CH628077A5 - Process for preparing sulpho-free basic azo compounds - Google Patents

Abstract

Process for preparing sulpho-free basic azo compounds of the formula <IMAGE> characterised in that in a compound of the formula <IMAGE> where the symbols are each as defined in Claim 1, the radical -Y-R0 is detached using a dissociable acid H-A; the azo compounds are useful for dyeing or printing textile and non-textile materials, such as plastics, leather or paper.

Description

628 077

PATENT CLAIMS 1. Process for the preparation of basic azo compounds of the formula free from sulfonic acid groups

R2

1 ^

N,

R-C- ^ X

R, -C,

, C - N = N - K

1

I.

R_

©

(I),

wherein K is a radical of the formula

R,

(II),

R,

, / R6

O

-N - Rc

O,

/

N

i

R

(III), CH Rr

R

6 \

(IV)

O.

CH-CVR6

/ Xr6

o — CH-R-

(V),

or o

-N

I.

H

\

/, CH-R?

R and Rj independently of one another are each hydrogen or an unsubstituted (1-4C) -alkyl radical,

R5 is hydrogen or a (l ^ t-C) -alkyl radical which is optionally substituted by a hydroxyl group,

Rg in each case hydrogen or an unsubstituted (1-4C) -R2 and R3 independently of one another in each case a given alkyl radical,

optionally substituted by a hydroxyl group (1-4C) -alkyl- R7 independently of one another hydrogen or an unsub radical, substituted (1-4C) -alkyl radical and

Ae is an anion, and the radicals R and Rj together can form R4 chlorine, fluorine, an unsubstituted (1-4C) -alkyl- or a tri- or tetramethylene bridge, thereby

(1-4C) alkoxy radical,

40

R2

characterized in that in a compound of the formula \

R-C

X

vc \ y

N

C - N = N - K

I.

R.

©

A

©

(VI),

wherein K0 is a radical of the formula o

(vii),

N - Y - R

CH ^

n \ —n / Cvr6 <i> :)

or

Y "Ro

628 077

wherein Y is -CO- or -SO, and

R0 is a (1-4C) -alkyl radical, with a dissociatable plastic.

5. The method according to claim 3 for dyeing or printing

acid H-A,

in which A denotes a radical which can be converted into an anion A ©,

splits off the rest-Y-R0.

2. Compounds of the formula I, prepared by the process of leather, ren according to claim 1.

3. A process for dyeing or printing non-textile materials with azo dyes of the formula (I) according to claim 2.

4. Dyed or printed non-textile materials, produced by the method according to claim 3.

6. The method according to claim 3, for dyeing or printing paper.

5 7. The method according to claim 3, for dyeing or printing

The invention relates to a process for the preparation of basic azo compounds of the formula free from sulfonic acid groups

R2

1 I

R

"C - N

R, -C,

N / '

N - K

(I),

where K is a radical of the formula R.

3rd

(II) r

R,

(III),

O

- Rr

:O,

R

6 \

(IV)

CH-Rc

/ 6

N

i

H

ö,

CH "C" ^ r6

/ Xr6 «

H

or

O — CH-R, \ '

(V),

O

-N

i

H

/ CH "R7

R and R! independently of one another each hydrogen or R6 each hydrogen or an unsubstituted (1-4C) -

an unsubstituted (1-4C) alkyl radical, alkyl radical,

R2 and R3, independently of one another, each a given - R7 independently of one another, hydrogen or an unsub-

also substituted by a hydroxyl group (1-4C) -alkyl-substituted (1-4C) -alkyl radical and radical, A © is an anion, and the radicals R and Rj together

R4 can form chlorine, fluorine, an unsubstituted (1-4C) alkyl or a tri or tetramethylene bridge

(1-4C) alkoxy. characterized that one in a compound of the formula

Rj is hydrogen or a (1- ^ C) -alkyl radical which is optionally substituted by a hydroxyl group,

* 2

»4

_r / N

R-C

R, -c ./

9

R_

C - N = N - K

©

(VI),

where K "is a radical of the formula o

R,

(VII), N - Y - R

O

R_

O

/ Y-R

(VIII), CH-R,

628 077

O

CH CV * 6

/ (IX), Or

N 6

Y-R

Y-R

wherein Y is -CO or -S02 and

R0 is a (1-4C) -alkyl radical, with a dissociable acid H-A,

in which A denotes a radical which can be converted into an anion A ©, cleaves the radical -Y-Rq.

