CH624138A5 - Process for the preparation of fibre-reactive dyes - Google Patents

Abstract

The fibre-reactive dyes of the formula <IMAGE> wherein D is the radical of an organic dye containing sulpho groups, R1, R2 and R3 independently of one another are hydrogen or alkyl having 1 to 4 carbon atoms, B is an alkylene or arylene radical and A is an alkoxy, alkoxyalkoxy or alkylthio group, which are distinguished by high reactivity, are prepared by condensing an organic dye, containing sulpho groups, of formula <IMAGE> 2,4,6-trichloro-1,3,5-triazine, an alkylenediamine or arylenediamine of formula <IMAGE> 2,4,6-trifluoro-1,3,5-triazine and a compound of formula H-A (8> or, if D is the radical of an azo dye, by starting from the diazo and coupling components and from the other above-mentioned starting materials. The dyes of formula (1) are particularly suitable for dyeing and printing cotton fibres.

Description

The present invention relates to a method for producing fiber-reactive dyes of the formula

(6),

—It — e — h — c ^ c — a.

il I II H

(1) ,

r,

r,

R1 R2

Cl r,

wherein R2, R3 and B have the meanings given under formula (1), 2,4,6-trifluoro-1,3,5-triazine of the formula

1 11

(7),

and a compound of the formula

HA

(8th),

wherein A has the meaning given under formula (1), condensed to a fiber-reactive dye of formula (1).

2. The method according to claim 1, characterized in that one carries out the reaction step by step, the order of the simple condensations between the individual reaction components of the formulas (4) to (8) can be chosen freely.

wherein D is the residue of an organic dye containing sulfo groups, R 1, R 2 and R 3 independently of one another are hydrogen or alkyl having 1 to 4 carbon atoms, B is an alkylene or arylene radical and A is an alkoxy, alkoxyalkoxy or alkylthio-50 group.

The radical D is in particular the radical of a dye containing sulfo groups from the monoazo or polyazo, metal complex, formazane, anthraquinone, phthalocyanine, stilbene, oxazin, dioxazine, triphenylmethane, nitro or azomethine series. 55 For R 1, R 2 and R 3 as alkyl having 1 to 4 carbon atoms, the following are suitable: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. The radical B is an alkylene radical, preferably with 2-6 C atoms or especially a radical of the benzene, naphthalene or diphenyl series; the arylene radical B can contain 60 further substituents, e.g. B. alkyl groups such as methyl, ethyl and propyl, alkoxy groups such as methoxy and ethoxy, carboxy and sulfo groups, and halogen atoms such as fluorine, chlorine and bromine. For the rest A come z. B. as an alkoxy group: methoxy, ethoxy, propyloxy, iso-65 propyloxy, butyloxy, isobutyloxy, sec-butyloxy, pentyloxy, hexyloxy, ß-methoxy-ethoxy, ß-ethoxy-ethoxy, y-methoxypropoxy, y-ethoxypropoxy, y -Propoxypropoxj ;, y-isopropoxypropoxy; as alkylthio group: methylthio and ethylthio.

624138

Reactive dyes which contain an alkoxy-fluorotrizylamino residue bonded to a dye residue are known from German Offenlegungsschrift 1 644 208.

Since the dyes of the formula (1) contain two cleavable halogen atoms, Cl and F, they are fiber (bi-) reactive. 5

Fiber-reactive compounds are to be understood as those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form covalent chemical bonds. 10th

The production of the fiber-reactive dyes of the formula (1) is characterized in that a sulfo-containing organic dye of the formula d-ljlh R,

(4), '5

wherein D and Ri have the meanings given under formula (1), 2,4,6-trichloro-1,3,5-triazine of the formula

Cl-C ^ -C-Cl I 11

Cl is an alkylene or arylenediamine of the formula hn-b-nh i l

R2 R3

(5),

25th

30th

(6)

wherein R2, R3 and B have the meanings given under formula (1), 2,4,6-trifluoro-1,3,5-triazine of the formula

40

f-ç ^ sjl-f

(7),

and a compound of the formula

HA

45

50

(8th),

wherein A has the meaning given under formula (1), condensed to a fiber-reactive dye of formula (1).

Since the individual process steps can be carried out in a different order, possibly partially at the same time, different process variants are possible. The starting materials to be used for each partial reaction result from formula (1). In general, the reaction is carried out step by step, the sequence of simple condensations between the individual reaction components of the formulas (4) to (8) being freely selectable.

According to a further process, the fiber-reactive dyes of the formula (1), in which D is the remainder of a sulfo-containing organic azo dye composed of two or 65 more than two components, can be prepared in such a way that the components of the remainder D, which together are at least contain a sulfo group, one of the components containing an -N-Ri-H group, in which Ri has the meaning given under formula (1), 2,4,6-trichloro

1,3,5-triazine of the formula (5), an alkylene or arylenediamine of the formula (6), in which R2, R3 and B have the meanings given under formula (1), 2,4,6-trifluoro-1,3, 5-triazine of the formula (7) and a compound of the formula (8), in which A has the meaning given under formula (1), to give the finished fiber-reactive dye of the formula (1).

Examples of such organic azo dyes composed of two or more than two components are: monoazo, disazo, trisazo, tetrazo and metal complex azo dyes.

In these the part of the azo dye residue to which the chloro-s-triazine residue is directly attached can be either the rest of the diazo component or the rest of the coupling component. This results in two variants of the method described above. These two variants of the process for the production of fiber-reactive dyes of the formula (1), in which D is the remainder of an azo dye containing sulfo groups, are characterized in that a) a diazotizable aromatic diamine which contains an -N-Ri-H group, wherein Ri has the meaning given under formula (1), a coupling component, the diazotizable aromatic diamine and the coupling component together containing at least one sulfo group, 2,4,6-tri-chloro-1,3,5-triazine of the formula (5 ), an alkylene or arylenediamine of the formula (6), in which R2, R3 and B have the meanings given under formula (1), 2,4,6-trifluoro-l, 3,5-triazine of the formula (7) and a compound of the formula (8), in which A has the meaning given under formula (1), by diazotization, coupling and condensation to give the finished fiber-reactive dye of the formula (1), or that b) a coupling component which has an -N- Ri-H group contains, wherein Ri specified under formula (1) has a meaning, a diazotizable aromatic amine, the coupling component and the diazotizable aromatic amine together containing at least one sulfo group,

2,4,6-trichloro-l, 3,5-triazine of the formula (5), an alkylene or arylenediamine of the formula (6), in which R2, R3 and B have the meanings given under formula (1), 2,4, 6-trifluoro-l, 3,5-triazine of the formula (7) and a compound of the formula (8), in which A has the meaning given under formula (I), by diazotization, coupling and condensation to give the finished fiber-reactive dye of the formula ( 1) implements.

Variants a) and b) described above for the production of fiber-reactive dyes of the formula (1), in which D is the remainder of a sulfo-containing azo dye, comprise in particular several embodiments, e.g. B .:

1. A coupling component containing an amino group is condensed with cyanuric chloride, the primary condensation product obtained is condensed with an alkylene or arylenediamine, a diazo component is coupled to the secondary condensation product, the azo compound obtained is condensed with cyanuric fluoride and the condensation product thus obtained is condensed lastly with an alcohol or alkyl mercaptan.

2. The procedure is as under 1. until the azo compound is produced. Cyanuric fluoride is also condensed with an alcohol or alkylmercaotane and the primary condensation product obtained is condensed with the azo compound mentioned above.

3. The procedure is as in 1. up to the preparation of the secondary condensation product from cyanuric chloride, a coupling component which contains an amino group and an alkylene or arylenediamine, the secondary condensation product is condensed with cyanuric fluoride, and the condensation product obtained is in turn condensed with an alcohol

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or alkyl mercaptan and couples a diazo component to the condensation product obtained last.

4. A coupling component which contains an amino group is condensed with cyanuric chloride, a diazo component is coupled to the primary condensation product and the azo compound is 5 condensed with an alkylene or arylenediamine. The resulting condensation product is condensed with cyanuric fluoride, and the condensation product obtained is condensed with an alcohol or alkyl mercaptan. io

5. A diazo component is coupled to a coupling component. The azo compound prepared, which contains an amino group in the remainder of the diazo component or in the remainder of the coupling component, is condensed with cyanuric chloride, and the primary condensation product is further condensed with an alkylene or arylenediamine. The secondary condensation product obtained is condensed with cyanuric fluoride, and the condensation product obtained is condensed with an alcohol or alkyl mercaptan. 20th

Instead of condensing the secondary condensation product of cyanuric chloride, an azo compound and an alkylene or arylenediamine with cyanuric fluoride and then with an alcohol or alkyl mercaptan, one can also first prepare the primary condensation product from cyanuric fluoride and an alcohol or alkyl mercaptan and this with the secondary mentioned above Condense the condensation product from cyanuric chloride, an azo compound and an alkylene or arylene diamine.

