DE1250941B - Process for the production of azo dyes - Google Patents

Description

GERMAN

PATENT OFFICE

EDITORIAL

German class: 22 a-1

Number: 1250941

File number: B 66415IV c / 22 a

Filing date: March 17, 1962

Opening day: September 28, 1967

It has been found that valuable new azo dyes are obtained if

a) Diazo compounds of heterocyclic amines of the formula IT

Process for the production of
Azo dyes

C-NH ₂

(Π)

in Z a divalent, optionally containing heteroatoms and to complete a five- or six-membered aromatic ring is a necessary radical, where the - optionally condensed Ring-bearing - heterocyclic system containing the usual substituents in azo dyes can, with heterocyclic methylene compounds of the formula III

(III)

(CH-

wherein R _{2 is} an aliphatic radical, A is a divalent radical, the applicant to complete:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Johannes stretching,

Dr. Günter Hansen, Ludwigshafen / Rhine

a five- or six-membered, optionally substituted mononuclear or polynuclear heterocyclic ring system is necessary, X is a formyl, a carboxyl, a carboxylic acid ester, an optionally substituted carboxamide or carboxylic acid hydrazide, an optionally substituted carboxylic acid thioamide, an optionally substituted amidine or an aliphatic or aromatic acyl group, E the equivalent of an anion and m and η denote the numbers 1 and 2, couples and, if appropriate, the azo dyes of the formula V thus obtained

C = N-N = C-C

N - (R ₂ ) m Λ

(CH-CH) _n -I

then with the formation of dyes of the general formula I.

= N-N = C-C (V)

(CH-CH) _n -!

where Z, X, A, R2, E, m and η have the meanings given above and R) denotes an aliphatic, cycloaliphatic or araliphatic radical, alkylated or if one

709 649/373

3 4

b) hydrazones of the formula IVa or IVb acetophenone, l-phenyl-benzimidazolyl-2-acetic acid

amide, 5 (6) -chlorobenzimidazolyl-2-acetic acid ethyl ester, Benzoxazolyl-2-acetic acid amide, benzthiazolyl-2-acetic acid, 1-pyridyl-2-acetic acid amide, pyridyl-5 4 - ethyl acetate, quinolyl 2 - acetic acid amide,

• ₌ jsj - NH - Y (IVa) quinolyl - 4 - acetic acid amide, pyridyl - 4 - acetic acid,

Pyridyl-2-thioacetamide, 2-hydroxyquinoxaline-3-acetic acid ethyl ester, Quinolyl-2-pyruvic acid ethyl ester.

ίο Starting materials of the formula III (m = 2) are, for example, peralkylation products, such as the salts of 1 ^, S-trimethyl ^ -forrnylmethylene-S-chloroindolenine, 1,3,3 - trimethyl - 2 - acetylmethylene - indolenine, 1, 3,3 - trimethyl - 2 -carbonamidomethylene - indolenine,

; ₌ jvj jsjjj γ (IVb) ' ⁵ M-dimethyl-2-carbonamidomethylene-benzimidazoline

and 1,3 - dimethyl - 2 - carboxymethylene - benzimidazoles.

Many of these heterocyclic methylene compounds are known. Compounds of formula III, 20, which have not yet been described, can be found in analogy to Production instructions for the well-known Subworin Z and Ri obtain the abovementioned entities.

have meanings and Y is a hydrogen atom The alkylation of the obtained in the usual way

or is an arylsulfonyl radical, or salts coupling products can be solvent-free or in this hydrazone with heterocyclic methylene in the presence of solvents or in diluent compounds of the formula III given above, preferably chloroform, with tempering the presence of dehydrogenation or oxy- ratures between 20 and 150 ⁰ C, optionally dating agents with the formation of dyes with the addition of acid-binding agents, such as magnesium of the above formula V or umoxide, sodium methylate, dimethylformamide, and dyes of the formula V, optionally 30.

still with the formation of dyes of the formula I. Any anions can be used as anions E

alkylated. subjects and complex acids, e.g. B. Cl-, Br-,

SO4-, PO ₄ -, ClO ₄ -, BF ₄ , CH ₃ COO, CH ₃ SO ₄ -,

The preferably five-membered heterocyclic C2H5SO4 ". CeHsSO ₃ ', ZnCl ₄ - or ZnBr4 ~, in diazotizable amines of the general considerations mentioned.

