CH615192A5 - Process for the preparation of novel aromatic amines - Google Patents

Description

615 192

2nd

PATENT CLAIMS 1. Process for the preparation of new aromatic amines of the formula:

with a sulfonating agent to an amine of the formula:

(1)

10th

wherein R1 is H, CH3, C2H5, OCH3, OC2H5 or Cl and R2 is H or, if R1 is CH3, can also be H, CHb or Cl, characterized in that an aminophosphonic acid of the formula:

(2)

reacted with a sulfonating agent.

2. The method according to claim 1 for the preparation of 2-amino-4-phosphonobenzenesulfonic acid.

3. The method according to claim 1 for the preparation of 2-methoxy-3-amino-5-phosphonobenzenesulfonic acid.

4. Process for the preparation of new azo dyes which have one or more radicals of the formula:

45

(2D

contain, characterized in that an amino phosphonic acid of the formula:

(2)

(1)

15

reacted, the amine of formula 1 diazotized and the resulting diazonium compound coupled with a coupling component.

5. The method according to claim 4 for the production of 20 azo dyes of the formula

30th

SO ^ H n = n-e1

(6)

wherein E1 represents the remainder of a coupling component E] H.

6. The method according to claim 5 for the production of new monoazo dyes of the formula:

A2-N = N-E1

wherein A2 is 2-sulfo-5-phosphonophenyl or 2-methoxy-3-sulfo-5-phosphonophenyl and E1 is free of phosphonic acid groups and represents the remainder of a pyrazolone, a naphtholsulfonic acid, an N-acetylnaphtholsulfonic acid or a pyridone.

7. The method according to claim 4 for the production of new disazo dyes of the formula:

50

n = n-m-n = n-e

(7)

fi "in which E1 has the meaning given in claim 5 and M represents the remainder of an amine coupling in the p-position, characterized in that (a) an aromatic amine of the formula 1 is diazotized and coupled with an amine of the formula HMNH2 coupling in the para position and (b) the aminoazo compound formed in step (a) is diazotized and coupled with a coupling component of the formula EJH.

8. The method according to claim 7 for the production of new disazo dyes of the formula:

3rd

615192

A2-N = N-M-N = N-E1

wherein A2 has the meaning given in patent claim 6, M represents the remainder of one of the following amine coupling amines: s o- and m-toluidine

0- and m-anisidine cresidine 2,5-xylidine

2,5-dimethoxyaniline io m-aminoacetanilide m-aminophenylurea

1-Naphthylamine-6- and -7-sulfonic acid and E1 is free of phosphonic acid groups and represents the remainder of a pyridone, a pyrazolone, an l-amino-8-naph-isolsulfonic acid or an N-acetyl derivative thereof.

9. The method according to claim 4 for the production of new disazo dyes of the formula:

n = n-e -n = n-a in which E2 is the remainder of a coupling component E2H2 capable of coupling twice and A is a second remainder of the formula:

(9)

po3h2

which may be the same as or different from the first residue of this type shown in Formula 8, characterized in that one mole of a diazonium compound from an aromatic amine of Formula 1 and one mole of a diazonium compound from the same or different one in any order aromatic amine of formula 1 couples with a coupling component of formula E2H2.

10. The method according to claim 9 for the production of new disazo dyes of the formula:

wherein E2 represents the rest of l-amino-8-naphthol-3,6-disulfonic acid or bis- (5-hydroxy-7-sulfonaphth-2-yl) urea.

11. The method according to claim 4 for the production of new dis- or poly-azo dyes of the formula:

n = n-e2-n = n-a1 (11)

P ° 3H2

wherein E2 has the meaning given in claim 9 and A1 means the residue of a diazotizable aromatic amine of the formula A ^ NHz, that of the amine of the formula:

(8) 25

30th

is different, characterized in that one mole of a diazonium compound from an aromatic amine of the formula 1 and one mole of a diazonium compound from an aromatic amine which is different from the amines of the formula 1 are coupled with a coupling component of the formula E2H2 in any order.

12. The method according to claim 11 for the production of new dis- or poly-azo dyes of the formula:

45

A2-N = N-E2-N = N-A>

(12)

in which A1 has the meaning given in claim 11, A2 has the meaning given in claim 6 and E2 means the rest of l-amino-8-hydroxynaphthalene-4-sulfonic acid or -3,6- or -4,6-disulfonic acid, where, if A2 is 2-methoxy-3-sulfo-5-phosphonophenyl, the group of the formula A2-N = N- must be ortho-divided to the hydroxyl group in E2.

n-e ~ -n = n

(10) Process for the Production of New Aromatic Amines 60 The present invention relates to a process for the production of new aromatic amines containing phosphonic acid groups.

The patentee is not aware of any publication on compounds having a single benzene ring with amino, sulfo-65 and phosphono substituents. From the US PS

No. 2,799,701, however, naphthalene derivatives are known which have such substituents on two rings.

Aminobenzenesulfonic acids are naturally extremely po3h2

615192

4th

well known, and also m-aminobenzene phosphonic acid is e.g. B. from GB-PS No. 1 411 306 known. The use of these compounds for the preparation of azo dyes is generally known.

An unsubstituted sulfobenzene phosphonic acid is known from US Pat. No. 2,776,985.

According to the invention, aromatic amines of the formula:

R

nh prepared in which R1 is H, GHb, C2H5, OCH3, OC2H5 or Cl and R2 is hydrogen or, if R1 is CH3, can also be H, CH3 or Cl.

It can be seen that the preferred compounds of formula 1 usually carry the groups R1 and R2 in the ortho and / or para position to the amino group because of the steric and directing influences, and that the S03H group usually also in the ortho or para position to the amino group stands.

Examples of preferred aromatic amines of Formula 1 are the following:

5-methyl-4-amino-2-phosphonobenzenesulfonic acid

5-ethyl-4-amino-2-phosphonobenzenesulfonic acid

5-methoxy-4-amino-2-phosphonobenzenesulfonic acid

5-ethoxy-4-amino-2-phosphonobenzenesulfonic acid

5-chloro-4-amino-2-phosphonobenzenesulfonic acid

5-methyl-2-amino-4-phosphonobenzenesulfonic acid

5-ethyl-2-amino-4-phosphonobenzenesulfonic acid

5-methoxy-2-amino-4-phosphonobenzenesulfonic acid

5-ethoxy-2-amino-4-phosphonobenzenesulfonic acid

5-chloro-2-amino-4-phosphonobenzenesulfonic acid

3,5-dimethyl-2-amino-4-phosphonobenzenesulfonic acid

3-chloro-5-methyl-2-amino-4-phosphonobenzenesulfonic acid

Particularly preferred aromatic amines of the formula 1 are 2-amino-4-phosphonobenzenesulfonic acid and 2-methoxy-3-amino-5-phosphonobenzenesulfonic acid.

The process according to the invention for the preparation of aromatic amines of the formula 1 is characterized in that an aminophosphonic acid of the formula:

r

Nh wherein R1 and R2 have the meanings given above, treated with a sulfonating agent.

