DE1259483B - Process for the production of metal-containing azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09b

German class: 22 a -1

Number: 1259 483

File number: F 43959IV c / 22 a

Filing date: September 11, 1964

Opening day: January 25, 1968

The present invention relates to the production of new, metal-containing carboxylic acid and sulfonic acid groups-free Azo dyes of the general formula

A-N = N-B

X / Y

\ 1 /

Me

X / Y

A-N = N-B

Il

- (- CH ₂ -NCR ₂

K ©

(I)

The radicals A here denote substituted or unsubstituted, identical or different phenyl or phenyl groups Naphthyl residues, B the residues of the same or different coupling components, X the residues - O- and / or - COO -, Y identical or different radicals

- O -, - NH -,

- N-aryl, - N-aroyl or - N-arylsulfonyl,

it being possible for the aryl radicals to be substituted or unsubstituted; the radicals X and Y are in A or in B in each case adjacent to the azo group; m is an integer from 1 to 4, Me is Cr or Co and K is a cation; R ₁ denotes hydrogen, alkyl or aryl; R2 stands for a saturated or unsaturated haloalkyl group, where the halogen can be in the α- or / 3-position, for a vinyl, α-halovinyl, di- or trihalovinyl, a u- or / J-alkylvinyl radical or one with an aliphatic or aromatic sulfonic acid esterified, substituted or unsubstituted α-hydroxymethylene or ß-hydroxyethylene radical.

By definition, the new dyes are free from sulfonic acid and carboxylic acid groups but have any other type of substituents customary in azo dyes, such as nitro, acylamino, ζ. B. acetylamino and benzoylamino groups and their substitution products, carbmethoxyamino groups, Alkyl, ζ. Β. Methyl, ethyl or propyl radicals, alkoxy, ζ. B. methoxy, ethoxy or cyclic alkoxy radicals, halogen, such as fluorine, chlorine and bromine substituents, and also cyano and Trifluoromethyl radicals, sulfonamide groups, mono- or disubstituted N-alkyl, e.g. B. methyl or ethyl sulfonamide groups, as well as alkyl sulfone, e.g. B. methyl sulfone or ethyl sulfone groups, and other azo groups.

Method of manufacture
metal-containing azo dyes

Applicant:

Paint factories Bayer Aktiengesellschaft,

5090 Leverkusen

Named as inventor:
Dr. Heinz Machatzke,
Dr. Edgar Siegel, 5090 Leverkusen

The radical Ri is preferably hydrogen, the methyl, ethyl and isopropyl groups in question.

Examples of the radical R ₂ include the following groups:

- CH ₂ Cl - CH ₂ CH ₂ Cl
C = CH ₂ - C = CCl ₂
Cl CI

CH = CH ₂
- C = CH ₂
CH,

Cl
-CH = CH-CH ₂ Cl -CH = CH-CH ₂ Br

- CH ₂ - O - SO ₂ CH ₃

- CH ₂ - O - SO ₂ - / \

- CH ₂ - O - SO ₂ - ^ ^ - CH ₃

- CH ₂ - CH ₂ - O - SO ₂ CH ₃

The main cations K are sodium, potassium, ammonium and hydrogen ions.

The new dyes (I) are obtained when identical or a mixture of one another is used

709 720/441

different metallizable azo dyes of the general formula

handener
formula

Aryl core

at least one O

Group of

Q HY

A-N = -N-B

Il

CH ₂ - N - C - R ₂

(H)

IO

where A, B ₅ Y, Ri and R2 have the meaning given, Q denotes an —OH, —COOH or —O-alkyl group which is in the o-position to the azo group in A, and m ' denotes the number 1 or 2 means treated with chromium or cobalt releasing agents in such a way that 1: 2 metal complex dyes are formed, that is to say those dyes which contain approximately 2 molecules of dyestuff bonded in complexes to 1 atom of Cr or Co. A dye of the general formula (II) can also be mixed with a second dye of the general formula -CH ₂ -NCR ₂

Ri

contains. The dyes (II a) are in principle the same way from starting materials without them Grouping established.

The dyes (II) on which the process according to the invention is based can also be obtained in this way ■ be that one dyes of the general formula (II a), where A, B, Q and Y have the meaning given and A and / or B at least one contains an aromatic nucleus bonded exchangeable hydrogen atom, in the presence of an acidic Condensation agent with compounds of the general formula

HY HO - CH, - N - C - R,

R ₁

(III)

A-N = N-B

(Ha)

convert into the 1: 2 metal complex compounds.

The metallization is preferably carried out in a weakly acidic, neutral or alkaline medium Using approximately 0.5 gram atom of heavy metal per mole of metallizable azo dye.

To prepare uniform 1: 2 chromium mixed complex dyes, one can proceed in such a way that one first 1 mol of a metallizable azo dye (II) or (II a) and 1 gram atom of a chromium (III) salt Heated in an acidic medium until the 1: 1 chromium complex has formed, and then this with one mole of another metallizable azo dye of the formula (II) or, if the 1: 1 metal complex dye already a group

Il

-CH ₉ -NCR ₂

⁴⁵

carries, also with a metallizable dye (II a) in a manner known per se in weakly acidic to alkaline medium to form 1: 2 chromium mixed complex.

The metallizable azo dyes of the formula (II) can be prepared in a manner known per se, by taking amines of the general formula

A - NH ₂

60

where A and Q have the meaning given and Q is adjacent to the amino group, diazotized and with compounds of the general formula HB - YH, where Y and B have the meanings given have, in the neighboring position to the group YH couples, whereby at least one of the starting components, i.e. / one of the diazo components A, the coupling components B or one optionally in Y above Ri and R2 have the meaning given, implemented in a manner known per se.

