GB1567191A - Process for the preparation of complex compounds of the cobalt phthalocyanine series - Google Patents

Description

(54) PROCESS FOR THE PREPARATION OF COMPLEX COMPOUNDS OF THE COBALT PHTHALOCYANINE SERIES (71) We, BAYER AKTIENGESELL SCHAFT of Leverkusen Federal Republic of Germany, a Company organised and existing under the laws of the Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement::- The subject of the invention is a process for the preparation of complex salts, which have six coordinate bonds, of trivalent cobalt, in which 4 of the 6 coordination positions on the cobalt are occupied by the phthalocyanine ring system, which has two negative charges, and the remaining two coordination positions are each occupied by an amine from the series comprising primary secondary or tertiary aliphatic, aromatic or heterocyclic monoamines or polyamines.

The compounds to be prepared according to the invention are known, for example from German Patent Specifications 1,569,753 and 1,619,546. They are extremely valuable dyestuffs for cotton and regenerated cellulose since, when applied in a simple manner, they are able to give very fast dyeings in clear and deep blue shades.

The cobalt phthalocyanine/amine complex salts have hitherto been prepared either from cobalt phthalocyanines by oxidation in the presence of anions and subsequent treatment of the oxidation product with the primary, secondary and tertiary amines or by reaction of cobalt phthalocyanines, which contained one or two halogen atoms bonded to the central cobalt atom, with the abovementioned amines.

It has now been found, surprisingly, that cobalt phthalocyanines, in which one or two alkyl groups are bonded to the central cobalt atom by covalent bonds, react, optionally after prior treatment with acids, with the abovementionea amines to give the cobalt phthalocyanine/amine complex salts known from the cited Patent Specifications.

According to the present invention, therefore, there is provided a process for the preparation of a 6-coordinate trivalent cobalt/phthalocyanine/amine complex salt in which four of the coordinate positions on the cobalt atom are occupied by a primary, secondary, or tertiary aliphatic, aromatic, or heterocyclic monoamine or polyamine, which process comprises reacting (a) a cobalt phthalocyanine, having one or two alkyl groups bonded to the cobalt atom by covalent bonds, or (b) the product of reacting said cobalt phthalocyanine with an acid, with (c) an amine as specified above, the reaction taking place in the presence of an anion when (a) is reacted with (c).

The alkyl groups which are bonded to the cobalt atom by covalent bonds preferably contain 1 to 4 C atoms.

The cobalt phthalocyanines can also be substituted in the benzene radicals by 1 to 4 C1-C4-alkyl groups, 1 to 4 C1-C4-alkoxy groups, 1 to 4 phenyl groups or 1 to 16 halogen atoms, preferably chlorine or bromine atoms.

However, the benzene nuclei of the cobalt phthalocyanine are preferably unsubstituted.

Aliphatic, aromatic and heterocyclic monoamines and polyamines which can be used, for example, primary alklyamines and hydroxyalkylamines, such as n - butylamine and hydroxyethylamine, benzylamine, aniline and its methyl and alkoxy derivatives, such as p-toluidine and anisidine, heterocyclic amines, such as 2 aminothiazole and 2 - aminopyridine, secondary amines which contain 2-alkyl groups or hydroxyalkyl groups, such as diethylamine or N - methylethanolamine, and those which have a cyclic structure, such as piperidine, morpholine and N methylpiperazine, tertiary alkylamines and tertiary nitrogen bases, such as tetramethylethylenediamine or .1 - dimethylaminopropan - 2 - ol, including those which have a cyclic structure and are of aromatic character, such as pyridine or 2 - methyl - imidazole and 1 - amino - 3 iminoisoindolenine, and also polyamines, such as ethylenediamine, 1 - amino - 2 dimethylaminoethane, 1,3 - diaminopropane, 1 - amino - 3 - methylamino- propane, 1 - amino - 3 - dimethylaminopropane, 1 - amino - 3 - diethylamino- propane, bis - 1,2 - dimethylaminoethane or bis - [3 - aminopropyl] - methylamine.

Amines of the formula where

A represents an ethylene or propylene radical, R1 represents hydrogen, methyl or ethyl and R2 represents hydrogen, methyl or ethyl are preferred.

Suitable amnions can be both those of inorganic acids and those of organic acids, for example those of hydrogen halide acids and of nitric acid, acetic acid, formic acid, sulphuric acid or carbonic acid.

