CH624981A5 - Process for the preparation of salts of 1:2 metal complex dyes which are free from sulphonic acid groups - Google Patents

Description

The present invention relates to the method defined in claim 1.

The starting materials for the process according to the invention are obtained by coupling the diazonium salts of the diazo components mentioned below with the coupling components listed below.

The numbers refer to the 3rd edition of the Color Index.

65 Salt formation is advantageous at temperatures between 40 and 80 ° C and a pH below 7.

The new color salts have a very good alcohol solubility, especially in lower alkanols, such as methanol,

624 981

4th

Ethanol, n-propanol or iso-propanol, in alkylene glycol mono-alkyl ethers, e.g. in ethylene glycol monomethyl or ethyl ether, in alkylene glycols, such as in propylene glycols, or in ar-aliphatic alcohols, such as in benzyl alcohol, or in mixtures of such alcohols. They are also in lower aliphatic ketones, e.g. Acetone, methyl ethyl ketone, methyl isobutyl ketone or also in cyclohexanone, furthermore in carboxylic acid esters, e.g. Methyl acetate, ethyl acetate, butyl acetate or glycol monoacetate, and also excellently soluble in halogenated hydrocarbons such as chloroform, methylene chloride, ethylene chloride or carbon tetrachloride. With regard to their solubility, color salts according to the invention are superior to known color salts of a similar structure.

Because of their good solubility in the above-mentioned ketones, especially acetone, the color salts obtainable according to the invention are suitable for dyeing cellulose 272 acetate in the dope; thanks to their good solubility in halogenated, lower aliphatic hydrocarbons, especially chloroform, they can also be used for the spin dyeing of cellulose triacetate.

As a result of their good solubility in organic solvents, the new color salts are particularly suitable for dyeing the solutions of polymers, such as polystyrene or polyamide, in particular solutions of film-forming polymers.

example 1

Slurrying of 51 g (0.05 mol) of the 1: 2 cobalt complex from the azo dye 2-aminophenol-4-suIf- (3'-isopropoxypropyl) -amide - »l-phenyl-3-methyl-5 -pyr-azolon in 1000 ml of water, a 50 ° C warm solution of 12.0 g of rhodamine B (CI 45170) in 150 ml of water is added dropwise. The mixture is stirred for 1 hour and then the solution of 8.2 g of Primene JM-T (primary branched aliphatic amine with 18-22 carbon atoms from Rohm & Haas) in 90 ml of water and 1.5 ml of formic acid is added dropwise. Then the mixture is made acidic with 2 ml of formic acid so that it turns litmus paper red, it is stirred for a further 5 hours, filtered and the material is washed with water. The product dried under vacuum weighs 64 g. It is very soluble in alcohols and ketones.

If solutions of the colored body and of nitrocellulose in ethanol are used for printing on paper or aluminum foils, red colorations of excellent purity and high color strength are obtained.

Example2

To a suspension of 42.2 g (0.05 mol) of the l: 2-chromium complex sodium salt from the azo dye 2-amino-5-ethylsulfonylphenol -> l-phenyl-3-methyl-5-pyrazolone in 1000 ml of water at 80 ° C, the solutions of 12.0 g of rhodamine B (CI 45170) in 150 ml of water at 50 ° C and 4.85 g (0.025 mol) of Primene 81-R (primary branched- aliphatic amine with 12-14 carbon atoms from Rohm & Haas) in 100 ml of water and 1.5 ml of formic acid. The mixture is adjusted to pH 3-4 with 2 ml of formic acid and stirred at 50 ° C. for 6 hours. The dye is then filtered off, washed thoroughly with water and dried. 58 g of a red powder are obtained, which is excellently soluble in acetone and in the solvent mixture methylene chloride-methanol 9: 1.

If 0.5% of the dye, based on the cellulose acetate, is added to a solution of cellulose-2.5-acetate in acetone, the mixture is stirred until uniform and the mass is spun using the dry spinning process, so that bright red fibers with good light are obtained. , Fastness to washing, water, sweat, solvents, over-dyeing, fulling and dry heat.