As diazo components for the synthesis of the starting dyes (II) or (II a), inter alia the following compounds are used: 1-aminobenzene-2-carboxylic acid, 4- or 5-chloro-1-aminobenzene-2-carboxylic acid, 4- or 5-nitro-l-aminobenzene-2-carboxylic acid, l-amino ^ -methylsulfonyl ^ -benzenecarboxylic acid, l-Amino-S-methylsulfonyl ^ -benzenecarboxylic acid, o-anisidine, 3-hydroxy-4-amino- (N-chloroacetyl) -benzylamine, 3-amino-4-hydroxy- (N-chloroacetyl) -benzylamine, 3-hydroxy-4-amino- (N-acryloyl) -benzylamine, 2 - amino - 4 - chlorophenol, 2 - amino-6-chlorophenol, 4-, 5-, 6-nitro-2-aminophenol, 4,6-dinitro-2-aminophenol, 4-chloro-5-nitro-2-aminophenol, 2-aminophenol-4-sulfonamide, 2-aminophenol-4-methylsulfonamide, 2-aminophenol-4-ethylsulfonamide, 2-aminophenol-4-dimethylsulfonamide, 2-aminophenol-4-N - ^ - hydroxyethylsulfonamide, 2-aminophenol-4-N-acryloyl-sulfonamide, 2-aminophenol, 2-aminophenol-4-N-phenyl-sulfonamide, 4-acetylamino-2-aminophenol, 4-chloro-2-aminophenol-6-sulfonamide, 6-nitro-2-aminophenol-4-N, N-dimeth \ 1-sulfonamide, 2 - aminophenol - 4,6 - dimethylsulfone, o-chloro ^ -aminophenoM-methylsulfone, 2-amino-4-ethyl-sulfonylphenol, 3-Amino-4-hydroxybenzene-2-methylene sulfone-1-ether.

Possible coupling components include: acylacetoarylides, such as acetoacetanilide, acetoacet-o-chloranilide, 4-acryloylsulfonamido-acetoacetanilide, acetoacet-4-methoxy-anilide, 1 ', 3'-dimethyl-3' (or 4 ') -chloroacetylaminomethylene , r, 4'-dimethyl-2 '(or 3') -acryloylaminomethylene-acetoacetanilide; Phenols such as p-cresol, 3-acetylamino-4-methylphenol; 5-pyrazolones, e.g. B. 1-phenyl-S-methyl-S-pyrazolone-, 1- (2 ', 3' or 4'-chlorophenyl) -3-methyl-5-pyrazolone, 1- (3'-acryloylsulfonamidophenyl) -3-methyl - 5 - pyrazolone, 1 - (3'- u - chloracryloyl - sulfonamidophenyl) - 3 - methyl-5-pyrazolone; Naphthols, e.g. B. 1- or 2-naphthol, 4-methyl-l-naphthol, 4-methoxy-l-naphthol, 1-acetylamino-4-acryloylsulfonamido-7-naphthol, 1-acryloylamino-7-naphthol, l-chloroacetylamino 7-naphthol, 2-naphthol-6-sulfonamide, 2-naphthol-6-acrylic

the wool from a weakly acidic or neutral bath in gray tones with excellent wet and light fastness properties colors.

If one proceeds as indicated in this example, only instead of 15 parts of methylolmonochloroacetamide 18 parts of N-methylol-2-chloropropionic acid amide used, a gray dye with very good wet fastness properties is also obtained.

Example 2

The mixture of 34 parts of the by diazotizing 2-aminophenol-4-sulfonamide and coupling on 2-naphthol and 40 parts of that obtained by diazotizing 4-nitro-2-aminophenol and coupling to 1-methylsulfonylamino-7-naphthol The dye obtained is introduced into 600 parts of 96% strength sulfuric acid. At a temperature of 0 ° there are proportionally 65 parts Methylolmonochloroacetamide entered. After 2 hours, the solution is allowed to warm to 20 ° and stir for another 10 hours. It is then poured onto 5000 parts of ice and the dyestuff which has precipitated out is sucked off off, washed with water and suspended the paste in 3000 parts of water at a pH of 7 to 8. At a temperature of 90 to 100 °, a solution of is added within 30 minutes 21 parts of potassium dichromate and 40 parts of glucose, dissolved in 200 parts of water, are added and sucked in 1 hour hot off the precipitated dye. After washing with water and drying, one obtains 70 parts of a dye, the wool from a weakly acidic to neutral bath in gray to black Dyes shades with very good light and wet fastness properties.

Example 3

The solution of 20 parts of the dry, by diazotization of 2-aminophenol-4-ethyl sulfone and Coupling obtained on l-acetylamino-7-naphthol Azo dyes in 150 parts of 96% strength sulfuric acid are mixed with 18 parts of N-methylol-2-chloropropionamide at 0 ° offset. After 2 hours, the mixture is allowed to warm to 20 °, stirred for a further 10 hours and poured onto 1000 parts of ice. One sucks off Washed with water, the paste suspended in 500 parts of water at a pH of 7 to 7.5 and there within 10 minutes at 100 ° a solution of 11 parts of potassium dichromate and 20 parts of glucose in 100 parts of water. After 1 hour, the pH of the solution is adjusted by adding sodium hydroxide to 12 and heated to 90 to 95 ° for 2 hours. It is allowed to cool to 20 ° and acidified with hydrochloric acid and sucks off the precipitated dye. It is washed with water and dried, and 17 parts are obtained a dye of the constitution

CH, = CH - C - NH -

CH, NH - C - CH = CH,

Well ^s

the wool from a weakly acidic bath in gray tones with very good fastness properties, especially wet fastness properties, colors.

