DE1066684B - Process for the preparation of dyes of the tetrazaporphin series - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

JTO9B

KL. 22 β 7/02

GERMAN

PATENT OFFICE

EXPLAINING PUBLICATION 1066 684

B46700IVb / 22e

REGISTRATION DATE: NOVEMBER 8, 1957

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL:

OCTOBER 8, 1959

It has been found that new valuable dyes of the tetrazaporphin series are obtained if amino groups are used containing tetrazaporphin compounds with Arylcarboxylic acid halide sulfonic acid haloalkylamides acylated.

Tetrazaporphin compounds containing amino groups are primarily those containing amino groups Derivatives of copper phthalocyanine into consideration, but also amino group-containing derivatives of nickel, Cobalt, iron, molybdenum, aluminum, zinc phthalocyanine or metal-free phthalocyanine. the Derivatives containing amino groups can also be derived from substituted phthalocyanines, e.g. B. from Di- or tetraphenyl copper phthalocyanine, tetraphenyl sulfone copper phthalocyanine or tetrachloro- or bromopper phthalocyanine. Also amino group-containing derivatives of azaphthalocyanines or naphthophthalocyanines can be used. Derivatives containing amino groups are also suitable for the new process of tetraza-mono-, -di or -tribenzoporphinen, so z. B. of Tetraza-tetramethyl- or -tetraphenyldibenzokupfer- or nickel porphines, as well as tetrazaporphines, such as tetraza-tetramethyl-tetraphenyl-nickelporphine or tetraza-octaphenyl-copper phthalocyanine.

The amino group can be used directly or via any group located outside the actual tetrazaporphine nucleus bound to the nucleus of the tetrazaporphine and be present one or more times in the same molecule. It is beneficial if the Tetrazaporphin derivatives containing amino groups or groups which make them soluble in water, such as sulfonic acid, SuIf onsäureamid- or carboxyl groups contain. Compounds of this type are, for example, tetramino copper phthalocyanine - tetrasulfonic acid, diamino copper phthalocyanine dicarboxylic acid or -disulfonic acid or -disulfonic acid amide, bis- or tetrakis- (aminometh3d) -copper phthalocyanine-di- or -tetrasulfonic acid, bis- [N-ethyl-N- (y-aminopropyl) -aminomethyl] -copper- or -nickelphthalocyanine-di-, -tri- or -tetrasulfonic acid, also reaction products of chlorinated tetrazaporphines with aminophenols or aminophenol ethers or their sulfonic acids in sulfuric acid liquid, such as hydroxyl or alkoxyl, amino and sulfonic acid groups bearing benzyl or methyl naphthyltetrazaporphine z. B. by converting bis, tris or tetrakis (chloromethyl) copper or nickel phthalocyanines with z. B. l-hydroxy-3- or -4-aminobenzene, 1-methoxy or ethoxy - ^ - or ^ -aminobenzene.Hydroxyaminonaphthalen or 1-hydroxy-aminobenzoM-sulfonic acid can be obtained. In particular, products are mentioned that are completely or partially Implementation of sulfochlorinated tetrazaporphines with aryl sulfonic acids that contain at least two free amino groups contain, can be obtained, example process

for the production of dyes of the tetrazaporphin series

Applicant:

Badisdie Aniline & Soda Factory

Corporation,

Ludwigshafen / Rhine

Dr. Arnold Tartter, Lambsheim (Palatinate), Dr. Fritz Graser, Dr. Werner Rohland,

Ludwigshafen / Rhine,

Dr. Erich Stödd, Mannheim,

Dr. Curt Schuster, Dr. Robert Gehm,

Dr. Julius Eisele, Ludwigshafen / Rhine,

and Wilhelm Federkiel, Frankenthal (Palatinate),

have been named as inventors

wise the reaction products of copper, nickel, cobalt, iron or aluminum phthalocyanine tri- or -tetrasulfonic acid chlorides with z. B. 1,3- or 1,4-diaminobenzene-monosulfonic acid, 1,4-diaminobenzene disulfonic acid, 4,4'-diaminodiphenylamine-3-sulfonic acid, 4,4'-diaminodiphenylsulfide disulfonic acid, 4,4'-diaminodiphenyl mono- or disulfonic acids, diaminostilbene disulfonic acids or 1,5-diaminonaphthalene-3,7-disulfonic acid. If the sulfonic acid chloride groups are only partially converted, the remaining sulfonic acid chloride groups can z. B. saponified or by treatment with monoaminoalkyl or -arylsulfonic acids or monoaminohydroxyarylsulfonic acids be converted into the corresponding sulfonic acid amide groups.

