CA1080231A - Heterocyclic symmetrical azomethine complex pigments - Google Patents

Abstract

Abstract of the Disclosure A compound of the formula wherein M denotes a divalent transition metal A denotes an alkylene residue having from 2 to 8 carbon atoms or an isocyclic, aromatic or heterocyclic residue;
R is an alkyl residue having from 1 to 6 carbon atoms, an aryl residue having from 6 to 10 carbon atoms or an aralkyl residue having from 7 to 10 carbon atoms; and X and Y can be the same or different and each is hydrogen, halogen or a non-water solubilising group or X and Y
together form an aromatic or heterocyclic residue, is useful for pigmenting high molecular weight organic materials.

Description

The present invention relates to new, valuable bis-azomethine metal complex pigments.

Tl~e present invention provides a novel compound of the formula Zl ~22 N ~ 0 \0 ~ - R tI) X~ ~X

Y Y

wherein M denotes copper or nickel; R denotes alkyl containing 1 to 4 carbon atoms and phenyl, provided that both Rs are the same; X and Y denote hydrogen and nitro, provided that both Xs and Ys are the same or X and Y together form a fused benzene residue; Zl and Z2 denote hydrogen, nitro, alkyl containing 1 to 4 carbon atoms, alkoxy containing 1 to 4 carbon atoms, phenoxy and phenylalkyl wherein alkyl contains 1 to 4 carbon atoms or Zl and Z2 together form a fused benzene residue or a fused imidazolone residue.

It is well known in the literature that compounds of formula I
where R is hydrogen are of use as pigments.
In U.S.P. 3,132,140 is described the product of formula I when R
is hydrogen, M is nickel, X, Y, Zl and Z2 are hydrogen. This product, as prepared by the method in U.S.P. 3,132,140, although having good durability towards light is colouristically a weak, dull yellow of no commercial value. However in the present invention there are described products of h;gh tinctorial value and purity of shade with excellent stability towards heat and light. This unpredictable result is only achieved if R is alkyl of 1 to 4 carbon atoms or phenyl as described hereinabove. This substantial improvement in colouristic . ~

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properti.es now permits the preparation of products of commercial interest and value in both paints and plastic8.

The present invention also provides a process for producing a symmetrical metal complex pigment of formula II comprising reacting 2 moles of a compound having the formula:
OH
HO II
N

R
wherein R, X and Y have their previ.ous significance wlth one mole of a 1,2-dia~ine of the formula:
æl Z2 ~ III

and the resultant ligand of formula:
' Zl'~5~;~2 ,: \ ~
~N N ~ IV

R--N )--OH HO~ N R
~Y
wherein R, X and Y, Zl and Z2 have their previous significance, which ligand may or may not be isolated by, for example, filtration, is then metallised to yield products of formula I.

Compounds of formula II may be synthesized by formylation of the corresponding substituted quinolone using a modification of the ..

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0~31 method of R.F.C. Brown et al. Austral. J. Chem. 7, (1954), 374.

In a furtller, one stage process, the present invention provides a process for the production of a symmetrical metal complex pigment comprising rea~ting 2 moles of an aldehyde of formula:
OB
X~fHO

wherein R, X and Y have their previous significance and B is hydrogen or an alkali metal, especially sodium, with a 1,2-diamine of formula III, as hereinbefore defined, then metallising the product.

Examples of compounds which may be used for metallisation iDclude the acetates, stearates, chlorides, su]phates, nitrates and phosphates salts of, in particular, nickel and copper.