6. An alcohol or alkyl mercaptan is condensed with 20 cyanuric fluoride, the primary condensation product is condensed with an alkylene or arylene diamine and the secondary condensation product thus obtained is condensed with cyanuric chloride. An azo compound is also produced by coupling a diazo component to a coupling component and contains an amino group in the rest of the diazo component or in the rest of the coupling component. The azo compound is condensed with the intermediate compound described first.

This procedure is generally applicable, i. H. also 40 on dyes of all other classes by using any sulfo-containing dye which contains an amino group instead of the azo compound.

7. The procedure is as under 6. until the intermediate is prepared from alcohol or alkyl mercaptan, cyanuric fluoride, alkylene or arylenediamine and cyanuric chloride; this intermediate compound is condensed with a coupling component which contains an amino group, and a diazo component is coupled onto the condensation product.

8. The procedure is as under 6. until the secondary condensation product is prepared from alcohol or alkyl mercaptan, cyanuric fluoride and alkylene or arylenediamine. An azo compound which contains an amino group in the rest of the diazo component or in the rest of the coupling component is also prepared by coupling a diazo component to a coupling component, and the azo compound is condensed with cyanuric chloride. The primary condensation product thus obtained is condensed with the above-mentioned secondary condensation product.

This procedure is also generally applicable, eo by condensing any sulfo-containing dye which contains an amino group with cyanuric chloride instead of the azo compound, and condensing the primary condensation product obtained with the secondary condensation product of alcohol or alkyl mercaptan, cyanuric fluoride and alkylene-65 or arylenediamine .

9. The procedure is as under 6. up to the preparation of the secondary condensation product from alcohol or alkyl mercaptan, cyanuric fluoride and alkylene or arylene diamine. Cyanuric chloride is also condensed with a coupling component which contains an amino group, the primary condensation product obtained is condensed with the above-mentioned secondary condensation product and a diazo component is coupled to the last condensation product formed.

10. The procedure is as under 6. until the intermediate compound is prepared from alcohol or alkyl mercaptan, cyanuric fluoride, alkylene or arylenediamine and cyanuric chloride; this intermediate compound is condensed on one side with a diazo component which contains a further amino group in addition to the diazotizable amino group, the resulting condensation product is diazotized and coupled with a coupling component.

The following may be mentioned as starting materials for the production of the fiber-reactive dyes of the formula (1):

a) organic dyes of the formula containing sulfo groups

(4)

1. Monoazo compounds of the formula

■ WaR

(15),

wherein Di is an at most bicyclic aryl radical free of azo and -NHR groups, R is hydrogen or alkyl, and the -NHR group is preferably attached to the 5-, 6-, 7- or 8-position of the naphthalene nucleus and which may contain a sulfonic acid group in the 5- or 6-position of the naphthalene nucleus.

Di can mean a radical of the naphthalene or benzene series which contains no azo substituents, for example a stilbene, diphenyl, benzthiazolylphenyl or diphenylamine radical. In this class, the related dyes should also be noted, in which the -NHR group, instead of being bound to the naphthalene nucleus, to a benzoyl-amino- bonded to the 5-, 6-, 7- or 8-position of the naphthalene nucleus or anilino group.

Particularly valuable starting dyes are those in which Di denotes a sulfonated phenyl or naphthyl radical, in particular those which contain an -SCbH group ortho to the azo bond; the phenyl radical can be further substituted, for example by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino groups such as acetylamino and alkoxy radicals such as methoxy.

2. Disazo compounds of the formula (15), in which Di is a radical from the azobenzene, azonaphthalene or phenylazonaphtha-lin series and the naphthalene nucleus is substituted by the -NHR group and, if desired, by sulfonic acid, as in class 1

3. Monoazo compounds of the formula

-nhr

(16)

wherein Di is an at most bicyclic aryl radical, as described in class 1 and preferably denotes a disulfonaphthyl or stilbene radical, R is hydrogen or alkyl, and the benzene nucleus further substituents, such as halogen atoms or alkyl, alkoxy, carboxylic acid, ureido and acylamino groups may contain.

4. Mono or disazo compounds of the formula h-n-d, -n = n-k I 1 r

(17)

5

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wherein Di is an arylene radical, e.g. B. a residue of azobenzene, class 3:

Azonaphthalene or phenylazonaphthalene series, or preferred 2- (4'-amino-2'-methylphenylazo) -naphthalene-4,8-disulfonic acid,

have a maximally bicyclic arylene radical of the benzene- 2- (4'-amino-2'-acetylaminophenylazo) -naphthalene-5,7-disulfone-

or naphthalene series and K the remainder of a naphtholsulfonic acid,

acid or the rest of an enolized or enolizable s 4-nitro4 '- (4 "-methylaminophenylazo) -stilbene-2,2'-disulfone-

Ketomethylene compound (such as an acetoacetarylide or an acid,

5-pyrazolone) with the OH group ortho to the azo-4-nitro4 '- (4 "-amino-2" -methyl-5 "-methoxy-phenylazo) group, and R is hydrogen or alkyl. Di means stilbene-2,2'-disulfonic acid,

preferably a residue of the benzene series which is a sulfonic acid-4-amino-4 '- (4 "-methoxyphenylazo) -stilbene-2,2'-disulfonic acid,

group contains. 10 4-amino-2-methylazobenzene-2 ', 5'-disulfonic acid.

5. Mono- or disazo compounds of the formula

Class 4:

Di-N = N-Ki-NHR (18), 1- (2 ', 5'-dichloro4'-sulfophenyl) -3-methyl4- (3 "-amino-6" -

sulfophenylazo) -5-pyrazolone,

in which Di is a radical of those defined for Di in classes 1 and 2 above- '5 i- (4'-sulfophenyl) -3-carboxy4- (4 "-amino-2" -sulfophenyl-

types and Ki the rest of an enolizable ketome- azo> 5-pyrazolone,

ethylene compound (such as an acetoacetarylide or a 5-pyrazo-l- (2'-methyl-5'-sulfophenyl) -3-methyl4- (4 "amino-2" sulfo

lon) with the OH group ortho to the azo group phenylazo> 5-pyrazolone,

mean. l- (2'-Sulfophenyl) -3-methyl4- (3 "-amino-6" -sulfophenylazo) -5-

6. The metal complex compounds, e.g. B. the copper, 20 pyrazolone,

Chromium and cobalt complexes, the dyes of the formulas (15) 4-amino4 '- (3 "-methyl-l" -phenyl-4 "-pyrazole-5" -onylazo) -

to (18), in which Di, K and Ki have the meanings indicated in each case. 2,2'-disulfonic acid,

gene and also a metallizable group (for example 4-amino-4 '- (2 "-hydroxy-3", 6 "-disulfo-l" -naphthylazo) -

a hydroxyl, lower alkoxy or carboxylic acid stilbene-2,2'-disulfonic acid,

group) is present in the ortho position to the azo group in Di. 25 8-acetylamino-l-hydroxy-2- (3'-amino-6'-sulfophenylazo) -

naphthalene-3,6-disulfonic acid,

Examples 7- (3'-Sulfophenylamino) -l-hydroxy-2- (4'-amino-2'-carboxy-

Class 1: phenylazo) -naphthalene-3-sulfonic acid,

6-amino-l-hydroxy-2- (2'-sulfophenylazo) naphthalene-3-sulfone-8-phenylamino-l-hydroxy-2- (4 "-amino-2" -sulfophenylazo) acid, 30 naphthalene 3,6-disulfonic acid,

6-methylamino-l-hydroxy-2- (4'-acetylamino-2'-sulfopheny-6-acetylamino-l-hydroxy-2- (5'-amino-2'-sulfophenylazo) -lazo> naphthalene-3-sulfonic acid , naphthalene-3-sulfonic acid. 8-amino-l-hydroxy-2- (2'-sulfophenylazo) -naphthalene-3,6-disul-

fonic acid, class 5:

8-amino-l-hydroxy-2- (4'-chloro-2'-sulfophenylazo) -naphthalene-35 l- (3'-aminophenyl) -3-methyl4- (2 ', 5 / -disulfophenylazo) -5- pyra-

3,5-disulfonic acid, zolon,

7-amino-2- (2 ', 5'-disulfophenylazo> l-hydroxynaphthalene-3-sul-l- (3'-aminophenyl> 3-carboxy4- (2'-carboxy-4'-sulfophenyfonic acid, lazo) -5-pyrazolone,

7-methylamino-2- (2'-sulfophenylazo) -l-hydroxynaphthalene-3- 4-amino4 '- [3 "-methyl4" - (2 "', 5" 'disulfophenylazo) -l "-

sulfonic acid, 40 pyrazole-5 "-onyl] -stilbene-2,2'-disulfonic acid,

7-methylamino-2- (4'-methoxy-2'-sulfophenylazo) -l-hydroxy-l- (3'-aminophenyl) -3-carboxy-4- [4 "- (2" ', 5 "' - disulfonaphthalene-3-sulfonic acid, phenylazo) -2 "-methoxy-5" -methylphenylazo] -5-pyrazolone.

