GB1572473A

GB1572473A - Unsymmetrical azomethine-1:2-chromium complexes

Info

Publication number: GB1572473A
Application number: GB1679777A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1976-04-23
Filing date: 1977-04-22
Publication date: 1980-07-30
Also published as: IT1115903B; FR2348953A2; DE2617748A1; JPS52130823A; BE853819R; FR2348953B2

Description

(54) UNSYMMETRICAL AZOMETHINE-1 :2-CHROMIUM COMPLEXES (71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company, of 6700 Lfldwigshafen, 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 invention relates to unsymmetrical azomethine-1 :2-chromium complexes which are useful as dyes. The invention more particularly is a modification of the invention described in the specification of our copending GB Patent Application No.

1522/76 (Serial No. 1,531,563).

The said patent application describes and claims unsymmetrical azomethine 1:2chromium complexes in which the anion has the general formula I

where A is an aromatic carbocyclic radical containing one or more SOsH or SO,- groups and having a complex-forming -0- or -0-0=0 groups in the carbocyclic ring position adjacent to the point of attachment to the carbocyclic ring of the azomethine bridge, B and D are each independently an aromatic carbocyclic radical having a complex-forming -0- group in the carbocyclic ring position adjacent to the point of attachment to the carbocyclic ring of the azomethin bridge, E is an aliphatic radical or a carbocyclic radical having a complex-forming -0- or 0--0=0 group in the position adjacent to the point of attachment of the azomethine bridge to the radical E, Q is an optionally protonated group of the formula -SO,- or -COO- and forming part of A, B, D or E, m is an integer and, when m is more than one, (Q)m may represent identical groups or two or more different groups, and n is the total number of Q groups in non-protonated form. (It is to be noted that the symbol Q in the above formula appears as X in Specification 1,531,563 where care must be taken to avoid confusing references to it with references to the other symbol X appearing in formula Ia in that specification and below.) We have found that compounds of the formula I, where A, B, D, Q, m and n have the stated meanings and E is an aliphatic radical with a complex-forming amino group and having the formula given below, also have very valuable properties.

The radicals E have the formula

where Z is an aliphatic radical which is optionally substituted by aryl, and L is an organic radical, preferably an alkyl, cycloalkyl, aralkyl or aryl radical which is optionally substituted by one or more hydroxyl, ether, ester, halogen or hydroxysulfonyl groups.

Preferably, the radicals Z are of 2 to 10 carbon atoms and the radicals L of 1 to B carbon atoms.

Examples of cations which may be present in the complexes are alkali metal, ammonium and substituted ammonium cations, e.g. sodium, potassium, ammonium, trimethylammonium, tributylammonium, dimethyldibenzylammonium, diTP-hydroxy- ethylammonium, fi-ethylhexylammonium, y y-(B-ethylhexoxy)-propylammonium and i- propoxypropylammonium.

Preferred dyes are those in which the anion, in the form in which Q is protonated, has the general formula Ia

where A' is hydrogen, hydroxysulfonyl, chlorine, bromine, methyl, methoxy, ethoxy, nitro, alkanoylamino of 1 to 4 carbon atoms or benzoylamino, R1 is hydrogen, chlorine, bromine, nitro, hydroxysulfonyl, phenylazo which optionally bears one or more substituents selected from chlorine, bromine, methyl, methoxy, ethoxy, nitro and hydroxysulfonyl, or naphthylazo substituted by hydroxysulfonyl, and R2 is hydrogen, chlorine, bromine or nitro, or Rl and R2 together form a fused benzene ring, R3 and R4 independently of one another are selected from the same radicals as R1 and R2, X is

L is alkyl of 1 to 6 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, fi-cyanoethyl, alkoxyethyl or alkoxypropyl (where alkoxy is of 1 to 4 carbon atoms), phenoxyethyl or phenoxypropyl, alkanoyloxyethyl or alkanoyloxypropyl (where alkanoyl is of 2 to 4 carbon atoms), benzoyloxyethyl or benzoyloxypropyl, phenylsulfonyloxyethyl orphenylsulfonyloxypropyl, tolylsulfonyloxyethyl or tolylsulfonyloxypropyl, cyclohexyl, benzyl, phenylethyl or phenyl which optionally bears one or more substituents selected from chlorine, bromine, methyl, ethyl, methoxy, ethoxy and hydroxysulfonyl and q is 2, 3, 4 or 6.

Examples of alkanoylamino radicals Al are butyrylamino, propionylamino, formylamino and especially acetylamino.

Examples of N-substituted sulfamoyl radicals A2 are monoalkylsulfamoyl and dialkylsulfamoyl, where alkyl is of 1 to 4 carbon atoms, e.g. methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, butylsulfamoyl, dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl and dibutylsulfamoyl, phenylsulfamoyl, sulfopyrrolidide, sulfopiperidide and sulfomorpholide.

