DE1150479B - Process for the production of coupling-capable phthalocyanine derivatives - Google Patents

Description

It has been found that valuable couplable phthalocyanine derivatives are obtained when on Phthalocyaninesulfonic acid halides or carboxylic acid halides Esters of such couplable Allows hydroxyl compounds to act that contain primary or secondary amino groups in the molecule, and then saponifying the ester group in the products obtained.

Both metal-free phthalocyanines and phthalocyanines that contain a metal are suitable as phthalocyanines as the central atom, preferably copper, nickel or cobalt. The phthalocyanines can die Sulphonic acid halide or carboxylic acid halide groups in the benzene nuclei of the macrocyclic Ring or also in fused aromatic rings or in aryl radicals, either directly or via bridging atoms, such as. B. —CO—, —SO, - or —NH—, with the macrocyclic Phthalocyanine ring are linked.

In addition to the acid halide groups, the phthalocyanine radicals can also contain other, noninogenic substituents, such as halogen, nitro, alkyl, alkoxyl or acylamino groups.

The amines containing ester groups that react with the acid halide groups of phthalocyanine are derived preferably from primary or secondary amines of the benzene, naphthalene, acylacetic acid amide, Arylpyrazole or other compounds of the heterocyclic series. As a couplable Hydroxyl compounds are therefore, for example, aminophenols, aminonaphthols, aminonaphtholcarboxylic acid arylides, Aminoacyl acetic acid amides, acyl acyl acetic acid aminoarylamides or aryl, in particular phenylpyrazolones, containing amino groups underlying.

During the reaction, either all or only the acid halide groups of the phthalocyanine can be used some of them react with the amino groups of the amines containing ester groups. Acid halide groups, which do not react with the ester amines can optionally with ammonia or others non-coupling amines are implemented. If desired, unreacted, excess can Subsequent sulfonic acid halide or carboxylic acid halide groups of the phthalocyanine molecule are saponified, at the same time a cleavage of the ester group of the amino groups Component can occur.

The reaction of the phthalocyanines containing acid halide groups with the definition to be used amines is preferably in an organic medium, such as chlorobenzene, pyridine, nitro

Process for the production of couplable Phthalocyanine derivatives

Applicant:

Paint factories Bayer Aktiengesellschaft,
Leverkusen

Dr.-Ing. Berthold Bienertf, Leverkusen,

Dr. Kurt Breig, Dr. Manfred Groll

and Dr. Heinz Gutjahr, Cologne-Stammheim,

have been named as inventors

so benzene, alcohols or dimethylformamide, made to hydrolyze the acid halide groups to prevent.

The technically particularly easily accessible phthalocyaninesulfonic acid chlorides can also be reacted with the Esteras amines in the form of moist pastes, organic solvents such as ketones or aromatic halogenated hydrocarbons, at the same time as solvents for the esteramine and the Serve sulfochloride. The good solubility of the amines containing ester groups and their reaction products in organic solvents makes this possible the production of very pure compounds without significant hydrolysis of the acid halide groups entry.

The esters initially obtained according to the process are made more alkaline, such as methyl alcohol Caustic soda or dilute pyridine and caustic soda, easily to the desired end products saponified. These are as dyes, for example for dyeing cotton or for Spinning in synthetic fibers or suitable for dyeing plastics. They can also be used as Use coupling components to build up azo dyes.

US Pat. No. 2,459,771, Example 2, shows the reaction of copper phthalocyanine tetrasulfochloride and l-3'-aminophenyl) -3-methyl-5-pyrazolone in a ratio of 1: 3.08. Is also from the example of British patent specification 520199 the reaction product of 1 mole of copper phthalocyanine tetrasulfochloride and 4 moles of 5-amino-2-oxybenzene-1-carboxylic acid known. Compared to these

309 617/238

Compounds show the dyes obtainable according to the process which are obtained using the same Molar ratios with the O-ester of 1- (3'-aminophenyl) -3-methyl-5-pyrazolone or the O- and carboxylic acid esters of 5-amino-2-oxybenzene-1-carboxylic acid, better wet fastness of the Dyeings on cotton and better wash fastness (test according to DIN 539563 c) that with diazo compounds developed dyeings or prints on cotton.