If, in the processes of Examples 1 to 3, equivalent amounts of those listed in the table below are used Diazo and coupling components, so you get other valuable chromium and cobalt complex dyes, dye the wool from a neutral to slightly acidic bath in the specified shades.

The metal-free azo dyes from the tabulated compounds of columns I and II are with the compounds of the general formula indicated in column IV

60 HO-CH ₂ NHOCR ₂

by entering the latter in a sulfuric acid solution of the former exactly as indicated implemented at the beginning of Example 1; then the dyes are in the column III labeled metal complexes.

loyl sulfonamide; 5-amino-pyrazoles, e.g., 1-phenyl-3 - methyl - 5 - aminopyrazole; Naphthylamine, ζ. Β. 2 - naphthylamine, N - methyl - 2 - naphthylamine, N- (3'-methylsulfonylamino-benzoyl) -1-amino-7-naphthol, N- (3'-methylamino-sulfonyl-benzoyl) -l-amino-7-naphthol; Pyrazolobenzimidazole, 2-phenyl-5-amino-l, 2,3-benzotriazole; "4-Hydroxynaphthalene-2-methylene-sulfone-1-ether.

Another process for the preparation of the new dyes is that one of the dyes general formula

A N = N B "

application of auxiliaries, applied at elevated temperature.

In comparison with the chromium complex azo dye known from Example 56 of the published documents of Belgian patent 579 968, the chromium complex according to the invention gives the azo dye of the formula
OH

Me

N = N

HO

SO ₂ C ₂ H ₅

(IV)

A N = N B

where A, B, X, Y and K have the meaning given for formula (I), with a methylene compound of general formula O

CH,

HO - CH ₂ - N - C - Κ

(V)

where Ri and Ro have the meaning already given have, reacted in the presence of an acidic condensing agent and free the starting components of sulfonic acid and carboxylic acid groups. In the case of partial demetallization of the Metal complexes are the process products with chromium or cobalt salts with the formation of 2:! Complexes treated.

The new dyes are ideal for dyeing and printing natural or regenerated Protein fibers such as wool, silk, polyamide, polyurethane and polyacrylonitrile fibers. For coloring and printing, the dyes are advantageously based on the 1: 2 complex dyes for wool which are free from acid groups and silk known techniques in weakly acidic to neutral solution, if necessary using

ClCH ₂ - C - NH - CH CH ₂ NHCOCH ₂ Cl

Dyes on wool, which are characterized by superior potting fastness.

In the following examples, parts stand for parts by weight; the temperature data are degrees Celsius.

example 1

To dissolve 20 parts of the dry, by diazotization of 2-aminophenol-4-ethyl sulfone and Coupling obtained on l-methylsulfonylamino-7-naphthol Azo dyes in 150 parts of 96% strength sulfuric acid are partially 15 parts of methylolmonochloroacetamide at 0 ° given. After 1 hour the ice cooling is removed and at room temperature for 15 hours touched. Ice is poured out onto 1000 parts and suctioned off. The dye paste comes in 500 parts Suspended water and at 95 to 100 ° and a pH of 7 to 7.5 with the combined solution of 11 parts of potassium dichromate, dissolved in 100 parts of water, and 20 parts of glucose in 100 parts of water dissolved, added within 15 minutes. After 1 hour, the precipitated dye is filtered off with suction and washed with water and dry. 21 parts of a dye of the constitution are obtained

H ₃ CO ₂ S SO ₂ C ₂ H ₅

CH ₂ NH - C - CH ₂ Cl

Na®

Tabel

I. II III IV hue Diazo component Coupling component metal Reactive component
HIGH ₂ -NHCOR ₂
R ₂ = yellow 2-aminophenol-4-sulfonamide Γ, 3'-dimethylacetoacetanilide Co Chloromethyl yellow 2-aminophenol-4-sulfonamide 1 '^' - Dimethylacetoacetanilide Co Chloroethyl yellow 2-aminophenol-4-sulfonamide 2 ', 5'-dimethylacetoacetanilide Co vinyl orange 2-aminophenol-4-ethyl sulfone 1 - (4'-methylphenyl) -3-methyl-
pyrazolone-5 Cr Chloromethyl yellow 2-aminophenol-4-ethyl sulfone l- (4'-methylphenyl) -3-methyl-
pyrazolone-5 Co Chloromethyl orange 2-aminophenol-4-dimethyl-
sulfonamide l- (4'-methylphenyl) -3-methyl-
pyrazolone-5 Co vinyl yellow 2-aminophenol-4-dimethyl-
sulfonamide l- (4'-methylphenyl) -3-methyl-
pyrazolone-5 Co α-chlorovinyl Gray 2-aminophenol-4-ethyl sulfone 1-methylsulfonylamino-7-naphthol Cr α-chlorovinyl Gray 2-aminophenol-4-methyl-
suifonamid 1-methylsulfonylamino-7-naphthol Cr vinyl Gray O ΙΛΧΧ V / λ XCLXXXXlX
2-aminophenol-4-methylsulfone 1-carbomethoxyamino-7-naphthol Cr Chloromethyl blue 2-amino-4-chlorophenol 4-hydroxynaphthalene-2-methylene
sulfone-1 ether Cr Chloromethyl blue 2-amino-4-chlorophenol 4-hydroxynaphthalene-2-methylene
suifon-1 ether Cr vinyl blue 2-amino-4-chlorophenol O LJ-XX WXX X Cl LXXwX
4-hydroxynaphthalene-2-methylene
sulfone-1 ether Cr α-chlorovinyl Blue-gray 2-aminophenol-4-ethyl sulfone 1-methoxy-4-hydroxynaphthalene Cr Chloromethyl Gray purple 2-aminophenol-4-ethyl sulfone α-naphthol Cr Chloromethyl Brown 2-amino-4-nitrophenol 3,4-dimethylphenol Co Chloromethyl Brown 2-amino-4-nitrophenol 3,4-dimethylphenol Cr vinyl

