CH633572A5 - Process for the preparation of dyes - Google Patents

Description

633 572 2

PATENT CLAIMS 1. Process for the preparation of dyes of the formula I

R

50, H.

(I)

(Iii)

wherein

R 'for the methyl or ethyl group and Z "for amino, mono-C1-C4-alkylamino, di-QC, -alkylamino, phenylamino, optionally substituted by C1-C4-alkyl, sulfo, carboxy, halogen, C1- C4-alkoxy, produces.

wherein

R for Ci-C4-alkyl and

Z for an optionally substituted amino group, an optionally etherified hydroxyl group, an optionally etherified thiol group or an optionally substituted 20

Is hydrocarbon radical, characterized in that the present invention relates to dyes of the formula (IV) for the preparation of dyes of the formula (I)

is a process

HO, S

(IV)

HO, S

30th

(i)

Z.

wherein R has the above meanings, with a 1,3,5-triazine of the formula wherein

R for C1-C4-alkyl and

_ p Z for an optionally substituted amino group, an optionally etherified hydroxyl group, an optionally T-IL 4o etherified thiol group or an optionally substituted

Is hydrocarbon radical, which is characterized by the fact that dyes of the formula (IV)

implements.

2. The method according to claim 1, characterized in that dyes of the formula (II)

HO, S

(IV)

HO, S

(n)

S03H

wherein R has the above meanings, with a 1,3,5-triazine of the formula

55

60

Z m JF

bliss

R 'for the methyl or ethyl group and implemented.

Suitable Z radicals are, for example, amino, mono-Q-Z 'represents an optionally substituted amino group, 65 C4-alkylamino and di-Q-Q-alkylamino, the alkyl being prepared. grappe can optionally be substituted, for example

3. The method according to claim 1, characterized by OH, sulfo or OSO3H, phenylamino, optionally that dyes of the formula (III) substituted by C1-C4-alkyl, sulfo, C1-C4-alkoxy, carboxy,

633 572

Halogen, especially chlorine and the corresponding N-Q- C4-alkyl-N-phenylamino groups; Phenyl-Q-Q-alkylamino, where the phenyl radical can be substituted as indicated above; and the corresponding N-C1-C4-alkyl-N-phenyl-C1-C4-alkylamino residues, naphthylamino optionally substituted by sulfo, QQ-alkoxy, optionally substituted by hydroxy, phenoxy, optionally substituted by QQ-alkyl, sulfo, C1-C4- Alkylthio, optionally substituted by OH, phenylthio.

Examples of substituents Z on the trianzine ring are as follows: the amino, methylamino, ethylamino, β-hydroxyethylamino, dimethylamino, morpholino, piperidino, N- (o-, m-, p-sulfophenylamino- , N- (o-, m-, p-methylphenyl) amino-, N- (o-, m-, p-methoxyphenyl) amino, N- (o-, m-, p-chlorophenyl) - amino, N- (2,4- or 2,5-disulfophenyl) amino, N- (2-sulfo-4-methoxyphenyl) amino, N- (2-sulfo-4-methylphenyl) amino, N- (2-sulfo-4-chlorophenyl) amino, N- (2-carboxy-4- or 5-sulfophenyl) amino, N- (2-carboxyphenyl) amino, N- (4-sulfomethylphenyl) amino , N-methylamino-benzyl-, N-methylaminobenzyl-3-sulfonic acid, N- (4- or 5- or 6- or 7- or 8-sulfonaphthyl-l) -amino-, N- (5- or 6- or 7- or 8-sulfo-naphthyl-2) amino, N- (4,8-disulfonaphthyl-2) amino group; the methoxy, ethoxy, β-hydroxyethoxy, phenoxy, methylphenoxy, phenylthio and the 2-mercapto-benzothiazole group and amino groups with dye character, such as, for example, amino group-containing dye residues of the mono- or polyazo, phthalocyanine, Formazan, anthraquinone, stilbene, oxazine, dioxazine, triphenylmethane, nitro or azo-methine series. The radical Z can also contain further reactive groups.