example 1

21.9 parts by weight of l- (3'-nitrophenyl) -3-methylpyrazolone- (5) are with 4 parts by weight of sodium hydroxide and 5 parts by weight of soda in 500 ml of water solved. 17.6 parts by weight of benzenesulfonic acid chloride are left in this solution over the course of 1 hour drip. The pyrazolone ester separates out oily at first, but becomes after stirring overnight solid and can be suctioned off. The reduction of the nitro group is done in alcoholic solution with Raney nickel made in a known manner. The 1 - (3'-aminophenyl) -3-methylpyrazolone- (5) -benzenesulfonic acid ester obtained in this way melts at 90 to 91 ° C. The p-toluenesulfonic acid ester can be prepared in an analogous manner and from the l- (4'-nitrophenyl) -3-methylpyrazolone- (5) derl- (4'-aminophenyl) -3-methylpyrazolone- (5) -benzenesulfonic acid ester.

27 parts by weight of the p-toluenesulfonic acid ester des l- (3'-aminophenyl) - 3-methyl-5-pyrazolones are added to 90 parts by weight of pyridine and with 19.4 parts by weight of Ni phthalocyanine (3) tetrasulfochloride are added. When the conversion has ended, the mixture is stirred the melt in ethanol, sucks off and washed with ethanol. The resulting reaction product is in Usually with sodium hydroxide solution, optionally with the addition of a little pyridine, saponified, precipitated with acid, vacuumed, washed and dried. A particularly pure sulfonic acid amide is obtained in this way. The product is a blue powder that dyes cotton in blue tones.

The reaction of the pyrazolone ester with the phthalocyanine sulfochloride can also be indifferent Solvents, such as chlorobenzenes, can be made.

The reaction product obtainable in this way can, if appropriate, by customary processes with sodium hydroxide solution be saponified in the presence of a little pyridine. The saponification product is acidified precipitated, filtered off, washed and dried. This is a particularly pure phthalocyanine sulfonic acid amide available. The product is a blue powder, the cotton in blue tones colors. The saponified phthalocyaninesulfonic acid amide obtained by following the procedure of this example can be used to produce a green print in the following manner. The coupling component (Phthalocyaninesulphonic acid amide) is equivalent to its coupling capacity Amount of a diazonium compound obtained from diazotized 1-amino-2-methyl-4,5-dichlorobenzene and 2-ethylamino-5-sulfobenzoic acid mixed. 60 parts by weight of this mixture are mixed with 100 parts by volume of dilute sodium hydroxide solution (concentrated sodium hydroxide solution 38 ° Be diluted with water at a ratio of 1:10). The solution is made into a mixture 500 parts by weight of starch thickener and 240 parts by volume of water are stirred in. The one available in this way Printing paste, when printed on cotton and regenerated celulose, results in neutral or acid steaming a green print.

Example 2

In 90 parts by weight of pyridine, 27 parts by weight of that obtainable according to the information in Example 1 are obtained Benzenesulfonic acid ester of 1- (3'-aminophenyl) -3-methyl-5-pyrazolone and then

ίο 19.4 parts by weight of nickel phthalocyanine (3) tetrasulfochloride registered. After the conversion has ended, the melt is stirred into ethanol, filtered off with suction and washes with ethanol. A blue powder is obtained which can easily be dissolved in organic solvents such as Acetone, o-dichlorobenzene, nitrobenzene or dimethylformamide dissolves and is saponified according to the information given in Example 1.

Is used in place of the 1- (3'-aminophenyl) -3-methyl-5-pyrazolone-benzenesulfonic acid ester 38 parts by weight of 3-aminobenzoyl acetic anilide-O-benzenesulfonic acid ester, a reaction product with similar properties is thus obtained.

The 3-aminobenzoyl acetic anilide-O-benzenesulfonic acid ester can be obtained in the following way:

In a solution of 28.5 g of 3-nitrobenzoyl acetic anilide 27 parts by weight of benzenesulfonyl chloride are left in 100 parts by volume of pyridine with vigorous stirring drip. After about 2 hours, the reaction mixture is poured into 1 liter of water, with the reaction product initially turns out oily. After prolonged stirring, the oil solidifies and can be suctioned off will. The 3-nitrobenzoyl acetic anilide-O-benzenesulfenic acid ester is obtained by recrystallization from alcohol in pure form (160 to 161 ° C). By reducing the nitro group with Raney nickel in Tetrahydrofuran gives the corresponding amino compound.