Specific examples of suitable compounds of formula III for use in the processes of the present invention are:-3-formyl-4-hydroxy-1-methyl-2-quinolone 3-formyl-4-hydroxy-1-ethyl-2-quinolone 3-formyl-4-hydroxy-1-n-propyl-2-quinolone 3-formyl-4-hydroxy-1-n-butyl-2-quinolone 3-formyl-4-hydroxy-1-phenyl-2-quinolone and 3-formyl-4-hydroxyl-1-benzyl-2-quinolone 5,6-benzo-4-hydroxy-3-formyl-1-phenyl-2-quinolone 6,7-ben~o-4-hydroxy-3-formyl-1-methyl-2-quinolone 7,8-benzo-4-hydroxy-3-formyl-1-methyl-2-quinolone 6-methyl-4-hydroxy-3-formyl-1-methyl-2-quinolone 6-chloro-4-hydroxy-3-formyl-1-methyl-2-quinolone as well as the corresponding sodium salts.

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,~, ~ . . ., ~ , , -1080;~31 Of the diamines of formula III, preferred compounds are those wherein Z] and ~2 may be the same or different and each is hydrogen, alkyl containing 1 to 4 carbon atoms, alkoxy containing 1 to 4 carbon atoms, phenoxy, phenylalkyl wherein alkyl contains 1 to 4 carbon atoms, nitro or wherein the two radicals Zl and Z2 form a fused benzene ring or a fused benzimidazole residue.

The following may be mentioned as examples of such preferred diamines: 1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 4,5-dichloro-1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, mixtures of 3- and 4-methyl-1,2-phenylened;amines, 4,5-dimethyl-1,2-phenylene-diamine, 3,5-dimethyl-1,2-phenylenediamine, 4-methoxy-1,2-phenylene-diamine, 4,5-dimethoxy-1,2-phenylenediamine, 4-trifluoromethyl-1,2-phenylenediamine, 4-phenylisopropyl-1,2-phenylenediamine, 1,2-diaminonaphthalene, 2,3-diaminonaphthalene, 4-phenoxy-1,2-phenylene-diamine, 4-carboxy-1,2-phenylenediamine, 4-cyano-1,2-phenylenediamine, 4-acetyl-amino-1,2-phenylenediamine, 4-benzoylamino-1,2-phenylene-diamine, 4-nitro-1,2-phenylenediamine, 4-methoxy-5-chloro-1,2-phenylenediamine, 4-methyl-S-chloro-1,2-phenylenediamine, 5,6-diamino-benzimidazol-2-one.

The processes of the present invention may be effected in solution or in finely-divided suspension, using either water or an organic solvent as the reaction medium. If an organic solvent is used, examples of suitable solvents include ethylene glycol, methoxyethanol, glacial acetic acid, dimethylformamide, o-dichlorobenzene, nitrobenzene and carbitol. The reactions are conveniently effected at an elevated temperature, preferably at a temperature between 50 C and the temperature at which the reaction mixture refluxes. If water is used then the aldehyde of formula II or V may be reacted with the diamine of formula III at a pH of 2 to 9 using very efficient agitation preferably at a temperature between 35 to 95 C. The resultant ligand of formula I~, which may then be isolated or not, is then metallised by reacting with a water soluble transition metal salt at a pH
of 4 to 9 in the presence of a suitable buffer salt for which pul-pose -~ "

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1080'~31 sodium acetate iB particularly suited. The temperature of the reaction is desirably held at 90 to 1~0C until the reaction i6 complete and the pigment i~ then isolated by filtration. The colo~lrall~s obtained are valuable pigments which may be used directly after production, according to the proces6 o this invention, tha~ is after they have been filtered off from their reQction mixture and dried. Alternatively they may fir6t be processed using known wet or dry conditioning techniques such as gr;nding either alone or in the presence of a water soluble salt or other medium which can sub6equen~1y be removed for instance by washing.

Such grinding may be optionally followed by a solvent ~restment.

A further method of proce6sing the pigments of the invention involves the pressure treatment of an aq~eous slurry of the pigment produced by any of the above procedures in an autoclave at temperatures from 50 to 200C. A still further method of processing the colourant~ entails the solvent treatment of the pigment produced by any of the above procedures. Suitable 601vents include ethanol, methanol, xylene, orthodichlorobenzene, timethylformamide and N-methyl-pyrrolidone, the conditioning generally being carried out at the boiling point of the solvent.