Preferred compounds which can be prepared according to the invention are compounds of the formula (II)

S03II

R '= methyl or ethyl.

The following processes can be mentioned in detail: The dye of the formula (IV)

10th

R ° -p-N = N II03 s ho3 s

(IV)

wherein

R has the meaning given above, is reacted with a) with 2,4,6-trifluoro-l, 3,5-triazine with elimination of HF 'and then with HZ with elimination of HF or b) with condensation products of the formula (V )

20 F

(V)

25th

where so3h

Z represents an optionally substituted hydrocarbon radical, with the elimination of HF.

The reaction of IV with 2,4,6-trifluoro-l, 3,5-triazine or 30 its monocondensation product of the formula (V)

(V)

is generally carried out in aqueous solution or suspension at weakly acidic, neutral or weakly alkaline pH values, the hydrogen fluoride liberated in the reaction advantageously being continuously neutralized by adding aqueous alkali metal lyes, carbonates or bicarbonates.

Furthermore, the condensation product of the formula (VI)

wherein

R '= methyl or ethyl and Z' = residue of an optionally substituted amino group.

Compounds of the formula (III) which can be prepared according to the invention are particularly preferred

45

r.

(VI)

50

II03 p

NH

/ ° * H HO

R »0-TVn = N

ho3 s ho3 s

(III)

55

well vv

Z has the meaning given above, with a di-azo compound of an amine of the formula (VII)

NH-

Z "

wherein

(VII)

Z "= amino, mono-C1-C4-alkylamino, di-C1-C4-alkylamino, phenylamino optionally substituted by C1-C4-alkyl, sulfo, carboxy, halogen, C1-C4-alkoxy in which

R has the meaning given above, are converted to (I).

633 572

4th

The coupling is generally carried out in an aqueous medium, the acid originating from the diazotization and the acid released during the reaction being removed by adding bases.

Examples of compounds of the formula wherein

Z have the meaning given above are, for example:

2,4-difluoro-6-amino-l, 3,5-triazine,

2,4-difluoro-6-phenylamino-l, 3,5-triazine,

2,4-difluoro-6- (4'-sulfophenyl) amino-l, 3,5-triazine,

2,4-difluoro-6- (3'-sulfophenyl) amino-l, 3,5-triazine,

2,4-difluoro-6- (2'-sulfophenyl) amino-l, 3,5-triazine,

2,4-difluoro-6- (2'-methylphenyl) amino-l, 3,5-triazine,

2,4-difhior-6- (2'-methoxyphenyl) amino-l, 3,5-triazine,

2,4-difluoro-6- (2'-chlorophenyl) amino-l, 3,5-triazine,

2,4-difhior-6- (4'-methylphenyl) amino-l, 3,5-triazine,

2,4-sifluoro-6- (N-methyl-benzyl) amino-l, 3,5-triazine,

2,4-difluoro-6- (4'-sulfo-naphthyl-r) -amino-l, 3,5-triazine,

2,4-difluoro-6- (6 '-suifonaphthyl-2') -amino-1,3,5-triazine,

2,4-difluoro-6- (4'-sulfomethylphenyl) amino-l, 3,5-triazine,

2,4-difluoro-6- (2'-carboxyphenyl) amino-l, 3,5-triazine,

2,4-difluoro-6-piperidino-l, 3,5-triazine,

2,4-difluoro-6-morpholino-l, 3,5-triazine,

2,4-difluoro-6-methylamino-l, 3,5-triazine,

2,4-difluoro-6-ß-hydroxyethylamino-l, 3,5-triazine,

2,4-difluoro-6-dimethylamino-l, 3,5-triazine,

2,4-difluoro-6-methoxy-l, 3,5-triazine,

2,4-difluoro-6-phenoxy-l, 3,5-triazine,

as well as the intermediate products with dye character such as

Reaction products of dyes of mono- or poly

azo, phthalocyanine, formazan, anthraquinone, stilbene,

Oxazine, dioxazine, triphenylmethane, nitro or azomethine

series with 2,4,6-trifluoro-l, 3,5-triazine.

