GB2285990A

GB2285990A - 2:1 aluminium complexes

Info

Publication number: GB2285990A
Application number: GB9503500A
Authority: GB
Inventors: Bansi Lal Kaul; Dominique Pflieger
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1991-09-05
Filing date: 1992-09-01
Publication date: 1995-08-02
Anticipated expiration: 2012-09-01
Also published as: GB9503500D0; GB2285990B

Abstract

A compound of formula II <IMAGE> in which each n independently is 1 or 2; each R1 independently together with the -C=C- group to which they are attached form a single or fused aromatic ring system that is substituted or unsubstituted; each R2 independently is unsubstituted or substituted phenyl, C1-12alkyl and C1-4alkoxy-C2-8alkyl; and X<+> is a cation.d

Description

2:1 ALUMINIUM COMPLEXES This application is a divisional application of GB 9218500.8, which describes certain new aluminium complex-water solubilizing group-free compounds suitable as dyestuff.

The present invention relates to new aluminium complex-water solubilizing group-free compounds suitable as dyestuffs.

According to the invention, there is provided a compound of formula Il

in which each R1 independently together with the -C=C- group to which they are attached form a single or fused aromatic or heteroaromatic ring system that is substituted or unsubstituted; each R2 independently is unsubstituted or substituted phenyl, C"2alkyl and C,,alkoxy C2.8alkyl; and X+ is a cation.

Preferred single or fused ring systems of R, are those of the benzene series, the naphthalene series and of the heteroaromatic series. Preferred heteroaromatic groups comprise five or six membered nitrogen and/or sulphur containing rings, most preferably of the pyrazolone or pyridone series.

Preferred substitutents by which any aromatic groups of R, or R2 can be substituted are selected from halogen (preferably Cl and Br), OH, C, 4alkyl, C1-4alkoxy, cyano, -NO2, C, 4alkylcarbonyl, SCN, C1-4alkoxycarbonyl, benzoyl, phenoxycarbonyl, C1-4alkylcarbonyl- oxy, aminocarbonyl, mono(C1-4alkyl)aminocarbonyl, di(C,4alkyl)aminocarbonyl, mono (C1-4alkoxy-C2-4alkyl)aminocarbonyl, di(C1-4alkoxy-C2-4alkyl)aminocarbonyl, aminosulphonyl, mono(C1 4alkyl)aminosulphonyl, di(C1-4alkyl)aminosulphonyl, mono(C1alkoxy-C24alkyl)- amino sulphonyl, di(C,4alkoxy C24alkyl) amino sulphonyl and phenylaminosulphonyl.

More preferred substituents on the aromatic groups of R, or R2 are halogen (chloro or bromo) C, 4alkyl, C, 4alkoxy or acetyl.

Preferably X+ is X,+ where X,+ is selected from alkali metal ions (especially Na+ and K+), ammonium, mono C, 4alkyl ammonium, di(C1 4alkyl)ammonium, tri(C, 4alkyl)ammonium and (most preferred) 4-amino-2,2,6,6-tetramalkylpiperidinium, 4-hydroxy-2,2,6,6-tetraalkylpiperidinium and 4-keto-2,2,6,6-tetraalkylpiperidinium.

More preferably X+ is X2+ where X2+ is a sodium, potassium, ammonium, 4-amino2,2,6,6-tetramethyl-piperidinium, 4-hydroxy-2,2,6,6-tetramethylpiperidinium or 4-keto2,2,6,6-tetramethylpiperidinium.

Preferred compounds of formula Il are of the formula lla

in which each R3 independently is hydrogen, C1-4alkyl, C1-2alkoxy-C2.3alkyl or phenyl, each R5 independently is a 2-ethyl hexyl or a phenyl group, unsubstituted or substituted by 1 to 3 substituents selected from chloro, bromo, C",alkyl, C",alkoxy and acetyl (or preferably one or two C1.2alkoxy groups and/or one chloro or bromo atom or one methyl group, especially one or two methoxy groups).

Preferably in the compound of the invention the -SO2NH-R3 groups are in the 4 or 5 position.

Compounds of formula Il can be prepared by known methods for producing 2:1 metal complex dyes for example by coupling a diazotized compound of formula V

with a compound of formula VI CH3-CO-CH2-CO-N H R2 (Vl) where R, and R2 are as defined above, followed by metallization and introduction of the cation.