Advantageous compounds correspond to the formula

R -C-

'N

2a

X

w If

R, -C ~

la no

C - N = N - K,

3a e

. ©

(XI),

where K! a remainder of the formula

R6a CH-CH

\ 2 / R

(XIV) 6a

O

C.

R6a

I.

H

or

R6 "av" / R6a

(XIII),

/ CH-R

/ 63 «

H

O

O-ch2 (XV), ✓CH-R7a

N

I.

H

Ra and Rla independently of one another are each hydrogen or 45 -CH3,

R?., And R, a independently of one another each -CH3 or-C2H5, R4a chlorine, fluorine, -CH3 or -OCH3,

RSa hydrogen or -CH3

? H3

R6a is hydrogen or —CH3 and R7a is hydrogen or —CH3.

Particularly advantageous compounds correspond to the formula

»A

HC

C - N

N - K,

1

CH-

©

(XVI),

in which K2 is a radical of the formula (XV),

R,

or

CH.

2 \ (VXIII) CH-R

na- / 6a

H and R4b are chlorine or fluorine.

5

628 077

The compounds of formula VI can be prepared if the diazo compound is formed from an amine of the formula H2N-K0 with a coupling component of the formulas

R

R- <r ^ îSw j>

1

or left CH couples,

the azo compound obtained is alkylated and then quaternized.

In the above formulas, R is increasingly important for Ra or for hydrogen; Rt for Rla or for hydrogen; R2 for R2a or for -CH3; R3 for R3a or for -CH3; R4 for R4a or for R4b; Rs for R5a; R6 for R6a; R7 for R7a; K for K1; or for K2.

R and Ri in the meaning of an unsubstituted alkyl radical are mainly for -CH3. R2 and R3 in the meaning of an unsubstituted alkyl radical are mainly -CH3 or -C2H5. R4 in the meaning of an unsubstituted alkoxy radical mainly stands for -CH3 or -OCH3. R5 in the meaning of an unsubstituted alkyl radical mainly stands for -CH3. R6 in the meaning of an unsubstituted alkyl radical mainly stands for ~ CH3. R7 in the meaning of an unsubstituted alkyl radical mainly stands for -CH3.

The removal of the radical -Y-Rq in a compound of formula (VI) is advantageously carried out in aqueous solution using a strong mineral acid, e.g. Hydrochloric acid or with a mixture consisting of a mineral acid at temperatures of 50-100 ° C, preferably from 60-80 ° C.

The alkylation and quaternization can be carried out by conventional methods, e.g. in an inert solvent or, if appropriate, in an aqueous suspension or without additional solvent in an excess of the alkylating or quaternizing agent, if necessary at elevated temperature and in a buffered medium.

Examples of alkylating or quaternizing agents are alkyl halides, e.g. Methyl or ethyl chloride, bromide or iodide, alkyl sulfates such as dimethyl sulfate or benzyl chloride.

In the compounds of formula (I), the anion A © can be exchanged for other anions, e.g. by means of an ion exchanger or by reaction with salts or acids, optionally in several stages, e.g. via the hydroxide or via the bicarbonate or according to French Patent Nos. 2 028 725 or 2 028 726.

Anion A ©, as it is formed during production or can be exchanged for other anions after production, is to be understood to mean both organic and inorganic ions, e.g. Halogen, such as chloride, bromide, sulfate, bisulfate, methyl sulfate, aminosulfonate, perchlorate, benzene sulfonate, oxalate, maleinate, acetate, propionate, lactate, sucinate, Tartrate, malate, methanesulfonate or benzoate ions or complex anions such as that of double chlorine zinc; further the anions of the following acids; Boric acid, citric acid, glycolic acid, diglycolic acid or adipic acid.

The new compounds can be converted into coloring preparations. The processing, e.g. into stable, liquid or solid coloring preparations can be done in a generally known manner, e.g. by grinding or granulating or then by dissolving in suitable solvents, optionally with the addition of an auxiliary, e.g. a stabilizer or solubilizer, such as urea. Such preparations can be obtained, for example, according to the information in French patents 1,572,030 and 1,581,900 or according to German laid-open publications 2 001 748 and 2 001 816.

The new compounds are used for dyeing or printing fibers, threads or textiles made therefrom, which consist of or contain homopolymers or copolymers of acrylonitrile or as. Dicyanoethylene.

