DE941307C - Process for the production of tetra-aza-porphines - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

ISSUED APRIL 5, 1956

GERMAN PATENT OFFICE

PATENT LETTERING

941 307 CLASS 22 e GROUP 7 02

I 6883 IVb122 e

Harold France, Blackley (Great Britain)

has been named as the inventor

Imperial Chemical Industries Limited, London

Process for the production of tetra-aza-porphines

Patented in the territory of the Federal Republic of Germany on February 7 , 1953, patent application published on October 13, 1955

Patent issued March 8, 1966 The priority of the application in Great Britain on February 6, 1952 has been claimed

The invention ¹ relates to an improved method for the production of dyes and, in particular, to an improved method for the production ¹ of dyes of the tetraazaporphinx series.

The dyes which are produced by the process according to invention ¹ are tetraaza-porphines, which can be represented in one of their HiOg ¹ IiChCn formers for the magnesium compound by the formula below, where R _{1 is} an alky radical, R _{2 is} a hydrogen atom or an alkyl radical denotes and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ denote hydrogen atoms or hydrocarbon radicals or where one or more of the substituent pairs R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R _{8 are} constituents of an alicydisoid , aromatic or ohinoid ring system.

According to the invention there is provided a method of making 'tetra-aza-porphines as follows described. suggested which

is characterized in that an alkyl-substituted fumaric acid ^{dinitrile or a mixture 1} thereof with a differently alkyl-substituted fumaric acid dinitrile, a maleic acid dinitrile. a substituted maleic acid dinitrile, a 'zf ^1. -Tetrahydrophthalonitrile or a Phi'haLonitril is heated with a magnesium alcoholate or with the compound which is obtained by decomposing a Grignard reagent with an alcohol and optionally the resulting magnesium tetraf-azapocrphine Heating with an acid is demetallized or converted into another metal-tetraaza-porphine by heating it in an organic solvent with a metal other than magnesium or with a salt of such a metal.

The compound which is obtained by decomposition of the Grignard's reagent, e.g. with) an alcohol is to be understood as · a magnesium halide alkotiolate.

The reaction is preferably carried out in an excess of the alcohol, the -zur Formation of the alcoholate or for the decomposition of the Grignard reagent is used.

Suitable alcohols are, for example, methyl,

Ethyl, propyl, butyl, amyl and tetrahydrofuran furyl alcohols, Ethylene glycol and cyclohexanol, however, are generally n-propyl alcohol and η-amyl alcohol preferred.

It will be noted that when a mixture of two or more nitriles is used, the resulting Pigments have an asymmetrical structure, while, however, when using only one Nitrile a symmetrical pigment is obtained in which each pyrrole nucleus has the same pair of substituents wearing.

An example of an alkyl-substituted fumaric acid dinitrile that can be mentioned is dimethyl fumaric acid dinitrile will.

Suitable substituted maleic acid dinitriles are, for example, methyl- and dimethyl-maleic acid dinitriles. If desired, the maleic acid dinitrile and / or the fumaric acid dinitrile during formed during the reaction in the reaction mixture from the corresponding succinic acid dinitrile will.

The process is suitably carried out so that the ingredients are in excess of the alcohol are heated together, the alcohol is distilled off under reduced pressure if desired, the easily soluble impurities! extracted from the residue and finally the pigment extracted and recrystallized will.

By the method according to the invention, the magnesium tetra-aza-porphine with good Yield can be obtained from readily available starting materials.

The magnesium tetra-aza-poirp'hine produced by the process according to the invention are themselves green, blue or violet pigments with good coloring power and good color fastness; she . however, are particularly valuable as intermediates for use in the manufacture of others Tetraraza-porphine as they are easily related to the metal-free pigments demetallized or by metal exchange. · into the corresponding pigments that can be converted into certain metals other than magnesium, for example Copper or nickel. The method according to the invention therefore also sees a suitable one Process by which · the valuable copper and nickel pigments are obtained. the Demetallization can be done by. Heating: of the magnesia pigment with an acid such as formic acid or acetic acid. The metal exchange can be achieved by heating the magnesium pigment in one. organic solvents with a suitable metal or a suitable metal salt, for example by heating with copper bronze or copper acetate in boiling pyridine or with nickel chloride in boiling cyclohexanone. Optionally, the metal-free obtained as described Pigment can be converted into the copper pigment by adding it. with copper bronze in simmering Pyridine or when converted into the nickel pigment is heated with nickel chloride in boiling pyridine.

