CH617449A5 - Process for preparing monoazo compounds - Google Patents

Description

The present invention relates to a process for the preparation of compounds of the formula wherein

Rt and R2 each represent hydrogen or a substituent,

R is a linear or branched alkyl radical which is optionally interrupted once, twice or three times by an oxygen atom and / or is substituted by hydroxy, containing a total of 1 to 12 carbon atoms and

M is hydrogen or the equivalent of a colorless cation, the number of molecules in the molecule for R, R! and R2 present-2 »where carbon atoms together are 4 to 12 and the molecule contains a single sulfonic acid group and also only one sulfonic acid group and is free of carboxyl groups, the compounds of the formula I prepared by the process or mixtures thereof and their use as 25 dyes .

Monoazo compounds with an 1-aminobenzene-2-sulfonic acid reamide as the diazo component and 2-amino-8-hydroxynaphtha-lin-6-sulfonic acid as the coupling component are already known from the German patent specification 702,932. The compounds disclosed m mainly contain a sulfonamide residue which is disubstituted by aromatic and / or aliphatic groups on the N atom; corresponding monosubstituted radicals carry an aromatic or cycloaliphatic radical, but not an aliphatic radical. French patent specification 971.104 also relates to monoazo compounds with an aminobenzenesulfonic acid amide as the diazo component, the amide group of which is monosubstituted by an (8-18C) alkyl radical. However, the compound disclosed with 2-amino-8-hydroxynaphthalene-6-sulfonic acid as the coupling component carries the sulfonamide group in the aniline diazo component in the 3-position to the azo group.

R in the meaning of a (1-12C) alkyl radical preferably contains 4 to 12, in particular 6 to 12 and very particularly preferably 6 to 10 carbon atoms. It can be present as radical 45 (CH2) n — CH3 with n = 0 to 11, preferably 5 to 9, or as a branched radical, with a branching carbon atom and in particular the β-carbon atom preferably forming the branching point.

If the carbon chain of the radical R is interrupted by more than one 50 oxygen atoms, there are at least 2 and preferably 2 or 3 carbon atoms between 2 oxygen atoms.

If the radical R is substituted by hydroxy, it can be 55 in a linear or branched chain on an a, middle or terminal carbon atom. If the radical R contains ether groups, the terminal carbon atom preferably bears a hydroxyl group which is separated from the ether oxygen atom by at least 2 carbon atoms W). R is particularly preferably present as an unsubstituted linear or branched alkyl radical.

As a substituent R! and R2 come for example halogen such as fluorine, chlorine or bromine, (1-6C) alkyl radicals such as methyl, ethyl, n-butyl, tert-butyl or tert-amyl or cycloali - (, 5 phatic radicals with up to 6 carbon atoms such as cycolhexyl, (1-4C) alkoxy groups such as methoxy, ethoxy or butoxy, the amino group, mono- or dialkylamino group, the alkyl radicals of which contain 1 to 4 carbon atoms and optionally

617 449

r s02nh-r nh,

with a compound of the formula

II

are substituted, for example, by hydroxy or cyan; an acylamino radical of the formula -NH-cor3, in which R3 (1-4C) alkyl,

Phenyl, benzyl, (1-4C) alkoxy or phenoxy, or a carboxylic acid ester radical of the formula -COOR4, in which R4 is (1-4C) alkyl, phenyl or benzyl, into consideration.

If the phenyl radical in compounds of the formula I contains a further substituent Rj or R2, this can be in all open positions 3 to 6, but is preferably bonded in position 4 or 5.

If both R [and R2 stand for a radical not equal to hydrogen and the phenyl radical thus bears 2 further substituents, such as 2 methyl, 2 chlorine, methyl / chlorine, chlorine / methoxy or chlorine / ethoxy, these are preferably in 4.5 -Position.

Rj and R2 are preferably Rj '

and R2 ', where R / and R2' each independently of one another for chlorine, methyl, methoxy or ethoxy or also R / for hydrogen and R2 'for hydrogen, nitro, chlorine, bromine, (1-6C)

Alkyl, (1-4C) alkoxy, -NH-CORi 'with R / in the meaning of (1-4C) alkyl or (1-4C) alkoxy, for the ß-hydroxyethylamino or ß-cyanoethylamino radical or for the Radical -coor4 'with R4' have the meaning of (1-4C) alkyl.

R! for hydrogen and R2 in acidic to neutral medium.

the meaning of R2 '' for hydrogen, chlorine or bromine, The diazotization of an amine of the formula II is after

(1-4C) alkyl or (1-4C) alkoxy, acetylamino, ß-hydroxy- 25 usual methods carried out, for example by the ethylamino or ß-cyanoethylamino in position 4 or 5. amine in aqueous saline at about 50 to 100 ° C.