5 You can also dye or print synthetic polyamides or synthetic polyesters modified by acidic groups. Such polyamides are known for example from Belgian patent 706 104. Corresponding polyesters are known from US Pat. No. 3,379,723; textile material is dyed particularly advantageously in an aqueous, neutral or acidic medium at temperatures from 60 ° C. to boiling temperature or at temperatures above 100 ° C. under pressure.

The textile material can also be dyed with the compounds of formula (I) in organic solvents, e.g.

according to the information in German Offenlegungsschrift 2,437,549.

Good light fastness is obtained on the substrates mentioned above. The dyes have good combinability with other basic dyes. The dyes obtained according to the invention have the advantage of a low combination index. Also good is the drawing power, the fastness to washing, welding, sublimation, pleating, decaturing, ironing, water, sea water, dry cleaning, over-dyeing and solvent-fastness. The dyes are resistant to hydrolysis and have good solubility in water and result in strong, level dyeings. Dyes with a molecular weight less than 270 migrate well.

The compounds are also used to dye synthetic materials, leather and paper.

In the following examples, parts are parts by weight and percentages are percentages by weight; the temperatures are given in degrees Celsius.

35 Example 1

37 parts of 3-chloro-4-acetylamino-aniline are diazotized in 350 parts of water and 50 parts of water and 50 parts of 30% hydrochloric acid and at 0-5 ° C. with 45 parts of sodium nitrite solution. After the excess nitrous acid has been destroyed with 1.5 40 parts of aminosulfonic acid, the clear diazonium salt solution is added dropwise to a cold solution consisting of 13.6 parts of dime. thylformamide and 1.5 parts pyridine. During the coupling, the pH is kept between 8 and 9 by the continuous addition of 30% sodium hydroxide solution. After Verts thin with 250 parts of ice water, the suspension is stirred for 4 hours and the precipitated dye is filtered off.

The filter cake is washed with 200 parts of water and dried at 500 in vacuo. 27.5 parts of the dried-50th and ground dye of the formula

55 HC

II

HC-

^ X

C - N = N

60

-N

i

H

NHCOCH.

are suspended in 150 parts of dimethylformamide with the addition of 3.5 parts of magnesium chloride and the suspension is heated to 50-60 °, the dye partially dissolving.

In this temperature range, 50.5 parts of dimethyl sulfate are added dropwise within 60 minutes, and after three hours of stirring, a thin-layer chromatographic check no longer indicates any starting product. After adding 360 parts approx. 26% -

628 077

6

brine, the dye suspension is stirred cold, suction filtered and washed with 100 parts of 15% sodium chloride solution.

The moist press cake is then stirred in 120 parts of glacial acetic acid and 30 parts of 30% hydrochloric acid and heated to 75 ° for 4 hours. A dark yellow solution is obtained. The cold-stirred solution is diluted with 300 parts of water, with

30% sodium chloride solution brought to a pH of 5 and salted out with 28 parts of zinc chloride.

After filtration of the crystalline dyestuff, it will be seen with 150 parts of 15% sodium chloride solution and dried at 50-60 ° in vacuo.

A dye of the formula is obtained

HC

CH. • -

■ N

HC \ / C

N

ÇR3

- N = N

Cl

O

NH.

©

ZnCl

-2

the polyacrylonitrile and anionically modified polyester fibers dye in real orange tones and have a good migration ability on polyacrylonitrile.

Staining instructions A

20 parts of the dye described in Example 1 and 80 parts of dextrin are ground in a powder mill for 4 hours. The same dye mixture can also be obtained by pasting in 100 parts of water and then spray drying. 1 part of the preparation obtained in this way is made into a paste with 1 part of 40% acetic acid, 200 g of demineralized water are poured over the slurry and the mixture is boiled briefly. It is diluted with 7000 parts of demineralized water, 2 parts of glacial acetic acid are added and the mixture is taken into the bath at 60 ° C. with 100 parts of polyacrylonitrile fabric. The material can be pretreated for 10-15 minutes at 60 ° in a bath consisting of 8000 parts water and 2 parts glacial acetic acid.

The mixture is heated to 98-100 ° in the course of 30 minutes, boiled for one hour and rinsed. An orange level dyeing with good light fastness and good wet fastness properties is obtained.

10 parts of the dye mentioned in Example 1 can also be dissolved in 60 parts of glacial acetic acid and 30 parts of water. A stable concentrated solution of the dye with a dye content of about 10% is obtained, which can be used for dyeing polyacrylonitrile in accordance with the above dyeing instructions.