Any conventional sulfonating agent and sulfonation conditions can be used provided they achieve the desired sulfonation. For example, oleum can be used as a sulfonating agent at a temperature chosen in direct relation to its concentration; e.g. B. 20% oleum can be used at temperatures of 140 to 180 ° C.

The following are mentioned as examples of aminosulfonic acids of formula 2:

3 - aminobenzene phosphonic acid 4- or 6-methyl-3-aminobenzene phosphonic acid 4- or 6-ethyl-3-aminobenzene phosphonic acid 4- or 6-methoxy-3-aminobenzene phosphonic acid 4- or 6-ethoxy-3-aminobenzene phosphonic acid 4- or 6-chloro 3-aminobenzenephosphonic acid 2,5-dimethyl-3-aminobenzenephosphonic acid 2-chloro-3-amino-5-methylbenzenephosphonic acid.

The above compounds, many of which are known, can conveniently be obtained by using an aromatic compound of the formula:

"O

reacted with phosphorus trichloride in the presence of a Friedel-Crafts catalyst and then hydrolyzed and oxidized to give the phosphonic acid, which is then nitrided and reduced to obtain the aminophosphonic acid of formula 2. If R1 is OCHs or OC2H5, the compound of the formula 3 can also be reacted with P2S5 and then hydrolyzed, nitrated and reduced in order to obtain an aminophosphonic acid of the formula 2 in which R1 is OCH3 or OC2H5.

The aromatic amines of formula 1 prepared according to the invention can be isolated by any conventional method; e.g. B. the sulfonation mixture can be diluted with water and the precipitated product filtered off and washed with water.

The aromatic amines of formula 1 are valuable chemical intermediates, e.g. B. in the production of phosphonic acid-containing dyes. Such dyes usually have good water solubility because they contain both phosphonic acid and sulfonic acid groups. They can generally be used for dyeing or printing textiles that can be dyed or printed with dyes that are solubilized by anionic groups, such as. B. natural and synthetic polyamide materials, such as wool, silk, poly-hexamethylene adipamide and polycaproimide, but in particular natural or regenerated cellulose textiles, e.g. B. cotton, linen and viscose rayon; in the case of cellulose textiles, they are preferably fixed on the fiber by in the presence of a carbodiimide, e.g. As cyanamide or dicyandiamide, heated to a temperature of 95 to 205 ° C, for example by means of the method described in British Patent No. 1411 306.

A preferred group of dyes of the above type comprises azo dyes which have one or more radicals of the formula: 2

R

n = n-

5

10th

is

20th

25th

30th

35

40

45

50

55

60

65

5

615 192

contain. According to the invention, these dyes are prepared by using an aminophosphonic acid of the formula:

(2)

resulting dye contains two residues of formula 4 above linked by the residue of a compound capable of coupling twice or by a residue formed by coupling and subsequent condensation reaction; e.g. B. are an amino group in the rest of each coupling component through a polyacyl group, a carbonyl group or a monocyclic or polycyclic heterocyclic group, z. B. a remainder of the formula:

-CO-

-CO-CH = CH-CO—

-CO-CóH-t-CO

or a remainder of the formula:

with a sulfonating agent to an amine of the formula:

(1)

reacted, the amine of formula 1 diazotized and the resulting diazonium compound coupled with a coupling component.

Such dyes can be represented by the formula:

n = n-e

Tr or-Tr-D3-Tr where Tr is 6-chloro-s-triazin-2,4-ylene and Ü3 is a diamine residue.

20 Special classes of the novel dyes of the formula 5 obtainable according to the invention are: (1) monoazo dyes of the formula

25th

30th

(6)

are reproduced, wherein E represents the rest of a coupling component.

The symbol E in formula 5 can mean a large number of residues, not only simple residues of a coupling component, but also more complicated residues which, in corresponding cases, result from modification of the dye obtained during the coupling, e.g. B. by diazotization and / or coupling to form polyazo dyes or by connecting two dye molecules by means of a suitable reaction.

In the simpler cases, the remainder E represents the remainder of a coupling component, e.g. B. the rest of a naphthol, aminonaphthol or acylaminonaphthol or an o- or p-coupling amine of the benzene or naphthalene series, an acetoacetarylide, pyrazolone, aminopyrazole, phenol, hydroxypyridone or hydroxypyrimidine, the rest substituents, z. B. halogen atoms, alkyl, alkoxy, carboxyl or sulfo groups and / or aromatic azo radicals. More complicated residues result as a result of further coupling and / or condensation reactions, so that the one in which E1 means the rest of a coupling component E! H.

Examples of coupling components which can give the remainder E1 are:

40 pyrazolones, e.g. B. 3-methyl-5-pyrazolone l-phenyl-3-methyl-5-pyrazolone (5) l-phenyl-3-methyl-5-pyrazolone-2 '-, - 3'-

and -4'-sulfonic acid l-phenyl-5-pyrazolone-3-carboxylic acid 45 1 -phenyl-3-aminocarbonyl-5-pyrazolone l- (2 /, 5'-dichloro-4'-sulfophenyl) -3-methyl- 5-pyrazolone 1 - (4'-sulfophenyl) -5 -pyrazolone-3-carboxylic acid l- (3 / -amino-4'-sulfophenyl) -3-methyl-5-pyrazolone l- (5'-amino-2 / -methyl-4'-sulfophenyl) -50 5-pyrazolone-3-carboxylic acid;

Naphtholsulfonic acids, e.g. B.

1-naphthol-2- and -4-sulfonic acid

2-Naphthol-4-, -6- and -7-sulfonic acid l-Naphthol-3,6-, -3,8- and -4,8-disulfonic acid ss 2-Naphthol-3,6-, -3,7 -, -3,8- and -6,8-disulfonic acid l-naphthol-3,6,8-trisulfonic acid;

Aminonaphtholsulfonic acids, e.g. B.

1-amino-8-naphthol-4- and -6-sulfonic acid

2-amino-5-naphthol-7-sulfonic acid 60 2-amino-3-naphthol-6-sulfonic acid

2-amino-8-naphthol-6-sulfonic acid

1-amino-8-naphthol-2,4-, -3,5-, -3,6-and -4,6-disulfonic acid

2-amino-5-naphthol-l, 7-disulfonic acid 65 2-amino-8-naphthol-3,6-disulfonic acid and its N-methyl, N-phenyl, N-benzoyl and N-acetyl derivatives;

Phenols, e.g. B.

615192

p-cresol 3-acetylaminophenol;

0- and p-coupling amines, e.g. B.