Example 3

In 300 ml of methyl isobutyl ketone, 45.3 g (0.05 mol)

1: 2 chromium complex sodium salt from the monoazo dye 2-amino-4-methylsulfonyI-5-nitro-l-phenoI - * l-PhenyI-3-methyl-5-pyrazolone and 12.0 g of rhodamine B (CI 45170) dissolved . 9.85 g of Primene JM-T (Rohm & s Haas) and 1.7 ml of formic acid are added dropwise to the solution, the whole is stirred for 1 hour at room temperature, the salts separated off are filtered off and the dye is removed from the filtrate by evaporation and Dry in a vacuum. This gives 65 g of a red-brown powder which is excellently soluble in acetone, ethyl acetate, ethylene glycol and ethylene glycol mono-xoethyl ether.

The procedure is analogous to Example 1-3, but 0.05 mol of the 1 ^ metal complex mentioned in the following table, column II, 12 g of rhodamine B (CI 45170) and 0.025 mol of the amine listed in column III of the table are used 15, one also obtains readily soluble color salts which, when incorporated into nitrocellulose solutions, provide bright red prints on paper.

20th

25th

30th

35

40

45

50

Table .1 II

Ex. 0.05 mol 1: 2-M complex No. (Na salt) from monoazo dye DH2

DH2

4 4-nitro-2-aminophenol - »1-phenyl-3-methyl-5-pyr-azolone

5 do.

6 2-AminophenoI-4-suIf-amide — ► l- (3'-chlorophe-nyI) -3-methyl-5-pyrazolone

7 th.

8 do.

9 th.

10 2-amino-4-chloro-5-sulf-amoylphenol -> 1-phenyl-3-methyl-5-pyrazolone

11 2-AminophenoI-4-suIf- (3'-isopropoxypropyl) -amide -> 1 -phenyl-3-methyl-5-pyr-azolone do.

13 do.

14 do.

15 do.

16 do.

17 do.

18 do.

19 do.

55

20 2-aminophenol-4-sulf- (3'-isopropoxypropyl) -amide - »l-phenyl-3-methyl-5-pyr-azolone

60 21 Anthranilic acid ->

l-phenyl-3-methyl-5-pyr-azolone

22 4-Nitro-2-aminophenol -> l- (3 '-sulfamoylphenyl) -3-methyl-5-pyrazolone

23 5-Nitro-2-aminophenol —► 1 -phenyl-3-methyl-5-pyrazolone

65

III

0.025 mole of amine A

M

Co Primene 81-R

Cr do. Co do.

Cr do.

Cr dicyclohexylamine

Cr dehydroabietylamine

Cr Primene 81-R

Co do.

Co 3- (2'-ethylhexoxy) -

propylamine Cr Primene 81-R Co 2-ethylhexylamine Co n-ethylcyclohexyl-

amine Co dodecylamine Co 3-dodecyloxy

propylamine Co stearylamine Co 0.0125 mole 4,4'-diamino-dicyclo-hexylmethane

Co diisobutylamine

Cr Primene 81-R

Cr do.

Cr do.

624 981

r h m

E.g.

No. 0.05 mol 1: 2-M-Comp! Ex 0.025 mol amine

(Na salt) from monoazo A dye DH2

DH2

5-sulfamoyl-2-aminophenol - »l-phenyl-3-methyl-5-pyrazolone

2-Amino-4-methylsulfonyl-phenol- »l-phenyl-3-methyl-5-pyrazoIon do.

2-aminophenol-4-suifamide - »acetoacetic anilide 2-aminophenol-4-sulf-methylamine -» acetoacetic acid-2-chloroanilide do.

do.

do.