Example 4

540 parts of N-methylolchloroacetamide are carried in 3000 parts of 96% strength sulfuric acid at a temperature of 0 ° to 10 ° and then adds 500 parts of the by diazotizing 2-aminophenol-4-sulfonamide and coupling to 2-naphthol obtained azo dyes. The mixture is stirred at 0 to 10 ° for 2 to 3 hours and then applies ice to 8000 parts. One sucks off, washes several times with water and suspends the dye paste in 8000 parts of water.

A pH value of 7 to 7.5 is set by adding sodium hydroxide solution, and the mixture is heated to 50 to 70 ° drops within 30 minutes a solution of 220 parts of cobalt sulfate and 55 parts of tartaric acid, in 800 parts of water dissolved, too. By simultaneous dropwise addition of dilute sodium hydroxide solution one cares for keeping the pH of the solution at 7 to 7.5. After 1 hour you suck the precipitated Dyestuff and dried in vacuo at 50 to 60 °. 1050 g of the reactive dye are obtained the constitution

ClCH ₂ C - NH - CH ₂ - NH - SO ₂

CH, NHCOCH, C1

ClCH ₂ C - NH - CH ₂ NH - SO ₂

709 720/441

of wool and polyamide fibers in bordeaux shades with excellent wet and light fastness properties stains.

If one proceeds as in Example 4, only 600 parts instead of 540 parts of N-methylolchloroacetamide N - methylol - 2 - chloropropionamide or 570 parts of N-methylol acrylamide or 600 parts of N-methylol methacrylamide If you use it, you get other valuable dyes, wool with good fastness properties dye bordo color.

Example 5

20 parts of N-methylolchloroacetamide are introduced into 200 parts of 96% strength sulfuric acid at 0 ° to 10 °

then adds 20 parts of the by diazotization of 2-aminophenol-4-sulfonamide and domes l-phenyl-S-methylpyrazolone-S obtained dye to. The mixture is then stirred for 24 hours at 10 ° to 20 ° and ice is poured onto 800 parts. After suction the dye paste is suspended in 800 parts of water at a pH of 7 to 7.5 and heated 90 to 100 ° and leaves a solution of 10 parts of potassium dichromate and 20 parts within 30 minutes Add glucose dropwise. The mixture is stirred for a further hour at 90 to 100 ° and a pH of 7 to 7.5, lets cool, sucks off and dries. 22 parts of a dye of constitution are obtained

ClCH ₂ CO - NH - CH ₂ - NH - SO ₂

Il

ClCH ₉ C-NHCH ₂

H, C

-CH,

N = N _β / ° Λ

Cr I H-CH ₂ NHCOCH ₂ Cl

SO ₂ NH - CH ₂ - NH - COCH ₂ Cl

Na®

of wool and polyamide fibers with excellent HO - CH2NHOCR2

Wash fastness is colored orange.

If you use 45 as described in Example 4 or 5 and then chrome or cobalt

you get more valuable chrome and

proceeds, only instead of the diazo and coupling components mentioned in Table 2 and also equivalent amounts of the compounds of the general formula given in column IV

you get more valuable chromium-cobalt reactive dyes, dye the wool and polyamide fibers from neutral to weakly acidic baths in the specified shades.

Tabel

I. π III IV hue Diazo component Coupling component metal Reactive component
.HOCH ₂ -NHCOR ₂
R ₂ = Corinth 2-aminophenol-4-sulfonamide 2-hydroxynaphthalene Cr Chloromethyl Corinth 2-aminophenol-4-sulfonamide 2-hydroxynaphthalene Cr Chloroethyl Gray 2-aminophenol-4-sulfonamide l-methoxy-4-hydroxynaphthalene Cr Chloromethyl Gray 2-aminophenol-4-sulfonamide 1-methylsulfonylamino-7-naphthol Cr Chloromethyl Gray 2-aminophenol-4-sulfonamide 1-acetylamino-7-naphthol Cr Chloromethyl Gray 2-aminophenol-4-sulfonamide 1 -Chloroacetylamino-7-naphthol Cr Chloromethyl blue 2-aminophenol-4-sulfonamide 4-hydroxynaphthalene-2-methylene ■ Cr Chloroethyl sulfone-1 ether

