C.sub.4 alkyl, unsubstituted or substituted by a chlorine atom or a --OH group, or are C.sub.7 -C.sub.9 aralkyl, C.sub.6 -C.sub.8 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 R.sup.3 and R.sup.4, together with the linking nitrogen atom, are a pyrrolidine, imidazolidine, piperidine, piperazine or morpholine radical, or R.sup.3, R.sup.4 and R.sup.5, 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.
| Inventors: | Hari; Stefan (Reinach, CH), Cseh; Georg (Posat, CH) |
| Assignee: |
Ciba-Geigy Corporation
(Tarrytown,
NY)
|
| Appl. No.: | 08/312,209 |
| Filed: | September 26, 1994 |
| Application Number | Filing Date | Patent Number | Issue Date | ||
| 207414 | Jun., 1988 | 4992495 | Feb., 1991 | ||
| 20059 | Feb., 1987 | ||||
| Reissue of: | 612764 | Nov., 1990 | 05151505 | Sep., 1992 | |
| Mar 10, 1986 [CH] | 961/86 | |||
| Current U.S. Class: | 534/728 ; 534/784; 534/793 |
| Current International Class: | C09B 29/01 (20060101); C09B 29/00 (20060101); C09B 29/50 (20060101); C09B 029/03 (); C09B 029/10 (); D06P 001/44 (); D06P 005/00 () |
| Field of Search: | 534/728,784,793 |
| 839605 | December 1906 | Kuchenbecker |
| 901675 | October 1908 | Boniger |
| 2490703 | December 1949 | Paige |
| 2842537 | July 1958 | Strobel et al. |
| 3671254 | June 1972 | Dostes |
| 3770638 | November 1973 | Checkak |
| 3802836 | April 1974 | Speck |
| 4388115 | June 1983 | Sugiuyama et al. |
| 4594411 | June 1986 | Henning |
| 4992495 | February 1991 | Hari et al. |
| 0225553 | Jun., 1987 | EP | |||
| 2616981 | Oct., 1977 | DE | |||
| 763555 | Dec., 1956 | GB | |||
| 1286770 | Aug., 1972 | GB | |||
| 1410862 | Oct., 1975 | GB | |||
| 1490139 | Oct., 1977 | GB | |||
Attorney, Agent or Firm:
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.
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 --CH.sub.3, .Iaddend.
c and d are each independently of the hydrogen, --Cl or --CH.sub.3,
R.sup.1 is --CH.sub.3, and
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 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 --CH.sub.3. .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.
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, --CH.sub.3, --C.sub.2 H.sub.5, --OCH.sub.3, --OC.sub.2 H.sub.5 or the group of formula --NHCO--C.sub.1 -C.sub.4 alkyl, c and d are each independently of the other hydrogen, halogen, --CH.sub.3, --C.sub.2 H.sub.5, --OCH.sub.3, --OC.sub.2 H.sub.5 or the group of formula --NHCO--C.sub.1 -C.sub.4 alkyl, and R.sup.1 is --CH.sub.3, phenyl, --COOCH.sub.3, --COOC.sub.2 .sub.5, --NHCO--C.sub.1 -C.sub.4 alkyl or --CONH--C.sub.1 -C.sub.4 alkyl, and R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each independently hydrogen, C.sub.1 -C.sub.4 alkyl, unsubstituted or substituted by a chlorine atom or a --OH group, or are C.sub.7 -C.sub.9 aralkyl, C.sub.5 -C.sub.8 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 R.sup.3 and R.sup.4, together with the linking nitrogen atom, are a pyrrolidine, imidazolidine, piperidine, piperazine or morpholine radical, or R.sup.3, R.sup.4 and R.sup.5, together with the linking nitrogen atom, are a pyrrole, pyridine, picoline, pyrazine, quinoline or isoquinoline radical.
The C.sub.1 -C.sub.4 alkyl moiety of --NHCO--C.sub.1 -C.sub.4 alkyl and --CONH--C.sub.1 -C.sub.4 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 R.sup.2, R.sup.3, R.sup.4 and R.sup.5 of phenyl is fluorine, chlorine, bromine or iodine, with chlorine or bromine being preferred and chlorine most preferred.
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 as C.sub.1 -C.sub.4 alkyl may be methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
C.sub.1 -C.sub.4 Alkyl substituted by a chlorine atom or a --OH group may be .beta.-chloroethyl or 2-hydroxyethyl.
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 as C.sub.7 -C.sub.9 aralkyl may be benzyl or ethylphenyl.
C.sub.5 -C.sub.8 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, --CH.sub.3 or --OCH.sub.3, c and d are each independently of the other hydrogen, --Cl, --Br, --CH.sub.3 or --OCH.sub.3, R.sup.1 is --CH.sub.3, --COOC.sub.2 H.sub.5, --CONHCH.sub.3 or --NHCOCH.sub.3, and R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each independently hydrogen or --CH.sub.3.
The most preferred compounds of formula I are those wherein a and b are each independently of the other --Cl or --CH.sub.3, c and d are each independently of the other hydrogen, --Cl or --CH.sub.3, R.sup.1 is --CH.sub.3 and R.sup.2, R.sup.3, R.sup.4 and R.sup.5 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
in the form of its chloride or sulfate, in which formulae II, III and IV above a, b, c, d, R.sup.1 and R.sup.2 to R.sup.5 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. NaNO.sub.2, 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.degree. 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 PVC Example Amine hydrochloride A (0.2% of pigment) __________________________________________________________________________ 2 ammonium chloride ##STR8## yellow 3 methylamine hydrochloride ##STR9## orange yellow 4 benzylamine hydrochloride ##STR10## yellow 5 trimethylamine hydrochloride ##STR11## yellow 6 tetramethylammonium chloride ##STR12## greenish yellow 7 2,5-dimethylaniline hydrochloride ##STR13## yellow 8 pyridine hydrochloride ##STR14## yellow 9 2-hydroxyethyl hydrochloride ##STR15## yellow 10 cyclohexylamine hydrochloride ##STR16## yellow 11 morpholine hydrochloride ##STR17## yellow 12 2-aminopyridine hydrochloride ##STR18## yellow 13 6-amino-benzthiazole hydrochloride ##STR19## yellow 14 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.degree. 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.degree. 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 PVC Example Amine of formula II of formula III formula IV (0.2% of pigment) __________________________________________________________________________ 16 ##STR21## ##STR22## NH.sub.3 yellowish orange 17 ##STR23## ##STR24## CH.sub.3 NH.sub.2 yellowish orange 18 ##STR25## ##STR26## NH.sub.3 yellow 19 ##STR27## ##STR28## CH.sub.3 NH.sub.2 yellow 20 ##STR29## ##STR30## NH.sub.3 orange yellow 21 ##STR31## ##STR32## NH.sub.3 orange yellow 22 ##STR33## ##STR34## NH.sub.3 orange 23 ##STR35## ##STR36## NH.sub.3 yellow 24 ##STR37## ##STR38## NH.sub.3 greenish yellow 25 ##STR39## ##STR40## NH.sub.3 greenish yellow 26 ##STR41## ##STR42## NH.sub.3 greenish yellow 27 ##STR43## ##STR44## NH.sub.3 greenish yellow 28 ##STR45## ##STR46## NH.sub.3 greenish yellow 29 ##STR47## ##STR48## NH.sub.3 yellow 30 ##STR49## ##STR50## CH.sub.3 NH.sub.2 orange 31 ##STR51## ##STR52## NH.sub.3 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.degree. 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.degree. to 22.degree. C. When coupling is complete, this suspension is heated to 80.degree. 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.degree. 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.degree. 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.degree. 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.
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