Suitable acids, with which the alkyl cobalt phthalocyanines are optionally treated prior to the reaction with amines, are, for example, hydrochloric acid, hydrobromic acid, hydriodic acid.

The alkyl-cobalt phthalocyanines used as starting materials are known, for example from: Z. Chem. 9 (1969), 115-116, J.

Organo-metal, Chem. 39(1972)2, C 79-C 81 and J. Chem. Soc. (A) 1968, 90 90--93.

They are obtained by reducing cobalt phthalocyanine and reacting the product with alkyl halides, especially alkyl bromides and alkyl iodides.

The reaction of the alkyl-cobalt phthalocyanines with the amines can be carried out at temperatures of 20 to 1000 C, preferably 40 to 700 C, and is effected either in a suspending medium, such as nitrobenzene, monochlorobenzene, trichlorobenzene, chloroform or carbon tetrachloride, or in an excess of the corresponding amine. In the case of alkyl groups which are difficult to split off, it is advantageous, under certain circumstances, to supply the reaction mixture with a small amount of air in order to complete the reaction in a short time.

The reaction proceeds in such a way that, as the reaction progresses, the cobalt phthalocyanine/amine complex is obtained, from the suspension or from the initially clear solution of the alkyl cobalt phthalocyanine in the amine, in the form of coarse crystals. When the reaction has ended, the dyestuff is isolated by filtering off and washing with low-boiling organic solvent or water.

If the reaction with the amine is preceded by treatment of the alkyl-cobalt phthalocyanines with hydrochloric acid, hydrobromic acid or hydriodic acid, the reaction can have been carried out either in organic solvents, such as alcohols, glycol compounds or ethers, or in the said acids themselves.

The procedure in suspension is such that 10 to 30% by volume of the corresponding aqueous, concentrated acid are added and the reaction is carried out at temperatures of 50 to 1000C, preferably 60 to 900C, until a sample of the reaction mixture, after isolating and working up, has a halogen content of 1--2 atoms of halogen per molecule.

These halogen-containing intermediate products are isolated by filtering off, washed with water until neutral and dried at 1000C in a drying cabinet. They are reacted according to known processes to give the cobalt phthalocyanine/amine complex salts.

Example 1 10 g of n-butyl-cobalt phthalocyanine are dissolved in 100 g of 3 - dimethylamine propylamine and, after adding 4 g of ammonium chloride to the solution, the mixture is stirred at 600C for 9 hours whilst a slow stream of air is passed over. The product is filtered off at room temperature, washed with a little amine and water and dried at 40--500C. 12.5 g of a dyestuff which is identical to that described in Example 5 of German Patent Specification 1,569,753 are obtained.

Example 2 10 g of isopropyl-cobalt phthalocyanine are suspended in 80 g of chlorobenzene.

After adding 20 g of 1 - amino - 3 - methyl aminopropane and 4 g of ammonium chloride to the solution, the mixture is warmed at 650C for 10 hours whilst a slow stream of air is passed over. After cooling to room temperature, the product is filtered off, washed with chlorobenzene and ligroin and dried at 40--500C. 12 g of a dyestuff which is identical to that described in Example 13 of German Patent Specification 1,569,753 are obtained.

Example 3 a) 10 g of n-butyl-cobalt phthalocyanine, prepared according to one of the processes known from the literature, are suspended in 200 g of ethylene glycol and, after adding 40 g of concentrated hydrochloric acid to the solution, the mixture is stirred for 17 hours at 900C. The mixture is filtered cold and the product is washed with water and methanol and dried at 1000C. 10 g of a product which contains about 9.60/, of chlorine bonded by covalent bonds are obtained.

b) 8 g of the chlorine-containing cobalt phthalocyanine prepared in this way are suspended in 80 g of chlorobenzene. After adding 14 g of 3 - dimethylaminopropylamine dropwise, the mixture is stirred for 1 hour at room temperature. The product is then filtered off, washed with ligroin and sucked dry. After additional washing with water and drying at 4-500C, 10 g of a dyestuff which is identical to that described in Example 1 are obtained.

Analogously to the procedure described in Example 3a, corresponding halogencontaining cobalt phthalocyanines are obtained when methyl-, ethyl- or propyl cobalt phthalocyanine is employed in place of the n-butyl-cobalt phthalocyanine.