Examples of sulfo-containing aromatic carbocyclic amine components of the formula HANK, from which the moiety A of the formula I can be derived are 2aminophenol - 4 - sulfonic acid, 4 - chloro - 2 - aminophenol - 6 - sulfonic acid, 4 - nitro - 2 - aminophenol - 6 - sulfonic acid, 6 - nitro - 2 - aminophenol - 4sulfonic acid, 2 - aminobenzoic acid - 4- and -5 - sulfonic acid, 5 - phenylazo - 2 - aminophenol - 4' - sulfonic acid, 4 - (2' - naphthylazo) - 2 - aminophenol - 5' - sulfonic acid, 4 - (2',5' - dichlorophenylazo) - 2 - aminophenol - 4'sulfonic acid and 4 - (2' - mcthoxyphenyl)azo) - 2 - aminophenol - 5' - sulfonic acid.

Examples of compounds H-B-CHO and H-DCHO from which the moieties B and D of the formula I can be derived are 2-hydroxybenzaldehyde, 2hydroxy - 1 - naphthaldehyde. 3 - nitro - 2 - hydroxybenzaldehyde, 5 - nitro - 2hydroxybenzaldehyde, 3,5 - dinitro - 2 - hydroxybenzaldehyde, 5 - bromo - 2hydroxybenzaldehyde, 3,5 - dichloro - 2 - hydroxybenzaldehyde, 2 - hydroxy- 1 naphthaldehyde - 3 - carboxylic acid, 2 - hydroxybenzaldehyde - 5 - sulfonic acid, 5 - (2',5 dichlorophenylazo) - 2 - hydroxybenzaldehyde, 5-sulfonic acid, 5- (2',5' - dichlorophenylazo) - 2 - hydroxybenzaldehydc, 5 - (2' - methoxyphenylazo) - 2 - hydroxybenzaldehyde - 5' - sulfonic acid methylamide or -sulfonic acid, 5 - (2' - chlorophenylazo) - 2 - hydroxybenzaldehyde - 5'- sulfonic acid and 5 - (phenylazo) - 2' - hydroxybenzaldehyde - 4' - sulfonic acid.

The 1 :2-chromium complexes may be manufactured by a stepwise process, advantageously starting from a l:l-chromium complex of an azomethine compound of the formula HA-N CH-BH, namely

where Ke is a cation, which may be obtained in accordance with a conventional process.

Such a l:1-chromium complex is then reacted with an azomethine compound of the formula HD-CH = N-EH or their individual components (namely HD--CHO and H2N-EH). These reactions may be carried out in aqueous solution or suspension, with or without the addition of organic solvents, e.g. alcohols or carboxylic acid amides. The formation of the 1 :2-complex is conveniently carried out in a weakly acid to alkaline range, preferably at a pH of from 6 to 9, at an elevated temperature, e.g. at from 500C to the boiling point.

The 1:2-complexes formed may be isolated by acidification, salting out with alkali metal salts or evaporation; this gives water-soluble complex salts. To manufacture water-insoluble, organophilic dyes, the complexes may be precipitated from aqueous solution by means of a nitrogen-containing base which furnishes the cation.

The nitrogen containing bases used to manufacture these solvent dyes are usually fairly long-chain alkylamines or cycloalkylamines, preferably of 6 to 16 carbon atoms, e.g. 2 - ethylhexylamine, di - (2 - ethylhexyl) - amine, 3 - (2' - ethylhexoxy)propylamine, dodecylamine, isotridecylamine, oleylamine, dicyclohexylamine, N,N'diphenyl - guanidine, N,N' - di - (2 - methylphenyl) - guanidine, phenylbiguanide, 4-chlorophenylbiguanide or il-methylphenyl) -biguanide.

The dyes may be used for dyeing or printing natural or synthetic nitrogencontaining materials, e.g. wool, polyamide fibers or polyurethane fibers and leather.

The water-soluble, but organo-soluble, dye salts with amine bases may be used for dyeing organic fluids, resins or surface coatings wood stains or ballpoint pen pastes, for dyeing anodized aluminum, or in spin dyeing, e.g. for the manufacture of colored cellulose ester fibers or nylon fibers.

Complexes in which the anion, in the form in which Q is protonated, has the formula Ib

where R is hydrogen, chlorine, bromine or nitro and Rs is hydrogen, chlorine, bromine or nitro, and A1, R1, L and Z have the meanings given above, are of particular industrial importance as dyes.

Preferably, A1 is hydrogen, methyl, chlorine or nitro, Z is -CH2CH2-, --CH2--CH2--CH2--,

and L is alkyl of 1 to 4 carbon atoms, P-hydroxyethyl or ,,B-hydroypropyl, methoxyethyl, phenylsulfonyloxyethyl, tolylsulfonyloxyethyl, cyclohexyl, or phenyl which may or may not be substituted by chlorine, methyl, methoxy or hydroxysulfonyl.

In the Examples which follow parts and percentages are by weight, unless stated otherwise.

EXAMPLE 1.