2-naphthylamine-6- and -7-sulfonic acid 2-naphthylamine-5,7-disulfonic acid

1-naphthylamine-6- and -7-sulfonic acid

1-naphthylamine-3,6,8-trisulfonic acid m-toluidine

2-methoxy-5-methylaniline m-aminoacetanilide m-ureidonalinine;

2,6-dihydroxypyridines or 2-hydroxypyrid-6-ones,

e.g. B. 2,6-dihydroxypyridine

2,4,6-trihydroxypyridine

4-methyl-3-cyano-2,6-dihydroxypyridine

4-methyl-3-aminocarbonyl-2,6-dihydroxypyridine

4-methyl-2,6-dihydroxypyridine

4-methyl-1-ethyl-2-hydroxypyrid-6-one

4-methyl-3-aminocarbonyl-l- (4'-sulfophenylethyl) -2-

hydroxypyrid-2-one

4-methyl-3-cyano-l-ethyl-2-hydroxypyrid-6-one 4-methyl-3-aminocarbonyI-1-ethyl I-2-hydroxypyrid-6-one

It can e.g. B. also derivatives of aminonaphtholsulfonic acids or l- (aminophenyl) pyrazolones are used which contain a conventional cellulose-reactive group bonded to the amino group, i. H. a group which forms a covalent bond with cellulose in the presence of alkali, e.g. B.

1- (2 ', 4 / -Dichloro-s-triazin-6'-yl) amino-8-naphtho-3,6-disulfonic acid

2- (2'-chloro-4'-amino-s-triazin-6'-yl) amino-5-naphthol-7-sulfonic acid

1- [3 '- (2 // - chloro-4 // - p-sulfoanilino-s-triazine

6'-yl) amino-4'-sulfophenyl] -3-methyl-5-pyrazolone.

If desired, the coupling component can also contain phosphonic acid groups, such as. B.

3- (8-Hydroxy-6-sulfonaphth-2-ylamino) benzene phosphonic acid 3- (8-hydroxy-6-sulfonaphth-3-ylamino) benzene phosphonic acid

8-hydroxy-6-sulfonaphth-2-ylaminomethanephosphonic acid

3- (Naphth-l-ylamino) benzene phosphonic acid

3- (5,7-disulfonaphth-2-ylamino) benzene phosphonic acid

Acetoacetanilide-3- and -4-phosphonic acid

3- and 4-Acetaoacetylaminobenzylphosphonic acid

3-acetoacetylamino-4-methylphenylphosphonic acid

3-acetoacetylamino-6-methoxyphenylphosphonic acid

4-acetoacetylamino-2-fluorophenylphosphonic acid

2-acetoacetylamino-5-chlorophenylphosphonic acid

3-acetoacetylamino-4-chlorophenylphosphonic acid

4-acetoacetylamino-2-bromophenylphosphonic acid

1-acetoacetylaminonaphthalene-6- and -7-phosphonic acid

2-acetoacetylaminonaphthalene-7-phosphonic acid

2-Acetoacetylamino-5-sulfonaphthalene-7-phosphonic acid 1- (3-phosphonophenyl) -3-methyl-5-pyrazolone 1- (4-phosphonophenyl) -3-methyl-5-pyrazolone 1- (3-phosphonomethylphenyl) -3 -methyl-5-pyrazolone 1- (4-phosphonomethylphenyl) -3-methyl-5-pyrazolone 1- (2-methyl-5-phosphonophenyl) -3-methyl-5-pyrazolone 1- (2-methoxy-5-phosphonophenyl ) -3-methyl-5-pyrazolone l- (4-chloro-3-phosphonophenyl) -3-methyl-5-pyrazolone l- (2-chloro-5-phosphonophenyl) -3-methyl-5-pyrazolone l- ( 3-bromo-4-phosphonophenyl) -3-methyl-5-pyrazolone 1- (6-phosphononaphth-l-yl) -3-methyl-5-pyrazolone 1- (7-phosphononaphth-l-yl) -3-methyl -5-pyrazolon l- (7-phosphononaphth-2-yl) -3-methyl-5-pyrazolon l- (7-phosphono-5-sulfonaphth-2-yl) -3-methyl-5-

pyrazolone and the 3-carboxy, 3-carbomethoxy

or 3-carboethoxy analogs of the above pyrazolones l- (3-phosphonophenyl) -3-methyl-5-aminopyrazole l- (2-methyl-5-phosphonophenyl) -3-methyl-

5-aminopyrazole

Particularly preferred dyes of the formula 6 are those of the formula:

A2-N = N-E1

wherein A2 is 2-sulfo-5-phosphonophenyl or 2-methoxy-3-sulfo-5-phosphonophenyl and E1 is free of phosphonic acid groups and the remainder of a pyrazolone, a naphtholsulfonic acid, an N-acetylnaphtholsulfonic acid or a pyridone.

(2) disazo dyes of the formula:

n = n-m-n = n-e po3H2

wherein M represents the remainder of a p-coupling amine, especially the benzene or naphthalene series.

Examples of coupling components that make up E1 have been given above for class (1). The following may be mentioned as examples of p-coupling amines which give the radical M:

Aniline o- and m-toluidine o- and m-anisidine

Anthranilic acid

Cresidine

2,5-xylidine

2,5-dimethoxyaniline m-aminoacetanilide m-aminophenylurea m-aminobenzylphosphonic acid

6- and 7-sulfo-l-naphthylamine

6- and 7-phosphono-l-naphthylamine

2-ethoxy-6-sulfo-l-naphthylamine

Particularly preferred dyes of the formula 7 are those of the formula:

A2-N = N-M-N = N-E1

where M represents the residue of one of the following p-coupling amines:

o- and m-toluidine

0- and m-anisidine cresidine 2,5-xylidine 2,5-dimethoxyaniline m-aminoacetanilide m-aminophenylurea

1-Napththiamine-6- and -7-sulfonic acid and E1 is free of phosphonic acid groups and represents the remainder of a pyridone, a pyrazolone, an l-amino-8-naphtholsulfonic acid or an N-acetyl derivative thereof. (3) disazo dyes of the formula:

6

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

615192

n = n-e -n = n-a p03h2

wherein E2 represents the remainder of a coupling component E2H2 which is capable of coupling twice, and A represents a second remainder of the formula:

10th

is

(9)

means which may be the same as or different from the first residue of this general type shown in Formula 8.

The following may be mentioned as examples of coupling components which are capable of forming the radical E2: 1,8-aminonaphthol-4-sulfonic acid and -3,6-and -4,6-disulfonic acid 2-amino-5-naphthol-7- sulfonic acid 2-amino-8-naphthol-6-sulfonic acid and -3,6-disulfonic acid resorcinol pyrogallol l, 5-dihydroxynaphthalene-3,7-disulfonic acid di- (5-hydroxy-7-sulfonaphth-2-yl) amine bis - (5-hydroxy-7-sulfonaphth-2-yl) urea 2,2-diphenylolpropane (bisphenol A)

Diphenylolmethane (Bisphenol F)

Particularly preferred dyes of the formula 8 are those of the formula:

n = n-e -n = n where E2 is the remainder of l-amino-8-naphthol-3,6-disulfonic acid or bis- (5-hydroxy-7-sulfonaphth-2-yl) urea.