Formula II can contain, for example, benzene or naphthalene rings as fused rings as alkylating agents. Diethyl sulfate, toluenesulfonic acid methyl, ethyl and, in particular, diazo components include the chloroethyl ester, methyl iodide, butyl bromide, diazotized amines of the heterocyclic thiazole, benzene, but especially dimethyl sulfate,
thiazole, thiadiazole, oxdiazole, pyrazole, triazole, 40 The dyes obtainable according to the invention ge-tetrazole, cinnoline, pyridazine or indazole into consideration. belong partly to the class of disperse dyes, the heterocycles or the heterocyclic ring partly to the class of basic dyes. Of these systems can by the usual in azo dyes are the basic dyes, especially those having substituents such. B. alkyl, alkoxy, aralkyl, aryl, which have a mesomeric cyanine system and can be referred to as nitro, acyl, acylamino, alkylsulfonyl, sulfone, diazapolymethine dyes, acid or carboxamide groups or halogen, are preferred.

be substituted. The new color available according to the invention

Starting materials of the formula IV are, for. B. Benz substances are suitable in solution or in suspension thiazolon- (2) -hydrazone, 3-methyl-benzthiazolon- (2) - excellent for dyeing and printing hydrazone, ö-methoxy ^ -methylbenztbiazolon ^ -hy- 50 textiles , e.g. B. of stained cotton, of leather drazon, 5 - methylmercapto - 3 - methylthiadiazolon or of structures such as fibers, flakes, threads, 2-hydrazone, S-phenylamino-S-methylthiadiazolon foils or webs, made of cellulose esters or 2- hydrazone, 1-methyl-quinolone-2-hydrazone and ethers or from synthetic substances, such as poly the corresponding stick amides on the 1- or 3-position, polyurethanes or polyesters; Particularly substance atom of the heterocyclic ring by ethyl, ₅₅ on structures made of polyacrylonitrile or structures made of butyl, cyclohexyl, benzyl or phenyl radicals containing copolymers containing acrylonitrile give tuated compounds. the dyes obtainable according to the process,

Arylsulfonyl groups (Y = SOaAr) carrying hy- preferably the diazapolymethine dyes, dyeings Drazones of the formula IV are, for example, 3-methyl and prints in pure and very real color shades. benzthiazolon - ^ - N'-benzenesulfonyl-hydrazone, 3-Me- 60 Compared to the next comparable, from the German ethyl-6-methoxy-benzthiazolon- (2) -N -benzenesulfonyl patent specification 1,065,544 and the French patent hydrazone. font 1 286 203 known dyes deliver the

The starting materials of the formula TII (w = 1) are dyes obtainable according to the invention which are deeper in color named for example: benzimidazolyl-2-acetic acid and clearer dyeings on polyacrylonitrile fabrics amide and dimethylamide, benzimidazolyl-2-acetic acid 65 or deeper colorations on polyester and acid, benzimidazolyl-2-acetic acid ethyl ester and -me- cellulose-2V2-acetate tissue.

ethyl ester, benzimidazolyl - 2 - acetic acid - hydrazide, The parts mentioned in the following examples

<u- (Benzimidazolyl-2) -acetone, w- (Benzimidazolyl-2) - and percentages are, unless otherwise stated,

Weight units. The parts of space relate to parts by weight like the liter to the kilogram Normal conditions.

example 1

A solution of 18 parts of 3-methylbenzthiazolone-2-hydrazone is combined in 500 parts of 0.2 normal aqueous hydrochloric acid at room temperature the suspension of 18 parts of benzimidazolyl-2-acetic acid amide in 250 parts of water and gradually added to the mixture with stirring and cooling 300 parts by volume of aqueous 2 molar iron (III) chloride solution and 250 parts by volume of 50% sodium acetate solution flow at the same time, but separately.