Example 3

In 100 parts by weight of chlorobenzene there are 17 parts by weight of the benzenesulfonic acid ester obtainable according to Example 1 of l- (3'-aminophenyl) -3-methyl-5-pyrazolone and then 9.63 parts by weight Ni - phthalocyanine - (3) -tetrasulfonochloride registered.

3.2 parts by weight of pyridine are added and the mixture is stirred at normal or slightly elevated temperature up to Completion of implementation. The reaction product is precipitated with alcohol, filtered off with suction and washed. The blue powder thus obtainable, which is readily soluble in organic solvents, is as in Example 1 indicated, saponified.

Instead of the benzenesulfonic acid ester of l- (3'-aminophenyl) 3-methyl-5-pyrazolone one can the ester of 1- (4'-aminophenyl) -3-methyl-5-pyrazolone also achieved similar success use. The nickel phthalocyanine- (3) -tetrasulfochlorid can by the copper phthalocyanine- (3) -tetrasulfochlorid and the pyridine by other suitable acid-binding agents, such as triethylamine, sodium acetate or excess Esters, themselves to be replaced.

Instead of chlorobenzene, other solvents such as o-dichlorobenzene, acetone or Methyl ethyl ketone can be used.

g Example 4

In 100 parts by weight of chlorobenzene, 17 parts by weight of the analogous to the information in Example 1 available benzenesulfonic acid ester of l- (4'-amino-

5 6

phenyl) - 3 - methyl - 5 - pyrazolons 4.0 parts by weight If instead of copper phthalocyanine NaHCO ₃ and then at low temperature 9.63 Ge (4) tetrasulfochloride 9.65 parts by weight nickel phthalo parts by weight nickel phthalocyanine- (3) -tetrasulfochlo- cyanine- (4) -tetrasulfochloride entered in the form of a moist rid in the form of an aqueous paste. Paste is obtained in good yield and is stirred very well until the reaction is complete and the pure form precipitates an end product, which is obtained in dilute reaction product with methanol, sucks caustic soda with a blue-green color, dissolves,
and washes briefly with methanol. Instead of l- (4'-aminophenyl) -3-methyl-5-pyrazolone-The dried compound obtained in this way is a benzenesulfonic acid ester, blue powder can be used in the process, which can easily be found in organic l- (3'-aminophenyl) Use -3-methyl-5-pyr solvents such as acetone, o-dichlorobenzene, nitro-ίο azolon-benzenesulfonic acid esters. Benzene or dimethylformamide is obtained and dissolves. The saponification of the ester is obtained analogously to Example 1 and in a very pure form. They dissolve easily in methyl alcoholic sodium hydroxide solution or dilute dilute sodium hydroxide solution with a blue-green color,
carried out pyridine-containing sodium hydroxide solution. Then ". . .,
The saponified product is then precipitated with acid, Example 0
Aspirated and washed neutral. A dry powder of pure, dry pyridine blue in 120 parts by weight is obtained, which dyes cotton in blue shades. are cooled with water at about 15 ° C. A cotton fabric can be printed with the following 13.0 parts by weight of 1- (4'-ethylaminophenyl) -3-mebeschribed printing paste according to conventional techniques, ethyl-5-pyrazolone-benzenesulfonic acid ester and then printed. After drying and incorporation, 7.24 parts by weight of dry nickel phthalocyanine were introduced into an entanine (3) tetrasulfochloride containing a diazo compound. After a 24-hour winding bath, the tissue is squeezed off, a washing bath is run by stirring at room temperature for 4 hours and then about 75 parts by weight of hot bath are introduced while stirring at 30 to 35 ° C, the 15 parts by volume of sodium pyridine is distilled off in vacuo and the reacbisulfide (38 ° Be) per liter. Then 25 tion product from the remaining solution is washed with and soaped. A full amount of precipitated methanol is obtained. The dye is sucked off, green print. By pressing together with more methanol and hot water until the naphthol is more colorless, multi-color effects can be achieved and washed loose. The pigment is removed. stands in good yield and can be saponified in pyridine-water Composition of the printing paste: 3o with sodium hydroxide solution. Before saponification.,,,. . . The condensation product is readily soluble in the ^organic _{weight of the solvent} obtained in this example, such as chlorobenzene, pyridine, saponified phthalocyanine _sulfone-O- dichlorobenzene and dimethylformamide,
acid amides 1- (4'-ethylaminophenyl) -3-methyl-5-pyrazolone-30 parts by weight Monobrillantol, benzenesulfonic acid ester can be obtained in the following way with 50 _{parts by weight of alcohol:}