(4) dis- or polyazo dyes of the formula:

wherein A1 is the residue of a diazotizable aromatic amine A1-NH2, which is different from the amine A-NH2, wherein A has the meaning given in class (3). The rest A1 can contain azo bonds and have the most diverse substituents including phosphonic acid groups (8). As examples of amines A1-NH2, the rest

A1, the following are mentioned:

(a) Aromatic amines containing a phosphonic acid grappe

0-, m- and p-aminophenylphosphonic acid 3- and 4-aminobenzylphosphonic acid

3-amino-4-methylphenylphosphonic acid

4-amino-2-fluorophenylphosphonic acid

2-amino-5-chlorophenylphosphonic acid

3-amino-4-chlorophenylphosphonic acid

4-amino-2-bromophenylphosphonic acid

4-amino-3-nitrophenylphosphonic acid

1-naphthylamine-6- and -7-phosphonic acid

2-naphthylamine-7-phosphonic acid

5-sulfo-2-naphthylamine-7-phosphonic acid 8-sulfo-1-naphthylamine-3-phosphonic acid 4,8-disulfo-l-naphthylamine-3-phosphonic acid and also the monoazo compounds obtained by coupling the diazonium salts obtained from these amines couplable aromatic primary amines can be obtained, e.g. B. with the following amines:

Aniline m-toluidine o-toluidine 2,5-dimethylaniline

0-anisidine m-anisidine 2,5-dimethoxyaniline 5-methyl-2-methoxyaniline anthranilic acid

4-methyl-2-aminobenzoic acid

3-acetylaminoaniline m-ureidoaniline 3-acetylamino-6-methylaniline 3-acetylamino-6-methoxyaniline 3-benzoylaminoaniline 3-aminobenzylphosphonic acid

1-naphthylamine-6-sulfonic acid 1-naphthylamine-7-sulfonic acid

(10) 2-ethoxy-l-naphthylamine-6-sulfonic acid 1-naphthylamine-6-phosphonic acid l-naphthylamine-7-phosphonic acid and also the monoazo compounds,

such as by coupling a couplable aromatic amine,

which contains a phosphonic acid group,

such as B. 3-aminobenzylphosphonic acid l-naphthylamine-6-phosphonic acid or ss l-naphthylamine-7-phosphonic acid can be obtained with an aromatic diazonium salt, e.g. B. with any of the above list or the following lists (b) and (c).

25th

30th

35

40

45

p ° 3h2

n = n-e2-n = n-a1

(11)

(b) Aromatic amines containing a sulfo or carboxyl group aniline-2-, -3- and -4-sulfonic acid aniline-2,5-disulfonic acid aniline-3,5-disulfonic acid aniline-2,4-disulfonic acid 4- and 5-sulfoanthranilic acid 2-nitroaniline-4-sulfonic acid 4-nitroaniline-2-sulfonic acid

615192

3-nitroaniline-6-sulfonic acid 5-nitro-2-aminoanisole-4-sulfonic acid 2-methylaniol-4,5-disulfonic acid 2,5-dichloroaniline-4-sulfonic acid

4-methylaniline-2-sulfonic acid

5-chloro-4-methylaniline-2-sulfonic acid 4-methoxyaniline-2-sulfonic acid

4-chloroaniline-3-sulfonic acid

5-AcetyIaminoaniline-2,4-disulfonic acid anthranilic acid

2-aminoterephthalic acid m-aminobenzoic acid

3- or 4-aminophthalic acid p-aminobenzoic acid

5 -nitroanthranilic acid

6-nitro-3-aminobenzoic acid

5-nitro-2-aminoterephthalic acid 1-naphthylamine-4-sulfonic acid 2-naphthylamine-4,8-disulfonic acid

6-nitro-2-naphthyalmin-4,8-disulfonic acid 2-naphthylamine-6,8-disulfonic acid

2-naphthylamine-5,7-disulfonic acid

3- and 4-acetylaminoaniline-6-sulfonic acid 3-dichloro-s-triazinylaminoaniline-6-sulfonic acid

3-chloromethoxy-s-triazinylaminoaniline-6-sulfonic acid 2-aminoanisole-4- or -5-sulfonic acid

5-amino-2-hydroxybenzoic acid

1-naphthyalmin-5-, -6- or -7-sulfonic acid

2-naphthylamine-1-, -5-, -6-, -7- or -8-sulfonic acid

1-naphthylamine-3,6-disulfonic acid

2-naphthylamine-1,5-disulfonic acid 2-naphthylamine-1, 6-disulfonic acid 2-naphthylamine-6,8-disulfonic acid 6-acetylamino-2-naphthylamine-4,8-disulfonic acid 2-naphthylamine-3,6,8- trisulfonic acid

2-naphthylamine-4,6,8-trisulfonic acid

(c) Aromatic amines which are free from sulfo, carboxyl or phosphonic acid groups

Aniline o-, m- and p-toluidine

2,4- and 2,5-dimethylaniline 5-methyl-2-methoxyaniline o-, m- and p-chloroaniline o-, m- and p-bromoaniline

(d) Aromatic amines containing azo groups and free of phosphonic acid groups are monoazo compounds which are obtained by coupling the diazoni salts of any amines from lists (b) and (c) with any of the following amines: aniline o- and m Toluidine

0- and m-anisidine anthranilic acid cresidine

2,5-xylidine 2,5-dimethoxyaniline m-aminoacetanilide m-aminophenylurea

4-methyl-2-aminobenzoic acid

3-acetylamino-6-methylaniline 3-acetylamino-6-methoxyaniline 3-benzoylaminoaniline

1-naphthylamine-6- and -7-sulfonic acid

2-ethoxy-1-naphthylamine-6-sulfonic acid

Particularly preferred dyes of the formula 11 are those of the formula:

A2-N = N-E2-N = N-A1 (12)

wherein E2 represents the rest of l-amino-8-hydroxynaphthylin-4-sulfonic acid or -3,6- or -4,6-disulfonic acid.

When A2 is 2-sulfo-5-phosphonophenyl, the group of the formula:

A2 — N = N-

ortho to either the hydroxyl group or the amino group in E2, but when A2 is 2-methoxy-3-sulfo-5-phosphonophenyl, the group of the formula must:

A2 — N = N—

be in ortho position to the hydroxyl group.

It will be appreciated that the coupling component used to prepare the Formula 5 dyes may either be a coupling component required to directly produce the desired dye or may form an intermediate dye with which other reactions are carried out to produce the desired dye to manufacture. So z. B. a coupling component of the formula E ^ directly give a dye of the formula 6, while a coupling component of the formula:

HE2-N = N-A1

would directly result in a dye of formula 11.

The reaction of the diazonium salt of an amine of formula 1 with a coupling component of formula E2H2 would provide an intermediate dye which could be further reacted with a diazonium salt of an amine of formula AJ-NH2 to give dyes of formula 11.

Thus, for the production of dyes from classes (3) or (4) defined above, a coupling component of the formula E2H2 in any order with one mole of the diazonium compound from an amine of the formula 1 and with one mole of the diazonium compound from an amine of the formula ANH2 or A1NH2 can be implemented.

The dyes from class (2) defined above can be prepared by coupling the diazonium compound from an amine of formula 1 with an amine coupling in para position, diazotizing the resulting aminoazo compound and coupling it with a coupling component of formula E! H.