8- (3'-Aminobenzoylamino) -l-hydroxy-2- (2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid, class 6:

8-Amino-l-hydroxy-2,2'-azonaphthalene-l ', 3,5', 6-tetrasulfone-45 The copper complex of 8-amino-l-hydroxy-2- (2'-hydroxy-5 "-

acid, sulfophenylazo> naphthalene-3,6-disulfonic acid,

8-amino-l-hydroxy-2,2'-azonaphthalene-l ', 3,5'-trisulfonic acid, the copper complex of 6-amino-l-hydroxy-2- (2'-hydroxy-5'-

6-amino-l-hydroxy-2,2'-azonaphthalene-l ', 3,5'-trisulfonic acid, sulfophenylazo> naphthalene-3-sulfonic acid,

6-methylamino-l-hydroxy-2,2'-azonaphthalene-l ', 3,5'-trisulfone - the copper complex of 6-amino-l-hydroxy-2- (2'-hydroxy-5'-acid, 50 sulfophenylazo) naphthalene-3,5-disulfonic acid,

7-amino-l-hydroxy-2,2'-azonaphthalene-l ', 3-disulfonic acid, the copper complex of 8-amino-1-hydroxy-2- (2'-hydroxy-3'-

8-amino-1-hydroxy-2- (4'-hydroxy-3'-carboxyphenylazo> naph-chloro-5'-sulfophenylazo) -naphthalene-3,6-disulfonic acid, thalin-3,6-disulfonic acid, the copper complex of 6-methylamino-l-hydroxy-2- (2'-car-6-amino-l-hydroxy-2- (4'-hydroxy-3'-carboxyphenylazo) -naph-boxy-5'-sulfophenylazo) -naphthalene 3-sulfonic acid, thalin-3,5-disulfonic acid. 55 the copper complex of 8-amino-l-hydroxy-2- [4 '- (2 "-sulfo-

phenylazo) -2'-methoxy-5'-methylphenylazo] -naphthalene-3,6-

Class 2: disulfonic acid,

8-amino-l-hydroxy-2- [4- (2 "-sulfophenylazo> 2'-methoxy- the copper complex of 6-amino-l-hydroxy-2- [4 '- (2", 5 "-di

5'-methylphenylazo] -naphthalene-3,6-disulfonic acid, sulfophenylazo ^ 2'-methoxy-5'-methylphenylazo] -naphthalene

8-amino-l-hydroxy-2- [4 '- (4 "-methoxyphenylazo) -2'-carboxy-60 3,5-disulfonic acid,

phenylazoj-naphthalene-S.ö-disulfonic acid, the copper complex of l- (3'-amino4'-sulfophenyl) -3-methyl-

8-Amino-l-hydroxy-2- [4 '- (2 "-hydroxy-3", 6 "-disulfo-l" - 4- [4 "- (2"', 5 "'- disulfophenylazo) -2 "-methoxy-5" -methyl-

naphthylazo> 2'-carboxyphenylazo] -naphthalene-3,6-disulfone-phenylazo] -5-pyrazolone,

acid, the copper complex of 7- (4'-amino-3'-sulfoanilino) -l-

4,4'-bis (8 "-amino-1" -hydroxy-3 ", 6" -disulfo-2 "-naphthyl-65-hydroxy-2- [4" - (2 "', 5"' - disulfophenylazo ) -2 "-methoxy-5" -

azo> 3,3'-dimethoxydiphenyl, methylphenylazo] -naphthalene-3-sulfonic acid,

6-Amino-l-hydroxy-2- [4 '- (2 "-sulfophenylazo> 2'-methoxy-5'- the copper complex of 6- (4'-amino-3'-sulfoanilino) -l-

methylphenylazo] naphthalene-3,5-disulfonic acid. hydroxy-2- (2 "-carboxyphenylazo) -naphthalene-3-sulfonic acid,

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the 1,2-chromium complex of 7-amino-6'-nitro-l, 2'-dihydroxy-

2,1'-azonaphthalene-3,4'-disulfonic acid,

the 1,2-chromium complex of 6-amino-l-hydroxy-2 - ('- carboxy-

phenylazo) -naphthalene-3-sulfonic acid,

the 1,2-chromium complex of 8-amino-l-hydroxy-2- (4'-nitro-

2'-hydroxyphenylazo> naphthalene-3,6-disulfonic acid,

the 1,2-cobalt complex of 6 <4'-amino-3'-sulfoanilino) -l-

hydroxy-2- (5 "-chloro-2" -hydroxyphenylazo) -naphthalene-3-sulfone-

acid,

the 1,2-chromium complex of H3'-amino4'-sulfophenyl) -3-methyl4- (2 "-hydroxy4" -sulfo-1 "-naphthylazo) -5-pyrazolone, the 1,2-chromium complex of 7- (4th '-Sulfoanilino) -l-hydroxy-2- (4 "-amino-2" -carboxyphenylazo) -naphthalene-3-sulfonic acid, the 1,2-chromium complex of l- (3-aminophenyl) -3-methyl4- (4th "-nitro-2" carboxyphenylazo> 5-pyrazolone.

Particularly important azo dyes which can be used to prepare the fiber-reactive dyes of the formula (1) are the azo dyes of the formulas

(S03H) 0-3

N = N - K

(19),

H; 0CH3; NH acyl

(HO, 3)

3 '0-3 1 ;.

N = N

(S ° 3H) i_3

(20) and

-H

(H0_S). -

3rd

1

H; CH3; 0CH3; -NH-acyl i r »n = n

CH ^; NH acyl

(S03H »0-3

(21),

where K is the rest of a coupling component of the benzene, so shear, and Ri is the one in the explanation of the formula (1)

Naphthalene or the heterocyclic series, acyl has a low-specified meaning, and the metal complex azo color

Molecular aliphatic substances of the formulas acyl radical containing a maximum of 3 carbon atoms or an aromatic compound containing a maximum of 8 carbon atoms

(HO-S)

3 '0-3

E} OH, NO

V

, S03n) l-3

(22) and

H; Cl; NO,

7

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(SO3H) O-20

NH2 (or NH-a <yl)

(S ° 3H) ^

(23),

wherein Ri and acyl have the meanings given in the explanation of the formulas (19), (20) and (21) and Me stands for Cu, Cr or Co. 20th

7. Anthraquinone compounds which contain a group of the formula -NHR, in which R is hydrogen or alkyl, to an alkylamino or arylamino group which is itself attached to the a position of the anthraquinone nucleus, in particular of the formula 25

just co i

'YVso, H

(24),

nh-z'-ner

35

wherein the anthraquinone nucleus can contain an additional sulfonic acid group in the 5-, 6-, 7- or 8-position and Z 'represents a bridge member which is preferably a divalent radical of the benzene series, for example a phenylene, diphenylene or 4,4'-stilbene or azobenzene residue. Preferably Z 'should contain one sulfonic acid group for each benzene ring 40 present.