As arylcarboxylic acid halide sulfonic acid haloalkylamides, such as benzene or naphthalenecarboxylic acid chloride or bromide sulfonic acid chlorine or bromoalkylamides, whose aryl radicals also have substituents, e.g. B. alkyl, aralkyl, aryl, hydroxyl, alkoxyl, aroxyl, sulfonic acid, Sulfonic acid haloalkylamide or nitro groups and / or halogen atoms, such as chlorine atoms or bromine atoms, Above all, compounds whose sulfonic acid haloalkyl amide groups are suitable are Contain halogen and nitrogen bonded to two adjacent carbon atoms, such as Arylcarbonsäurehalogenid-sulfonsäure-jö-chloräthylamide, - / J-chlorpropylamide, - / S-chlorobutylamide or - / 3-chloroisopropylamide.

909 «37/375

3 4

Such compounds can be z. B. by Um- the copper phthalocyanine, setting of suitable arylcarboxylic acid sulfonic acid is dissolved in 700 parts of water with the addition of dilute aqueous sodium hydroxide with the corresponding chlorine or hydroxyl solution up to a pn value of about 8. One alkylamines and subsequent treatment, e.g. B. with stirs this solution in thionyl chloride within 1 to 2 hours. Ah suitable aryl carbon. 5 small parts in a ^{mixture of acid sulfonic acid chlorides cooled to 0} ° C. are, for example, 1-carboxy- 40 parts benzoylchloride-m-sulfonsäiireclüoräthylamid, benzene-3- or -4-sulfonic acid chloride, 1-carboxy-4-chloro-200 parts acetone and 100 parts parts of ice water and are one or bromobenzene-3-sulfonic acid chloride, .l.-carboxy-2-ni- same time 70 parts of an approximately 10 ° / ₀ aqueous trobenzol-4-sulfonsäurech.lorid, l-carboxy-3-nitrobenzene Sodium carbonate solution is added to the extent that the 5-sulfonic acid chloride, 1-carboxy-2- or -4-methoxyben- io pji value of the reaction mixture is 6 to 7. After zol-5-sulfonic acid chloride, 1 -carboxy-2-hydroxybenzene- removal of the cooling, the mixture is left to stir for a further 2 hours at 4-sulfonic acid chloride, carboxymethylbenzenesulfonic acid 10 to 20 ° C. and then the conversion chlorides, 2 - carboxynaphthalene - 3 - sulfonic acid chloride, product by adding potassium chloride, filter it, l-hydroxy-2-carboxynaphthalene-4-sulfonic acid chloride, wash it with methanol and dry it in the air.
2-Hydroxy-3-carboxynaphthalene-1-sulfonic acid chloride 100 parts of a dye which is readily soluble in water or 1-carboxy-2-hydroxynaphthalene-6-sulfonic acid and which is known for dyeing tree chloride are obtained. The Arylcarbonsäurehalogenid-sulfon- wool can be used.

Acid haloalkylamides can optionally also contain dyes of a more greenish-blue color

contain free sulfonic acid groups. one in a corresponding way if one in place of

You can use the new dyes z. B. in organic sulfochlorinated copper phthalocyanine nickel, iron solvents produce, especially in miscible with water or aluminum phthalocyanine trisulfonic acid chlorides Solvents such as acetone, dioxane, glycol.

ether, dimethyl- or dietliylformamide or N-methyl - BeisDiel 2
pyrrolidone. The most economical way to work, however, is in

aqueous liquid and, if necessary, only uses 35 Das by reacting 13 parts of a mixture

such a large amount of an organic solvent, copper phthalocyanine di- and tri-sulfonic acid chloride

z. B. acetone, as used for the solution of the aryl carboxylic acid with 7 parts of 4,4'-Diaminodiphcnyl-3-sulfonsäurc in

halide sulf onsäurehalogenalkylamide is required. Presence of excess aqueous sodium carbonate

The reaction can take place at ordinary temperature or the product obtained is as a moist filter material in

with cooling, preferably at temperatures between 30 about 500 parts of water and cooled with ice water.