Other reactions that can be used to convert dye intermediates to dyes of the above type are e.g. B. connecting two such dye intermediates containing amino groups by reaction with reactants that can react in a difunctional manner, such as diacid chlorides or heterocyclic halogen compounds such as cyanuric chloride or its derivatives, and also the acylation of amino or hydroxyl groups in the dye intermediate with monofunctional means.

Coupling according to the above method can be carried out in a conventional manner; e.g. B. the clutch depending on the type of coupling component used in z. B. 0 ° C or higher, especially 10 to 30 ° C, in alkaline, neutral or weakly acidic aqueous media.

The dyes can be isolated using any conventional method, such as salting out or spray drying. The dye can be in the form of salts, e.g. B. alkali metal salts such as sodium salts can be isolated. It is often preferred to isolate the dyes as ammonium salts.

The amines of Formula 1 can be used in the

8th

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615192

the above coupling method can be converted into their diazonium salts by any conventional method, e.g. B. by reaction with mineral acid and sodium nitrite in aqueous solution at 0 to 5 ° C. However, it has been found that for many of the amines of Formula 1 it is possible to prepare the diazonium salt by contacting the amine with an aqueous solution of alkali metal nitrite without the addition of mineral acid. This can be advantageous not only because it saves the cost of the acid, but also because the absence of this acid can simplify the subsequent process.

The dyes of the above type have good water solubility, which contributes to the application of the dyes and to the washing out of unfixed dye. Textiles dyed with these dyes show good fastness to washing.

The following examples, in which all parts are by weight, illustrate the invention.

example 1

173 parts of m-aminophenylphosphonic acid are added to 440 parts of concentrated sulfuric acid with stirring until a homogeneous mixture is obtained. 220 parts of 60% oleum are added and the mixture is heated at 160 ° C for 6 hours. The sulfonation mixture is then slowly poured onto 1000 parts of ice and the resulting mixture is refluxed for 3 hours, after which it is brought to 3000 parts by weight with the addition of water. The suspension is filtered at room temperature and gives monosulfonated m-aminophenylphosphonic acid in a yield of over 90%. It is assumed that the product has the following structure:

Example 2

173 parts of m-aminophenylphosphonic acid are added in portions with stirring to 720 parts of 20% oleum; when mixing is complete, the mixture is heated to 160 ° C for one hour. The sulfonation mixture is cooled to 80 ° C and slowly poured onto 1000 parts of ice, and the resulting mixture is heated to reflux for 6 hours before being allowed to cool to room temperature. The mixture is stirred with 100 parts of sodium chloride for 3 hours and then filtered to give monosulfonated m-aminophenylphosphonic acid in a yield of over 90%.

The product is assumed to have the following structure:

nh

Example 3

Preparation of 4- (2-sulfo-5-phosphonobenzolazo) -3-carbonamido-l-ethyl-6-hydroxy-4-methylpyrid-2-one 12.65 parts of 2-amino-4-phosphonophenylsulfonic acid are slurried in 50 parts of water and cooled to a temperature below 5 ° C. 3.45 parts of sodium nitrite in 20 parts of chilled water are slowly added until the solution reacts consistently to iodine starch. After 15 minutes, the excess nitrite is destroyed by adding sulfamic acid. 9.45 parts of 3-carbonamido-1-ethyl-6-hydroxy-4-methylpyrid-2-one are stirred into 50 parts of water, by adding ammonia solution with a specific weight of 0.88 until a pH of 7 has been reached. 5 dissolved and the solution cooled to below 5 ° C. The cooled solution is poured onto the diazo suspension prepared above and the resulting mixture is brought back to pH = 5 to 6 by adding further ammonia solution with a specific weight of 0.88. The liquid is allowed to warm to room temperature; the clutch is considered to be terminated after 30 minutes. The dye can be precipitated by adding 20 parts by weight of ammonium chloride to 100 parts by volume of liquid, or the liquid can be used directly for dyeing. When the dye is applied to cellulosic fibers by the method specified in British Patent No. 1,411,306, it dyes them in a greenish yellow hue.

Example 4

12.65 parts of 2-amino-4-phosphonophenylsulfonic acid are slurried in 50 parts of water, 7.5 parts of 10 normal hydrochloric acid are added and the suspension is cooled to below 5 ° C. 3.45 parts of sodium nitrite in 20 parts of chilled water are slowly added until the solution is resistant to iodine starch. After 15 minutes, the excess nitrite is destroyed by adding sulfamic acid. This diazo solution is used in the coupling process described in Example 3 and gives a similar dye.

Example 5

12.65 parts of 2-amino-4-phosphonophenylsulfonic acid are diazotized according to the procedure given in Example 4.

14.1 parts of 2-acetylamino-8-naphthol-6-sulfonic acid are dissolved in 100 parts of water with the addition of ammonia solution with a specific weight of 0.88 to pH = 7, whereupon the solution is cooled to 5 ° C. with stirring. The above diazo suspension is added dropwise to this solution, the pH being maintained at 6-7 by adding ammonia solution of specific gravity 0.88. The liquid is allowed to warm to room temperature and the coupling is considered to have ended after one hour; a solution is obtained which dyes cellulose in a reddish-orange shade.

Examples 6 to 28 According to the procedure of Example 3 for pyridones, pyrazo-ions and p-coupling amines as coupling components or according to the procedure of Example 5 for naphthols, ami-nonaphthols and acylaminonaphthols as coupling components and replacing the 3-carbonamido-l- Ethyl-6-hydroxy-4-methylpyrid-2-one by an equivalent amount of the coupling component specified in column II of Table I gives dyes, the cellulose by the method of British Patent No. 1 411 306 in the color specified in column III to dye.

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Table I

I.