2-amino-4-methylisulfonylphenol - »acetoacetic acid-2,5-dimethoxyanilide 2-aminophenol-4-sulfamide -» l-phenyl-3-ethoxycar-bonyl-5-pyrazolone 2-aminophenol-4- sulf-N, N -diethylamide - »l- (4'-methylphenyl) -3-methyl-5-pyrazolone

2-aminophenol-4-sulf-N, N-di- (2'-hydroxyethyl) amide - »l- (2'-ch! Orphe-nyl) -3-methyl-5-pyrazolone 2-aminophenol-4- sulf-N-methyl-N-cyclohexylamide - »l- (2'-ethylphenyl) -3-methyl-5-pyrazolone 2-aminophenol-4-sulf-N-ethyl-N-phenylamide -»

1-phenyl-3-methyl-5-pyr-azolone

2-aminophenol-4-sulf-N- (3 ', 4' -dimethylphenyl) -amide - »l-phenyl-3-methyl-5-pyrazolone l: 2-Cr mixed complex of 2-amino-4-nitrophenol - »

1-phenyl-3-methyl-5-pyr-azolone and

2-aminophenol-4-sulfamide -> l-phenyl-3-methyl-5-pyrazolone

Example 40

To a slurry of 136 g of the 1: 2 Cr complex sodium salt from the azo dye 2-amino-4-methylsulfo-

24th

25th

26

27

28

29

30th

31

32

33

34

35

36

37

38

39

M

Cr do. Cr do.

Cr Primene JM-T Co do.

Co Primene 81-R

Co dehydroabietylamine Co 3- (2'-ethylhex-

oxy -) - propylamine Co Dicyclohexylamine Co Primene 81-R

Co do.

Cr Primene 81-R

Cr do.

Cr do.

Cr do.

Cr do.

Cr do.

nyl-5-nitro-l-phenol - »l-phenyl-3-methyl-5-pyrazolone in 1500 ml of water at 50 ° C is first the solution of 36 g of rhodamine B in 400 ml of water at 60 ° C, then the Solution of 30 g of Primene JM-T (Rohm & Haas) in 210 ml of water and 5 ml of 5 formic acid was added dropwise. The weakly acidic mixture is stirred at 75 ° C. for 1 hour, then the color salt is filtered off, washed thoroughly with water and dried. The result is 184 g of a red-brown powder with excellent solubilities in ketones and acetic acid esters.

io Valuable color bodies can also be obtained with the same procedure if instead of 36 g 28.8 g resp. 43.2 g rhodamine B and instead of 30 g 36 g resp. 24 g of Primene JM-T are used.

Example 41

15 To a suspension of 45.3 g (0.05 mol) of 1: 2-chromium complex sodium salt from the azo dye 2-amino-4-methylsulfonyl-5-nitro-phenol - »l-phenyl-3- methyI-5-pyrazolone in 500 ml of water at 50 ° C. the solutions of 6.35 g (0.015 mol) of rhodamine G (CI 45150) in 100 ml of hot water and of 6.8 g (0.035 mol) are added dropwise Primene 81-R (Rohm & Haas) in 150 ml water and 3 ml formic acid. The acidic mixture is stirred for 1 hour, filtered, the filter cake is washed with water and dried. The color salt produced in this way is a brown-red powder that dissolves in alcohols, ketones and 25 carboxylic acid esters in high concentrations.

Color salts which are also readily soluble can be obtained by an analogous procedure if, instead of 6.35 g (0.015 mol) of rhodamine G, 0.015 mol of one of the rhodamine dyes C.I. 45160, 45165, 45175 resp. 45210 inserts.