^{25 G} ^ iii. ^steep sodium hydroxide _{329 g} i. ₍₄ '-aminophenyl) -3-methyl _P yrazolon

^ ₁ '., ", 5-benzenesulfonic acid ester, prepared by reaction

375 Volumentei e water _{from the ENTs} p _re sponding 4'-nitrophenyl compound,

500 weight point starch thickening. _4o ^ _{400ml of alcohol are dissolved in the solution}

1000 parts by weight. 6 ml of acetaldehyde and 0.8 g of Raney nickel

admitted. The hydrogen uptake begins at

^Bei P ^{iel 5} 50 ° C by further heating to 60 ° C is the

In a mixture cooled to -10 to -15 ° C, the reaction is complete. The alcoholic

of 110 parts by weight of chlorobenzene, 15.1 parts by weight 45 hydrogenation solution is after separation of the catalyst

share l- (4'-aminophenyl) -3-methyl-5-pyrazolone ben- lysators poured into ice water with stirring, wherein

zolsulfonsäureester and 4.0 parts by weight of sodium- the product initially precipitates in oily form. To

bicarbonate is stirred 11.6 parts by weight of copper - stirring for about 1 hour gives a solid product

phthalocyanine- (3) -trisuh ° chloride product as a moist paste that can be easily vacuumed off. You get

a. The mixture is then stirred for 24 hours at -10 50 l- (4'-ethylaminophenyl) -3-methylpyrazolone-5-ben-

to 0 ° C, 24 hours at 0 to 30 ° C and 4 hours zolsulfonsäureester. After drying, the

at 30 to 35 ° C. bond has a melting point of 58 to 62 ° C. From

The reaction mixture is recrystallized for the saponification of the petroleum ether, giving colorless

resulting ester directly into excess needles, which melt at 66 to 67 ° C.

Stir in sodium hydroxide solution. After saponification and 55 are substituted for the l- (4'Aminophenyl) -3-me-

after neutralizing the sodium hydroxide solution, the thylpyrazolone- (5) -benzenesulfonic acid ester l-G'-ami-

Chlorobenzene blown off with steam. The in nophenyl) -3-methylpyrazolon- (5) -benzenesulfonic acid-

pyrazolone ester deposited in a readily filterable form, l- (3'-ethyl-

vat is filtered off with suction, washed with hot water aminophenyl) -3-methylpyrazolon- (5) -benzolsuh ^c on-

and dried. The dye gives, after the pigment 60 acid ester; this connection can also be made with nickel

ment printing process, on cellulose blue phthalocyanine- (3) -tetrasulfochlorid according to the above

Prints. process described condensed and the con-

In this example, instead of the densation product, it can then be saponified.

Copper phthalocyanine (3) trisulfochloride 9.7 wt

share copper phthalocyanine- (4) -tetrasulfochloride in 65 one when using l- (4'-propyl- or -benzyl-

In the form of a moist paste, an aminophenyl) -3-methyl-5-pyrazolone-benzenesulfone-

Pigment, which is found on cotton in the pigment acid ester in place of l - ^ '- ethylaminophenyl) -

printing process results in blue prints. S-methyl-S-pyrazolone-benzenesulfonic acid ester.