-5 and +10 ⁰ C in acidic to weakly alkaline liquid. A solution of is carried into this solution with stirring

can be made. If necessary, 10 parts of benzoyl chloride-rn-sulfonic acid chloroisopropyl-

heat gently towards the end of the reaction. To the binamide in 100 parts of acetone slowly in small portions

formation of the halogen released in the acylation. At the same time one leaves a dilute aqueous

Hydrogen is used acid-binding agents, such as sodium 35 sodium carbonate solution to flow in such a way that the reaction

odcr potassium carbonate, bicarbonate, acetate or version of the reaction mixture remains neutral. To

dilute aqueous alkali metal hydroxide solutions. The required several hours of reaction time are given in diluted form

If necessary, add hydrochloric acid by salting out and / or acidification until the p ^ value is about 4. To

separated dyes are filtered off and preferably the salting out with sodium chloride is filtered

at a moderately elevated temperature, advantageously below the reaction product and dries it at a low temperature

reduced pressure, dried. That the sucked off under reduced pressure. 55 parts are obtained

Water adhering to dyes can also be replaced by a blue dye that contains salt and is used for printing or

your to be removed by organic means. Dyeing of all kinds of textiles can be used.

The dyes obtainable by the new process. Similar dyes are obtained from 4-chloro or

are generally very soluble in water, and can 45 4 - bromobenzoyl chloride - 3 - sulfonic acid chloroisopropylamide

for dyeing and printing all kinds of textile goods or NaphthaHn ^ -carboxylic acid chloride-S-sulfonic acid chloride

be turned. One obtains dyeings or prints of ethylamide and some of the 4,4'-diaminodiphenyl

very good general properties, especially on disulfonic acid, 1,4-diaminobenzene disulfonic acid or

Formed from active and regenerated cellulose. 4,4 '-diaminodiphenylamine-3-sulfonic acid reacted

Of the known water-soluble phthalocyanine dyes 50 copper phthalocyanine di-, tri- or tetra-sulfonic acid ^ materials, as they are, for. B. in the French patent chlorides.
838 418, Example 15, U.S. Patent 2,542,327,
Example 3, and US Pat. No. 2,795,585, Example 1, the new dyes obtainable according to In a neutralized aqueous solution of 30 parts of the invention differ by the fact that they have a washing fastness which is better than a hydroxyaminobenzylsulfonic acid group and their washing fastness according to the alkaline padding. holding Kupf erphthalocyanins, the dyeings obtainable by conversion process. of tetrakis (chloromethyl) copper phthalocyanine with

The parts given in the examples are by weight 1-hydroxy-2-aminobenzene in sulfuric acid monohydrate

share. and subsequent sulfonation in 10% oleum

Example 1 ^{6o erna} ft ^cn , a

Solution of 25 parts of benzoyl chloride-p-sulfonic acid chloro-

25 parts of copper phthalocyanine are in 200 parts of ethylamide in acetone and 50 parts of about 10 ^ gene

Chlorosulfonic acid was heated for 3 hours at 13O ⁰ C. The registered by aqueous sodium carbonate solution in such a way that

slowly running the acidic solution into ice water, the reaction mixture remains weakly acidic. To

and filtering the separated sulphonyl chlorination product 65 with stirring for several hours at ordinary temperature

is mixed with 25 parts of 1,4-diaminobenzene-2-sulfonic acid in one separates the reaction material at a pn value of

Presence of dilute aqueous sodium carbonate 6.5 by adding potassium chloride and nitrating it.

solution implemented and, after precipitation, washed with dilute that with aqueous potassium chloride solution

Sucked off hydrochloric acid. The filter material, a sulfone filter material, is then dried at a lower temperature.

acid (aminobenzenesulionic acid) amide groups contain- 70 About 65 parts of a saline green-blue are obtained

Claims (1)