30th

Example 42

To a suspension of 89 g (0.1 mol) of 1: 2 chromium complex sodium salt of the azo dye 2-amino-4-t-amyl-6-nitro-phenol -> l-phenyl-3-methyl-5- pyrazolon in 500 ml of methyliso-35 butyl ketone, the solutions of 14.4 g (0.03 mol) of rhodamine B in 200 ml of hot water and of 14.3 g (0.075 mol) of Primene 81-R (Rohm & Haas) are added 300 ml of water and 4 ml of formic acid. Then the mixture is made lactic acid with formic acid, stirred for 10 hours at 50 ° C. and filtered. The 40 filtrate is separated in a separating funnel, the ketone solution is washed twice with water and evaporated to dryness. The residue weighs 110 g. It is excellently soluble in chloroform, acetone, ethyl acetate and ethanol.

45 Example 43

To a 50 ° C warm suspension of 44.3 g (0.05 mol) of 1: 2 chromium complex sodium salt from the azo body 2-amino-phenol-4-sulfamide - * l- (3'-chlorophenyl) -3- methyI-5-pyrazo-ion, the solution of 4.8 g (0.01 mol) of rhodamine B in water so hot and the solution of 13.1 g (0.04 mol) of Primene JM-T in dilute formic acid are stirred the acidic reaction mixture is filtered for 1 hour and washed with water. The product weighs 58 g after drying. If solutions of the colored salt and of nitrocellulose in etha-55 nol-ethyl acetate mixtures are applied to paper, the result is a bright scarlet-red color.

Instead of 4.8 g (0.01 mol) of 19.2 g (0.04 mol) of rhodamine B and instead of 13.1 g (0.04 mol) of 3.3 g (0.01 mol) of Primene JM- T on, and otherwise proceeds as described in the previous example, a well-soluble color salt is also obtained, which provides brilliant, bluish-red colorations.

C.

Claims (5)

