Bis-(dialkoxycarbonylphenylazo)acetoacetamidoarylenes

Abstract

Compounds of the formula ##STR1## wherein each R 1 is alkyl of 1 to 3 carbon atoms, and A is phenylene, substituted phenylene, diphenylene, substituted diphenylene or naphthylene, wherein each substituent of substituted phenylene is independently fluoro, chloro, bromo, methyl, methoxy, ethoxy, trifluoromethyl or cyano and each substituent of substituted diphenylene is independently chloro, bromo, methyl or methoxy, With the proviso the two CO--O--R 1 groups on each ring are meta or para to each other. These compounds are eminently suitable as pigments for the mass pigmentation of synthetic polymers and resins such as polyethylene, polystyrene, polyvinyl chloride, poromerics and rubber latices.

Claims

Having thus disclosed the invention what we claim is: 1. A compound of the formula wherein each R 1 is alkyl of 1 to 3 carbon atoms, and A is phenylene, phenylene substituted by fluoro, chloro, bromo, methyl, methoxy, ethoxy, trifluoromethyl or cyano, diphenylene, diphenylene substituted by chloro, bromo, methyl or methoxy or naphthylene, with the provisos that (1) when A is substituted phenylene or substituted diphenylene having more than one substituent, the substituents are the same or different, and (2) the two --CO--O--R 1 groups on each benzene 2. A compound according to claim 1 wherein A is 1,4-phenylene, 1,4-phenylene substituted by 1 to 4 substituents, 4,4'-diphenylene, 4,4'-diphenylene substituted by 1 or 2 substituents on each benzene ring, 1,4-naphthylene, 1,5-naphthylene, 2,6-naphthylene or 4. A compound according to claim 3 wherein A is 1,4-phenylene or 1,4-phenylene substituted by 1 to 4 substituents. 5. A compound according to claim 4 having the formula ##STR6## wherein each R 2 is independently hydrogen, chloro, bromo, methyl, methoxy or ethoxy. 6. The compound according to claim 5 having the formula ##STR7## 7. The compound according to claim 5 having the formula ##STR8## 8. The compound according to claim 5 having the formula ##STR9## 9. The compound according to claim 5 having the formula ##STR10##
This application is a continuation-in-part of application Ser. No. 90 027, filed Nov. 16, 1970, and now abandoned. It has been found that excellent properties as pigments are shown by compounds of the formula ##STR2## in which the symbols R 1 stand for an alkyl group containing 1, 2 or 3 carbon atoms and A stands for unsubstituted phenylene or phenylene substituted by fluorine, chlorine, bromine, methyl, methoxy, ethoxy, trifluoromethyl or cyano, unsubstituted diphenylene or diphenylene substituted by chlorine, bromine, methyl or methoxy, or naphthylene, and in which the groups --CO--O--R 1 are bound in meta- or paraposition to each other on the pertinent benzene nuclei. The compounds of formula (I) are produced by the diazotization of 2 moles of an amine of the formula ##STR3## and coupling of the resulting diazonium compound with 1 mole of a compound of the formula H.sub.3 C--CO--CH.sub.2 --CO--NH--A--NH--CO--CH.sub.2 --CO--CH.sub.3 (III). the coupling reaction is generally carried out in weakly acid medium within the temperature range of -5° C to +20° C, more especially at 0° C to +5° C. The preferred compounds have the formula ##STR4## wherein the symbols R 2 stand for hydrogen, chlorine, bromine, methyl, methoxy or ethoxy. The disazo compounds, especially when they are submitted to the normal preparatory treatments for pigments, are suitable for the pigmentation of synthetic polymers and synthetic resins, such as