Amino-phenol in pyridine is allowed to act at 10 ° C and then the reaction mixture first ½ hour to 60 ° C. and then a further ½ hour heated to a gentle boil. The solution is poured into ice water, with the product after solidified for a short time. After suctioning off and drying, 4-acetylaminophenolbenzenesulfonic acid ester is obtained with a melting point of 122 to 123 ° C. The product can be mixed with alcoholic hydrochloric acid

1- (4'-Propyl- and -benzylaminophenyl) -3-methyl-5-pyrazolone-benzenesulfonic acid esters can be prepared by adding 32.9 g of 1- (4'-aniinophenyl) -3-methylpyrazolone- (5) -benzenesulfonic acid ester after this
procedure given above with 7.8 ml of propionaldehyde or equivalent parts of benzaldehyde
hydrogenated. 1- (4'-Propylaminophenyl) -3-methylpyrazolone- (5) -benzenesulfonic acid ester is obtained (according to
Recrystallize from petroleum ether, colorless crystals
F. 70 to 71 ° C) and l- (4-benzylaminophenyl) - to amino compound are saponified, which after the 3-methylpyrazolon- (5) -benzenesulfonic acid ester (from recrystallization from alcohol at 100 to 101 ° C ligroin redissolved F. 90 up to 92 ° C). melts.

. . If you use in place of the 4-aminophenol

ispiel7 benzenesulfonic acid ester equimolecular amounts of the

A reaction product with similar 1 - (4'-aminophenyl) -3-methyl-5 is kept in a mixture of 175 parts by weight of dioxane, 15 l-amino-7-naphthol-benzenesulphonic acid ester, 40 parts by weight of acetone, and 26.4 parts by weight -pyrazolon-benzenesulfonic acid ester and 6.6 parts by weight of sodium bicarbonate is the moist paste of a at 0 to 10 ° C
aza-Nickelphthalocyaninsulfochlorids registered wel- 20
Ches from 23.3 parts by weight of 2 moles of pyridine-2,3-dicarboxylic acid and 2 moles of 4-sulfophthalic acid
aza-nickel phthalocyaninesulphonic acid, which is unknown in the urea process, is formed by handling with chlorosulphonic acid and thionyl chloride at 25 trisulphochloride in the form of a moist paste at an elevated temperature. up to 15 ° C. You leave until the end

Stir the reaction at 15 to 35 ° C and the reaction product precipitates with ligroin. It can be in Pyridine — water saponified with dilute sodium hydroxide solution will.

The replacement of l- (4-aminophenyl) -3-methyl-5-pyrazolone-benzenesulfonic acid ester the corresponding l- (3'-aminophenyl) derivative leads to a similar product. Both dyes can

Properties.

Example 9

In a solution of 25.6 parts by weight of 1- (4'-aminophenyl-3-methyl-5-pyrazolone benzenesulfonic acid ester in 10.0 parts by weight of chlorobenzene there are 6 parts by weight of sodium bicarbonate and 18.6 parts by weight 3, 4-dichloronickel phthalocyanine-3 ', 3 ", 3'" -

The mixture is left at -5 to 0 ° C. for 24 hours, at 0 to 30 ° C. for 10 hours and at 30 to 35 ° C. for 2 hours stir. Then 16 parts by weight of pyridine are added and the mixture is stirred for a further 2 hours at 30 ° C.

The reaction mixture is filtered and the ester
precipitated from the filtrate with water. After this
The product can be suctioned off and washed with water in 10% pyridine water with sodium hydroxide solution
to be saponified. The phthalocyanine pyrazolone derivative, 35 can be used in pigment printing, which turns blue in dilute sodium hydroxide solution. Similar reaction products are obtained if

Color dissolves can be used as a blue dye instead of the reaction mentioned in paragraph 1. participants 18.1 parts by weight 4,5,4 ', 5'-tetrachloro

Similar products are obtained by using nickel phthalocyanine-3 " ^r , 3"'- disulfochloride, 4 parts of the benzene nuclei of nickel or copper phthalate, 40 parts by weight of sodium bicarbonate and 17.1 parts by weight of cyanine by weight from 2 mol of pyridine-2,3-dicarboxylic acid and parts (l- (4'-aminophenyl) -3-methyl-5-pyrazolone-

benzenesulfonic acid ester or 18.2 parts by weight of 4.5, -4 ', 5' - tetrachloro copper phthalocyanine - 3 ", 3"'- disulfochloride, 4 parts by weight of sodium bicarbonate and 17.1 parts by weight of 1- (4'-aminophenyl) -3-methyl-5 -pyrazolone-benzenesulfonic acid ester used. The phthalocyanine sulfochlorides substituted by chlorine can be prepared in a known manner from mixtures of chlorine

2MoI phthalic anhydride with chlorosulfonic acid thionyl chloride Introduces sulfochloride groups and the products obtained in place of the one used above Sulphochloride is used.

