DE1544474C - Cationic azo compounds, their preparation and use - Google Patents

Description

The present. The invention relates to cationic azo compounds of the general formula

H ₂ NC

CR ₂

_A e

(D

HC

C-R,

H ₂ NC N

\ _N /

IO

40

45

in which Ri and Ra have the same meanings as above have;

b) by coupling the diazo derivative of a base B® - NH2 with a / 3-acetonitrile of the formula

R ₂ - CO - CH ₂ - CN (II)

or a / Mminonitrile of the formula
R ₂ -C-CH ₂ -CN

NH

(III)

where R ₂ in formulas (II) and (III) has the meaning given above, and conversion of the azo dyes thus obtained into aminopyrazole dyes by condensation with a hydrazine of the formula

Ri - NH - NH ₂

(IV)

as well as a process for their preparation and the use of these compounds as dyes for Acrylonitrile polymer fibers.

In the above formula, Ri denotes a hydrogen atom or a phenyl group, R ₂ denotes a methyl or phenyl group, B® denotes an N, N'-dimethyl-6-indazolium-, N, N'-dimethyl-2-methyl-6-benzimidazolium- , N, N '- dimethyl - 2 - phenyl - 6 - benzimidazolium, Ν, Ν', 3,5 - tetramethyl - 4 - pyrazolium, N - methyl-2 - phenyl - 6 - benzothiazolium or 4 - (N ', 6'-dimethyl-2'-benzothiazolium) phenyl radical and A ^{3 is} a monovalent anion or its equivalent. The phenyl groups and B® radicals can be substituted with nonionic groups.

4-Azo- or 5-Azopyrazolium are already from French patents 1,217,306 and 1,322,747 known. The pyrazolium nucleus is the only heterocycle in these dyes. The invention, Compounds which can be used as dyes differ from the known compounds in that they have two nitrogen heterocycles, namely a non-quaternized pyrazole core and the ring B.

The compounds of formula (I) can be obtained:

a) by coupling the diazo derivative of a base B® - NH2 with a 5-aminopyrazole of formula

in which Ri has the meaning given above.

The dyes according to the invention are readily soluble in water; they are for usual purposes basic dyes can be used and especially for dyeing and printing fibers on the Base of polymers or copolymers of acrylonitrile valuable, making these fibers lively and strong shades with excellent general fastness properties.

Compared to dyes with a comparable constitution, such as those used for. B. from the Swiss patent specification 340 926 and French patent 1 322 331 and Belgian patent 628 278 are known, show the dyes according to the invention in their dyeings on polyacrylonitrile fabric better lightfastness.

In the examples below, the parts given are based on weight, unless this is stated otherwise.

example 1

28 parts of 6-amino-1,2-dimethyl-indazolium chloride are dissolved with a titer of 70.5%, molecular weight 197.5, in 100 parts of water; 7 parts of sodium nitrite are added and pour the cooled solution into a mixture of 25 parts by volume of hydrochloric acid with stirring of 20 ° Be and 50 parts of ice. When the diazotization has ended, the excess nitric acid is removed and gradually leads the solution of the diazo derivative into a solution of 8.2 parts of diacetonitrile in 50 parts of water to which 10 parts by volume of hydrochloric acid at 20 ° Be have been added. The dye is gradually eliminated; it is filtered and dried. 25 parts are obtained.

2.88 parts of this dye are introduced into a solution of 0.82 parts of hydrazine chlorohydrate in 30 parts of water which is kept acidic against Congo red paper by adding hydrochloric acid. The mixture is heated I ¹ Z reflux for ₂ hours, allowed to cool and falls from the dye by addition of sodium acetate and sodium chloride. The dye obtained corresponds to the following formula

H, C - N

N = N-C-

Ii Η, Ν —C -C-CH,

Cl®

It dyes acrylic fibers in a very pure golden yellow shade with excellent general fastness properties.