15.3 parts of 5-phenylazo-2-hydroxybenzaldehyde-4'-sulfonic acid are stirred with 200 parts of water and after adding 5.6 parts of 1;(2'-hydroyethylamino)-2- aminoethane the mixture is heated for 30 minutes at 400C. 23 parts of the 1:1 .chromium complex compound of the azomethine obtained from 4-nitro-2-amino- phenol-6-sulfonic acid and 2-hydroxybenzaldehyde are added and the mixture is brought to pH ~ 6.5-6.8 with sodium hydroxide solution.

The batch is heated at 750C, whilst stirring, and the stated pH is maintained by further addition of sodium hydroxide solution.

After completion of the 1:2-complex formation, the batch is diluted with a solution of 200 parts of sodium chloride in 500 parts of water and the dye which has precipitated is filtered off and dried.

44 parts of a dye of which the complex anion has the formula

and which gives neutral yellow dyeings having good light fastness and wet fastness on nylon fibers, are obtained.

The following dyes are obtained by a similar method.

Ex- l:l-Chromium complex of Azomethine Hue ample

orange yellow yellow orange reddish yellow yellow greenish yellow

Cl 8 N HSO3 X N:N CH:N-(CH12)3 orange C1 \OH HN-C3H6-OCH3

orange yellow

Claims

WHAT WE CLAIM IS:

1. An unsymmetrical azomethine-1 :2-chromium complex in which rhe anion has the general formula:

where A is an aromatic carbocyclic radical containing one or more SOB or SO- groups and having a complex-forming -0- or -O-C= 0 group in the carbocyclic ring position adjacent to the point of attachment to the carbocyclic ring of the azomethine bridge, B and D are independently an aromatic carbocyclic radical having a complex-forming -0- group in the carbocyclic ring position adjacent to the print of attachment to the carbocyclic ring of the azomethine bridge, E is an aliphatic radical with a complex-forming amino group and having the formula ,Z--NN-L where Z is an aliphatic radical which is optionally substituted by an aryl and L is an organic radical, Q is an optionally protonated group of the formula -SO,- or -COO and forming part of A, B, D or E, m is an integer and, when m is more than one, (Q) may represent identical groups or two or more different groups, and n is the total number of Q groups in non-protonated form.

2. A complex as claimed in claim 1 in which the anion, in the form in which Q is protonated, has the general formula:

where A1 is hydrogen, hydroxysulfonyl, chlorine, bromine, methyl, methoxy, ethoxy, nitro, alkanoylamino of 1 to 4 carbon atoms or benzoylamino, R1 is hydrogen, chlorine. bromine, nitro, hydroxvsulfonyl, phenylazo which optionally bears one or more substituents selected from chlorine, bromine, methyl, methoxy, ethoxy, nitro and hydroxysulfonyl, or naphthylazo substituted by hydroxylsulfonyl, and R2 is hydrogen, chlorine, bromine or nitro, or R' and R2 together form a fused benzene ring, R3 and R4 independently of one another are selected from the same radicals as R1 and R2, X is -O- or -COO-, Z is (CH2)Q-,

I is alkyl of 1 to 6 carbon atoms, hydroxyalkyl of 2 to 3 carbon atoms, s-cyanoethyl, alkoxyethyl or alkoxypropyl (where alkoxy is of 1 to 4 carbon atoms), phenoxyethyl or phenoxypropyl, alkanoyloxyethyl or alkanoyloxypropyl (where alkanoyl is of 2 to 4 carbon atoms), benzoyloxyethyl or benzoyloxopropyl, phenylsulfonyloxyethyl or phenylsulfonyloxypropyl, tolylsulfonyloxyethyl or tolylsulfonyloxypropyl, cyclohexyl, benzyl, phenylethyl or phenyl which optionally bears one or more substituents selected from chlorine, bromine, methyl, ethyl, methoxy, ethoxy and hydroxysulfonyl, and q is 2, 3, 4 and 6.

3. A complex as claimed in claim 1 in which the anion in the form in which Q is protonated, has the general formula:

where R is hydrogen, chlorine, bromine or nitro, Rs is hydrogen, chlorine, bromine or nitro and Al, R1, L and Z are each as defined in claim 2.

4. A complex as claimed in claim 1 and identified in any of the foregoing Examples.

5. A process for the maintenance of a complex as claimed in claim 1 wherein a 1:1-chromium complex of the general formula:

where K is a cation and A and B are as defined in claim 1, is reacted with an azomethine compound of the general formula: HD-CH = N-EH where D and E are as defined in claim 1, or with the individual components from which such an azomethine compound is derived, namely HD-CHO and H2N-EH.

6. A process as claimed in claim 5 carried out substantially as described in any of the foregoing Examples.

7. A complex as claimed in claim 1 whenever obtained by a process as claimed in claim 5 or 6.

8. A method of dyeing natural or synthetic nitrogen-containing fibers, wherein the fibers are treated with a complex as claimed in any of claims 1 to 4 or 7 which has an alkali metal or ammonium cation.

9. A method of dyeing an organic fluid, resin finish, wood stain, ballpoint pen paste or for coloring anodized aluminum, or for spin dyeing, wherein a complex as claimed in any of claims 1 to 4 or 7 which has a substituted ammonium cation is used as a dye.