Example 8

24.8 parts by weight of 4-aminophenol-benzenesulfonic acid ester are dissolved in 650 parts by weight of o-dichlorobenzene and the solution is cooled to 15.degree.
Adding 10.1 parts by weight of sodium bicarbonate, 19.3 parts by weight of nickel phthalocyanine (3) tetrasulfochloride are added as a moist paste at about 15 ° C. while cooling with water. The mixture is then stirred for 24 hours at 15 ° C and 4 hours at 30 to 35 ° C. The deposited reaction product is filtered off with suction, washed with benzene and ligroin and dried. To remove soluble salts, it is obtained for 1 hour with 800 parts by weight of water of substituted phthalonitriles and phthalonitrile. After 50 and treatment of the pigments obtained therefrom with chlorosulphonic acid.

Example 10

In 80 parts by weight of dimethylformamide, 24 parts by weight of 1- (4'-aminophenyl) -3-methylpyrazolyl- (5) -ethyl carbonate, 8 parts by weight of sodium bicarbonate and 19.4 parts by weight of nickel phthalocyanine-3,3 ', 3 ", 3"' - tetrasu-chloride entered

stirred, filtered off with suction, washed with water and countered. The temperature is increased while stirring dries. The ester obtained in this way dissolves slowly at 20.degree. C. and is stirred there for 18 hours centered sulfuric acid with a dull yellow-tinged temperature and briefly at 30 ° C. To the green color and separates when the work is stirred in, the melt is poured into water and stirred sulfuric acid solution in water in the form of blue with hydrochloric acid and sucks off. Then greener Flakes off. It can be used with pyridine-water. The reaction product is soaped with sodium hydroxide solution Caustic soda can be saponified. Pyridine water, acidifies, sucks off and washes new

4-aminophenol-benzenesulfenic acid ester can be neutral. The reaction product dissolves in dilute obtained when you add benzenesulfonyl chloride to 4-acetyl sodium hydroxide solution with a blue-green color.

1- (4'-aminophenyl) -3-methylpyrazolyl- (5) ethyl carbonate can be obtained in the following way:

21.9 parts by weight of 1- (4'-nitrophenyl) -3-methylpyrazolone-5 are with 4 parts by weight of sodium hydroxide and 5 parts by weight of soda in 300 parts by weight Slurried water. This slurry is left with stirring at 0 to 5 ° C Slowly flow in 12 parts by weight of ethyl chloroformate. After stirring for 3 hours, it is suctioned off and washed with water. The l- (4'-nitrophenyl) -3-methylpyrazolyl-5-ethyl carbonate thus obtained after recrystallization from alcohol melts at 85 to 86 ° C. By reduction with Raney nickel l- (4'-aminophenyl) methyl-S-pyrazolyl-S-ethyl carbonate is obtained in methanol.

Example 11

In 50 parts by weight of tetrahydrofuran at 10 to 15 ° C 21 parts by weight of 1- [4 '- (3 "-Aminobenzoyl) - aminophenyl] - 3 - methylpyrazolone - (5) -benzenesulfonic acid ester, 4 parts by weight sodium bicarbonate and 9.7 parts by weight of nickel phthalocyanine-3, 3 ', -3 ", 3"' -tetrasulfochloride entered in the form of an aqueous paste. The reaction mixture is stirred for a few hours, first at 15 to 20 ° C., then at 30 to 50 ° C, the melt pours into methanol and sucks off.