I. 1,259,483 III 14th IV hue 13th Diazo component metal Reactive component
HIGH ₂ -NHCOR ₂
R ₂ = orange 2-aminophenol-4-sulfonamide continuation Cr vinyl yellow 2-aminophenol-4-sulfonamide II Co Chloromethyl yellow 2-aminophenol-4-sulfonamide Coupling component Co Chloroethyl Gray 2-aminophenol-4-sulfonamide l-phenyl-S-methylpyrazolone-S Cr Chloroethyl Gray 2-aminophenol-4-sulfonamide 1 -PhenyW-methylpyrazolone-S Cr a-chlorovinyl Brown 2-aminophenol-4-sulfonamide l-phenyl-S-methylpyrazolone-S Co Chloromethyl Brown. 2-aminophenol-4-sulfonamide 2-phenylaminonaphthalene Co Chloromethyl Bordo 2-aminophenol-4-sulfonamide 2-benzoylaminonaphthalene Co Chloromethyl blue 2-aminophenol-4-sulfonamide 1-hydroxy-3,4-dimethylbenzene Cr vinyl blue 2-aminophenol-4-sulfonamide l-hydroxy ^ -acetamino ^ -methyl-
benzene Cr vinyl Brown 2-aminophenol-4-sulfonamide 1-hydroxy-4-methylnaphthalene Co Chloroethyl Red - 2-aminophenol-4-sulfonamide 1-hydroxy-4-methylnaphthalene Cr Chloromethyl Red 2-aminophenol-4-sulfonamide 1-hydroxy-S ^ -dichloronaphthalene Cr «-Chlorovinyl Bordo 2-aminophenol-4-methylsulfone
arnid 2-phenyl-5-aminobenzotriazole- (1,2,3) Co Chloromethyl Corinth 2-aminophenol-4-methylsulfone 1,3-dihydroxyisoquinoline Cr Chlorovinyl amide Pyrazolobenzimidazole Gray 2-aminophenol-4-methylsulfone
amide 2-naphthol Cr Chloromethyl Gray 2-aminophenol-4-methylsulfone 2-naphthol Cr Chloromethyl amide orange 2-aminophenol-4-methylsulfone l-methoxy-4-hydroxynaphthalene Cr Chloroethyl amide l-acryloxylamino-7-naphtho] yellow 2-aminophenol-4-methylsulfone
ainid Co Chloromethyl Brown 2-aminophenol-4-methylsulfone 1-AcTyloylamino-7-naphthol Co Chloromethyl amide blue 2-aminophenol-4-methylsulfone
amide l- (4'-methylphenyl) -3-methyl-
nvra7olon-5 Cr vinyl Gray 2-aminophenol-5-sulfonamide 1-hydroxy-3,4-dimethylbenzene Cr Chloromethyl blue 2-aminophenol-5-sulfonamide Cr Chloromethyl Bordo 2-aminophenol-5-sulfonamide 1-hydroxy-S ^ -dichloronaphthalene Co Chloromethyl Red 2-aminophenol-5-sulfonamide 1-carbomethoxyamino-7-naphthol Cr Chloromethyl blue 2-aminophenol-5-sulfonamide 1-methoxy-4-hydroxynaphthalene Cr Chloromethyl Gray 2-aminophenol-5-methylsulfone 2-hydroxynaphthalene Cr Chloromethyl amide 1-phenyl-S-methylpyrazolone-S Bordo 2-aminophenol ~ 5-methylsulfone- 1-hydroxy-5,8-dichloronaphthalene Co u-chlorovinyl amide 1-chloroacetylamino-7-naphthol Red 2-aminophenol-5-methylsulfone
amide Cr Chloroethyl blue 2-aminophenol-5-methylsulfone
amide 2-hydroxynaphthalene Cr Chloroethyl yellow 2-amino-4-sulfbnamido-
henzoic acid Cr Chloromethyl yellow 2-amino-4-sulfonamido- l- (4'-methylphenyl) -3-methyl-
pyrazolone-5 Cr Chloromethyl benzoic acid 4-hydroxynaphthalene-2-methylene
sulfone-1 ether yellow 2-amino-4-sulfonamido- 1-phenyl-S-methylpyrazolone-S Cr Chloroethyl benzoic acid l- (2'-ethylphenyl) -3-methyl- yellow 2-amino-5-sulfonamido- pyrazolone-5 Cr Chloroethyl benzoic acid l- (4'-methylphenyl) -3-methyl- pyrazolone-5 1-phenyl-3-methylpyrazolone-5

continuation

I. II III IV hue Diazo component Coupling component metal Reactive component
HIGH ₂ -NHCOR ₂
R ₂ = yellow 2-amino-5-sulfonamido- l- (4'-methylphenyl) -3-methyl- Cr Chloromethyl benzoic acid pyrazolone-5 Red 4-chloro-2-aminophenol- 1-phenyl-3-methylpyrazolone-5 Cr Chloromethyl 5-sulfonamide violet 4-chloro-2-aminophenol- 2-hydroxynaphthalene Co Chloromethyl 5-sulfonamide violet 4-chloro-2-aminophenol- 3-hydroxythionaphthene Co Chloromethyl 5-sulfonamide Red 4-methoxy-5-sulfonamido 1-phenyl-S-methylpyrazolone-S Cr Chloromethyl 2-aminophenol blue 4-methoxy-5-sulfonamido 1-acetylamino-7-naphthol Co Chloromethyl 2-aminophenol Red 5-nitro-2-aminophen ol- 1-phenyl-3-methylpyrazolone-5 Cr Chloromethyl 4-sulfonamide green 4-nitro-2-aminophenol- 1-hydroxy-4-methylnaphthalene Cr Chloromethyl 6-sulfonamide blue 4-methoxy-2-aminophenol l-hydroxy-3-sulfonamido- Cr Chloromethyl naphthalene blue 4-chloro-2-aminophenol 1 -hydroxy-3-sulfonamido- Cr Chloromethyl 8-acetylaminonaphthalene violet 4-chloro-2-aminophenol l-hydroxy-3-sulfonamido- Co Chloromethyl 8-acetylaminonaphthalene violet 4-chloro-2-aminophenol l-hydroxy-3-sulfonamido- Cr Chloroethyl 8-acetylaminonaphthalene violet 4-chloro-5-nitro-2-aminophenol l-hydroxy ^ o-disulfonamido- Cr Chloromethyl naphthalene