Because of their economical and simple mode of preparation, combined with their excellent pigmentary properties, the compounds of formula I are valuable as pigments in a wide variety of organic media, for example, surface coatings, inks and polymers, paints and plastics.

The compounds of formula I are valuable pigments which in a finely d;vided form can be used for pigmenting high molecular weight organic materials, for example, cellulose ethers and cellulose esters such as ethylcellulose, cellulose acetate, cellulose butyrate; natural resins or ~ynthetic re~ins, such as polymerisation resins or condensation resins, for example aminoplasts, especially urea-formaldehyde and mela-mineformaldehyde resins, alkyd resins, phenoplasts, polycarbona~es t 1080Z3~

polyesters, polyamides or polyurethanes, polyolefines, polystyrene, polyacrylonitrile, polyacrylic acid ester, rubber, casein, silicones and silicone resins, and acrylonitrile/butadiene/styrene terpolymers, individually or as mixtures.

The proportion of the pigment of formula I in the compositions of the invention is preferably from 0.1 % to 10 % by weight based on the weight of the organic material.

For these purposes it is immaterial whether the high molecular weight compounds mentioned are in the form of plastic masses or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the end use, it may be advantageous to use the new pigments as toners or in the form or preparations.

In addition to the pure pigment, the preparations can, for example, also contain natural resins, such as abietic acid or its esters, ethyluellulose, cellulose acetobutyrate, alkaline earth metal salts of higher fatty acids, fatty amines, such as stearylamine or rosin amine, vinyl chloride/vinyl acetate copolymers, poly-acrylonitrile or polyterpene resins or water-soluble dyestuffs, for example dyeYtuff sulphonic acids or their alkaline earth metal salts.

The pigments of formula I are strong in colour, clean and have excellent light- and solvent fastness properties, combined with very high thermal stability.

The following Examples further illustrate the present invention.

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, 10~ 31 Example 1 PART A. Preparation of ]i~nd A mixture of 3-Eormyl-4-hydroxy-1-methyl-2-quinolone (6.0 g) and 3,4-diaminonitroben~ene (2.3 g) is stirred and refluxed in ethanol (200 ml) for 4 hours. When cool, the mix~ure is filtered, washed with ethanol and dried at 50 to 60 C to afford the product as a yellow solid (7.6 g) [96.8 %] of mp 265-7 C.

Analysis: C H N
Calculated for C28H21N506: 64.24 4.02 13.38 Found : 63.15 4.31 14.13 PART B. Preparation of Nickel complex A solution of Nickel acetate [Ni(OCOCH3)2.4H20] (3.5 g) in methyl cellosolve (50 ml) is added to a stirred suspension of the yellow product of PART A (7.3 g) in methyl cellosolve (S0 ml) and the mixture then heated to reflux for 3 hours. It is filtered hot, washed with hot methyl cellosolve then ethanol and dried at 50 to 60 C to afford a red shade yellow pigment (7.5 g) 189.3 %]
which does not melt below 360 C.

Analysis C H N Ni 28 19 56 H20: 56.22 3.51 11.71 9.8 Found : 55.84 3.33 11.80 9.8 By a process similar to that described in Rxample l(A), the carbonyl and amine components of Examples 2 to 20 (Table I) were reacted to give the corresponding ligands.

By a process similar to that described in Example l(B).
copper and nickel complexes were prepared using the ligands obtained ' .

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as shown in Table T; the copper complexes were prepared by substituting copper acetate for nickel acetate.