polyethylene, polystyrene, polyvinyl chloride, poromerics (synthetic leather) and rubber latices, in the presence or absence of solvents. Further suitable uses include the dyeing of viscose rayon and cellulose acetate fibres in the spinning solution, the pigmentation of oil and water based paints, including lacquers and enamels, the pigmentation of printing inks, paper dyeing in the stock, and the coloration and printing of textiles. The yellow coloration imparted by the pigments in these various materials is resistant to migration and fast to light. The fastness to washing, cross dyeing, blind vats, rubbing, overspraying, solvents and bleaching with chlorine, hypochlorite or peroxide is good to very good. The pigments show notably good transparency and heat stability. In the following Examples the parts and percentages are by weight and the temperatures in degrees centigrade. EXAMPLE 1 8.4 Parts of 5-amino-iso-phthalic acid dimethyl ester are dissolved in 300 parts of water and 20 parts of concentrated hydrochloric acid with heating. The solution is allowed to cool to 20°, clarified by filtration and diazotized at 5° with 40 parts of 1 normal sodium nitrite solution. The diazo solution is adjusted to pH 4 with 50 % sodium acetate solution, whereupon a solution of 7.6 parts of 1,4-bis-(acetoacetylamino)-2,5-dichlorobenzene in 100 parts of water, cooled to about +5°, is slowly dropped in, along with 20 parts of ethanol and 10 parts of 30 % sodium hydroxide solution. After the coupling reaction is complete, stirring is continued for 1 hour at 80°, then the precipitate is filtered, washed free from salt and vacuum dried at 70°. A loose yellow powder pigment is obtained which has very good migration and heat resistance, light fastness and, in paints and lacquers, very good overspraying fastness. EXAMPLE 2 A solution of 8.4 parts of 2-aminoterephthalic acid dimethylester in 200 parts of water and 10 parts of concentrated hydrochloric acid is stirred for 2 hours at room temperature. It is then poured onto 200 parts of ice and diazotized with 40 parts of 1 normal sodium nitrite solution. The clear diazo solution is adjusted to pH 4 with 50 % sodium acetate solution and to it is slowly added a solution of 7.15 parts of 1,4-bis-(acetoacetylamino)-2-chloro-5-methylbenzene in 100 parts of water, cooled to about +5°, together with 20 parts of ethanol and 10 parts of 30 % sodium hydroxide solution. Subsequent to coupling, the mixture is stirred for 1 hour at 80°; then the product is isolated by filtration, freed from salt by washing with hot water, and dried at 70° with vacuum. It is a loose yellow pigment with notably good migration and heat resistance, light and overspraying fastness. The procedures of Examples 1 or 2 can be employed with the diazo and coupling components named in columns I and II of the following Table below, the pigments thus formed having the shades noted in column III of the table. TABLE______________________________________ExampleNo. I II III 3 2-Amino-iso- 1,4-Bis-(acetoacetyl- yellow phthalic acid dimethyl amino)-benzene ester 4 " 1,4-Bis-(acetoacetyl- " amino-2,5-dimethyl- benzene 5 " 1,4-Bis-(acetoacetyl- orange amino)-2,5-dimethoxy- benzene 6 " 1,4-Bis-(acetoacetyl- yellow amino)-2-methyl-5- chlorobenzene 7 " 1,4-Bis-(acetoacetyl- " amino)-2-methylbenzene 8 " 1,4-Bis-(acetoacetyl- " amino)-2-chlorobenzene 9 " 1,4-Bis-(acetoacetyl- " amino)-2-methoxybenzene10 " 1,4-Bis-(acetoacetyl- " amino)-2-methoxy-5- chlorobenzene11 " 1,4-Bis-(acetoacetyl- " amino)-2,3,5,6-tetra- chlorobenzene12 " 