Example 4 a) 10 g of n-butyl-cobalt phthalocyanine are suspended in 50 g of concentrated hydrochloric acid and the suspension is slowly warmed to 900C. After stirring for 16 hours at 900 C, the mixture is filtered cold and the product is washed with water until neutral and rinsed with methanol. After drying for two hours at 100"C in a drying cabinet, 8 g of a chloro - cobalt phthalocyanine which contains about 8.2% of chlorine are obtained.

b) 8 g of the intermediate product prepared in this way are suspended in 80 g of chlorobenzene and, after adding 14 g of 3- dimethylaminopropylamine dropwise, the mixture is stirred overnight at room temperature. The product is filtered off and washed with chlorobenzene. After drying in vacuo at 4W50 C, 8.2 g of a product which is identical to the dyestuff described in Example 1 are obtained.

Example 5 10 g of n-butyl-cobalt phthalocyanine are suspended in 150 ml of ethylene glycol and, after adding 40 ml of 48% strength aqueous hydrobromic acid, the mixture is warmed to 9W95 C for 30 hours. After cooling, the product is filtered off, washed with water and methanol and dried at 100"C. 11 g of a reaction product which has a bromine content of 21.0 /n are obtained.

If 10 g of the intermediate product prepared in this way are used analogously to Example 3b, 12 g of a dyestuff which is identical to the dyestuff described in Example 16 of German Patent Specification 1,569,753 are obtained.

Example 6 10 parts of n-butyl-cobalt phthalocyanine, prepared according to one of the processes known from the literature, in 150 ml of diethylene glycol dimethyl ether and 40 ml of conc-ntrated hydrochloric acid are warmed to 90"C for 30 hours. After the mixture has been worked up analogously to Example 5, 10 g of a reaction product which has a chlorine content of 10% are obtained.

If 10 g of the intermediate product prepared in this way are used analogously to Example 4b, 12.5 g of a dyestuff which is identical to that described in Example 4b are obtained.

WHAT WE CLAIM IS: 1. A process for the preparation of a 6 coordinate trivalent cobalt/phthalocyanine/amine complex salt in which four of the coordinate positions on the cobalt atom are occupied by the phthalocyanine ring system having two negative charges, and the remaining two coordinate positions are each occupied by a primary, secondary or tertiary aliphatic, aromatic, or heterocyclic monoamine or polyamine, which process comprises reacting (a) a cobalt phthalocyanine, having one or two alkyl groups bonded to the cobalt atom by covalent bonds, or (b) the product of reacting said cobalt phthalocyanine with an acid, with (c) an amine as specified above, the reaction taking place in the presence of an anion when (a) is reacted with (c).

2. A process according to claim 1 wherein the or each alkyl group in the cobalt phthalocyanine contains from 1 to 4 carbon atoms.

3. A process according to claim 1 or 2 wherein the benzene nuclei in the cobalt phthalocyanine are unsubstituted.

4. A process according to any of claims 1 to 3 wherein the amine is of the formula wherein

A represents an ethylene or propylene radical, R, represents hydrogen, methyl, or ethyl, and R2 represents hydrogen, methyl, or ethyl.

5. A process according to any of claims 1 to 4 wherein the anion is that of a hydrogen halide acid, nitric acid, acetic acid, formic acid, sulphuric acid, or carbonic acid.

6. A process according to any of claims 1 to 5 wherein the reaction of the cobalt phthalocyanine with the amine is effected at from 20 to 1000C.

7. A process according to claim 6 wherein said reaction is effected at from 40 to 700C 8. A process according to any of claims 1

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (1)

1. **WARNING** start of CLMS field may overlap end of DESC **.

   at 900C. The mixture is filtered cold and the product is washed with water and methanol and dried at 1000C. 10 g of a product which contains about 9.60/, of chlorine bonded by covalent bonds are obtained.

   b) 8 g of the chlorine-containing cobalt phthalocyanine prepared in this way are suspended in 80 g of chlorobenzene. After adding 14 g of 3 - dimethylaminopropylamine dropwise, the mixture is stirred for 1 hour at room temperature. The product is then filtered off, washed with ligroin and sucked dry. After additional washing with water and drying at 4-500C,

   10 g of a dyestuff which is identical to that described in Example 1 are obtained.