The invention is illustrated by the following examples, to which, however, it is not restricted. The parts are parts by weight.

example 1

120 parts of magnesium are dissolved in 3000 parts of anhydrous methyl alcohol and 5000 parts of η-amyl alcohol are added to the solution. The mixture is stirred and slowly distilled until the temperature of the vapor phase has reached 134 to 135 ⁰ , which is the boiling point of the n-amyl alcohol. 212 parts of dimethylfumaric acid dinitrate are added to the gelatinous residue of the distillation, and the mixture is then stirred and refluxed for 2 hours. The excess of amyl alcohol is then distilled off under reduced pressure, the dark blue residue was cooled, pulverized and slowly 5o ^fl / cent acetic acid is added to 10,000 parts at a temperature below 2 ⁰ and the suspension thus obtained stirred for a further 15 minutes at a temperature below z ° will. The undissolved material is filtered and washed with soVoiger acetic acid at 0 ° until the wash extracts are colorless; then it is washed with hot water until the wash extracts are free from acetic acid. The residue from crude magnesium octa-methyl-tetra-azaporphin is dried. The bluish-violet powder obtained can be further purified by extracting it with boiling benzene, which contains 1 to 2% ethyl alcohol, and cooling the benzene extract, whereby the dye in the form of bronze-shimmering dark blue-violet microcrystals crystallizes out, which is filtered off and dried will. ■

Instead of the one used in the example above η-amyl alcohol can be n-propyl alcohol, isoamyl alcohol or ethylene glycol can be used.

- Example 2

400 parts of methyl iodide slowly turns into one stirred suspension! given by 60 parts of magnesium in 3500 parts of an anhydrous ether. the Mixture is gradually boiled, if necessary, to complete dissolution of the magnesium. The solution is then cooled and 2500 parts of n-amyl alcohol are slowly distilled off of the ether added .. The white precipitate, which initially forms, dissolves in the. stir back on. There are 212 parts of dimethylfumaric acid dinitrile added and the mixture stirred and gradually boiled under the reflux condenser for 3½ hours. The blue dye begins to form shortly after the mixture begins to boil.

The mixture is cooled to io °, 4500 parts of methyl alcohol are added to the stirred mixture at a temperature below 15 ^0, and thereafter 2000 parts of glacial acetic acid are zuigegeben to the stirred mixture at a temperature below 12 ^0th The insoluble microcrystalline dye present as a suspension is immediately filtered off and first washed with a mixture of 2000 parts of methyl alcohol and 400 parts of acetic acid at 0 ° until the wash water becomes colorless. It is then washed with methanol at 0 ° until the wash water shows a pale reddish fluorescence, and finally it is washed with 10,000 parts of boiling water. The residue from crude magnesium octa-methyl-tetraaza-porphine forms small, bronze-shimmering dark blue-violet needles which can be further purified by recrystallization, as described in Example 1.

Example 3

120 parts of magnesium are dissolved in 3000 parts of anhydrous methyl alcohol and 5000 parts of η-amyl alcohol added to the solution which is then stirred and distilled until the vapor Temperätur to 135 reaches ⁰ 134th A mixture of 52 parts of dimethylmaleic dinitrile and 160 parts of dimethylfumaric dinitrile is then added to the gelatinous residue, and the mixture is then added to the reflux condenser for 2 hours

.50 cooked. The product is, as described in Example 1, separated; the bronze shimmering dark blue-violet microcrystalline obtained Compound corresponds to that obtained in Example 1.

Example 4

A mixture of magnesium n-amylate and n-amyl alcohol is made from 120 parts of magnesium, as described in Example 1, prepared. the

Mixture is cooled to 90 ⁰ and a mixture of 106 parts and 128 parts of phthalonitrile Dimethylfumarsäuredinitril added. The mixture is rapidly heated at reflux at 135 ⁰ and stirred for 2 hours at 135 to 137 ^0th The product is separated off as described in Example 1, a glossy, navy blue powder 6 g being obtained, which can be further purified by recrystallization from benzene.

Instead of the 128 parts of phthalonitrile used in the above example, 132 parts can also be used ^ -Tetrahydrophthalonitrile can be used, with a blue one; Pigment is obtained.

Example 5

327 parts of that prepared as in Example 1 Magnesium-oetarmethyl-tetra-aza-porphins are yg dissolved in 1000 parts of dry pyridine. The solution is boiled on the reflux condenser, and 292 parts of copper acetate are added. The bluish-red fluorescent solution is refluxed cooked with the copper acetate until an oo cloudy blue suspension! is formed. After this Cooling the suspension, the crude product is filtered off and successively with 200 parts of pyridine, 200 parts of methanol, 250 parts of dilute hydrochloric acid and finally 8g with hot water to wash. The product can be made from o-dichlorobenzene be recrystallized. It becomes a bronze shimmering dark blue-violet microcrystalline Powder received.

Instead of the go Copper acetate, an appropriate amount of copper bronze can be used.

Claims (2)

PATENT CLAIMS: i. Process for the production of, Tetra-azaporphinen, characterized in that an alkyl-substituted fumaric acid dinitrile or a Mixture of the same with a differently alkyl-substituted fumaric acid dinitrile, a Maleic acid dinitrile, a substituted one; Maleic acid dinitrile, a z ^ -Tetrahydrophthaloniiril or a phthalonitrile with a magnesium alcoholate or heated with the compound obtained by decomposing a Grignard's reagent with an alcohol, and possibly the magnesium obtained in this way * - tetra-aza-porphin by heating with a Acid is demetallized or converted into another metal-tetra-aza-poirphin, by putting it in an organic. Solvent no heated with a metal other than magnesium or with a salt of such a metal will. 2. The method according to claim 1, characterized in that that the alkyl-substituted fumaric acid dinitrile is dimethylfumaric acid dinitrile. © 509 686 3.56