Example 6

27 parts of N-methylolchloroacetamide are carried in 200 parts of concentrated sulfuric acid at 0 ° to 10 ° and then 30 parts of that obtained by diazotizing 2 - aminophenol - 4 - ethyl sulfone and coupling 2-naphthol obtained dye. After 3 hours, ice is poured onto 1000 parts, suctioned off and washes several times with water. The dye paste is dissolved in 500 parts of water at pH suspended from 7 to 7.5. A solution of 6 parts is added dropwise at 50 ° to 70 ° over the course of 30 minutes Cobalt sulfate and 3 parts of tartaric acid, dissolved in 50 parts of water, ensuring that in the Solution a pH of 7 to 7.5 is maintained. After 1 hour, the mixture is allowed to cool and filtered off with suction. 36 parts of the dye of constitution are obtained

SO ₂ C ₂ H;

CH ₂ NH - COCH ₂ Cl

which dyes wool and polyamide fibers in excellent wet and lightfast shades.

Example 7

In 200 parts of 96% strength sulfuric acid, 15 parts of N-methylol-β-chloropropionic acid amide are carried at from 0 to 10% and then adds 20 parts of the diazotization of 2-aminophenol-4-ethylsulfone and Coupling to l- (4'-methylphenyl) -3-methylpyrazolon-5 obtained dye. Then stir 24 hours at 15 to 20 ° and applies

800 pieces of ice cream. After suction, the dye paste is suspended in 800 parts of water at a pH of 7 to 7.5, heated to 50 to 70 ^{° C.} and a solution of 10 parts of cobalt sulfate and 5 parts of tartaric acid is added dropwise within 30 minutes, being careful that a pH value of 7 to 7.5 is maintained by adding dilute sodium hydroxide solution. After 1 hour, the product is filtered off with suction and, after drying at 60 °, 22 g of dye of the constitution is obtained

SO, C, H

H, C

CH, NHC OCH, CH, Cl

Na®

which dyes wool and polyamide fibers orange with very good wet and light fastness properties.

If one proceeds as in Examples 6 and 7, only instead of the diazo and coupling components mentioned in Table 3 and equivalent amounts of the compounds of the general formula HO — CH ₂ NHOCR _{2 given in column IV}

If you use it, you get other valuable chromium and cobalt complex dyes, wool and polyamide fibers dye from neutral to weakly acidic bath in the specified shades.

Tabel

I. π III IV hue Diazo component Coupling component metal Reactive component
HIGH ₂ -NHCOR ₂
R ₂ = Bordo 2-aminophenol-4-methylsulfone 2-hydroxynaphthalene Co Chloromethyl Corinth 2-aminophenol-4-methylsulfone 2-hydroxynaphthalene Cr Chloroethyl Bordo 2-aminophenol-4-ethyl sulfone 2-hydroxynaphthalene Co Chloroethyl Corinth 2-aminophenol-4-ethyl sulfone 2-hydroxynaphthalene Cr Chloroethyl Bordo 2-aminophenol-4-dimethyl- 2-hydroxynaphthalene Co Chlorovinyl sulfonamide Corinth 2-aminophenol-4-dimethyl- 2-hydroxynaphthalene Cr vinyl sulfonamide Gray 2-aminophenol-4-ethyl sulfone 1-methoxy-4-hydroxynaphthalene Cr vinyl Gray 2-aminophenol-4-ethyl sulfone 1-acetylamino-7-naphthol Cr Chloromethyl orange 2-aminophenol-4-ethyl sulfone 1-phenyl-S-methylpyrazolone-S Cr Chloromethyl