Examples 1-Amino4- (4'-aminoanilino) -anthraquinone-2,3'-disulfonic acid and the corresponding 2,3 ', 5-, 2,3', 6- and 2,3 ', 7-trisulfone 45 acids, l-amino4- (4 "-amino4'-benzoyl-aminoaniline) -anthraquinone-2,3'-disulfonic acid and the corresponding -2,3 ', 5-trisulfonic acid, l-amino-4- [4 '- (4 "-aminophenylazo) anilino] anthraquinone-2,2", 5-trisulfonic acid, l-amino4- (4'-amino-3'-carboxy-anilino) -anthraquinone-2,5 -disulfonic acid, l-amino4- (3'-amino-anilino) -anthraquinone-2,4 ', 5-trisulfonic acid and the corresponding 2,4'-disulfonic acid, l-amino4- [4' - (4 "-aminophenyl) -ani-lino] -anthraquinone-2,3 ", 5-trisulfonic acid, l-amino4- (4'-methylamino> anilinoanthraquinone-2,3'-disulfonic acid and the corresponding 2,3 ', 5-trisulfonic acid, l -Amino4- (4'-n-butylamino) -anili-noanthraquinone-2,3'-disulfonic acid, l-amino4- (4'-methylamino-3'-carboxyanilino> anthraquinone-2-sulfonic acid, l-amino4- (3rd '-ß-hydroxyethylamino) anilinoanthraquinone-2,5-disulfonic acid, l- (4'-aminoanilino> anthraquinone-2,3'-disulfonic acid and l-amino4- (4'-amino-2'-meth oxyanilino) anthraquinone-2,3'-disulfonic acid.

8. Phthalocyanine compounds of the formula

50

wherein Pc is a phthalocyanine nucleus, preferably copper phthalocyanine, cd -OH and / or -NH2, Z 'is a bridge member, preferably an aliphatic, cycloaliphatic or aromatic bridge, and n and m are each 1, 2 or 3 and are the same or different can, provided that n + m is not greater than 4.

The phthalocyanine series dye compounds which can be used as starting materials are preferably metal-containing phthalocyanines, such as copper phthalocyanine, which contain at least one water-solubilizing group, such as a sulfonic acid group, and at least one group of the formula -NHR, in which R is hydrogen or alkyl. The -NHR group or groups can be bonded directly or via a divalent bridge to the benzene rings of the phthalocyanine nucleus, for example via a -phenylene, -CO-phenylene, -SCh-phenylene, -NH-phenylene, -S-phenylene, -O-phenylene-, -CH2S-phenylene, -CHîO-phenylene-, -CH2-phenylene-, -SCHî-phenylene, -SChCHî-phenylene, -SChNRi-phenylene-, - CH2-, -SOzNRi-arylene-, -NRiCO-phenylene-, -NR1SO2-phenylene-, -SChO-phenylene, -CHîNRi-phenylene-, -CH2NH-CO-phenylene-, SChNRi-alkylene-, -CH2NRi-alkylene- , -CONRi-phenylene, -CONRi-arylene, -SO2 or a -CO bridge. In the above-mentioned divalent bridge members, R 1 is hydrogen, alkyl or cycloalkyl, arylene is a divalent aromatic, optionally z. B. by halogen, alkyl or alkoxy substituted radical, in which the terminal bonds can be bound to the same or different nuclei, and alkylene a divalent aliphatic radical, which can include heteroatoms, such as nitrogen, in the atomic chain, for example the radical -CH2CH2 -NH-CH2CH2-.

Examples of such divalent aromatic radicals, which are denoted by arylene, may be mentioned: aromatic nuclei, for example a benzene, naphthalene, acridine and carbazole nucleus, which can carry further substituents, and radicals of the formula

55

(26),

<S02-W> n

(s02nh-z'-nhr) m in which the benzene rings can carry further substituents and -D- denotes a bridging group, for example -CH = CH-, -NH-, -S-, -O-, -SO2-, -NO = N-, -N = N-, -NH-CO-NH-CO-NH-, -O-CH2CH2O- or

(25),

it n li I! -c c-

V

(27)

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Examples

3- (3'-amino4'-sulfophenyl> sulfamyl copper phthalocyanine-tri-3-sulfonic acid,

Di-4- (3'-amino4'-sulfophenyI) sulfamyl copper phthalocyanine di4-su! Fonic acid,

3- {3'-aminophenylsulfamyl) -3-sulfamyl copper phthalocyanine-di-3-sulfonic acid,

Copper phthalocyanine4-N- (4-amino-3-sulfophenyl) sulfonamide-4 ', 4 ", 4"' trisulfonic acid, cobalt phthalocyanine 4,4'-di-N- (4'-amino4'-sulfophenyl) carbonamide4 ", 4" '- dicarboxylic acid and copper 4- (4'-amino-3'-sulfobenzoyl) phthalocyanine.

Mixtures of phthalocyanines can also be used. For example, a mixture of approximately equal parts of copper phthalocyanine-N- (4-amino-3-sulfophenyl) sulfonamide trisulfonic acid and copper phthalocyanine di-N- (4-amino-3-sulfophenyl) sulfonamide disulfonic acid can be used.

9. nitro dyes of the formula z

i

02n-d-n-q (28),

where D is a naphthalene or benzene nucleus, which may be further substituted, the nitrogen atom N in the ortho position

8th

to the nitro group, Z is hydrogen or an optionally substituted hydrocarbon radical and Q is hydrogen or an organic radical bonded to the nitrogen by a carbon atom, and wherein Q and Z are not both 5 hydrogen and Q is to Z if Z is a hydrocarbon radical, or may be attached to D ortho to the nitrogen atom N to form a heterocyclic ring, and which contain at least one group of the formula -NHR, wherein R is hydrogen or alkyl; in particular 10 nitro dyes of the formula

, 5 y-nh-b-nhr (29),

no2

where V and B are monocyclic aryl nuclei and the nitro group in V is ortho to the NH group.

example

25 4-Amino-2'-nitro-diphenylamine-3,4'-disulfonic acid.

10. metal complexes of formazan dyes of the formula m-a-y,

/ 1

q — ce nm-A-Y ,,

R

i

-eh

(n = 1 or 2)

(30),

n in which Q is an organic radical, a nitro or cyano group, A and B radicals of diazo components of the benzene, naphthalene * or heterocyclic series and Yi and Y2 each have a substituent bonded in the o-position to the azo group and capable of complexing with a heavy metal mean and R has the meaning given. The radical Q is above all a benzene series radical, such as phenyl or sulfophenyl, or a low molecular weight alkyl radical, such as methyl, a low molecular weight alkanoyl group, a low molecular weight carbalkoxy group, preferably containing 1 to 4 carbon atoms, a benzoyl group or a heterocyclic radical, and A and B are preferably phenyl radicals substituted with sulfo, sulfonamido or alkylsulfonyl groups. The hydroxyl and carboxyl groups come into consideration as substituents Y1 and Y2. Suitable heavy metals are copper, chromium, cobalt and nickel.

Examples

Copper complex of 2'-carboxy-2 "-hydroxy-3" -amino-l, 3,5-triphenylformazan4 ', 5 ", 3'" - trisulfonic acid,

Copper complex of 2 ', 2 "-dihydroxy-3'-amino-5'-methyl-sulfonyI-l, 3,5-triphenyl-3", 5 ", 4"' - trisulfonic acid, copper complex of 2'-carboxy4'- amino-2 "-hydroxy-l, 3,5-triphenylformazan-3", 5 ", 2" '- trisulfonic acid,

Copper complex of 2'-hydroxy-2 "-carboxy4" '-amino-1,3,5-triphenylformazan4', 4 "-disulfonic acid,

Copper complex of 2 ', 2 "-dihydroxy-5-amino-l, 5-diphenyl-3-methylformazan-5', 3" -disulfonic acid,

Copper complex of 2'2 "-dihydroxy-5'-amino-l, 3,5-triphenyl-formazan-3 ', 3", 5 "-trisulfonic acid,

Copper complex of 2'-carboxy-3'-amino-2 "-hydroxy-3" '(1 "" -4o phenyl-3 "" -methyl-pyrazole-5 "" -onyl4 "" -azo) -l, 3rd , 5-triphenyl-formazan-3 ", 5", 2 "", 5 "" -tetrasulfonic acid,

Nickel complex of 2 ', 2-dicarboxy-l, 5-diphenyl-3- (m-amino-benzoyl) -formazan4', 4 "-disulfonic acid.