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Example 21 PART A PRF.PARATION OF !.IGAND

Conc. Ilydrochloric acid (5.2 ml) is added to an efficiently stirred mixture of the sodium salt of 3-formyl-4-hydroxy-1-methyl-2-quinolone (9.0 g) and o-phenylene diamine (2.l( g) in water (300 ml) which is then b~ated by steam inj~Lion to ~ 95 C. After 40 minutes the yellow solid i9 filtered hot and washed with hot water (1000 ml). A weighed sample of thefilter-cake paste is dried at 50 to 60 C to afford the ligand as a yellow powder.
Analysis: C W N
Calculated for C26H22N404 : 70.29 4.40 11.72 Found : 69.87 4.82 11.47 PART B PRl~PARATION OF NICKEL COMPLEX

With tlle water content thus ascertained, the ligand is used in the metallisation stage in the form of its filter-cake paste. A slurry of the paste of Part A in water (400 ml) is efficiently stirred and heated by steam injection to ~ 95 C. Sodium acetate trihydrate (8.55 g) is added followed by nickel nitrate monohydrate (5.8 g).
After 3 hours the mixture is filtered hot, washed with hot water (1500 ml) and dried at 50 to 60 C to afford a red shade yellow pigment (8.5 g), (8g% yield) of mp not less than 360~ C.

Analysis: C H N Ni 28 20 4 4 2 60.79 3.98 10.13 10.62 Found : 60.61 3.70 10.09 10.40 ~,. .

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j 1080'~31 Example 22 PART A. Preparation of ligand -A mixture of 3-formyl-4-hydroxy-1-methyl-2-quinolone (18.3 g) and o-phenylene diamine (4.7 g) is stirred and refluxed in methyl-cellosolve (500 ml) for 4 hours. ~hen cool, the mixture is filtered, washed with ethanol and dried at 50 ~o 60 C to afford the product as a yel]ow solid (21.3 g) [99 %]

Analysis C H N
Calculated for C28H22N404 : 70.29 4.60 11.72 Found : 70.07 4.59 11.58 PART B. Preparation of nickel complex A slurry of the yellow product of PART A (10.0 g) in water (600 ml) is efficiently stirred and heated by steam injection to ~ 95 C
when a solution of nickel acetate [Ni(OCOCH3)2.4H20] (6.5 g) in water (250 ml) is added. After 4 hours the mixture i8 filtered hot, washed with hot water (1500 ml) and dried at 50 to 60 C to afford a red shade yellow pigment (10.0 g) [95 ~].

Analysis C H N Ni Calculated f 28 20 4 4 2 60.79 3.98 10.13 10.62 Found : 61.11 3.76 10.19 10.70 , :, ' ,~ : ' :

-` 1080,'~:31 Examp1e 23 A mixture of 3-fonmyl-4-hydroxy-1-methyl-2-quinolone (10.15 g) and o-phenylenediamine (2.7 g) i8 efficiently stirred in water (600 ml) containing concentrated hydrochlori-~ acid (2.0 ml), for 1 hour. Sodium acetate [NaOAc.3H20] (3.4 g) is added to the yellow suspension which is II,~u heated to ~95 C by steam ;njection and after I 1/2 hours Nick~l acetate [Ni(OAc)2.4H20] is added. After a further 2 hours the mixture is filtered hot, washed with hot water (2000 ml) and dried at 50 to 60 C to afford a red shade yellow pigment (12.0 g) (90 % yield).

Analysig C H N Ni Calculated for C28H22NiN404 2 60.79 3.98 10.13 10.62 Found : 60.84 3.77 9.91 9.86 Example 24 Conc. Hydrochloric acid (5.2 ml) is added to an efficiently stirred mixture of the sodium salt of 3-formyl-4-hydroxy-1-methyl-

2-quinolone (6.75 g), o-phenylenediamine (1.62 g) and Texafor B9 (a polyoxyethylene ether condensate) (0.4 g) in water (400 ml) which is then heated by steam iniection to> 95 C . After 1 hour sodium acetate[NaOAc.3H20] (8.55 g) is added followed by Nickel Nitrate [Ni(N03)2.11120] (4.8 g) in water (25 ml). After a further 3 1/2 hours the mixture is filtered hot, washed with water (2000 ml) and dried at 50 to 60 C to afford a red shade yellow pigment (7.6 g) (95 % yield).
Analysis C H N Ni Calculated fo 28 20 4 4 2 60.79 3.98 10.13 10.62 Found : 61.98 4.06 9.96 10.1 F~
.