709 720/441

continuation

I. II III IV hue Diazo component Coupling component metal Reactive component
HIGH ₂ -NHCOfI ₂
R ₂ = yellow 2-aminophenol-4-ethyl sulfone l-phenyl-S-methylpyrazolori-S Co Chloromethyl yellow 2-aminophenol-4-ethyl sulfone l- (4'-ethylphenyl) -3-methy] -
Dvrazolone-5 Co Chloromethyl orange 2-aminophenol-4-ethyl sulfone l- (4'-ethylphenyl) -3-methyl- Cr Chloromethyl pyrazolone-5 Gray 2-aminophenol-4-ethyl sulfone 2-phenylaminonaphthalene Cr Chloromethyl Brown 2-aminophenol-4-ethyl sulfone 1-hydroxy-3,4-dimethylbenzene Co Chloromethyl blue 2-aminophenol-4-ethyl sulfone 1-hydroxy-5,8-dichloronaphthalene Cr Chloromethyl blue 5-nitro-2-aminophenol 2-amino-6-sulfonamidonaphthalene Co vinyl Brown 4-chloro-2-aminophenol l-phenyl-3-methylpyrazolone -5 Co vinyl Brown 4-chloro-2-aminophenol l-phenyl-3-methylpyrazolone -5 Co Chloromethyl Red 4-chloro-2-aminophenol l-phenyl-S-methylpyrazolone-S Cr Chloromethyl Brown 4,6-dichloro-2-aminophenol l-phenyl-3-methylpyrazolor-5 Co Chloromethyl Brown 4-nitro-2-aminophenol 1-phenyl-3-methylpyrazolone-5 Co Chloromethyl Red 6-nitro-4-chloro-2-aminophenol 1-phenyl-S-methylpyrazolone-S Cr Chloromethyl Red 4-methyl-6-nitro-2-amino- l- (4'-methylphenyl) -3-methyl- Cr Chloromethyl phenol pyrazolone-5 yellow 2-aminobenzoic acid l- (4'-methylphenyl) -3-methyl- Cr Chloromethyl pyrazolone-5 yellow 2-aminobenzoic acid 1-phenyl-3-methylpyrazolone-5 Cr Chloromethyl yellow 2-aminobenzoic acid 1-phenyl-S-methylpyrazolone-S Cr vinyl yellow 2-aminobenzoic acid l- (2'-ethylphenyl) -3-methyl- Cr Chloromethyl pyrazolone-5 Bordo 3-amino-4-hydroxybenzene 1 - (2'-ethylphenyl) -3-methyl- Cr Chloromethyl 2-methylene sulfone pyrazolone-5 Bordo 3-amino-4-hydroxybenzene 1 - (2'-ethylphenyl) -3-methyl- Cr Chloromethyl 2-methylene sulfone pyrazolone-5 blue 5-nitro-4-chloro-2-aminophenol 1 -hydroxy-SJ-disulfonamido- Cr Chloromethyl naphthalene blue 4-nitro-2-aminophenol 1-hydroxynaphthalene-4-sulfonamide Cr Chloromethyl violet 4-chloro-2-aminophenol 2-hydroxynaphthalene-6-sulfonamide Cr Chloromethyl ruby 4-chloro-2-aminophenol 2-hydroxynaphthalene-6-sulfonamide Co Chloromethyl blue 4-chloro-2-aminophenol 1-methyl-4-hydroxynaphthalene Cr Chloromethyl violet 4-nitro-2-aminophenol 1-methyl-4-hydroxynaphthalene Co Chloroethyl Bordo 2-aminophenol-4-ethyl sulfone 1-methyl-4-hydroxynaphthalene Cr Chloroethyl Red 5-nitro-2-aminophenol 1-phenyl-S-methylpyrazolone-S Cr Chloromethyl Red 5-nitro-2-aminophenol l- (4'-methylphenyl) -3-methyl- Cr Chloroethyl pyrazolone-5 Red 2-aminophenol-4-phenyl- 2-Hydroxy-3-carboxynaphth £ .lin Co Chloromethyl sulfonamide yellow 2-aminophenol-4-sulfonamide l- [3 '- (2-Hydroxyäthylsulfonamido) - Cr Chloromethyl phenyl] -3-methylpyrazolone-5 Red 5-nitro-2-aminophenol-
4-methvisnifon l-phenyl-S-methylpyrazolone-S Cr Chloromethyl Red ^ T XX.Lx. ' LlJk. V XO U-XX V / XX
5-nitro-2-aminophenol- i -Phenyl-S-methylpyrazolone-S Cr Chloromethyl 4-ethyl sulfone green 4,6-dinitro-2-aminophenol 4-methyl-1-naphthol Cr Chloromethyl blue 4-chloro-2-aminophenol 4-methyl-1-naphthol Cr Chloromethyl Bordo 4-nitro-2-aminophenol 4-methyl-1-naphthol Co Chloromethyl Brown 4-nitro-2-aminophenol 3,4-dimethylphenol Co Chloromethyl

continuation

I. II III IV hue Diazo component Coupling component metal Reactive component
HIGH ₂ -NHCOR ₂
R ₂ = Brown 4-nitro-2-aminophenol 3,4-dimethylphenol Cr Chloromethyl Brown 4-nitro-2-aminophenol 2-acetylamino-4-methylphen oil Co Chloromethyl blue 5-nitro-2-aminophenol 6-sulfonamido-2-aminonaphthalene Co Chloromethyl Gray 5-nitro-2-aminophenol 2-hydroxynaphthalene Cr Chloromethyl violet 5-nitro-2-aminophenol 2-hydroxynaphthalene Co Chloromethyl blue 4-methoxy-2-aminophenol 2-hydroxynaphthalene Cr Chloromethyl blue 4-methoxy-2-aminophenol 2-hydroxynaphthalene Cr Chloroethyl blue 4-methoxy-2-aminophenol 2-hydroxynaphthalene Cr Chlorovinyl blue 5-nitro-2-aminophenol 1 -acetylamino-7-hydroxy-
nanhthalin Cr Chloromethyl blue 5-nitro-2-aminophenol IJ. Cl L / JJ LXAd ₁ IAJLJ
l-chloroacetylamino-7-hydroxy- Cr Chloromethyl naphthalene blue 5-nitro-2-aminophenol l-methylsulfonylamino-7-hydroxy-
naohthalin Cr Chloromethyl Brown 4,6-dichloro-2-aminophenol l-PhenyW-methylpyrazolone-S Co Chloromethyl Red 2-aminophenol-4-ethyl sulfone 1-phenyl-3-methylpyrazolone-5 Cr Chloromethyl violet 4-methyl-6-nitro-2-amino- 2-hydroxynaphthalene Co Chloromethyl phenol Gray 2-aminophenol-4-dimethyl- l-acetylamino-7-hydroxy- Cr Chloromethyl sulfonamide naphthalene Brown 4-nitro-2-aminophenol 2-hydroxynaphthalene Cr Chloromethyl

B e i s ρ i el 8

The mixture is stirred in 300 parts of 96% sulfuric acid at a temperature of 0 ° to 10 °, 40 parts of N-methylolchloroacetamide and then 34.5 parts of the dye obtained by diazotizing 2-aminophenol-4-sulfonamide and coupling on 2-hydroxynaphthalene and stirred at 0 to 10 ^? 3 hours. It is then applied to 1000 parts of ice, the dyestuff which has separated out is suctioned off thoroughly, and it is washed several times with water until the reaction is neutral