The resulting yellow precipitate is filtered off with suction, washed with water and dried. Maa receives a yellow dye which dissolves in 80% aqueous acetone with a yellow color and dyes polyamide fibers in yellow tones with very good fastness.

Is used instead of 18 parts 3-methylbenzthiazolon-2-hydrazone 21 parts of 6-methoxy-3-methylbenzthiazolon-2-hydrazone, a coupling product, likewise yellow, with similar coloring properties is obtained in this way.

Example 2

According to Example 1, paragraph 1, dye is heated with 500 parts of chloroform to 50 to 6O ⁰ C. 10 parts of magnesium oxide and 26 parts by volume of dimethyl sulfate are added and the mixture is stirred at the temperature mentioned until complete methylation has occurred. This can be determined, for example, by paper chromatography. The chloroform is then distilled off and 300 parts of 10% aqueous acetic acid are added at the same time. After cooling, the precipitated dye is filtered off with suction and dried at 70.degree. A yellow powder is obtained which dissolves in hot water with a yellow color and dyes polyacrylonitrile fabric from an acetic acid or sulfuric acid bath in yellow shades. The dyeings obtained in this way have excellent wet and light fastness properties. With o-methoxy-S-methylbenzthiazolon ^ hydrazone as the hydrazone component, a reddish-tinged yellow methylation product with similar properties is obtained.

Example 3

A solution of 18 parts of 3-methylbenzthiazolon-2-hydrazone in 500 parts of 0.2 normal aqueous hydrochloric acid is made according to Example 1 with the suspension 19.4 g of benzimidazolyl-2-acetic acid oxidative to the Dye coupled. The dye obtained in this way, a brownish-tinged yellow powder, dissolves with red-yellow Color in dimethylformamide and supplies yellow on polyacrylonitrile fabric from a sulfuric acid bath Dyeings with good fastness properties.

Example 4

If the total amount of the dye obtained in Example 3 is obtained by following the procedure of Example 2 reacted, a water-soluble orange-colored methylation product is obtained which delivers true yellow dyeings on polyacrylonitrile fabrics made from acetic acid or sulfuric acid liquor.

In Example 3, instead of 18 parts of 3-methylben2thiazolon-2-hydrazone, 21 parts of 6-methoxy-3-methylbenzthiazolon-2-hydrazone or 28 parts of 5 - phenylamino - 3 - methylthiodiazolon - 2 - hydrazone used and the reaction products according to the If the process instructions of Example 2 are alkylated, orange-colored methylation products with similar ones are obtained coloring properties.

Example 5

35 parts of a 40% solution of nitrosylsulfuric acid in concentrated sulfuric acid are slowly run at 0 to 5 ° C. to a solution of 15 parts of 2-aminobenzothiazole in 100 parts of 60% strength sulfuric acid. After stirring for 3 hours, the diazo solution is allowed to run, with cooling, into a suspension of 26 parts of 2- (benzoylmethyl) benzimidazole in 500 parts of water and 500 parts of ice. After stirring for about 1 hour, the dyestuff which has precipitated is filtered off with suction and washed with water. Then one stirs the filter residue with a solution of 20 parts by volume of 25 ^u / pc alcohol aqueous ammonia in 1000 parts of water at, filtered off, washed with water and the product is dried. A yellow dye is obtained which dissolves in dimethylformamide with a yellow color and gives true yellow dyeings on polyacrylonitrile fibers from sulfuric acid liquor.

If instead of 26 parts of 2- (benzoylmethyl) benzimidazole, 23 parts of benzimidazolyl-2-acetic acid ethyl ester are used or 18 parts of benzimidazolyl-2-acetic acid amide, this gives dyes with similar properties that are also based on polyamides, Cellulose esters and polyesters produce true yellow colorations.

Example 6

Will be the total amount of the according to example obtained dye implemented according to the method of Example 2 - using 35 parts by volume instead of 26 parts by volume of dimethyl sulphate - it becomes a water-soluble orange color Obtained methylation product which gives true yellow dyeings on polyacrylonitrile fabric.