b) 2,4,6-trichloro-l, 3,5-triazine of the formula (5) cyanuric chloride 45 c) alkylene and arylene diamines of the formula (6) ethylenediamine,

n-propylenediamine,

n-butylenediamine,

1-methyl-n-propylenediamine,

so n-hexylenediamine,

2-ethyl-n-butylenediamine,

1,4-cyclohexane-bis- (methylamine),

1,3-diaminobenzene,

1,4-diaminobenzene,

55 l, 3-diamino4-chlorobenzene,

l, 3-diamino-4-methylbenzene,

l, 3-diamino-4-ethylbenzene,

1,3-diamino-4-methoxybenzene,

l, 3-diamino-4-ethoxybenzene,

60 2,6-diamino-naphthalene,

1,3-diamino-2,4,6-trimethylbenzene,

1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene,

4,4'-diaminodiphenyl (benzidine),

65 3,3'-dimethylbenzidine,

3,3'-dimethoxybenzidine,

3,3 'dichlorobenzidine,

3,3'-dicarboxybenzidine,

3,3'-dicarboxymethoxy-benzidine,

2,2'-dimethylbenzidine,

4,2'-diaminodiphenyl (diphenylin),

2,6-diaminonaphthalene4,8-disulfonic acid,

1,4-diaminobenzene-2-sulfonic acid,

1,4-diaminobenzene-2,5-disulfonic acid,

1,4-diaminobenzene-2,6-disulfonic acid,

l, 3-diaminobenzene-4-sulfonic acid,

1,3-diaminobenzene4,6-disulfonic acid,

1,4-diaminobenzene-2-carboxylic acid,

1,3-diaminobenzoil4-carboxylic acid,

1,4-diamino-2-methylbenzene,

4,4'-diaminodiphenyl oxide,

d) 2,4,6-trifluoro-l, 3,5-triazine of the formula (7) (cyanuric fluoride)

e) compounds of the formula (8)

1. alcohols methanol,

Ethanol,

Propanol,

Isopropanol,

Butanol,

Isobutanol,

sec-butanol,

Pentanol,

Hexanol,

ß-methoxyethanol,

ß-ethoxyethanol,

y-methoxypropanol,

y-ethoxypropanol,

y-propoxypropanol,

y-isopropoxypropanol,

2. Alkylmêrcaptane methyl mercaptan,

Ethyl mercaptan,

Propyl mercaptan,

Isopropyl mercaptan,

Butyl mercaptan,

Isobutyl mercaptan,

sec-butyl mercaptan,

tert-butyl mercaptan.

The following can be mentioned as diazotizable aromatic amines and couplable compounds which can be used according to processes a) and b) described above for the production of fiber-reactive dyes of the formula (1), in which D is the remainder of a sulfo-containing azo dye:

Diazo components

Aniline, o-, m- and p-toluidines, o-, m- and p-anisidines, o-, m- and p-chloroanilines, 2,5-dichloroaniline, a- and ß-naphthylamine, 2,5-dimethylaniline , 5-nitro-2-aminoanisole, 4-aminodiphenyl, aniIin-2,3- and 4-carboxylic acids, 2-aminodiphenyl ether, 2-, 3-or 4-aminobenzenesulfonamide, or -sulfomonomethyl- or -ethylamides or -sulfonedimethyl- or -sulfone diethylamide, dehydrothio-p-toluidine monosulfonic acid or dehydrothio-p-toluidine sulfonic acid, aniline-2-, -3- and 4-sulfonic acids, aniline-2,5-disulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 3-aminobenzo- trifluoride4-sulfonic acid, 4-chloro-5-methylaniline-2-sulfonic acid, 5-chloro4-methylaniline-2-sulfonic acid, 3-acetylaminoaniline-6-sulfonic acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-2- sulfonic acid, 3,4-dichloroaniline-6-sulfonic acid, 4-methylaniline-2-sulfonic acid, 3-methylaniline-6-sulfonic acid, 2,4-dimethoxyaniline-6-sulfonic acid, 4-methoxyaniline-2-sulfonic acid and 5-methoxy-lin-2-sulfonic acid, 2,5-dichloroaniline 4-sulfonic acid, 2-naphthyl-amine 4,8- and -6, 8-disulfonic acid, l-naphthylamine-2-, 4-, -5-, -6-or -7-monosulfonic acid, l-naphthylamine-3,6-disulfonic acid, 2-naphthylamine-3,6- and -5,7 -disulfonic acid, 2-naphthylamine-3,6,8-trisulfonic acid, m- and p-nitroaniline, 4-nitroaniline-2-sulfone-

624138

acid, 3-nitroaniline-6-sulfonic acid, m- or p-aminoacetanilide and 4-amino-2-acetylaminotoluene-5-sulfonic acid.

Coupling components:

3-cresol, phenol4-sulfonic acid, β-naphthol, 2-naphthol-6- or -7-sulfonic acid, 2-naphthol-3,6- or -6,8-disulfonic acid, 1-naphthol4-sulfonic acid, l-phenyl-3-methyl-5-pyrazolone, l- (4'-sulfophenyl> 3-methyl-5-pyrazolone, l- (2 ', 5'-dichloro4'-sulfophenyl) -3-methyl-5 -pyrazolone, 3-aminocarbonyl4-methyl-6-hydroxypyridone-2, l-ethyl-3-cyan or -3-chloro-4-methyl-6-hydroxypyri-don-2, l-ethyl-3-sulfomethyl4-methyl -6-hydroxypyridone-2,2,4,6-triamino-3-cyanopyridine, 2- (3'-sulfophenylamino) 4,6-diamino-3-cyanopyridine, 2- (2'-hydroxyethylamino) -3-cyan4- methyl-6-aminopyridine, 2,6-bis (2'-hydroxyethylamino) -3-cyano4-methylpyridine, 2-benzoylamino-5-naphthol-7-sulfonic acid, 1-benzoylamino-8-naphthol-3 , 6- or 4,6-disulfonic acid, phenol, p-cresol, acetoacetanilide and acetoacet-2-methoxyaniline-5-sulfonic acid, l- (4'-sulfophenyl) -pyrazolone- (5) -3-carboxylic acid, 3 -Methylpyra-zolon- (5), 4-hydroxyquinolone- (2), 8-acetylamino-l-naphthol-3-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 1-naphthol-4,6- or 4, 7-disulfonic acid.

The condensation of the 2,4,6-trichloro-l, 3,5-triazine of the formula (5) and the 2,4,6-trifluoro-l, 3,5-triazine of the formula (7) with the sulfo-containing dyes of Formula (4), the alkylene or arylene diamines of the formula (6) and the alcohols or alkymercaptans of the formula (8) or the diazotizable or couplable components containing an H-Ri-N group are preferably carried out in aqueous solution or suspension, at low temperature and with a weakly acidic, neutral to weakly alkaline pH. The hydrogen fluoride liberated during the condensation is advantageously continuously neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates. The intermediate products containing a diazotizable amino group are generally diazotized by the action of nitrous acid in aqueous serum mineral acid solution at low temperature, the coupling at weakly acidic, neutral to weakly alkaline pH values.

The dyes of the formula (1) are notable for high reactivity.

They are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, superpolyamide fibers and superpolyurethanes, but in particular cellulosic materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable both for the exhaust process and for dyeing according to the pad dyeing process, according to which the goods are impregnated with aqueous and, if appropriate, also salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, if appropriate with the action of heat.

They are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibers, e.g. B. of wool, silk or wool containing blended fabrics.

It is advisable to subject the dyeings and prints to a thorough rinsing with cold and hot water, if appropriate with the addition of a dispersing agent and promoting the diffusion of the unfixed portions.

In the examples below, the parts are parts by weight and the temperatures are given in degrees Celsius.

Example 1 :

31.4 parts of 8-amino-l-naphthol-3,6-disulfonic acid are first condensed with 18.5 parts of 2,4,6-trichloro-1,3,5-triazine. The primary condensation product obtained is then mixed with 21 parts of 1,4-diaminobenzene-3-sulfonic acid sodium

9

5

10th

15

20th

25th

30th

35

40

45

50

55

• 60

65

624138

10th

condensed salt and the condensation product obtained with the addition of 2N sodium hydroxide solution, the pH value at 6.5 a prepared from 17.3 parts of l-aminobenzene-2-sulfonic acid. holds.

diazo compound coupled at pH 7 to 8. When the condensation is complete, isolation is carried out using a red dye solution, and 15 parts of 2 parts of sodium chloride are now dripped at 15-20 ° C. The dye of the formula methoxy-4,6-difluoro-1,3,5-triazine, where one by simultaneous 5

C-OCH_

II 3 -n

It dyes cellulose fibers in wet-fast brilliant red tones. zol-2-sulfonic acid equivalent parts of those listed in column 4 are used instead of 8-amino-l-hydroxynaphthalene compounds and instead of 2-methoxy-4,6-difluorotriazine 3,6-disulfonic acid equivalent parts of those in column 2 of the - equivalent parts of the compounds mentioned in column 5, the following table 1, instead of so, dyestuffs with similar dyeing properties of 1,4-diaminobenzene-3-sulfonic acid are obtained, the equivalent parts of the shafts in 20 and those in column 6 called nuance.