   Analogously to the procedure described in Example 3a, corresponding halogencontaining cobalt phthalocyanines are obtained when methyl-, ethyl- or propyl cobalt phthalocyanine is employed in place of the n-butyl-cobalt phthalocyanine.

   Example 4 a) 10 g of n-butyl-cobalt phthalocyanine are suspended in 50 g of concentrated hydrochloric acid and the suspension is slowly warmed to 900C. After stirring for 16 hours at 900 C, the mixture is filtered cold and the product is washed with water until neutral and rinsed with methanol. After drying for two hours at 100"C in a drying cabinet, 8 g of a chloro - cobalt phthalocyanine which contains about 8.2% of chlorine are obtained.

   b) 8 g of the intermediate product prepared in this way are suspended in 80 g of chlorobenzene and, after adding 14 g of 3- dimethylaminopropylamine dropwise, the mixture is stirred overnight at room temperature. The product is filtered off and washed with chlorobenzene. After drying in vacuo at 4W50 C, 8.2 g of a product which is identical to the dyestuff described in Example 1 are obtained.

   Example 5

   10 g of n-butyl-cobalt phthalocyanine are suspended in 150 ml of ethylene glycol and, after adding 40 ml of 48% strength aqueous hydrobromic acid, the mixture is warmed to 9W95 C for 30 hours. After cooling, the product is filtered off, washed with water and methanol and dried at 100"C. 11 g of a reaction product which has a bromine content of 21.0 /n are obtained.

   If 10 g of the intermediate product prepared in this way are used analogously to Example 3b, 12 g of a dyestuff which is identical to the dyestuff described in Example 16 of German Patent Specification 1,569,753 are obtained.

   Example 6

   10 parts of n-butyl-cobalt phthalocyanine, prepared according to one of the processes known from the literature, in 150 ml of diethylene glycol dimethyl ether and 40 ml of conc-ntrated hydrochloric acid are warmed to 90"C for 30 hours. After the mixture has been worked up analogously to Example 5, 10 g of a reaction product which has a chlorine content of 10% are obtained.

   If 10 g of the intermediate product prepared in this way are used analogously to Example 4b, 12.5 g of a dyestuff which is identical to that described in Example 4b are obtained.

   WHAT WE CLAIM IS: 1. A process for the preparation of a 6 coordinate trivalent cobalt/phthalocyanine/amine complex salt in which four of the coordinate positions on the cobalt atom are occupied by the phthalocyanine ring system having two negative charges, and the remaining two coordinate positions are each occupied by a primary, secondary or tertiary aliphatic, aromatic, or heterocyclic monoamine or polyamine, which process comprises reacting (a) a cobalt phthalocyanine, having one or two alkyl groups bonded to the cobalt atom by covalent bonds, or (b) the product of reacting said cobalt phthalocyanine with an acid, with (c) an amine as specified above, the reaction taking place in the presence of an anion when (a) is reacted with (c).

   2. A process according to claim 1 wherein the or each alkyl group in the cobalt phthalocyanine contains from 1 to 4 carbon atoms.

   3. A process according to claim 1 or 2 wherein the benzene nuclei in the cobalt phthalocyanine are unsubstituted.

   4. A process according to any of claims 1 to 3 wherein the amine is of the formula wherein

   A represents an ethylene or propylene radical, R, represents hydrogen, methyl, or ethyl, and R2 represents hydrogen, methyl, or ethyl.

   5. A process according to any of claims 1 to 4 wherein the anion is that of a hydrogen halide acid, nitric acid, acetic acid, formic acid, sulphuric acid, or carbonic acid.

   6. A process according to any of claims 1 to 5 wherein the reaction of the cobalt phthalocyanine with the amine is effected at from 20 to 1000C.

   7. A process according to claim 6 wherein said reaction is effected at from 40 to 700C 8. A process according to any of claims 1

   to 7 wherein the reaction product (b) is produced by reacting the alkyl cobalt phthalocyanine with hydrochloric acid, hydrobromic acid, or hydriodic acid.

   9. A process for the preparation of a 6 coordinate trivalent cobalt/phthalocyanine/amine complex salt substantially as herein described in any of the Examples.

   10. A 6-coordinate trivalent cobalt phthalocyanine/amine complex salt when prepared by the process claimed in any of claims 1 to 9.