example

II

Coupling component m

hue

6

1- (4'-Sulfophenyl) -3-methyl-5-pyrazolone

yellow

7

1- (2 ', 5' -Dichlor-4'-sulfophenyl) -3-methyl-5-pyrazolone

yellow

8th

l-phenyl-3-methyl-5-pyrazolone

yellow

9

l- (4'-Sulfophenyl) -3-carboxy-5-pyrazolone

yellow

10th

l-acetylamino-8-naphthol-3,6-disulfonic acid

red

11

2-acetylamino-5-naphthol-7-sulfonic acid

orange

12

2-acetylamino-5-naphthol-l, 7-disulfonic acid

orange

13

l-acetylamino-8-naphtho-4,6-disulfonic acid

red

14

2- (2'-chloro-4'-m-sulfoanilino-s-triazine

6'-yl) amino-5-naphthol-7-sulfonic acid

orange

15

N-methyl-2-benzoylamino-8-naphthol-6-sulfonic acid

orange

16

l-naphthol-4-sulfonic acid

red

17th

2-naphthol-6-sulfonic acid

orange

18th

l-naphthol-3,6-disulfonic acid

orange

19th

l-naphthol-3,6,8-trisulfonic acid

orange

20th

2-naphthol-3,6-disulfonic acid

orange

21st

2-naphthol-6,8-disulfonic acid

orange

22

1-naphthylamine-6-sulfonic acid

yellow

23

2-naphthylamine-6-sulfonic acid

orange

24th

3- (8'-hydroxy-6'-sulfonaphth-3'-yl) -

orange

aminobenzene phosphonic acid

25th

1- (3'-phosphonophenyl) -3-methyl-5-pyrazolone

yellow

26

l-ethyl-2-hydroxy-4-methyl-5-cyano-6-pyridone

yellow

27th

l-ß- (4-sulfophenylethyl) -2-hydroxy-4-

yellow

methyl-5-carbamoyl-6-pyridone

28

l-ß- (4-sulfophenyethyl) -2-hydroxy-4-

yellow

methyl-5-cyano-6-pyridone

Example 29

12.65 parts of 2-amino-4-phosphonophenylsulfonic acid are diazotized according to the procedure of Example 3. 6.85 parts of cresidine are stirred into 100 parts of water, adjusted to pH = 5 with ammonia of specific gravity 0.88 and cooled to below 5 ° C. The above diazo suspension is added dropwise to this cooled suspension while stirring, while keeping the temperature below 5 ° C. and the pH value with ammonia solution of specific gravity 0.88 to 5. After the addition is complete, the monoazo solution is stirred at 5 ° C for one hour, after which the reaction is considered to be complete. The resulting solution contains a yellow dye that can also be used to make polyazo dyes.

Example 30

10 parts of 10 normal hydrochloric acid and then 3.45 parts of sodium nitrite in 20 parts of cooled water are added dropwise to a cooled monoazo solution prepared as in Example 29. After 15 minutes, the excess nitrite is destroyed by adding sulfamic acid.

18.1 parts of l-acetylamino-8-naphthol-3,6-disulfonic acid are dissolved in 50 parts of water and adjusted to pH = 7 with ammonia of specific gravity 0.88, after which the solution is cooled to below 5 ° C. The above diazotized monoazo solution is added dropwise to this cooled solution with stirring, the pH being maintained at a specific weight of 0.88 to 7 by adding ammonia solution. The coupling is considered complete after one hour and results in a solution that stains cellulose in a blue shade.

Example 31

11.15 parts of l-naphthylamine-6-sulfonic acid are dissolved in 100

Parts of water are stirred in and the pH is adjusted to 5 with ammonia solution of specific gravity 0.88, whereupon the suspension is cooled to below 5 ° C. A diazotized monoazo solution, which was obtained as in Example 30, was added dropwise to this cooled suspension with stirring, the pH being maintained at a specific weight of 0.88 to 6 with ammonia solution. One hour after the end of the addition, a suspension of 9.4 parts of cyanuric chloride in 50 parts of water with ice is added, the pH being allowed to drop to 4 and kept at this value by adding 1.0 normal sodium hydroxide solution until the first condensation has ended (for about an hour). A solution of 8.65 parts of metanilic acid in 50 parts of water is then added and the resulting mixture is heated to 35 ° C. and maintained at pH = 4 to 5 by adding 1.0 normal sodium hydroxide solution until the second condensation has ended; a solution is obtained which stains cellulose in a brown shade.

Examples 32 to 75 cresidine or an equivalent amount of the p-coupling amine shown in column II of Table II is coupled to diazotized 2-amino-4-phos-60 phonophenylsulfonic acid using the procedure of Example 29. The resulting

Monoazo compounds are diazotized and coupled to the coupling component (EH) indicated in column III, following the procedure of Example 30 if E'H is an aminonaphtholsulfonic acid or an acyl derivative thereof or 65 a naphtholsulfonic acid, or following the procedure of Example 31 if E'H is a p-coupling amine, whereby dye solutions are obtained which dye cellulose in the shade indicated in column IV.

40

45

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Table II

I.