Column 3 mentioned compounds, instead of 1-aminoben-

Table 1

No.

Coupling component

Diamine

Diazo component

Amine

Color on cotton

2nd

l-amino-8-hydroxy

1,2-diamino

1-aminobenzene

2-methoxy4,6-di-

red

naphthalene-3,6-di-

äthan

2,5-disulfone

fluoro-l, 3,5-triazine

sulfonic acid

acid

3rd

dito

1,3-diamino-benzene-4-sul-fonic acid

2-aminonaph-

thalin-l, 5-di-

sulfonic acid ditto red

4th

l-amino-8-hydroxy

dito

1-aminobenzene

2-ethoxy4,6-

red

naphthalene-4,6-di-

2,4-disuIphone

difluoro-1,3,5-triazine

sulfonic acid

acid

5

l-amino-8-hydroxy

naphthalene-3,6-di-

sulfonic acid ditto

2-aminonaph-thalin-l-sulfonic acid ditto bluish red

6

1- (4'-aminobenzoyl-amino) -8-hydroxy-naphthalene-3,6-disulphonic acid

2-aminonaph-

thalin-l, 5-di sulfonic acid ditto red

7

2-amino-5-hydroxy

1,4-diamino

l-aminobenzene-2-

2-methoxy4,6-di-

orange

naphthalene-l, 7-di-

benzene-3-sul-

sulfonic acid fluoro-l, 3,5-triazine

sulfonic acid fonic acid

8th

2-amino-5-hydroxy

1,3-diamino

1-aminobenzene

ditto orange

naphthalene-7-sulfone

benzene-4-sul-

2,5-disulfone

acid fonic acid

9

2-amino-5-hydroxy

1,2-di ^ fiino-

1-aminobenzene

2-methoxy4,6-di-

orange

naphthalene-7-sul-

äthan

2-sulfonic acid fluoro-l, 3,5-triazine

fonic

10th

2-amino-5-hydroxy

1,3-diamino

2-aminonaph-

2-methylthio4,6-

orange

naphthalene-7-sul-

benzene-4-sul-

thalin-l, 5-di-

difluoro-l, 3,5-triazine

fonic acid fonic acid sulfonic acid

11

2-amino-8-hydroxy

ditto ditto

2-isopropoxy4,6-

yellowish

naphthalene-6-sul-

difluoro-l, 3,5-triazine red

fonic

Example 2:

31.4 parts of 8-amino-1-naphthol-3,6-disulfonic acid are condensed at 0 ° and pH 1 to 2 with cyanuric chloride. An aqueous solution of 21 parts of the sodium salt of 2,4-diaminobenzenesulfonic acid is added to the suspension of the primary condensation product and condensation is carried out at a pH of 4 to 5. After the condensation has ended, 18.7 parts of 2-amino are converted into the diazo compound -5-methylbenzenesulfonic acid coupled at pH 6 to 6.5. 19.1 parts of 2- (n-propoxy) -4! 6-difluoro-l, 3,5-triazine are now added dropwise to the red dye solution obtained.

The hydrogen fluoride released during the condensation is continuously neutralized by adding sodium carbonate solution. After the condensation has ended, the reaction product is isolated as a red dye powder by evaporating the water under reduced pressure. The dye dyes cellulose fibers in real, bluish red tones. 65 dyes with similar dyeing properties are obtained if the difluorotriazinyl compounds listed below are used instead of 2- (n-propoxy> 4,6-difluoro-l, 3,5-triazine) for the final condensation step.

11

624138

No. difluorotriazinyl derivative

Parts

1 2-methoxy-4,6-difluoro-l, 3,5-triazine 14.7

2 2-ethoxy4,6-difluoro-l, 3,5-triazine 16.1

3 2-methylthio4,6-difluoro-l, 3,5-triazine 16,3

4 2- (2 '-ethoxyethoxy) 4.6-difluoro-1,3,5-triazine 20.5

5 2-isopropoxy4,6-difluoro-l, 3,5-triazine 19.1

6 2-n-Butoxy4,6-difluoro-l, 3,5-triazine 18.9

Example 3:

9.42 parts of 6-amino-1-naphthol-3,5-disulfonic acid are condensed with 5.55 parts of cyanuric chloride. The primary condensation product obtained is condensed with 6.3 parts of 1,4-diaminobenzene-2-sulfonic acid. 4.9 parts of 2-methoxy-4,6-difluoro-1,3,5-triazine are added dropwise to the solution of the condensation product thus obtained, the pH being kept at 7 by simultaneous addition of 2N sodium hydroxide solution . To the solution of the coupling component of the formula thus obtained

SO ^ E

a suspension of the diazonium compound prepared in a customary manner from 5.19 parts of 2-aminobenzene-1-sulfonic acid .20 is then added and the mixture is coupled at pH 6 to 7. After the coupling has ended, the dye is precipitated by adding sodium chloride. A dye powder is obtained by drying and grinding, with which cellulose fiber materials from aqueous bath are dyed in real 25 orange tones.

If instead of 6-amino-1-naphthol-3,5-disulphonic acid, equivalent parts of the compounds listed in column 2 of the table below are used, instead of 1,4-diamino-benzene-2-sulfonic acid, the compounds mentioned in column 3 - 30 gen, instead of 2-methoxy4,6-difluoro-l, 3,5-triazine, the fluorotriazine compounds listed in column 4, and s0, e finally, instead of 2-aminobenzene-l-sulfonic acid, the diazo compounds mentioned in column 5, see above this gives dyes which dye fabrics made of cellulose fibers in the shade mentioned in column 6.

The letters AG in column 4 mean the reactive components: A: 2-methoxy4,6-difluoro-l, 3,5-triazine B: 2-ethoxy4,6-kiifluoro-l, 3,5-triazine C: 2-n- Propoxy4,6-difluoro-l, 3,5-triazine D: 2-isopropoxy4,6-difluoro-l, 3,5-triazine E: 2- (2'-methoxyethoxy) 4,6-difluoro-l, 3,5- triazine F: 2- (2'-ethoxyethoxy) 4.6-difIuor-l, 3,5-triazine G: 2-methylthio4,6-difluoro-l, 3,5-triazine.

Table 2

I.

II

III

IV

V

VI

No.

Coupling component

Diamine

Reactive component

Diazo component

Color on cotton

1

1 - (6 '-Amino4', 8 '-di-sulfonaphth-2'-yl) -3-methylpyrazolon- {5)

1,3-diamino4-methyl-benzene

A

l-aminobenzene-2,5-disulphonic acid yellow

2nd

8-amino-1-naphthol-3,6-disulfonic acid

1,4-diaminobenzene

D

2-aminonaphthalene-1,5-disulfonic acid red

3rd

dito

1,4-diaminobutane

B

2-aminobenzene-l-sulfonic acid red

4th

dito

1,4-diaminobenzene-2-sulfonic acid

C.