Suitable compounds of the formula H-Z are, for example:

Methanol, ethanol, phenol, thiophenol, ammonia, ethylamine, dimethylamine, diethylamine, ethanolamine, diethanolamine, morpholine, piperidine, 2,3- or 4-aminotoluene, 2,3- or 4-amlnoanisole, 2,3- or 4-chloroaniline , 2,3- or 4-SuIfoanilin, aniline, N-methylaniline, 4-aminobenzylsulfonic acid, 2,3- or 4-aminobenzoic acid, N-methylbenzylamine, N-methylbenzylamine-3- or -4-sulfonic acid, naphthylamine mono -, Di- and trisulfonic acids and amino group-containing dyes of the mono- or polyazo, phthalocyanine, formazane, anthraquinone, stilbene, oxazine, dioxazine, triphenylmethane, nitro or azomethine series.

The following may be mentioned as examples of compounds of the formula VII:

l-amino-2,5-disulfo-4-methoxy-benzene,

l-amino-2,5-disulfo-4-ethoxy-benzene.

The new dyes which can be prepared according to the invention are suitable, for example, for dyeing and printing materials containing hydroxyl or amide groups, such as textile fibers, threads and fabrics made of wool, silk, synthetic polyamide and polyurethane fibers, and for true-to-life dyeing and printing of native materials or regenerated cellulose, the treatment of cellulose materials expediently being carried out in the presence of acid-binding agents and, if appropriate, by the action of heat by the processes which have become known for reactive dyes.

The formulas given for the dyes are those for the corresponding free acids. The dyes were generally isolated in the form of the alkali salts, in particular the Na salts, and used for dyeing.

5

example 1

59.6 g of trisodium salt of the dye 2,5-disulfo-4-meth-oxy- (1 azo 2) l-hydroxy-3-sulfo-6-amino-naphthalene is stirred in 1 liter of ice / water. At 0 ° C, 13.5 g of 2,4,6-tri-lo fluoro-l, 3,5-triazine are added dropwise, with dilute sodium hydroxide solution being added at the same time in order to keep the pH at 5-6. After adding the trifluorotriazine, stirring is continued for 5 to 10 minutes and then 10.7 g of o-toluidine are added dropwise in the form of its hydrochloric acid solution. The temperature is allowed to rise to 10-15 ° C. and the pH is kept at 5-6 by adding dilute sodium hydroxide solution. The acylation is complete when no more sodium hydroxide solution is used. The dye is separated by adding table salt. After suction, drying and grinding, a light red dye powder is obtained, 20 which dissolves in water with a yellowish red color. In the form of the free acid, the dye corresponds to the following formula:

SO3II H0

25th

30th

Coloring example printing instruction

35 If you print cotton nettle with a printing paste that contains 20 g per kilogram of the dye shown in Example 1, 100 g urea, 300 ml water, 500 g alginate thickener (60 g sodium alginate / kg thickener) and 10 g soda, and that was made up to 1 kg with water, dried, steamed for 1 40 minutes at 103 ° C, rinsed with hot water and boiling with soap, this gives a clear, strongly yellowish red print of good wet and light fastness.

Block regulation

45 30 parts of the dye shown in Example 1 are dissolved in 1000 parts of water. A cotton fabric is padded with this solution and pressed down to a weight loss of 90%. The still moist cotton is treated at 70 ° for 30 minutes in a bath which contains 50 300 parts of calcined sodium sulfate and 10 parts of calcined sodium carbonate dissolved in 1000 parts of water. The coloring is then finished in the usual way. A brilliant, strongly yellowish scarlet with excellent wet and light fastness results.