Dyeing Instructions B

20 parts of the dye from Example 1 are mixed with 80 parts of dextrin in a ball mill for 48 hours; 1 part of the preparation obtained in this way is pasted with 1 part of 40% acetic acid, the slurry is poured with 200 parts of demineralized water and briefly boiled. This stock solution is used for staining as follows:

a) It is diluted with 7000 parts of demineralized water, 21 parts of calcined sodium sulfate, 14 parts of ammonium sulfate, 14 parts of formic acid and 15 parts of a carrier based on reaction products of ethylene oxide with dichlorophenols are added and the mixture is passed through at 60 ° with 100 parts of polyester fabric acidic groups is modified into that

Bath a. The material can be pretreated for 10-15 minutes at 60 ° 20 in a bath consisting of 8000 parts water and 2 parts glacial acetic acid. The mixture is heated to 98-100 ° within 30 minutes, boiled for 1 hour and rinsed. A level orange coloration with good wet fastness properties is obtained.

b) It is diluted with 3000 parts of demineralized water, 10 parts of calcined sodium sulfate and 6 parts each

Ammonium sulfate and formic acid and goes into the bath at 60 ° with 100 parts of polyester fabric, which is modified by acidic groups. The mixture is heated to 110 ° in the closed vessel within 45 minutes, maintained at this temperature for 30 hours with shaking, then cooled to 60 ° within 25 minutes and the material to be washed is rinsed. A level orange coloration with good wet fastness properties is obtained.

c) The procedure is the same as in b), but the closed vessel is heated to 120 ° for 1 hour.

35

Staining instructions C

20 parts of the dye from Example 1 are mixed with 80 parts of dextrin in a ball mill for 48 hours.

1 part of the preparation obtained in this way is pasted with 1 part 40% 40 acetic acid, the slurry is poured over with 200 parts demineralised water and briefly boiled. This solution is added to the dye liquor prepared below.

The solution is diluted with 7000 parts of demineralized water, 21 parts of calcined sodium sulfate, 14 parts of 45 ammonium sulfate, 14 parts of formic acid and 15 parts of a carrier based on reaction products of ethylene oxide with dichlorophenols are added, and the liquor is buffered to pH with an acidic buffer solution -Value from 6, and goes at 25 ° with 100 parts of polyamide fabric, which is modified by anionic 50 groups, in the bath with a liquor ratio of 1:80. The bath is heated within 45 minutes.

under running water from 70-80 ° then under cold water. The fabric can be centrifuged to dry and then ironed. An orange color 55 with good fastness properties is obtained.

The following table shows the structure of other dyes. They can be produced according to the information in Example 1 and according to the formula

R-C

n

Ve

* 2

ylS

©, c

R,

- N = N

- Rr

.G

where R, Rj-R5 have the meanings given in the columns. Anions © are those listed in the description.

7

table

628 077

E.g.

No.

R

rI

r2

r3

r4

r5

2nd

H

H

ch3

ch3

F

H

3rd

H

H

do.

do.

do.

ch3

4th

h h

do.

do.

Cl do.

5

H

H

do.

do.

do.

c2h5

6

h h

do.

do.

do.

c2h4oh

7

H

H

do.

do.

ch3

H

8th

h h

do.

do.

och3

H

9

H

H

do.

do.

ch3

ch3

10th

H

H

c2h5

c2h5

Cl h

11

H

H

do.

do.

F

H

12

ch3

H

ch3

ch3

Cl h

13

H

ch3

do.

do.

do.

H

14

ch3

do.

do.

do.

do.

H

R and Rj together

15

-ch2) 3-

do.

do.

do.

H

example

16

CH

© c hC \ n /

CH-,

HC

n

- N -

ZnCl,

-2

example

CH • ^

HC '^ X

17th

hc \ n ^

CH,

© C - N = N-

-CH

2 ^ H

X

Nv CH H

ZnCl

-2

example

18th

ch3

® ^ C - N = N-

HC> N /

«

CH_

CH

X

CH. N

t

H

ZnCl

-2

628 077

example

19th

ZnCl

-2

T3

HS - N = N (O

CH-,

H-j-CH

2 N2

CH2 ZnCl 2 4

Example 21

H

HC

II

HC

- N = N— (O!

N

CH.

ZnCl

-2

The dyes of Examples 2,7,8,10-13 and 16-21 yield dyes of Examples 3-6,9,14 and 15 a reddish-orange color on polyacrylonitrile, an orange shade and the shade.

C.