ditto red

5

ditto 1,4-diaminobenzene-2-carboxylic acid

F

ditto red

6

dito

1,4-diaminobenzene-2-sulfonic acid

A

2-amino-5-methylbenzene-1-sulfonic acid red

7

ditto ditto

A

4-chloroaniline-2-sulfonic acid red

8th

ditto ditto

E

4-aminobenzoic acid red

9

8-amino-1-naphthol-3,5-disulfonic acid

1,3-diamino4-methoxy benzene

F

2-aminobenzene-l-sulfonic acid red

10th

8-amino-1-naphthol-3,5-disulfonic acid

2,6-diaminonaphthalene-4,8-disulfonic acid

A

2-aminobenzene-l-sulfonic acid red

11

8- (4'-aminobenzoyl-aminoM-naphthol-

3,6-disulfonic acid 1,3-diaminobenzene4-sulfonic acid

G

ditto red

12

2-amino-5-naphthol-7-

1,3-diaminobenzene4-

A

1-aminobenzene-2,4-di-

orange

sulfonic acid sulfonic acid

sulfonic acid

13

ditto ditto

A

2-aminonaphthalene-3,6,8-trisulfonic acid

Scarlet fever

14

dito

1,3-diaminobenzene

F

dito

Scarlet fever

624138

12th

I II

No. coupling component

III

Diamine

IV V

Reactive diazo component

VI

Color on cotton

15 8-amino-1-naphthol-3,6-disulfonic acid

16 2-Methylamino-5-naphthol-7-sulfonic acid

17 ditto

18 ditto ditto l, 4-diaminobenzene-2-sulfonic acid ditto l, 3-diaminobenzene 4-sulfonic acid

E B

4-aminobenzoic acid red

2-aminobenzene-l-sulfonic acid orange l-amino-5-methoxy-scarlet benzene-l-sulfonic acid ditto scarlet fever

Example 4: 9.25 parts of cyanuric chloride in acetone at 0 °, stirred at 0 ° to

12.56 parts of 8-amino-l-naphthol-3,6-disulfonic acid are used to complete the condensation, the pH value at 6 being obtained by simultaneous addition of 7.4 parts of cyanuric chloride with 7.4 parts of cyanuric chloride as described in Example 2 , 5 holds. Then densified and the condensation product obtained with the dia-20, a solution of 10.8 parts of 1,3-diaminobenzene in zo compound from 6.92 parts of 1-aminobenzene-2-sulfonic acid is added to water and condensed at room temperature at the same coupling. A solution of 8.4 parts of the sodium pH is then added. The intermediate dye obtained is precipitated by salting the 1,4-diaminobenzene-3-sulfonic acid and then sprinkling in sodium chloride, and the mixture is filtered off and weighed at 10 to 12 °, the pH of the solution being determined by that in water at 0 ° dissolved To this solution is added dropwise at 6 stops with the addition of 2N sodium hydroxide solution. 10.25 parts of 2- (2'-ethoxyethoxy) 4,6-difluoro-1,3,5-tria dye solution are now added dropwise at 0 ° to the red 25 20 minutes obtained, 5.88 parts of 2-methoxy-4, 6-zin, with difluoro-1,3,5-triazine being added by simultaneous addition of 2N sodium hydroxide solution, the pH being kept at 7 by simultaneous addition of 2N sodium hydroxide solution from the aqueous dye solution, the pH being 6, 5 holds. The dye is spray-dried by sprinkling potassium chloride and the entire dye solution is obtained. It dyes cotton in wet-fast scarlet tones, dark red dye powder, with which strong red tones are obtained on cellulose fibers made from 30 other reactive dyes, according to the information given by the aqueous liquor. of the example, if you take the one made up of the components

Aminoazo dye of column 2 with cyanuric chloride, Example 5: then first with the diamine of column 3, and

10.15 parts of 2-amino-5-methoxybenzenesulfonic acid are finally condensed with the reactive component of column 4 and the suspension obtained is evenly densified to form a 35. The letters AG correspond to the well-stirred solution of 13.05 parts of the sodium salt of the compounds as listed in Example 3. The loaded dyes that flow into the 2-amino-5-hydroxynaphthalene-7-sulfonic acid dye cotton or regenerated cellulose. The pH is kept constant during the addition at 8.5 fibers in the shade indicated in the last column. After the coupling has been completed, a solution is added

Table 3

No aminoazo dye diamine reactive hue component

11

2-amino4-acetylaminobenzenesulfonic acid -

1-naphthol4,7-disulfonic acid (saponified)

2-naphthylamine-3,6,8-trisulfonic acid - l-amino-3-ureidobenzene

2-amino-4-acetylaminobenzenesulfonic acid - 1-ethyl

3-sulfomethyl4-methyl-6-hydroxypyridon- (2) (saponified)

2-Naphthylamine4,6,8-trisulfonic acid - aniline - aniline

2-amino-5-nitrobenzenesulfonic acid - l- (2 ', 5'-

Dichlor4'-sulfophenyl) -3-methylpyrazolone- (5)

(reduced)

1-aminobenzene-2-sulfonic acid - 4-amino-l-hydroxy-naphthalene-3-sulfonic acid

2-Amino-5-methoxybenzenesulfonic acid - methyl-amino-l-hydroxynaphthalene-3-sulfonic acid 2-naphthylamine 4,8-disulfonic acid -> ■ l-amino-3-methylbenzene l-aminobenzene-2,5-disulfonic acid - l- (3rd 'Amino-phenyl) -3-carboxypyrazolone (5) l-aminobenzene-2-sulfonic acid - 8- (4'-nitro-benzoyl-amino) -l-naphthol-3,6-disulfonic acid (reduced)

1,4-phenylenediamine

3-sulfonic acid ditto ditto

1,3-diamino4-methyl-benzene

1,4-diaminobenzene

B C D

F G

Scarlet reddish yellow greenish yellow orange yellow

1,4-phenylenediamine

3-sulfonic acid ditto

1,4-phenylenediamine-3-sulfonic acid 1,4-phenylenediamine-3-sulfonic acid 1,4-diamine butane

A A F F B

orange scarlet yellow yellow red

13

624138

No aminoazo dye

11 2-Amino-5-methylbenzenesulfonic acid - 6-ethyl-amino-1-naphthol-3-sulfonic acid

12 2-aminonaphthalene-1,5-disulfonic acid - 6-acetylamino-l-naphthol-3-sulfonic acid (saponified)

13 2-aminonaphthalene-3,6,8-trisulfonic acid - 6-amino-1-naphthol-3-sulfonic acid

Diamine reactive color component

1,4-phenylenediamine-A orange

3-sulfonic acid

1,4-phenylenediamine-A orange

3-sulfonic acid ditto A scarlet fever

Example 6:

15 parts of 2-methoxy-4,6-difluoro-1,3,5-triazine are added dropwise to a solution of 21 parts of the sodium salt of 1,3-diaminobenzene-6-sulfonic acid and the mixture is stirred at room temperature, the temperature at which Condensation hydrogen fluoride formed is continuously neutralized by dropping 2N sodium hydroxide solution. As soon as 1,3-diaminobenzene-6-sulfonic acid is no longer detectable, the reaction mixture is cooled to 0 ° 15 and a solution of 18.5 parts of 2,4,6-trichloro-1,3,5-triazine in 50 is added Parts by volume of acetone and stirred at 0 °, keeping the pH at 6-7. When all the trichlorotriazine has been used up, a solution of the aminoazo dye of the formula is added

/ s03h ch.

h2n

• ^

a -à / ch "so-h

/ \ / vt, t / x / 2 3 • n = n - • •

II I

ho'Y "0

c2h5

to, warms to 25 to 30 ° and condenses at a pH of 6 to 7, which is maintained by the continuous addition of 2N sodium hydroxide solution.

(49 parts neutral sodium salt)

The reactive dye of the formula ch is isolated from the yellow solution.

0-cx yc-nh-V> -

* V

\ / i

• so3h .A.,

NH-Ç 'C-NH- «

(> -so3h

"c i

Cl n = n-

ch.

/% / ch2s03h - • •

/ V ^

ho, 0 c2h5

(33)

by sprinkling in sodium chloride. After column 2 of Table 4 below, components obtained

Drying and grinding a yellow dye powder, with which Celten, instead of 1,3-diaminobenzene-6-sulfonic acid equivalent lulose fibers, are colored in brilliant wet-fast yellow tones. Parts of the compounds listed in column 3 and instead of the. 55 of the aminoazo-pyridone dye equivalent parts of the in

Dyes of similar properties are obtained analogously to column 4 mentioned amino dyes.

the way of working described above, if instead of Here the letters of column 2 denote the same

2-methoxy-4,6-difluoro-l, 3,5-triazine equivalent parts of the reactive components as in Examples 3 and 5.

Table 4

I.