In the example 5 instead of 15 parts 2-aminobenzothiazole 20 parts of 6-methoxy-2-aminobenzothiazole is used and the dye obtained is methylated according to Example 2, an orange-colored one is obtained Methylation product with similar coloring properties.

In the same way the following Diazo component Dyes manufactured: Coupling component Hue of
Methylation
productcs on
Polyacyl nitrile
tissue example 6-methyl-2-aminobenzothiazole
3-amino-5-chloro-indazole Benzimidazolyl-2-acetic acid amide
the same yellow
yellow 7th
8th

continuation

Diazo component Coupling component Hue of example ivi ciny ι icr-
Product Polyacrylic 6-methoxy-2-aminobenzothiazole Benzimidazolyl ^ acetic acid amide tissue 9 3-Amino-5-phenyl-1,2,4-triazole the same yellow 10 2-Amino-5-phenyl-1,3,4-thiadiazole the same yellow 11 3-araino-5-ch] orindazole Benzimidazolyl-2-acetic acid yellow 12th 2-Amino-5-phenyl-1,3,4-thiadiazole the same yellow 13th 2-amino-thiazole the same yellow 14th 3-amino-triazole-carboxylic acid- (5) the same yellow 15th yellow

B e i s ρ i e 1 16

15 parts of 2-aminobenzothiazole are, as described in Example 5, diazotized and the diazo solution with cooling to a suspension of 19.4 parts of benzimidazolyl-2-acetic acid in 500 parts of water and 500 parts of ice. The precipitated dye is suctioned off after stirring for about 1 hour, washed with water and, as described in Example 5, worked up. The yellow thus obtained Powder dissolves in dimethylformamide with a yellow color and delivers in finely divided form on polyacrylonitrile fibers real yellow colorations from sulfuric acid liquor.

Example 17

If the total amount of the dye obtained in Example 16 by the method of Example 6 implemented, a water-soluble orange-colored methylation product is obtained which delivers true yellow colorations on polyacrylonitrile fabrics.

Claims (2)

Claim: Process for the preparation of azo dyes, characterized in that one a) Diazo compounds of heterocyclic amines of the formula II C - (Π) in Z a divalent, optionally containing heteroatoms and to complete a five- or six-membered aromatic ring is a necessary radical, where the - optionally condensed Ring-bearing - heterocyclic system which can contain substituents customary in azo dyes, with heterocyclic ones Methylene compounds of the formula IH CH ₂ -C (CH-CH) _n -I (III) -m 1 where R> is an aliphatic radical, A is such divalent radical, which is used to complete a five- or six-membered, optionally substituted mononuclear or polynuclear heterocyclic ring system is necessary, X is a formyl, a carboxyl, a carboxylic acid ester, an optionally substituted one Carboxylic acid amide or carboxylic acid hydrazide an optionally substituted carboxylic acid thioamide, an optionally substituted amidine or an aliphatic or aromatic acyl group, E the equivalent of an anion and m and «mean the numbers 1 and 2, couples and optionally the azo dyes of the formula V obtained in this way : = N-N = C-C (CH-CH) _n -I then with the formation of dyes of the general formula I. = N-N = C-C ' - (Room-1 (CH-CH) _n -I m-1 where Z, X, A, R. 2, E, m and «have the meanings given above and Ri denotes an aliphatic, cycloaliphatic or araliphatic radical, alkylated or that one b) hydrazones of the formula IVa or IV b = N-NH-Y (IVa) C = N-NH-Y (IVb) in which Z and Ri have the meanings given above and Y is a hydrogen atom or denotes an arylsulfonyl radical, or salts of these hydrazones with heterocyclic ones Methylene compounds of the formula III given above in the presence of Dehydrating or oxidizing agents with the formation of dyes of the abovementioned Formula V or I converts and dyes of the formula V, optionally with the formation of dyes of the formula I alkylated. Documents considered: German Patent No. 1 065 544; French patent specification No. 1 286 203. When the application was announced, two coloring tables with explanations were laid out. 709 649/373 9.67 θ Bundesdruckerei Berlin