55

Dyeing instruction

168 ml of water at 20-25 ° are placed in a staining beaker with a volume of 300 ml, which is in a heatable water bath. 0.3 g of the 60 dye obtained according to Example 1 is well mixed with 2 ml of cold water and 30 ml of hot water (70 °) are added; the dye dissolves. The dye solution is added to the water and 10 g of cotton yarn in this dye liquor is kept in constant motion. Within 10 minutes, the temperature of the 65 dye liquor is increased to 40-50 °, 10 g of anhydrous sodium sulfate are added and the dyeing is continued for 30 minutes. Then you add 4 g of anhydrous sodium carbonate to the dyeing liquor and dye for 60 minutes at 40-50 °. The dyed material is then removed from the dyeing liquor,

5

633 572

removes the adhering hotte by wringing it out or pressing it off and rinses the material first with cold water and then with hot water until the wash liquor is no longer bled on. The dyed material is then soaped in 200 ml of a liquor containing 0.2 g of sodium alkyl sulfate for 20 minutes at the boiling point, rinsed again and dried at 60-70 ° in a drying cabinet. A brilliant, strongly yellowish scarlet with excellent wash and light fastness results.

Dyes of similar hue are obtained when the procedure of Example 1 is repeated, replacing the o-toluidine with an equivalent amount of one of the following compounds.

In the form of the free sulfonic acid, the dye corresponds to the following formula:

/ ^ ° 3H HO 5CH3 O-Q-N = N

S03II

10th

F

One proceeds according to the information in this example, however

H

example

Amine

15 using an amount of amine equivalent to m-sulfanilic acid, this also results in valuable dyes

2nd

aniline

similar hue.

3rd

m-toluidine

4th

p-toluidine

example

Amine

5

o-chloroaniline

20th

14

6

o-anisidine p-sulfanilic acid

7

p-anisidine

15

o-sulfanilic acid

8th

p-methylsulfonylaniline

16

Anthranilic acid

9

Sulfuric acid half-ester of

17th

l-amino-2-methoxy-5-sulfobenzene

p- (β-hydroxyethyl) aniline

25th

2-amino-1-suifo-naphthalene

10th

4-amino-benzylsulfonic acid

19th

2-amino-8-sulfonaphthalene

11

N-methylbenzylamine

20th

1-Amino-2-sulfo-4-methoxy-benzene

12th

Benzylamine

Example 13

17.3 g of m-sulfanilic acid are dissolved in 0.5 l of ice water until neutral. 13.5 g of 2,4,6-trifluoro-l, 3,5-triazine are then added dropwise while maintaining a pH of 3-4 by adding dilute sodium hydroxide solution. After the addition of the 35 trifluorotriazine, stirring is continued for a few minutes and then a solution of 59.6 g of the trisodium salt of the azo dye used in Example 1 is added dropwise. The temperature is allowed to rise to 15-20 ° C. and the hydrofluoric acid released is blunted with dilute sodium hydroxide solution. After the condensation has ended, the dye is salted out, suction filtered, dried and ground. A light red dye powder is obtained which easily dissolves in water with a light red color. According to one of the dyeing examples listed in Example 1, clear, yellowish scarlet tones are obtained on cotton. 45

Example 21

17.3 g of m-sulfanilic acid are reacted with trifluorotriazine as described in Example 13. A solution of 26.1 g of the sodium salt of I-acid in 200 ml of water is added dropwise to the ice-cold solution of the monocondensation product. During the condensation, a pH of 5-6 is maintained by adding dilute sodium hydroxide solution. At the same time, the temperature is allowed to reach 15 °. After the condensation has ended, the diazonium laz solution prepared from 28.3 g of l-amino-2,5-disulfo-4-methoxy-benzene is added, the pH being adjusted to pH 6-7 by adding sodium hydrogen carbonate. The mixture is stirred for a few hours and then the dye is salted out. After vacuuming, drying and grinding, a light red dye powder is obtained.

It is identical to the dye obtained in Example 13.

C.