II

III

No reactive diamine component

IV

Amino dye

Color tone on cellulose

1

1,3-diaminobenzene-4-sulfonic acid l-amino-3-acetylaminobenzene-6-sulfonic acid -1 - (2 ', 5' -dichlor4 '-sulfophenyl) -3-methyl-pyrazolone- (5), (saponified)

yellow

624138

14

I II

No. reactive

III

Diamine component

IV

Amino dye

Color tone on cellulose

3rd

4th

5

G

D

F E

8 b

9 D

10 F

11 A

12 A

13 D

14 G

15 A

16 E.

17 A

18 A.

1,4-diaminobenzene

3-sulfonic acid

1,3-diaminobenzene

4-sulfonic acid

1,3-diaminobenzene-4-sulfonic acid

1,3-diaminobenzene-4-sulfonic acid

1,4-diaminobenzene-3-sulfonic acid

1,4-diaminobenzene

3-sulfonic acid

1,3-diaminobenzene

4-sulfonic acid

1,3-diaminobenzene-4-sulfonic acid

1,4-diaminobenzene

3-sulfonic acid

1,3-diaminobenzene

4-sulfonic acid

1,4-diaminobenzene-3-sulfonic acid

1,3-diaminobenzene-4-sulfonic acid

1,3-diaminobenzene-4-sulfonic acid

1,4-diaminobenzene-3-sulfonic acid ditto

1,2-diaminoethane l, 4-diamino-3-methyl-benzene

1-amino-3-acetylaminobenzene-6-sulfonic acid - 1 - (4 ', 8' -disulfonaphthyl-2 '-) - 3-methyl-pyrazolone- (5), (saponified) 2 {4'-amino-2' -ureidophenylazo) -naphthalene-3,6,8-trisulfonic acid

2- (4'-amino-2'-acetylaminophenylazo) -naphthalene-4,8-disulfonic acid l-amino-3-nitrobenzene-6-sulfonic acid - 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, (reduced)

1-amino-3-nitrobenzene-6-sulfonic acid -

2-sulfoacetylamino-8-hydroxynaphthalene-6-sulfonic acid (reduced)

l-amino-3-acetylaminobenzene-6-sulfonic acid - l-hydroxynaphthalene-3,6-disulfonic acid (saponified)

1-aminobenzene-2,4-disulfonic acid - l- (3'-nitro-benzoylamino> 8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

2-aminonaphthalene-l, 5-disulfonic acid l- <4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced) l-amino-3-nitrobenzene-6-sulfonic acid - * l-benzoylamino-8-hydroxynaphthalene4 , 6-disulphonic acid (reduced)

1 - Amino-4- (2'-methyl-3 '-amino-anilino) -anthraquinone-2,5'-disulfonic acid l-Amino4- (4'-N-methylaminomethyl-anilino> anthraquinone-2,2'-disulfonic acid OH

i ij l / \

yellow yellow yellow orange yellowish red redish orange red red red blue blue so h i

- •

/

-n = n-

-0-

your ho3s

45

-Cu

I.

1

so3h reddish blue

N-

: n "

J \ / \

i '• î

\ AA

i so3H

so3h y

0

.-1

Cu

0

1

NH i

V

h03s- \ / / \

V /

i nh

—N = n-

/ v ^

I II% / * \ ^

• •

i rS03H

blue so3h

2-Amino-l-hydroxynaphthalene-4,8-disulfonic acid - 8-amino-l-hydroxynaphthalene-3,6-disulfonic acid, Cu complex

3- (3'-aminophenylsulfamyl) -3-sulfamyl copper-phthalocyanine-di-3-sulfonic acid

4-amino-2'-nitrodiphenylamine-3,4'-disulfonic acid

2'-carboxy4'-amino-2 "-hydroxy-l, 3,5-

triphenylformazan-3 ", 5", 2 "-trisulfonic acid,

Cu complex blue greenish blue yellow blue

15

624138

Example 7: Staining Instructions I

A solution of 210 parts of the sodium salt and 2 parts of the dye obtained in Example 1 are added.

zes of 1,3-diaminobenzene-6-sulfonic acid with 191 parts of 2-isodes with the addition of 0.5 part of propoxy-4,6-difluoro-l, 3,5-triazine m-nitrobenzenesulfonate and stirred at 10 to 15 °, with sodium dissolved in 100 parts of water. A cotton fabric is impregnated with the resultant solution of the hydrogen fluoride released during the condensation, so that it increases by 75% of its weight, neutralized by the dropwise addition of 2N sodium hydroxide solution, and then dried.

becomes. As soon as 1,3-diaminobenzene-6-sulfonic acid is no longer re-impregnated, the tissue can be warmed to 20 ° C, the reaction mixture is cooled to 0 °, 185 ml of solution are added, 5 grams of sodium hydroxide and 300 per liter Parts of ground cyanuric chloride are added and condensed at pH 6 grams containing sodium chloride, squeezed to 75% by weight until 7 no more cyanuric chloride is present. Now add io take, steam the dyeing for 30 seconds at 100, an aqueous solution of 210 parts of the sodium salt which rinses to 101 °, soaped for a quarter of an hour in 1,3-diaminobenzene-6-sulfonic acid and condenses at one 0.3% boiling solution of an ion-free detergent, temperature of 15 ° at pH 6 further. Rinsed to the solution obtained and dried.

250 parts by volume of 4N sodium nitrite solution are then added and, after cooling to 0 °, 250 parts by volume of 32% hydrochloric acid are added. '5 Staining Instructions II

After destroying any excess of nitrous 2 parts of the dye obtainable according to Example 1,

Acid by adding sulfamic acid is added to the diazo- dene dissolved in 100 parts of water.

Compound 361 parts of 8-acetylamino-l-hydroxynaphthalene-3,6-. The solution is added to 1900 parts of cold water, 60 are added

disulfonic acid and increases the pH of the solution with all parts of sodium chloride and goes with 100 parts of a tree addition of sodium hydroxide solution to 7. 20 woolen fabric is added to this dyebath.

a deep red dye solution is obtained, from which the temperature is increased to 40 ° by addition, after 30 minutes of sodium chloride, filtering off, drying and grinding, the 40 parts of calcined soda and another 60 parts of sodium dye are obtained as red powder. It colors textile material made of chloride to be added. The temperature is kept at 30 minutes cellulose in brilliant, wet-fast red tones. at 40 ° C, then rinses and soaps the dyeing for 15 minutes

25 th in a 0.3% boiling solution of an ion-free detergent, rinse and dry.

G

Claims (4)

624138 PATENT CLAIMS 1. Process for the production of fiber-reactive dyes of the formula D — il — C p ì ®1 N-B-N-C ^ C-A r, Cl R ^ (1), 3 i in which D is the residue of an organic dye containing sulfo groups, R 1, R 2 and R 3 independently of one another are hydrogen 15 or alkyl having 1 to 4 carbon atoms, B is an alkylene or arylene residue and A is an alkoxy, alkoxyalkoxyl or alkylthio group, characterized in that that you have a sulfo-containing organic dye of the formula D-NH I R, (4), wherein D and Ri have the meanings given under formula (1>), 2,4,6-trichloro-l, 3,5-triazine of the formula 25th 30th 3. A process for the preparation of fiber-reactive dyes of the formula (1), in which D is the remainder of a sulfo-containing azo dye, characterized in that a diazotizable aromatic diamine containing an -N-Ri-H group, wherein Ri in which 1 has meaning given, a coupling component, wherein the diazotizable aromatic diamine and the coupling component together contain at least one sulfo group, 2,4,6-trichloro-1,3,5-triazine of the formula (5), an alkylene or arylene diamine of the formula (6), wherein R2, R3 and B have the meanings given in claim 1, 2,4,6-trifluoro-l, 3,5-triazine of the formula (7) and a compound of the formula (8), in which A is the has the meaning given in claim 1, by diazotization, coupling and condensation to give the finished fiber-reactive dye of the formula (1). 4. A process for the preparation of fiber-reactive dyes of the formula (1), in which D is the remainder of a sulfo-containing azo dye, characterized in that a coupling component containing an -N-Ri-H group, wherein Ri is the one specified in claim 1 A diazotizable aromatic amine, the coupling component and the diazotizable aromatic amine together containing at least one sulfo group, 2,4,6-trichloro-1,3,5-triazine of the formula (5), an alkylene or arylenediamine of the formula (6), in which R2, R3 and B have the meanings given in claim 1, 2,4,6-trifluoro-1,3,5-triazine of the formula (7) and a compound of the formula (8), in which A is the has the meaning given in claim 1, by diazotization, coupling and condensation to give the finished fiber-reactive dye of the formula (1). (5), N. 35 Cl is an alkylene or arylenediamine of the formula hn-b -nh