The following table summarizes some examples analogous to the previous example. The bases are used in the state of the (chlorohydrate or sulfomethylate) salts.

example Bs-NH ₂ Color tint
of the dyes
Acrylic fibers 2
3
4th 6-amino-l, 2,3-trimethyl-
benzimidazolium
6-amino-2-phenyl-1,3-di-
methylbenzimidazolium
2-p-aminophenyl-3,6-di-
methylbeiizothiazolium Yellow-greenish
Yellow-greenish
Orange colored

Further examples in which one 6-amino-l, 2-dimethylindazolium replaced by other amines B® - NH-2 in the state of salts, are in the following Table summarized:

15th 10 20th B ^; —NH ₂ - Color tint example o-amino-l ^ i-trimethyl- of the dyes 11th benzimidazolium Acrylic fibers 10 7 6-amino-2-phenyl-1,3-di- Greenish yellow methylbenzimidazolium 8th 2-p-aminophenyl-3,6-di- Greenish yellow methylbenzothiazolium 9 N-methyl-2-phenyl- Orange colored 6-aminobenzothiazolium 1,2,3,5-tetramethyl Golden yellow 4-aminopyrazolium Greenish yellow

Example 5

2.55 parts of that described in paragraph 1 of Example 1 are refluxed for 2 hours Dye with a solution of 1.08 parts of phenylhydrazine in 30 parts of water and 1 part by volume Hydrochloric acid with 20 ° Be. After cooling, the cyclized dye is separated off by adding sodium acetate and salt out. The dye obtained dyes acrylic fibers in a very vivid golden yellow Color shade with excellent fastness properties.

35

Example 6

As in Example 1, 5.6 parts of 6-amino-1,2-dimethylindazolium chloride are diazotized. The solution of the diazo derivative is gradually introduced into a solution of 3.5 parts of 1-phenyl-S-methyl-S-aminopyrazole in 10 parts of water to which 2 parts by volume of hydrochloric acid at 20 ° Be were added; one neutralizes gradually the mineral acidity by adding sodium acetate. When the diazo derivative absorbs the dye obtained is filtered and dried. It is identical to that of Example 5. Example 12

2.82 parts of a 75% 6-amino-1,2,3-trimethylbenzimidazolium chloride are diazotized in the usual manner containing product. The diazo derivative solution is gradually introduced into a solution of 1.6 parts of 3-phenyl-5-aminopyrazole in 30 parts of water to which 1 part by volume of hydrochloric acid at 20 ° Be was added. The coupling is ended by adding sodium acetate. The dye separates out, is filtered and dried. Man contains 3.2 parts of dye, readily soluble in water, it dyes polyacrylic fibers in a greenish-yellow shade.

Example 13

The procedure is as in Example 12, but replaces 3-phenyl-5-aminopyrazole by 2.4 parts of 1,3-diphenyl-5-aminopyrazole. 4.2 parts of a yellow dye are obtained, the polyacrylic fibers in a greenish yellow Tint colors.

Other examples corresponding to the invention are summarized in the table below:

example B * - NH ₂ Coupling agent Tint of the dye
on acrylic fibers 14th
15th
16
17th
18th
19th 6-amino-1,2-dimethyl-
indazolium
6-amino-1,3-dimethyl
2-phenylbenzimidazolium
2-p-aminophenyl-
3,6-dimethylbenzothiazolium
6-amino-1,2-dimethyl
indazolium
6-amino-1,3-dimethyl
2-phenylbenzimidazolium
2-p-aminophenyl-
3,6-dimethylbenzothiazolium 3-phenyl-5-aminopyrazole
the same
the same
1,3-diphenyl-5-aminopyrazole
the same
the same Golden yellow
Greenish yellow
Orange colored
Golden yellow
Greenish yellow
Orange colored

Claims (3)

Patent claims:
1. Cationic azo compounds of the formula B ·· - N = N ■ H ₂ NC IO in which Ri represents a hydrogen atom or a phenyl group. Rj represents a methyl or phenyl group. B- an N.N'-dimethyl-6-indazolium, N, N'-dimethyl-2-methyl-6-benzimidazolium, N.N'-dimethyl-2-phenyl-6-benzimidazolium, N, N '.3.5 - tetramethyl - 4 - pyrazolium-. N-methyl-2-phenyl-6-benzothiazolium or 4- (N ', 6'-dimethyl- 2' - benzothiazolium) -phenyl radical and A ^{e represents} a monovalent anion or its equivalent. 2. Process for the preparation of cationic azo compounds according to claim 1, characterized in that one a) the diazo derivative of a base of the formula B'-NHj with. an aminopyrazole of formula HC
I-C. C-R, Il " R, clutch or b) the diazo derivative of a base of the formula B · "- NHj with a compound of the formula Rj - CO - CH ₂ - CN or R-. - C - CH-> - CN Il NH couples and the dye obtained with a hydrazine of the formula R ₁ -NH- NH ₂ condensed. where B, Ri and R> have the same meanings as in claim 1. 3. Use of the cationic azo compounds according to claim 1 as dyes for Dyeing of acrylonitrile polymer fibers.