R 1 is preferably R / and particularly preferably melts, by adding hydrochloric acid into the hydrochloride which leads to hydrogen, R 2 for R 2 'and particularly preferably R 2 "and the aqueous suspension at 0 to 5 ° C. with concentrated and R for a linear or branched alkyl radical diazotized with 4 to 12 trated aqueous solution of alkali metal nitrite.

III

SO3M

particularly preferably 6 to 10 carbon atoms, the total number of carbon atoms for R1; R2 and R is 6 to 12.

Compounds of formula I in which the phenyl radical is not further substituted, i.e. where R! = R2 = hydrogen and R is a linear or branched (6-12C) alkyl radical.

The present invention also covers mixtures of compounds of the formula I which, for example with respect to the radical R, can have both isomeric alkyl radicals of the same number of carbon atoms and alkyl radicals of different carbon atoms. Such dye mixtures can generally be produced very easily by using starting materials which can be used, for example, in the form of technical products without further separation, in particular isomer separation. Surprisingly, it turns out that these dye mixtures are very well suited for dyeing, uniform dyeings being obtained which correspond to those of a single dye of the formula I with the average number of carbon atoms.

For M in the meaning of the equivalent of a colorless cation, for example, an alkali metal ion such as lithium, sodium or potassium ion, ammonium and unsubstituted or substituted alkylammonium are suitable. Unsubstituted alkyl radicals of an alkylammonium ion preferably have 1 to 3 carbon atoms, substituted alkyl radicals are preferably substituted by hydroxy and contain 2 to 4 carbon atoms. Examples of unsubstituted and substituted alkylammonium ions are mono-, di-, tri- and tetramethylammonium, triethylammonium, mono-, di- and triethanolammonium as well as mono-, di- and tri-isopropanolammonium. Due to the production process, M preferably represents an alkali metal ion, in particular sodium.

According to the invention, the compounds of the formula I or mixtures thereof are obtained by the diazonium compound of one or more amines of the formula

30 The coupling of the diazonium compound of the amine of formula II with the compound of formula III in an acid to neutral medium is carried out in a manner known per se, preferably in an acidic pH range in aqueous or organic-aqueous solution at temperatures from 0 ° C. to 35 Room temperature, preferably between 10 and 15 ° C. Examples of suitable organic solvents are low molecular weight alcohols such as ethanol or acid amides of low molecular weight aliphatic carboxylic acids such as formamide or dimethylform amide or low molecular weight aliphatic carboxylic acids such as 40 acetic acid.

The monoazo compounds of the formula I obtained are isolated by a method known per se, advantageously by salting out with sodium or potassium chloride, followed by filtering, washing and drying. 45 If they are not known, the starting compounds of the formula II can be obtained, for example, by using a compound of the formula

50

R

55 R2

s02c1

no,

IV

with an amine of the formula W) H2N-R V

implemented and then the nitro group in the usual way, preferably reduced with iron / hydrochloric acid in alcoholic solution.

The condensation of the sulfochloride with the amine is preferably carried out in an aqueous environment at temperatures around 60 ° C.

617 449

4th

Instead of a single pure amine of the formula V, it is also possible to use an amine mixture in which R includes both isomeric residues of the same number of carbon atoms and residues of different numbers of carbon atoms. After the nitro group has been reduced to the amino group, the resulting mixtures of the starting compounds can be used directly for diazotization and coupling, and a mixed product is obtained which, like a pure dye of the formula I, can be used.

The compounds of the formula IV are known or can be prepared in a manner known per se from known starting compounds.

The compounds of the formula I prepared according to the invention and mixtures thereof, in the form of their salts, are brown powders which show good solubility in water.

The dyes and their mixtures are suitable for dyeing and printing any nitrogen-containing organic substrates which can be dyed with anionic dyes, in particular for dyeing and printing natural and synthetic polyamides such as wool, silk or in particular nylon, base-modified polyolefins or polyurethanes, and also for dyeing Leather. The nuances of the colors obtained range from red to Bordeaux tones.

If a single dye of the formula I is used for dyeing, it preferably contains an even number of carbon atoms with respect to R.

The dyes according to the invention and their mixtures are particularly suitable for dyeing from neutral or weakly acidic, for example acetic acid bath. Thereby show: Compounds of formula I and their mixtures, which with respect to the radical R and in the phenyl ring as R! and R2 optionally present substituents containing a total of 8-12 carbon atoms, very good ability to draw from a neutral and weakly acidic dye bath combined with good migratability, while compounds of the formula I and their mixtures which are referred to as R 1 with respect to the radical R and in the phenyl ring and R2, if present, contain a total of 4 to 8 carbon atoms, have good drawing power, in particular from weakly acidic baths, and very good migration ability.

those which contain a straight-chain C10-alkyl radical for R, show the same build-up capacity for natural and synthetic polyamides as well as for synthetic polyamides and polyurethanes in the single-bath dyeing process.