il

III

IV

Example p-coupling amine

Coupling component E'H

hue

32

m-toluidine 1- (2'-chloro-4'-m-sulfoanilino-s-triazin-6'-yI) -

Orange brown

aminonaphthalene-6-sulfonic acid

33

m-toluidine

2-naphthol-7-sulfonic acid

Bluish red

34

m-toluidine l-phenylaminonaphthalene-6-sulfonic acid

red

35

m-toluidine l-acetylamino-8-naphthol-3,6-disulfonic acid

blue

36

m-toluidine

2-acetylamino-5-naphthol-7-sulfonic acid

violet

37

o-anisidine 1- (2'-chloro-4'-m-sulfoanilino-s-triazin-6'-yl) -

Orange brown

aminonaphthalene-7-sulfonic acid

38

o-anisidine l-amino-8-naphthol-3,6-disulfonic acid

Blue-black

39

o-anisidine l-acetylamino-8-naphthol-3,6-disulfonic acid

blue

40

o-anisidine

2-acetylamino-5-naphthol-7-sulfonic acid

violet

41

m-anisidine l-amino-8-naphthol-3,6-disulfonic acid

Blue-black

42

Cresidine

1 - (4 '-Sulfophenyl) - 3-carboxy-5-pyrazolone

Tan

43

Cresidine l-phenylaminonaphthalene-6-sulfonic acid

red

44

Cresidine l-amino-8-naphthol-3,6-disulfonic acid

Blue-black

45

Cresidine l-acetylamino-8-naphthol-3,6-disulfonic acid

blue

46

Cresidine

3-acetylaminophenylurea

orange

47

Cresidine

N-methyl-2-acetylamino-5-naphthol-7-sulfonic acid

violet

48

2,5-xylidine l-acetylamino-8-naphthol-3,6-disulfonic acid

blue

49

2,5-xylidine l-naphthol-3,6-disulfonic acid

Bluish-

r / - \ f

50

Aniline l-phenylaminonaphthalene-6-sulfonic acid

IUI

red

51

2,6-dimethoxyaniline l-acetylamino-8-naphthol-3,6-disulfonic acid

blue

52

2,6-dimethoxyaniline l-amino-8-naphthol-3,6-disulfonic acid

Blue-black

53

2,6-dimethoxyaniline 1- (2'-chloro-4'-m-sulfoanilino-s-triazin-6'-yl) -

Orange brown

aminonaphthalene-8-sulfonic acid

54

1-naphthylamine

l- (4'-Sulfophenyl) -3-carboxy-5-pyrazolone

Reddish brown

6-sulfonic acid

55

1-naphthylamine

4-methyl-3-aminocarbonyl-1-ethyl-2-hydroxypyrid-6-one

Reddish brown

6-sulfonic acid

56

1-naphthylamine

l-acetylamino-8-naphthol-3,6-disulfonic acid

blue

6-sulfonic acid

57

1-naphthylamine

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

Blue-black

6-sulfonic acid

58

1-naphthylamine

l-benzoylamino-8-naphthol-4,6-disulfonic acid

blue

6-sulfonic acid

59

1-naphthylamine

1 - (2 '-Chlor-4' -m-sulfoanilino-s-triazine-6 '-yl) ~

Reddish brown

6-sulfonic acid aminonaphthalene-7-sulfonic acid

60

1 -naphthylamine-

2-naphthol-6-sulfonic acid

violet

6-sulfonic acid

61

1-naphthylamine

l-acetylaminonaphthalene-6-sulfonic acid

Reddish brown

6-sulfonic acid

62

1-naphthylamine

1 - (4 '-Sulfophenyl) -3-carboxy-5-pyrazolone

Reddish brown

7-sulfonic acid

63

1-naphthylamine

4-methyl-3-aminocarbonyl-1-ethyl-2-hydroxypyrid-6-one

Reddish brown

7-sulfonic acid

64

1-naphthylamine

l-acetylamino-8-naphthol-3,6-disulfonic acid

blue

7-sulfonic acid

65

1 -naphthylamine-

1- (2'-chloro-4'-m-sulfoanilino-s-triazin-6'-yl) -

Reddish brown

7-sulfonic acid aminonaphthalene-6-sulfonic acid

66

1-naphthylamine

2-acetylamino-5-naphthol-7-sulfonic acid

violet

7-sulfonic acid

67

1-naphthylamine

l-naphthol-3,6-disulfonic acid

violet

7-sulfonic acid

68

1-naphthylamine

l-acetylaminonaphthalene-6-sulfonic acid

Reddish brown

7-sulfonic acid

69

1-naphthylamine

m-diethylaminoacetanilide

blue

7-sulfonic acid

70

o-toluidine l-acetylamino-8-naphthol-3,6-disulfonic acid

blue

71

m-aminoacetanilide l-acetylamino-8-naphthol-3,6-disulfonic acid

blue

72

m-aminoacetanilide

1 - (2 '-Chlor-4' -m-sulfoanilino-s-triazine-6 '-yl) -

brown

aminonaphthalene-6-sulfonic acid

73

m-aminophenyl

1- (2'-chloro-4'-m-sulfoanilino-s-triazin-6'-yl) -

brown

urea aminonaphthalene-6-sulfonic acid

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12

Table II (continued)

I n m IV

Example p-coupling amine coupling component E'H color

74 m-aminophenyl-l-acetylamino-8-naphthoI-3,6-disulfonic acid blue urea

75 m-aminophenyl-l-amino-8-naphthol-3,6-disulfonic acid blue-black urea

Example 76

16 parts of finely divided 8-amino-1-naphthol-3,6-disulfonic acid are stirred into 150 parts of water, adjusted to pH = 1.5 with hydrochloric acid and cooled to below 5 ° C. A suspension of diazotized 2-amino-4-phosphonophenylsulfonic acid, which was prepared as described in Example 4, is added dropwise to this suspension with stirring. After stirring for 5 hours, the coupling is regarded as complete and the reaction liquid is adjusted to pH = 7 with stirring with ammonia solution of specific gravity 0.88. The resulting solution contains a red monoazo dye, which can also be coupled further to produce polyazo dyes.

Example 77

The cooled solution from Example 76 is added dropwise to a suspension of diazotized 2-amino-4-phosphonophenylsulfonic acid, which was prepared as described in Example 4, while the pH was adjusted by adding ammonia solution with a specific weight of 0.88 stops at 7. The coupling is completed within an hour and results in a solution that stains cellulose in a blue-black shade.

Example 78

11.5 parts of di- (5-hydroxy-7-sulfonaphth-2-yl) amine are dissolved in 100 parts of water with stirring and addition of ammonia solution with a specific weight of 0.88 to pH = 7. The solution is cooled to below 5 ° C and a drop of diazotized 2-amino-4-phosphonophenylsulfonic acid, prepared as in Example 4, is added dropwise to the cooled solution while adjusting the pH by adding specific weight ammonia solution Holds 0.88 on 7. After an hour, the coupling is essentially complete and results in a solution that colors cellulose in an orange shade.

Example 79

12.5 parts of bis (5-hydroxy-7-sulfonaphth-2-yl) urea are dissolved in 100 parts of water with stirring and addition of ammonia solution with a specific weight of 0.88 to pH = 7. A suspension of diazotized 2-amino-4-phosphonophenylsulfonic acid, prepared as described in Example 4, is then added as in Example 78 to give a solution which stains cellulose in an orange shade.

Example 80

5 parts of 2- [2-chloro-4- (6 / -sulfo-8'-hydroxynaphth-2 / -20 ylamino) -s-triazin-2'-yl] -amino-5-naphthol-7-sulfonic acid are added Stirring and adding ammonia solution with a specific weight of 0.88 to pH = 7 dissolved in 100 parts of water. A suspension of diazotized 2-amino-4-phospho-nophenylsulfonic acid, prepared as described in Example 4, is then added as in Example 78 to give a solution that stains cellulose in an orange shade.

Example 81

11.15 parts of l-naphthylamine-6-sulfonic acid are stirred into 100 30 parts of water, the pH is adjusted to 6 with ammonia solution of specific gravity 0.88 and the suspension is cooled to below 5 ° C. This cooled suspension is added dropwise with stirring to a suspension of diazotized 2-amino-4-phosphonophenylsulfonic acid, which was prepared as described in Example 4, while the pH was adjusted to 0.88 to 6 by adding ammonia solution with a specific weight holds. After one hour, a suspension of 4.65 parts of cyanuric chloride in 50 parts of water mixed with ice is added and the pH is kept at 6 by adding 1.0 normal sodium hydroxide solution. After one hour the temperature is raised to 40 ° C and the pH is kept at 6 for 3 hours; after this time the first two chlorine atoms of the cyanuric chloride reacted. A solution is obtained which stains cellulose in a yellow shade.

Examples 82-84

If the coupling component in Example 80 is replaced by an equivalent amount of the coupling component (E2H2) given in column II of Table III, dyestuffs are obtained which dye cellulose in the shade indicated in column III.

Table III

I.

II coupling component (E2H2)

III

82

2 ', 4'-di- (5-hydroxy-8-sulfonaphth-2-yl-

orange

amino) -6'-chloro-s-triazine

83

2 ', 4'-di- (8-hydroxy-3,6-disulfonaphth-

red

l-ylamino) -6'-chloro-s-triazine

84

2- [2'-chloro-4 '- (8-hydroxy-3,6-disulfo-

Yellowish

naphth-1 -ylamino) -s-triazin-6 '-yl] -

red

amino-5-naphthol-7-sulfonic acid

■ 13

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Example 85

8.65 parts of finely divided m-aminophenylphosphonic acid are stirred into 50 parts of water and mixed with 10 parts of 10 normal hydrochloric acid, after which the solution is cooled to below 5 ° C. 3.45 parts of sodium nitrite in 20 parts of chilled water are added dropwise to this suspension until it reacts resistant to iodine starch. After 15 minutes, the excess nitrite is destroyed by adding sulfamic acid.

This diazo suspension is then added dropwise to a cooled solution of the monoazo dye obtained by the method of Example 76 while maintaining the pH of 0.88 by weight by adding ammonia solution. After an hour, the coupling is considered to be complete and results in a solution that colors cellulose in a blue-black shade.

Examples 86-108

If the m-aminophenylphosphonic acid in Example 85 is replaced by an equivalent amount of the diazo component from the amine AWH2 indicated in column II of Table IV, dyestuffs are obtained which dye cellulose in the shade indicated in column III.