624 981 2nd PATENT CLAIMS 1. Process for the preparation of salts of sulfonic acid group-free 1: 2 metal complex dyes of the formula h; m + m (l) wherein the V] .V2, X, Y and Z have the same or different meanings, where Vj is methyl and V2 is a group of the formula -CONH -Gl represent in which W is hydrogen, halogen, alkyl or alkoxy with 1-4 C atoms, or the rest L alkyl sulfonyl with 1-4 C-atoms bonded to a benzene ring or sulfamoyl of the formula -S02NV3V4, in which V3 is hydrogen, alkyl with 1-12 C-atoms, hydroxyalkyl with 1-4 C-atoms or alkoxyalkyl with 3-14 C-atoms and V4 represents the same as V3 or cyclohexyl, phenyl or phenyl substituted by halogen, alkyl or alkoxy with 1-4 C atoms, q is zero or the number 1 or 2 and the sum of m + n is the number 1, where m = 0.2 to 0.8 and n = 0.8 to 0.2, characterized in that 1 mol of a metal complex of the formula 25th 30th forms a group of the formula 40 45 50 55 Q Alk © (5) in which Q is alkyl with 1-4 C atoms or alkoxycarbonyl with 2-5 C atoms and W has the meaning given above, X is hydrogen or alkyl with 1-12 C atoms, Y is hydrogen, halogen, alkyl with 1-12 C atoms or nitro, Z is an O atom or a -COO group, M is a chromium or cobalt atom, B a basic xanthene dye, A is a primary or secondary aliphatic or cycloaliphatic amine with 8 to 25 C atoms, wherein Alk denotes an alkali atom, and the other symbols 60 have the meaning given, in an aqueous, aqueous-organic or organic medium in any order with 0.2 to 0.8 mol of a xanthene dye B + An ", wherein An denotes an anion, and 0.8 to 0.2 mol of a salt of a primary or secondary, aliphatic or cycloaliphati-65 see amine A having 8 to 25 carbon atoms. 2. The method according to claim 1, characterized in that 1 mol of a 1: 2 chromium or cobalt complex free of sulfonic acid groups of the dye of the formula 3rd 624 981 wherein X has the meaning given in claim 5, Y is hydrogen, alkyl with 1-4 C atoms or nitro, W is hydrogen, chlorine or alkyl with 1-4 C atoms, L alkylsulfonyl with 1-4 C atoms or sulfamoyl of the formula SOzNHV3, in which V3 has the meaning given in claim 5, and q is the number 2, with 0.4 to 0.6 mol of a xanthene dye and 0.6 to 0.4 mol of a primary aliphatic or cycloaliphatic amine with 8 -25 carbon atoms. 3. The method according to claim 1, characterized in that a basic xanthene dye of the formula Shark (7) ^ 9 R 8th • C — NIL l10 (4) Diazo components: 2-amino-4-alkylphenol, 2-amino-4,5-dialkylphenols, 2-amino-4- or -5-halophenols, 2-amino-4- or -5-ni-trophenol, 2-amino-4- alkyl-6-nitrophenols, 2-amino-4- or 5 -5-alkylsulfonylphenols, 2-aminophenol-4- or -5-sulfonic acid reamide, 2-aminophenol-4- or -5-sulfonic acid alkylamides, 2-aminophenol-4 - or -5-sulfonic acid alkoxyalkylamides, 2-amino-4-alkylsulfonyl-5-nitrophenol, 2-aminophenol-4-sulf-N, N-dialkylamides, 2-aminophenol-4-suIf-N, N-dihydr-lo oxylalkylamides, 2-aminophenol-4-sulf-N-alkyl-N-cyclohexyl-amide, 2-aminophenol-4-sulf-N-alkyl-N-phenylamide, 2-aminobenzoic acid, 2-aminobenzoic acid 4- or -5- sulfonic acid amide and 2-aminobenzoic acid 4- or -5-sulfonic acid alkyl amides. 15 Coupling components: l-phenyl-3-alkyl-5-hydroxy-pyrazole, l- (halophenyl, alkylphenyl- or alkylisulfonylphenyl) -3-alkyl-5-hydroxy-pyrazole, l- (sulfamoyl-phenyl) - or l- ( N-alkylsulfamoylphe-2onyl) -3-alkyl-5-hydroxy-pyrazoIe, acetoacetylphenylamide, acetoacetyl-halophenylamides, -alkylphenylamides or -alkyl-sulfonyl-phenylamides or acetoacetyl- (sulfamoyl-phenyl) -amides. In the specified diazo and coupling components 25, the alkyl radicals contain 1-4 carbon atoms. Examples of amines of the formula A are primary or secondary aliphatic amines with 8-25 C atoms, such as 2-ethylhexylamine, dodecylamine, stearylamine, 3-dodecyloxy propylamine, 3- (2'-ethylhexoxy) propylamine, N-butyl -N- (2-30 hydroxypropyl) amine, bis (2-ethylhexyl) amine or diisobutylamine called. Of particular interest are the products available under the trade names Primene 81-R® and Primene JM-T® from Rohm and Haas Co. These are a mixture of amines, which of the formula 35 Rq I9 r8 - C-NH2 40 i (4) 10th used, wherein R1-R7 have the meaning given in claim 3 and Hai halogen, in particular chlorine. 4. The method according to claim 1, characterized in that correspond with an amine of the formula in which Rg, R9 and R10 are alkyl radicals having a total of 7-24 carbon atoms. Examples of cycloaliphatic amines are dicy-45 clohexylamine, dehydroabietylamine and 4,4'-diaminodicyclo-hexylmethane. Examples of xanthene dyes are: 50 converts, wherein R8, Rg and R10 are alkyl radicals with a total of 7-24 55 carbon atoms. 5. Use of color salts of the formula (1) for dyeing solutions of polymers. 60 Rhodamine B Rhodamine 2G Rhodamine 3GO Rhodamine 4G Rhodamine 6G Rhodamine S • Rosamine Saccharein C.I. Basic Red 8 C.I. Basic Violet 11 Violamin 3 G Spirit Fast Violet R C.I. 45170 C.1.45165 C.1.45215 C.I. 45166 C.1.45160 C.I. 45050 C.1.45090 C.I. 45070 C.I. 45150 C.I. 45175 C.1.45195 C.1.45185