Metallization and introduction of the cation in compounds of formula Il can also occur at the stage of forming the reactants (compounds of formula V and VI respectively).

The new compounds of formula II (hereinafter the new compounds) are good for dyeing (especially for dyeing in the mass) of plastics material including solvent-free and solvent containing plastics masses and solvent-free or solvent containing plastics resins. For example in finishes based on oil or water based paints, in various lacquers, in spin dyeing of viscose or cellulose acetate, for dyeing of natural or synthetic polyamides, polyester, polyethylene, polystyrene, polyvinylchloride, rubber and synthetic leather. The new compounds can be used for printing of graphic material, for dyeing of paper masses, for coating of textile and leather or for printing uses.

In particular, the new compounds can be used in an ecologically beneficial way to print for example, aluminium foils used for packaging. This enables the aluminium to be recycled easily. Therefore the new compounds are useful in reducing waste that results from recycling and for reducing the amount of harmful products.

Dyeings with the new compounds have good properties generally, for example good heat withstanding properties, good light and weathering properties, good chemical resistance, good migration properties, low blooming, good overcoating properties, good fastness in solvent properties, good dyeing strength and good application properties (e.g. flocculation fastness).

Dyeing, printing and padding can be carried out with the new compounds on substrates by known methods.

The invention will now be illustrated by the following Examples.

Example 1 a) 26.4 parts of 2-hydroxy-4-phenylamino sulphonyl aniline are stirred into a solution of 350 parts of water and 50 parts of 30%HCI. After the addition of 100 parts of ice, the amine is diazotized with 27 parts by volume of 4N NaNO2 solution. After stirring for 3 hours at 0 C, the resulting diazonium salt solution is slowly added to a a mixture of 12.5 parts of 2,5-dimethoxyacetylacetanilide, 9.3 parts of 2methoxyacetoacetylanilide, 9 parts of 30% NaOH solution, 150 parts of water, 9 parts of glacial acetic acid and 100 parts of ice. The pH is held at 4.5 by the addition of 35 parts of 30% NaOH. The resulting precipitate is filtered, washed with 4000 parts of water and dried.

b) 44.19 parts of the monoazo dyestuff of part a) above are suspended in a mixture of 110 parts of water and 25 parts of 30% NaOH. This is warmed to 70"C and stirred for 1 hour. The pH value of the suspension is 12.3. After further warming to 90"C, over 1 hours a solution of 17.1 parts of aluminium sulphate (water free) in 340 parts of water is added, whereby a voluminous suspension of the aluminium complex results and the pH value sinks to 10.9. The temperature is allowed to sink to 45"C over 2 hours (while stirring well) and the suspension is slowly reacted with a solution of 8.58 parts of triacetondiamine in 10 parts of water and 11.2 parts of 30% HCI. The resulting precipitate is brought to pH 5.4 by the addition of above 2.4 parts of HCI. The mixture is stirred a further hour at room temperature, filtered and the residue is washed salt-free and then dried. A compound of formula Ila.

in which R3 is phenyl R5 is 2,5-dimethoxy phenyl (and 2-monomethoxy phenyl) and the sulphonamide groups are in the 4-position.

The resulting dyestuff colors nitrocellulose lacquers a yellow tone.

Examples 2-48 Compounds of formula 1

in which the symbols are defined in Table 1 below can be made from known compounds by a method analogous to that of Example 1. These dye color nitrocellulose a yellow nuance.

TABLE 1

Example R2 R6 R7 X1+ No.

2 2,5-dimethoxy H -SO2NHCH3 1) phenyl 3 do. H do. 2) 4 do. H do. 3) 5 do. H do. Na 6 do. H do. 4)

Example R2 R6 R7 X1+ No.

7 do. H do. 5) 8 2,5-dimethoxy H -SO2NHC6H5 1) phenyl 9 do. H do. 2) 10 do. H do. 3) 11 do. H -SO2NH(CH2)3OCH3 1) 12 do. H do. 2) 13 do. -SO2NHCH3 H 2) 14 do. do. H 3) 15 do. -SO2NHC6H5 H 1) 16 do. do. H 1) 17 do. -SO2NH(CH2)3OCH3 H 1) 18 do. do. H 2) 19 2-methoxyphenyl do. H 1) 20 do. H -SO2NHCH3 1) 21 do. H do. 2) 22 do. H do. 3) 23 do. H -SO2NHC6H5 1) 24 do. H do. 2) 25 do. H do. 1) 26 do. H -SO2NH(CH2)3OCH3 1)

Example R2 R6 R7 x1+ No.