Dye, cotton in green-blue tones with potassium chloride, sucks it off and dries it good wet fastness properties. by washing with methanol. He dyes cotton in Instead of the copper phthalocyanine greenish blue tones given above,
derivatives can also be obtained by converting chlorine methylated copper phthalocyanine with 1-methoxy-5 Example 6 4-aminobenzene, 1 - hydroxy - 7 - aminonaphthalene or 29 parts of a copper phthalocyanine derivative, from 1-Hydroxy-2-aminobenzene-4-sulfonic acid in sulfur - the three sulfonic acid chloride groups of which are previously one with acid obtained and optionally subsequently sulfol, 4-diaminobenzene-2-sulfonic acid or with 1,3-diamino- use ned products and these with bemoyl benzene-4-sulfonic acid and two with aminobenzene disulfone chloride-m-sulfonic acid chloroethylamide, benzoyl chloride-p-io acid have been reacted in 400 parts of water sulfonic acid chloroisopropylamide, 2-nitrobenzoyl chloride dissolved, with dilute aqueous alkali metal hydroxide solution 4-sulfonic acid chloroethylamide or 4-chlorobenzoyl chloride neutralized and, as described in Example 1 or 2, Acylate 3-sulfonic acid chloroethylamide. with a solution of 12 parts of benzoyl chloride p-sulfone . ■ \ λ säurechloräthylamid acylated in acetone. You get one Example 4 _{15 blue} dye, the structure of native and regenerated 25 parts of bis (aminomethyl) copper phthalocyanine-dispersed cellulose dyes in real blue tones, Fonsäure are dissolved in water and by adding acylates in a similar way the corresponding dilute aqueous sodium hydroxide solution, neutral derivative of tetraphynyl copper phthalocyanine, is obtained sated. Then one adds at 0 to +5 ⁰ C 150 parts of a dye that turns green in water 15 ⁰ / © i§en solution of benzoyl chloride-m-sulfonic acid chloro- ao dissolves, while the diazo copper phthalocyanine ethylamide in acetone and neutralizes the sa \ icr derivative or the tetramethyldibenzo-nickelporphine- reaction mixture becomes by adding vcr- derivative, whose sulfonic acid chloride groups previously with dilute aqueous sodium acetate solution. After termination - 1,4-dietninobenzene disulfonic acid and 1 - aminobenzene- the reaction is acidified, the solution is weakly converted to 3-sulfonic acid, dyes are produced, and salt out. The suctioned and by washing with * 5 which dissolve in water with a reddish blue color. Acetone-dried dye dissolves in with a blue color. Water and dye wool from acetic acid bath in blue Example 7 Tones. A neutral aqueous solution of 40 parts of a A similar blue dye is obtained from the product obtained by reacting 1 mole of copper with bis- (n-aminopropyl-N-methyl- or -ethyl-phthalocyanine trisulfonic acid chloride with 1.5 moles of 4,4'-diaminomethyl) copper phthalocyanine -disulphonic acid (crhal- aminodiphenylsulphide-disulphonic acid in the presence of th by treating the reaction product of bis-excess aqueous sodium carbonate solution obtained chloromethyl copper phthalocyanine with Ν, Ν-dimethyl or was and from a mixture of a copper phthalic acid -diethyl-propylene disulphonic acid diluted cyanidylenediamine in a and a copper alkali metal hydroxide solution and subsequent sulfonation in 35 ferphthalocyanine monosulfonic acid amide disulfonic acid be-23% oleum), while the corresponding circumstance is, in the manner described above, the tetraamino-copper phthalocyanine-tetra- 18 parts of benzoyl chloride-p- sulfonic acid chloroisopropylamide sulfonic acid is greener in color. acylated. A dye which is soluble in water is obtained. . _ the textile material made of cellulose ^{dyes in genuine greenish blue Beis} P ^ie15 40 shades. 33 parts of a monochloro copper phthalocyanine derivative, claim
of its four sulfonic acid chloride groups previously one with 4,4'-diaminodiphenyl-2-sulfonic acid and three with processes for the preparation of dyes of l-Hydroxy-2-aminobenzene sulfonic acid have been reacted, tetrazaporphin series, characterized in that are stirred into 400 parts of water, with dilute 45 amino group-containing tetrazaporphinver- aqueous sodium hydroxide solution and neutralized, such as bonds with Arylcarbonsäurehalogenid-sulfonic acid- described in Example 1 or 2, acylated with a solution of haloalkylamides. 15 parts of Bcnzoylchlorid-m-sulfonsäureclüorathylamid in Treated 100 parts of acetone. Then add to the pamphlets under consideration: Reaction mixture diluted hydrochloric acid until a 50 French Patent No. 838 418; pH 3 to 4 is reached and salts the dye USA. Patents Nos. 2,542,327, 2,795,585. When the registration was announced, 1 staining board was displayed. 909 637/375 ».59