1,4-Bis-(acetoacetyl- " amino)-2,5-dimethyl-3,6- dichlorobenzene13 " 4,4'-Bis-(acetoacetyl- " amino)-diphenyl14 " 4,4'-Bis-(acetoacetyl- " amino)-3,3'-dichloro- diphenyl15 2-Amino-iso- 4,4'-Bis-(acetoacetyl- yellow phthalic acid dimethyl amino)-3,3'-dimethyldi- ester phenyl16 " 4,4'-Bis-(acetoacetyl- " amino)-3,3'-dimethoxy- diphenyl17 " 4,4'-Bis-(acetoacetyl- " amino)-2,2'-dichloro- 5,5'-dimethyldiphenyl18 " 1,5-Bis-(acetoacetyl- " amino)-naphthalene19 " 1,4-Bis-(acetoacetyl- " amino)-2-trifluoro- methylbenzene20 2-Aminotere- 1,4-Bis-(acetoacetyl- " phthalic acid dimethyl amino)-benzene ester21 " 1,4-Bis-(acetoacetyl- " amino)-2-chlorobenzene22 " 1,4-Bis-(acetoacetyl- " amino)-2,5-dibromo- benzene23 " 1,4-Bis-(acetoacetyl- " amino)-2-methylbenzene24 " 1,4-Bis-(acetoacetyl- orange amino)-2,5-dimethoxy- benzene25 " 1,4-Bis-(acetoacetyl- yellow amino)-2-methoxybenzene26 " 4,4'-Bis-(acetoacetyl- " amino)-diphenyl27 " 4,4'-Bis-(acetoacetyl- " amino)-3,3'-dichloro- diphenyl28 2-Aminotere- 4,4'-Bis-(acetoacetyl- yellow phthalic acid dimethyl amino)-3,3'-dimethoxy- ester diphenyl29 " 4,4'-Bis-(acetoacetyl- " amino)-3,3'-dimethyl- diphenyl30 " 1,4-Bis-(acetoacetyl- " amino)-2,5-dimethyl- benzene31 " 1,4-Bis-(acetoacetyl- " amino)-2-methyl-5- methoxybenzene32 " 1,4-Bis-(acetoacetyl- " amino)-2-methoxy-5- chlorobenzene33 2-Aminotere- 1,4-Bis-(acetoacetyl- yellow phthalic acid dimethyl amino)-2-bromobenzene ester34 " 1,4-Bis-(acetoacetyl- " amino)-2-trifluoromethyl- benzene35 " 1,4-Bis-(acetoacetyl- orange amino)-2,5-diethoxy- benzene36 " 1,4-Bis-(acetoacetyl- yellow amino)-2,3,5,6-tetra- chlorobenzene37 " 1,4-Bis-(acetoacetyl- " amino)-2,3,5,6-tetra- methylbenzene38 " 1,4-Bis-(acetoacetyl- " amino)-2,5-dimethyl- 3,6-dichlorobenzene39 " 2,7-Bis-(acetoacetyl- " amino)-naphthalene40 2-Aminotere- 1,4-Bis-(acetoacetyl- yellow phthalic acid dimethyl amino)-2,6-dichloro- ester benzene41 " 1,4-Bis-(acetoacetyl- " amino)-2,6-dimethyl- benzene42 " 1,4-Bis-(acetoacetyl- " amino)-naphthalene43 " 1,5-Bis-(acetoacetyl- " amino)-naphthalene44 2-Aminotere- 2,6-Bis-(acetoacetyl- yellow phthalic acid dimethyl amino)-naphthalene ester45 4-Amino-iso- 1,4-Bis-(acetoacetyl- " phthalic acid dimethyl amino)-benzene ester46 " 1,4-Bis-(acetoacetyl- " amino)-2,5-dichloro- benzene47 5-Aminotere- 1,4-Bis-(acetoacetyl- " phthalic acid diethyl amino)-benzene ester48 5-Aminotere- 1,4-Bis-(acetoacetyl- " phthalic acid di-N-propyl amino)-2,5-dichloro- ester benzene49 2-Aminotere- 1,4-Bis-(acetoacetyl- " phthalic amino)-2,5-difluoro- acid dimethyl ester benzene50 " 1,4-Bis-(acetoacetyl- " amino)-2,5-dichloro- benzene51 2-Aminotere- 1,4-Bis-(acetoacetyl- orange phthalic-di- amino)-2,5-diethoxy- methylester benzene52 " 1,4-Bis-(acetoacetyl- yellow amino)-2,5-dimethyl- benzene53 " 1,4-Bis-(acetoacetyl- " amino)-2-methoxy-5- chlorobenzene54 " 1,4-Bis-(acetoacetyl- " amino)-2-methoxy-5- methylbenzene______________________________________ Representative dyestuffs of the foregoing Examples have formulae ##STR5##

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Patent Citations (4)

    Publication numberPublication dateAssigneeTitle
    FR-766857-AJuly 05, 1934Ste Ind Chim BaleNouveaux colorants azoïques non sulfonés
    GB-1076635-AJuly 19, 1967Ciba LtdProcesses for the manufacture of disazo pigments
    US-1879223-ASeptember 27, 1932Gen Aniline Works IncNew azodyestuffs
    US-3272858-ASeptember 13, 1966Pavelle CorpMethod of producing arylamino acid color couplers

NO-Patent Citations (0)

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