5 The dyes of the formula I according to the present invention or mixtures thereof can be used as such or in the form of liquid or solid preparations, such as granules.

10 In the following examples, parts mean parts by weight, parts by volume relate to parts by weight in the ratio of liters to kilograms. The temperatures are given in degrees Celsius.

15 Example 1

62.4 parts of l-aminobenzene-2-sulfonic acid-N-decylamide are stirred into a fine suspension in 200 parts of water and 50 parts of 30% hydrochloric acid are added. The mixture is stirred at room temperature for about 20 hours and diazotized

2 (1 then at 0-3 ° with 14.5 parts of sodium nitrite, dissolved in 50 parts of water. After the diazotization has ended, any excess of nitrous acid is destroyed with 0.5 parts of sulfamic acid.

20 parts of sodium acetate are dissolved in 200 parts of water and 48 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid are added to this solution. The diazonium salt suspension described above is slowly run into the suspension obtained with stirring; the pH is kept between 3 and 4 by the dropwise addition of 5% sodium hydroxide solution. The reaction mixture is stirred until the coupling has ended, then another 5% sodium hydroxide solution is added until a pH value of 10 is reached and the resulting dye suspension is stirred for 4 hours at 25-30 °. For working up, it is filtered, the filter material is washed with dilute sodium chloride solution and dried.

25th

The dye obtained, which has the formula ch2- (ch2) 8-ch3

The dyeings show good general fastness properties, in particular very good light fastness, as is particularly noteworthy for synthetic polyamides, and remarkable wet fastness properties, such as, for example, fastness to washing and sweating. They are also rub-fast and have good resistance to carbonization, ironing and acids such as alkalis.

In addition to their good water solubility and good drawability, especially from a neutral dyebath, the dyes of the formula I have the combination of two properties sought, namely good migration properties combined with good fastness to washing. In particular, if there is good migratability, very level dyeings are achieved, and streaky nylon is also covered without problems. Furthermore, the dyes of the formula I exhibit good combination behavior with other suitable dyes which have dyeing properties corresponding to the dyes according to the invention, the abovementioned properties of the dyeing being retained unchanged. In particular, such combination colors are not subject to the phenomenon of catalytic fading, that is to say the shade of such colors changes tone in tone when exposed to light. It should also be emphasized that the compounds of the formula I and in particular so2-nh nh,

S03Na is a brown powder that dissolves in water with a pure red color and on wool, silk and synthetics, polyamide fibers see brilliant bluish red dyeings of very good levelness, light and wash fastness. The dye shows excellent absorbency from a neutral dyebath.

Analogously to Example 1, further compounds of formula I can be obtained in the form of the sodium salts for which the radicals R, R! and R2 are specified. The dyeings on polyamide obtained with these dyes show graded shades of red.

5

617 449

table

Example No.R R2 (position) R, (position)

2nd

n-C6H13

H

H

3rd

n-C8H17

H

H

4th

-CH2-C H- (CH2) 3-CH3 |

H

H

c2h5

5

n-C () H | 3

CH3 (4)

H

6

n-C8H17

do.

H

7

n ~ C6H13

n-C4H9 (4)

H

8th

n-C10H21

OCH3 (4)

H

9

do.

OCH3 (5)

H

10th

n-C8H17

OCH3 (4)

H

11

do.

OCH3 (5)

H

12

n-C6H13

OC2H5 (4)

H

13

n — C8H | 7

do.

H

14

n-C10H2i do.

H

15

n-C6H13

OC2H5 (5)

H

16

n-C8H17

do.

H

17th

n-C10H2i do.

H

18th

n — C8H11

Cl (4)

H

19th

do.

Cl (5)

H

20th

do.

NH2 (4)

H

21st

do. '

NH2 (5)

H

22

n-C10H 21

Cl (4)

H

23

do.

Cl (5)

H

24th

do.

NH2 (4)

H

25th

do.

NH2 (5)

H

26

n-C8H17

-NHCOCH3 (4)

H

27th

do.

-nhcoch3 (5)

H

28

n-C6H13

-NHCOC4H9 (4)

H

29

n-C6H13

-NHCOC4H9 (5)

H

30th

n — C8H | 7

-NHCH2CH2OH (4)

H

31

do.

-NHCH2CH2OH (5)

H

32

do.

-NHCOOC2H5 (4)

H

33

do.

-NHCOOC2H5 (5)

H

34

do.

-NHCH2CH2CN (4)

H

35

do.

-NHCH2CH2CN (5)

H

36

do.

-COOC2H5 (5)

H

37

n-C6H13

Cl (4)

Cl (5)

38

do.

do.

CH3 (5)

39

do.