27 2-methoxyphenyl H -SO2NH(CH2)3OCH3 3) 28 2-ethylhexyl H -SO2NHCH3 1) 29 do. H do. 2) 30 do. H do. 3) 31 do. H -SO2NHC6H5 1) 32 do. H do. 2) 33 do. H do. 3) 34 do. H -SO2NH(CH2)3OCH3 1) 35 do. H do. 2) 36 do. H do. 3) 37 do. -SO2NHCH3 H 1) 38 do. do. H 2) 39 do. do. H Na 40 do. do. H 4) 41 do. do. H 5) 42 do. -SO2NHC6H5 H 1) 43 do. do. H 2) 44 do. do. H 3) 45 do. do. H K 46 do. -SO2NH(CH2)3OCH3 H 1) 47 2-ethylhexyl -SO2NH(CH2)3OCH3 H 2)

Example R2 R6 R7 x1+ No.

48 do. do. H 3) Application Example 5 parts of the dyestuff of Example 1 in a Dissolver apparatus are stirred into 95 parts of a nitrocellulose lacquer prepared from: 18.8% of Nitrocellulose A15 (in the form of white flocs wetted with 35% isopropanol) 6.3% of an acrylic acid butyl ester polymer, a softener resin (Acronal 4F from BASF) 3.3% of diphenyloctylphosphate, a softener (Santiciser 141 from Monsanto) 10.0% of methoxy propanol (Dowanol PM from Dow Chemical) 10.0% ethoxypropanol 41.6% ethanol, and 10.0% ethyl acetate.

This is dissolved overnight in a rolling block. The solubility is very good.

With a 25mm blade, a wet film of this lacquer composition is placed on aluminium foil and the lacquer is dried for 5 hours at 130 C. A yellow lacquer coating results with good light and migration fastness properties.

The application example can be repeated using 5 parts of any one of the new dyes of the invention of Examples 2-48 in place of that of Example 1.

Claims

CLAIMS:

1. A compound of formula II

in which each R, independently together with the -C=C- group to which they are attached form a single or fused aromatic ring system that is substituted or unsubstituted; each R2 independently is unsubstituted or substituted phenyl, C"2alkyl and C14 alkoxy -C2.8alkyl; and X+ is a cation.

2. A compound according to claim 1 in which X+ is X,+ where X,+ is selected from alkali metal ions ammonium, mono C,4alkyl ammonium, di(C1-4alkyl)ammonium, tri(C, alkyl)ammonium and 4-amino-2,2,6,6-tetraalkylpiperidinium, 4-hydroxy-2,2,6,6 tetraalkylpiperidinium and 4-keto-2,2,6,6-tetraalkylpiperidinium.

3. A compound according to claim 1 in which X+ is X2+ where X2+ is a sodium, potassium, ammonium, 4-amino-2,2,6,6-tetramethyl-piperidinium, 4-hydroxy-2,2,6,6- tetramethylpiperidinium or 4-keto-2,2,6,6-tetramethylpiperidinium.

4. A compound according to claim 1 of formula lla

in which each R3 independently is hydrogen, C,4alkyl, C,2alkoxy-C23alkyl or phenyl, each R5 independently is a 2-ethyl hexyl or a phenyl group, unsubstituted or substituted by 1 to 3 substituents selected from chloro, bromo, C,4alkyl, C,4alkoxy and acetyl.

5. A compound according to claim 1 in which the -SO2NH-R3 groups are in the 4 or 5 position.

6. A process for producing a compound of formula ll comprising coupling a diazotized compound of formula V

with a compound of formula VI CH3-CO-CH2-CO-N H R2 (Vl) where the symbols are defined in claim 1, followed by metallization and introduction of the cation.

7. A substrate to which a compound of formula Il according to any one of claims 1 to 5 has been applied.

8. A 2:1 metal complex compound substantially as herein described with reference to any one of the Examples.

9. A lacquer substantially as herein described with reference to the Application Example to which a 2:1 metal complex has been applied.