For saponification, the reaction product is introduced into 100 parts by weight of 25% strength pyridine water, 23 parts by weight of sodium hydroxide solution (d = 1.36) are added, the mixture is stirred for 4 hours at 15 to 20 ° C., the reaction product is precipitated with acid, filtered off with suction and washed neutral. The reaction product obtained dissolves in dilute sodium hydroxide solution with a blue-green color.

Instead of the 1- [4 '- (3 "-aminobenzoyl) aminophenyl] -S-methylpyrazolone-S-benzenesulfonic acid ester one can use l- [3 '- (3 "-aminobenzoyl) - aminophenyl] -3 -methylpyrazolone-5-benzenesulfonic acid ester with similar success use.

The pyrazolone esters mentioned in this example are obtained in the following way:

32.9 parts by weight of 1- (4'-aminophenyl) -3-methylpyrazolone- (5) -benzenesulfonic acid ester are dissolved in 120 parts by weight of acetone and 10 parts by weight of pyridine. This solution is added dropwise at room temperature slowly a solution of 18.5 parts by weight of 3-nitrobenzoyl chloride in 40 parts by weight of acetone a. After stirring for 2 hours, it is poured into 500 parts by weight of water, the 1- [4 '- (3 "-nitrobenzoyl) aminophenyl] -methyl-S-pyrazolone-S-benzenesulfonic acid ester fails. Recrystallized from alcohol, the compound melts at 168 to 169 ° C Reduction with Raney nickel in tetrahydrofuran gives 1- [4 '- (3 "-aminobenzoyl) aminophenyl ] - methyl - 3 -pyrazolon - 5 - benzenesulfonic acid ester, which, recrystallized from alcohol, at 163 melts up to 164 ° C.

If the 1- (4'-aminophenyl) -3-methylpyrazolone-5-benzenesulfonic acid ester is used instead the l- (3'-aminophenyl) -3-methylpyrazolon-5-benzenesulfonic acid ester, the 1 - [3 '- (3 "- aminobenzoyl) - aminophenyl] methyl-3-pyrazolone-5-benzenesulfonic acid ester is thus obtained in the same way, which, recrystallized from alcohol, melts at 141 to 142 ° C.

Example 12

In a solution of 33.4 parts by weight of 1- (4'-methylaminophenyl) -3-methyl-5-pyrazolone-p-toluenesulfonic acid ester 100 parts by weight of dry pyridine are 10.0 parts by weight at 0 to 50 ° C Copper phthalocyanine (4) tetracarboxylic acid chloride [obtained from the sodium salt of copper phthalocyanine (4) tetracarboxylic acid and phosphorus pentachloride in nitrobenzene at 120 to 130 ° C]. The mixture is stirred for 48 hours, the reaction product is then filtered off and poured into water stirred in and, after heating the solution to 60 ° C., filtered again. The precipitate thus obtainable is washed with water, purified by stirring in hydrochloric acid and nitrated again. The product can after the details of Example 1 are saponified.

Instead of copper phthalocyanine (4) tetracarboxylic acid chloride, nickel phthalocyanine (4) - or - (3) -tetracarboxylic acid chloride, nickel phthalocyanine- (4) - or - (3) -tricarboxylic acid chloride or copper phthalocyanine- (4) - or - (3) -tricarboxylic acid chloride can be used.

Claims (6)

PATENT CLAIMS: 1. A process for the preparation of couplable phthalocyanine derivatives, characterized in that esters of couplable hydroxyl compounds containing primary or secondary amino groups in the molecule are allowed to act on phthalocyaninesulfonic acid halides or carboxylic acid halides, and the ester groups in the compounds obtained are then saponified. 2. The method according to claim 1, characterized in that ester or aromatic heterocyclic hydroxyl compounds can be used. 3. The method according to claim 1, characterized in that esters of enolized aminoarylpyrazolones be used. 4. The method according to claim 1, characterized in that esters of enolized Aminoacylessigsäurearylamides be used. 5. The method according to claim 1, characterized in that esters of enolized acylacetic acid aminoarylamides be used. 6. Process according to Claims 1 to 5, characterized in that the reaction in. organic medium. References considered: British Patent No. 520 199; U.S. Patent No. 2,459,771. When the application was announced, two staining tables were displayed © 309 617/238 6.63