CH3 (4)

CH3 (5)

40

n-C8H | 7

Cl (4)

Cl (5)

41

do.

do.

CH3 (5)

42

do.

CH3 (4)

CH3 (5)

43

n-C10 H2J

Cl (4)

Cl (5)

44

do.

do.

CH3 (5)

45

do.

CH3 (4)

do.

46

-CH2CH2CH2 (OCH2CH2) 2OH

H

H

47

-CH2CH2CH2 (OCH2) 3OH

H

H

48

Diazo component mixture

regarding r with C9H19 ■ »

CioH2i / ■

H

H

QiH 23

49

Diazo component mixture

for r with C5H, [.

C6H13 l

H

H

c7H15)

50

n — gjhjjj h

H

617 449

Example No. R

6

R2 (position) R [(position)

51 - (ch2) 3-och3

52 ~ (ch2) 3-0- (ch2) 3-ch3

Cl (5) H

H H

53

ch,

-ch- (ch2) 3-c-oh h

H

I.

ch,

CH,

54

ch3 I

-c-ch2oh

[

ch3

n-C4H9 (4)

H

55

56

- (CH2) 4-OH ~ (CH2) 5-OH

do. do.

H H

57

C2H5

I.

-ch-ch2oh do.

The dyes of Example 1 and the table can, depending on the reaction and isolation conditions, (l gene instead of in the form of the sodium salt also in the form of the free acid or in another salt form, for example with a cation M mentioned in the description, getting produced.

35

Coloring example A

In a dye bath consisting of 400 parts of demineralized water, 4 parts of ammonium sulfate and 2 parts of the dye from Example 1, 100 parts of pre-wetted nylon cloth (nylon 66) are introduced at 40 °. The dyeing liquor is heated to boiling temperature in the course of 30 minutes and kept at this temperature for 1 hour. The evaporated water is constantly replaced during dyeing. Then you take the bluish red colored nylon cloth from the fleet, rinse it with water and dry it. Wool can also be dyed using the same method.

The dye bath is pulled out very well. The dyeings obtained show very good levelness, light and wash fastness.

If 2 parts of a commercially available leveling agent are added to the dye bath at the beginning of the dyeing process, nylon, which tends to streak dyeing, can be dyed in any way.

The same procedure can be used to dye 55 with the dyes listed in Examples 2 to 57 or with a mixture of two or more dyes in Examples 1 to 57.

Coloring example B

In a color tape <> »consisting of 4000 parts demineralised water and 2 parts of the dye from Example 2, 100 parts of pre-wetted synthetic polyamide fabric, e.g. Nylon, a.

The dyeing liquor is heated to boiling temperature over the course of 30 minutes, and is kept at this temperature for one

H

Hour, add 4 parts of glacial acetic acid and end the dyeing by heating to boiling temperature for a further 30 minutes.

The evaporated water is constantly replaced during dyeing. Then you take the bluish red colored nylon cloth from the fleet, rinse it with water and dry it. Wool can also be dyed using the same process. The dyeings have good light fastness and good wet fastness properties.

Following the same rule can be used in the examples

1 and 3 to 57 listed dyes or with a mixture of two or more dyes of Examples 1 to 57.

Printing instruction

Polyamide is printed with a printing paste of the following composition:

30 parts of dye according to Example 1 50 parts of urea 50 parts of a solubilizer (e.g. thiodiethylene glycol)

290 parts of water

500 parts of a suitable thickener

(e.g. based on locust bean gum) 20 parts of an acid dispenser (e.g. Ammontartrat) 60 parts of thiourea The printed textile is steamed for 40 minutes at 102 ° (saturated steam), then rinsed cold, then 5 minutes at 60 ° with a dilute solution of a commercially available detergent washed and rinsed cold again. You get a bluish red print of very good wet and light fastness.

In an analogous manner, printing pastes can be produced which contain one or more dyes of the examples as a constituent

2 to 57 included.

C.

Claims (3)

617449 PATENT CLAIMS 1. Process for the preparation of monoazo compounds of the formula R! and R2 each represents hydrogen or a substituent, R represents a linear or branched alkyl radical which is optionally interrupted once, twice or three times by an oxygen atom and / or is substituted by hydroxy, containing a total of 1 to 12 carbon atoms and M is hydrogen or the equivalent of a colorless cation, the number of carbon atoms in the molecule for R, Rj and R2 together is 4 to 12 and the molecule contains a single sulfonic acid group and also only one sulfonic acid amide group and is free of carboxyl groups, and Mixtures of compounds of the formula I, characterized in that the diazonium compound of one or more amines of the formula is coupled with a compound of the formula in an acidic to neutral medium. 2. The monoazo compounds prepared by the process according to claim 1. 3. Use of the monoazo compounds according to claim 2 or mixtures thereof for dyeing leather.