DE2555243A1 - PROCESS FOR THE PRODUCTION OF COMPLEX COMPOUNDS OF THE COBAL PHTHALOCYANINE SERIES - Google Patents

Description

Bayer Aktiengesellschaft 25 5 5 u 3

Central Patents Department. Trademarks and licenses

509 Leverkusen. Bayerwerk

Jo / Pt

Dec 8, 1975

Process for the production of complex compounds of the cobalt

phthalocyanine series

The invention relates to a process for the preparation of coordinatively hexavalent complex salts of trivalent cobalt, in which 4 of the 6 coordination points on cobalt by the double negatively charged phthalocyanine ring systems and the rest two coordination sites by one amine each from the series of primary, secondary or tertiary aliphatic, aromatic or heterocyclic mono- or polyamines are occupied.

The compounds to be produced according to the invention are, for example, from German patents 1,569,753 and 1,619,546 known. They are extremely valuable dyes for cotton and re generate ellulo se because they are easy to use are able to deliver highly fast dyeings in clear and deep shades of blue.

The cobalt phthalocyanine amine complex salts have heretofore been made either from cobalt phthalocyanines by oxidation in the presence of Anions and subsequent treatment with the primary, secondary or tertiary amines or by converting cobalt

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phthalocyanines !!, which contained one or two halogen atoms bonded to the central cobalt atom, with the amines mentioned above manufactured.

It has now been found, surprisingly, that cobalt phthalocyanines, in which one or two alkyl groups are covalently bonded to the central cobalt atom, with those mentioned above Amines in the presence of anions, if appropriate after previous treatment with acids, for those from the patents cited implement known cobalt phthalocyanine amine complex salts.

The alkyl groups which are covalently bonded to the cobalt atom preferably contain 1 to 4 carbon atoms.

The cobalt phthalocyanines can also be replaced by 1 to 4 C ^ -C »- Alkyl groups, 1 to 4 C 1 -C 4 alkoxy groups, 1 to 4 phenyl groups or 1 to 16 halogen atoms, preferably chlorine or bromine atoms, may be substituted in the benzene radicals.

Preferably, however, the cobalt phthalocyanine is in the benzene nuclei unsubstituted.

As aliphatic, aromatic and heterocyclic mono- and Polyamines come, for example, primary alkyl and hydroxyalkylamines, such as n-butylamine and oxethylamine, benzylamine, aniline and the like Methyl and alkoxyl derivatives such as p-toluidine and anisidine, heterocyclic Amines, such as 2-aminothiazole and 2-aminopyridine, secondary amines with 2-alkyl or hydroxyalkyl groups, such as diethylamine or N-methylethanolamine and such cyclic structure, such as piperidine, morpholine and N-methylpiperazine, tertiary alkylamines and tertiary nitrogen bases such as tetramethylethylenediamine or i-dimethylaminopropanol-2, including those with cyclic Structure of aromatic character, such as pyridine or 2-methyl-

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imidazole and i-amino-3-iminoisoindolenine, also polyamines, such as Ethylenediamine, i-amino-2-dimethylaminoethane, 1,3-diaminopropane, 1-amino-3-methylaminopropane, 1-amino -3 -dime thylaminopropane, i-Amino-3-diethylaminopropane, bis-1,2-dimethylaminoethane or Bis- / 3-aminopropyl7-methylamine possible.

Amines of the formula are preferred

H N A N

R ₂

wherein

A is an ethylene or propylene radical,

R ^ hydrogen, methyl or ethyl,

Rp hydrogen, methyl or ethyl

represents.

Suitable anions can be those of inorganic as well as those of organic acids, for example of Hydrohalic acids, from nitric acid, acetic acid, Formic acid, sulfuric acid or carbonic acid.

Suitable acids with which the alkyl cobalt phthalocyanines, if appropriate treated with amines before the reaction are, for example, hydrochloric acid, hydrobromic acid and Hydriodic acid.

The alkyl cobalt phthalocyanines used as starting materials are for example from:

Z. Chem. 2: 115-116 (1969) J. Organo-metal. Chem. 52 (1972) ² , C 79-C 81 and J. Chem. Soc. (A) 1966 , 90-93 known.

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

The reaction of the Alkylkobaltphthalocyanine with the amines may be carried out at temperatures of 20 to 10O ⁰ C, preferably take place 40 to 70 ° C, either in dispersion media such as nitrobenzene, monochlorobenzene, trichlorobenzene, chloroform or carbon tetrachloride is or worked in an excess of the corresponding amine . In the case of alkyl groups that are difficult to split off, it may be advantageous to add air to the reaction mixture in order to complete the reaction in a short time.

The reaction proceeds in such a way that from the suspension or from the initially clear solution of the alkyl cobalt phthalocyanine in the amine the cobalt phthalocyanine amine complex is obtained as the reaction proceeds in coarse crystals. After finished The dye is reacted by suction and washing with low-boiling organic solvents or water won.