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: -10~ 31 Example 25 60 parts of the product of Example 4 after comminution by salt-grinding were ball milled with 136 parts of a solution of an unmodified butylated melamine/formaldehyde re~in in n-butanol and 452 parts of xy]ol.

350 parts of a solu~ion of a hydroxy acrylic resin, a 1:1 mixture of xylene and n-butanol, were added gradually and ball milling cootinued. The resulting mixture had a pigment to binder ratio of 1:5; this was adjusted to 1:10 by the addition of more resin solution and the paint was thinned to the required viscosity for spraying.
Aluminium panels were sprayed and then stoved at 120 C for 30 minutes.
The resulting paint films had excellent fastness to light, heat and acids; for example, spotting the panels with 0.1 N hydrochloric acid left no discolouration after drying, and stoving the panels at 180 C for 30 minute-; had practically no detectable effect on the colour. The resulting coated panels were a very attractive transparent yel]ow colour.

When the stainer (with a l:S pigment to binder ratio) wbose preparation is described above was combined with a suitable paste of finely powdered aluminium to give a pigment to aluminium ratio of 75:25 and the mixture was again thinned to a suitable viscosity for spraying, very attractive greenish yellow metallic coatings were obtained which also had excellent fastness properties.

In the same way by replacing the product of Example 4 with the salt-ground products of any of the Examples 1 to 3 and 5 to 20 there could be obtained paint films having varying shades of yellow to red. All were, however, characterised by having the same excellent fastness properties.

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Example 26

3-Formyl-4-hydroxy-1-methyl-2-(luinolone (22.8 g), ortho-phenylene diamine (6.1 g), water (3.4 1) and concentrated hydro-chloric acid (1 ml) were stirred together for 10 minutes at room tempera~ure, using a high shear stirrer, then at 95 C for 2 hours.
Staybelite resin (2.8 g) dissolved in 50 % aqueous potassium hydroxide (2 ml) was added followed by hydrated sodium acetate (17.2 g).
Nickel nitrate hydrate (16.8 g) was then added and the mixture heated with high speed stirring at 95 to 98 C for 3 hours. The final pH was 4.3. The mixture was cooled to 60 C and filtered, the solid washed thoroughly with water and dried at 60 C in an air-circulating oven to obtain 29.8 g resinated pigment having a nickel content of 10.66 %.

Example 27 The pigment obtained in Example 26 was incorporated at 0.1 %
into high density polyethylene by two-roll milling for 8 minutes.
The hides produced were compression moulded at 170 C for 5 minutes.
The attractive red-shade yellow plastic so produced showed, both visually and microscopically, that the pigmeuL had readily dispersed into the plastic medium.

Example 28 The pigment obtained in Example 26, was invorporated at 0.1 %
together with titanium dioxide at 0.5 %, into 1100 g of high density polyethylene by two-roll milling. The hides produced were granulated and tested for heat stability using an Injection Moulding machine.
The pigmented plastic showed no sign of degradation when held for 5 minute periods at any temperature up to 375 C.

Claims (3)

What we claim is:

1. A compound of the formula:

(I) wherein M denotes copper or nickel; R denotes alkyl containing 1 to 4 carbon atoms and phenyl, provided that both Rs are the same;
X and Y denote hydrogen and nitro, provided that both Xs and Ys are the same or X and Y together form a fused benzene residue; Z1 and Z2 denote hydrogen, nitro, alkyl containing 1 to 4 carbon atoms, alkoxy containing 1 to 4 carbon atoms, phenoxy and phenylalkyl wherein alkyl contains 1 to 4 carbon atoms or Z1 and Z2 together form a fused benzene residue or a fused imidazolone residue.

2. A composition comprising a high molecular weight organic material and a pigmentary proportion of a compound of formula I as claimed in claim 1.

3. A composition as claimed in claim 2 wherein the proportion of the compound of formula I is from 0.1 % to 10 % by weight, based on the weight of the organic material.