Table IV

I.

I m

example

Amine A iNH2

hue

86

Aniline-2,5-disulfonic acid

Blue-black

87

Metanilic acid

Blue-black

88

Orthanilic acid

Blue-black

89

2,5-dichloroaniline-4-sulfonic acid

Blue-black

90

4-methoxyaniline-2-sulfonic acid

Blue-black

91

4-chloroaniline-2-sulfonic acid

Blue-black

92

4-chloroaniline-3-sulfonic acid

Blue-black

93

4-methylaniline-2-sulfonic acid

Blue-black

94

m-aminobenzoic acid

Blue-black

95

5-sulfoanthranilic acid

Blue-black

96

5-acetylaminoaniline-2-sulfonic acid

Blue-black

97

4-acetylaminoaniline-2-sulfonic acid

Blue-black

98

2-naphthylamine-l-sulfonic acid

Blue-black

99

2-anisole-5-sulfonic acid

Blue-black

100

l-naphthylamine-6-sulfonic acid

Blue-black

101

2-naphthylamine-1,5-disulfonic acid

Blue-black

102

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

Blue-black

103

2-naphthylamine-6-sulfonic acid

Blue-black

104

2-naphthylamine-4,8-disulfonic acid

Blue-black

105

2-naphthylamine-6,8-disulfonic acid

Blue-black

106

m-toluidine

Blue-black

107

p-chloroaniline

Blue-black

108

Cresidine

Blue-black

Example 109

15 parts of finely divided 2-naphthylamine-1,5-disulfonic acid are stirred into 50 parts of water and mixed with 10 parts of 10 normal hydrochloric acid, whereupon the suspension is cooled to below 5 ° C. 3.45 parts of sodium nitrite in 20 parts of cooled water are added dropwise to this suspension until it reacts with iodine starch. After 15 minutes, the excess nitrite is destroyed by adding sulfamic acid.

16 parts of finely divided l-amino-8-naphthol-3,6-disulfonic acid are stirred into 150 parts of water, adjusted to pH = 1.5 with 10 normal hydrochloric acid and cooled to below 5 ° C. The above diazo solution is added dropwise to this suspension with stirring. After stirring for 5 hours, the coupling is considered to be complete and the stirred reaction mixture is adjusted to pH = 7 with ammonia solution of specific gravity 0.88, a red monoazo dye solution being obtained which can be used for further coupling reactions.

Example 110

A suspension of diazotized 2-amino-4-phosphonophenylsulphonic acid (as prepared in Example 4) is added dropwise to the solution from Example 109, the pH being maintained at a specific weight of 0.88 to 7 by adding ammonia solution . The coupling is complete after one hour, a solution being obtained which stains cellulose in a blue-black shade.

Examples III to 118 If the 2-naphthylamine-l, 5-disulfonic acid in Example 109 is replaced by an equivalent amount of the diazo component from the amine A'NH2 indicated in column II of Table V and the resulting monoazo compound is prepared by the method of Example 110 diazotized 2-amino-4-phosphonophenylsulfonic acid couples, so you get dye solutions that dye cellulose in the color specified in column III.

Table V

I.

II in

example

Amine A'NH2

hue

111

Aniline-2,5-disulfonic acid blue-black

112

4-nitroaniline-2-sulfonic acid blue-black

113

AniIin-2,4-disulfonic acid blue-black

114

2-nitroaniline-4-sulfonic acid blue-black

115

5-sulfoanthranilic acid blue-black

116

2,5-dichloroaniline-4-sulfonic acid blue-black

117

2-naphthylamine-1,5-disulfonic acid blue-black

118

2-naphthylamine-4,8-disulfonic acid blue-black

Example 119

203 parts of 3-amino-4-methoxyphenylphosphonic acid are added in portions to 720 parts of 20% oleum with stirring; when mixing is complete, the mixture is heated to 150 ° C for one hour. The sulfonation mixture is cooled to 80 ° C. and slowly poured onto 1000 parts of ice. The resulting mixture is refluxed for 6 hours, after which it is allowed to cool to room temperature. The mixture is stirred with 100 parts of sodium chloride for 3 hours and then filtered to give a monsulfonated compound in a yield of more than 20%.

It is believed that the product of the formula:

och p

3rd

nh,

Examples 120 to 129 If the methods used in the examples, the numbers of which are given in column II of Table VI, are used and an equivalent amount of 3-amino-2-methoxy-5-phosphonobenzenesulfonic acid is used instead of 2-amino-4-phos- used phonobenzenesulfonic acid, the dyes indicated in column III are obtained. These dye cellulose in the color specified in column IV.

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30th

35

40

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Table VI

I.

I m

IV

example

Method of

dye

hue

120

Example 5

7-acetylamino-l-hydroxy-2- (2'-methoxy-5'-phosphono-3'-sulfophenylazo) naphthalene-3-sulfonic acid

red

121

Example 3

l-ethyl-2-hydroxy-3- (2'-methoxy-5'-phosphono-3'-sulfo-phenylazo) -4-methyl-5-carbamoyl-6-pyridone

Reddish yellow

122

Example 9

1 - (4 '-sulfophenyl) -3-carboxy-4- (2 "-methoxy-5" -phosphono-3 "-sulfophenylazo) ~ 5-pyrazolone

Reddish yellow

123

Example 12

6-acetylamino-l-hydroxy-2- (2'-methoxy-5'-phosphono-3'-sulfophenylazo) naphthalene-3,5-disulfonic acid

scarlet

124

Example 36

6-acetylamino-l-hydroxy-2- [3'-methyl-4 '- (2 "-methoxy-

5 "-phosphono-3" -sulfophenylazo) -phenylazo] -naphthalene

3-sulfonic acid

blue

125

Example 45

8-acetylamino-l-hydroxy-2- [2'-methoxy-5'-methyl-4 '- (2 "-

methoxy-5 "-phosphono-3" -sulfophenylazo) -phenylazo] -naphthaIin-

3,6-disulfonic acid

blue

126

Example 54

1- (4'-sulfophenyl) -3-carboxy-4- [6 "-sulfo-4" - (2 "'- methoxy-

5 "'- phosphono-3"' - sulfophenylazo) -naphth-l "-ylazo] -5-

pyrazolone

Reddish brown

127

Example 67

l-Hydroxy-2- [7'-suIfo-4 '- (2 "-methoxy-5" -phosphono-3 "-

sulfophenylazo) -naphth-l'-ylazo] -naphthalene-3,6-

disulfonic acid

blue

128

Example 111

8-amino-l-hydroxy-2- (2'-methoxy-5'-phosphono-3'-sulfo

phenylazo) -7- (2 ", 5" -disulfophenylazo) -naphthalene-3,6-di-

sulfonic acid

blue

129

Example 117

8-amino-l-hydroxy-2- (2'-methoxy-5'-phosphono-3'-suIfophenylazo) -7- (l ", 5" -disulfonaphth-2 "-ylazo) -naphthalene-3,6- disulfonic acid

blue