If the reaction with amine, a treatment of the alkyl cobalt phthalocyanines with hydrochloric acid, hydrobromic acid or hydroiodic acid is connected upstream, can either in organic solvents such as alcohols, glycol compounds, ethers or in the acids mentioned themselves been worked.

In suspension, the procedure is such that 10 to 30 vol. # Of the corresponding aqueous, concentrated acid are added and at temperatures of 50 to 100 ⁰ C, preferably 60 to

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9O ⁰ C is caused to react until an isolated, land-processed sample of the reaction mixture has a halogen content of 1-2 atoms of halogen per molecule.

These halogen-containing intermediate products are isolated by suction, washed neutral with water and ^{dried at 100 °} C. in a drying cabinet. They are converted to the cobalt phthalocyanine / amine complex salts by known processes.

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example 1

10 g of n-butyl cobalt phthalocyanine are dissolved in 100 g of 3-dimethylaminopropylamine and, after the addition of 4 g of ammonium chloride, stirred at 60 ° C. for 9 hours while gently passing air over it. It is filtered off at room temperature, washed with a little amine and water and at 40 - 50 ⁰ C dried to give 12.5 g of a dye which is identical to that described in Example 5 of the German Patent Specification 1,569,753.

Example 2

10 g of isopropyl cobalt phthalocyanine are suspended in 80 g of chlorobenzene. After the addition of 20 g of 1-amino-3-methylaminopropane and 4 g of ammonium chloride, the mixture is ^{heated at 65 °} C. for 10 hours while gently passing air over it. After cooling to room temperature, suction is performed , washed with chlorobenzene and ligroin and dried at 40 - 50 ° C. 12 g of a dye are obtained which is identical to that described in Example 13 of German Patent 1,569,753 «

Example 3

a) 10 g n-butyl-cobalt phthalocyanine, prepared according to one of the known processes, are suspended in 200 g ethylene glycol and stirred for 17 hours at 90 ⁰ C after the addition of 40 g concentrated hydrochloric acid trieter. It is suction filtered cold, washed with water and methanol and dried at 100 ⁰ C. 10 g of a product are obtained whose content of covalently bound chlorine is about 9.696.

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b) 8 g of the chlorine-containing cobalt phthalocyanine thus prepared are suspended in 80 g of chlorobenzene »Nach 14 g of 3-dimethylaminopropylamine are added dropwise Stirred for an hour at room temperature. Then it is suctioned off, washed with ligroin and sucked dry After additional washing with water and drying at 40-50 ° C., 10 g of a dye which is identical to that described in Example 1.

Analogously to that described in Example 3a, corresponding halogen-containing cobalt phthalocyanines are obtained, if instead of n-butyl cobalt phthalocyanine methyl, Ethyl or propyl cobalt phthalocyanine. Has been used «,

Example 4

a) 10 g n-butyl-cobalt phthalocyanine are suspended in 50 g of concentrated hydrochloric acid, and slowly heated to 90 ⁰ C, "After I6stündigem stirring at 90 ⁰ C is filtered off cold, washed neutral with water and methanol washed ₀ After drying for two hours at 100 ⁰ C in the drying cabinet, 8 g of a chlorobalt phthalocyanine containing about 8.2% chlorine _{or the like are obtained}

b) 8 g of the intermediate product thus represented are suspended in 80 g of chlorobenzene and, after 14 g of 3-dimethylaminopropylamine have been added dropwise, stirred overnight at room temperature. It is filtered off with suction and washed with chlorobenzene. After drying in vacuo at 40-5O ⁰ _{C, 8.2 g of a product β} identical to the dye described in Example 1 are obtained

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Example 5

10 g of n-butyl cobalt phthalocyanine are suspended in 150 ml and, after the addition of 40 ml of 48.6 aqueous hydrobromic acid for about 30 hours, heated to 90-95 ° C. After cooling, it is filtered off with suction, washed with water and methanol and with 100 ⁰ C dried. 11 g of a reaction product with a bromine content of 21 are obtained

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

Example 6

10 parts of n-butyl-cobalt phthalocyanine, prepared according to any one of the methods known from the literature, are heated in 150 ml of diethylene glycol dimethyl ether and 40 ml of concentrated Hydrochloric acid 30 hours at 90 ⁰ C. After working up as in Example 5, 10 g of a reaction product with a chlorine content of 10% are obtained. If 10 g of the intermediate product thus prepared as in Example 4b is used, 12.5 g of a dye identical to that described in Example 4b are obtained.

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Claims (1)

Claim; Process for the preparation of coordinatively hexavalent complex salts of trivalent cobalt, in which four of the six coordination sites on cobalt by the doubly negatively charged phthalocyanine ring system and the remaining two coordination sites by an amine each from the series of primary, secondary or tertiary aliphatic, aromatic or heterocyclic mono- or Polyamines are occupied, characterized in that cobalt phthalocyanines in which one or two alkyl groups are covalently bonded to the central cobalt atom are reacted with the abovementioned amines in the presence of anions, optionally after previous treatment with acids. Le A 16 656 709824/0872 ORIGINAL INSPECTED