NO

dries at 60 ° in a vacuum. The dry dye is at 100 ° to 34 parts of a solution of the 1: 1 chromium complex des by diazotizing 4-nitro-2-aminophenol and coupling onto l-phenyl-3-methyl-5-pyrazolone The dye obtained is added to 200 parts of ethylene glycol. Then you give 150 parts of formamide are added, the mixture is stirred at 100 ° for a further 30 minutes and discharges into 2000 parts of water. It is acidified to pH 5 and filtered off with suction. After drying, 85 parts of the dyestuff of the constitution are obtained

Na®

CH ₂ NHCOCH ₂ Cl

NH - CH ₂ NHCOCH ₂ Cl dyes wool and polyamide fibers in brown tones with very good wet and lightfast properties.

e i s ρ i e 1 9

24
Example 10

The mixture is stirred in 300 parts of 96% strength sulfuric acid at 0 to 10 ° 30 parts of N-methylolchloroacetamide and then 36 parts of the diazotization of 2-aminophenol-4-ethylsulfone and cupolas on 2-hydroxynaphthalene obtained dye, stirred for 3 hours at 0 to 10 °, carries out on 1000 parts of ice, sucks off the precipitated dye and washes with water until it reacts neutral. One gives the dry dye to 34 parts of the 1: 1 chromium complex des by diazotization of 2-aminophenol-4-sulfonamide and coupling the dye obtained on 2-hydroxynaphthalene in 200 parts of ethylene glycol to. The solution is heated to 90 ° to 100 °, 150 ml of formamide are added and more is stirred 30 minutes and then apply water to 2000 parts. It is acidified with dilute hydrochloric acid and the suction filter precipitated dye and, after drying, receives 80 parts of the 2: 1 chromium complex constitution

SO ₉ NH

A mixture of 43 parts of the constitution dye

COOH

N = N

HO

-CH,

CH ₂ NHCOCH ₂ Cl

and from 61 parts of the coloring matter of the constitution

OH

CH ₂ NHCOCH ₂ Cl

30th

Na®

CH ₂ - NHCOCH ₂ Cl

SO ₂ C ₂ H ₅

CH ₂ NHCOCH ₂ Cl

which dyes wool and polyamide fibers in corinth shades with very good wet and light fastness properties.

are suspended in 1000 parts of water at a pH of 7 to 8. The mixture is heated to 90 ° to 100 ° and a solution of 20 parts of potassium dichromate and 40 parts of glucose in 200 parts of water is added dropwise over the course of 30 minutes, taking care that a pH of about 8 is maintained by adding dilute sodium hydroxide solution. After 2 hours, the mixture is allowed to cool, acidified with dilute hydrochloric acid, suction filtered and dried at 60 ° ^C. in vacuo. 130 parts of a chromium mixed complex are obtained which dyes wool and polyamide fibers in olive shades with very good wet fastness properties.

example

A solution of 300 parts of the diazotization of 2-aminophenol-4-sulfonamide and domes Acetoacetanilide available azo dyes in 1500 parts of 96% sulfuric acid is on a Chilled temperature from 0 to 10 °. 200 parts of methylolchloroacetamide are then sprinkled in and the mixture is stirred 5 hours at a temperature of 0 to 10 °. Then one carries out on 7000 parts of ice, sucks the precipitated dye off and washed several times with water. The dye paste comes in 2500 parts Stirred up with water and adjusted to a pH of 7 to 8 with sodium hydroxide solution. One now drips in 60 ° a solution of 220 parts of cobalt sulfate and 55 parts of tartaric acid within 30 minutes, Care should be taken to ensure that the pH value is always 7.5 by adding further dilute sodium hydroxide solution up to 8 is complied with. The mixture is stirred for a further 2 to 3 hours and, after cobalting is complete, suctioned off. It is washed with water and dried at 60 ° in vacuo and 440 parts of a dye of the constitution are obtained

OPT

ⁿ HO - C - CH ₃

X-N = N-C-C-NH- ^ X

SO ₂ NH - CH ₂ - NH - C - CH ₂ Cl

• CH ₂ NH - CO - CH ₂ Cl

Co 2: 1 complex

Example 12

A solution of 300 parts made by diazotization of 4-nitro-2-aminophenol and domes Acetoacetanilide available azo dyes in 1000 parts of 96% sulfuric acid is on a Chilled temperature from 0 to 10 °. 120 parts of methylolchloroacetamide are then sprinkled in and the mixture is stirred 5 hours at a temperature of 0 to 10 °. Then one carries out on 7000 parts of ice, sucks the precipitated dye and washes several times

with water. The dye paste is stirred up in 2500 parts of water and diluted with sodium hydroxide solution pH adjusted from 7 to 8. A solution of 220 parts of cobalt sulfate is then added dropwise at 60 ° 55 parts of tartaric acid within 30 minutes, taking care that by adding more Sodium hydroxide solution always maintains a pH of 7.5 to 8. The mixture is stirred for a further 2 to 3 hours and sucks off after complete cobalting. It is washed with water and dried at 60 ° in vacuo and receives 340 parts of dye of the constitution

? ^H

N = N-C-C-NH

NO ₂

CH ₂ NH - CO - CH ₂ Cl

Co 2: 1 complex

If one proceeds as described in Example 12, only instead of the azo dyes mentioned there If those listed in Table 4 are used, other reactive dyes, such as wool and polyamide fibers, are obtained dye with very good wash and light fastness properties.

Tabel

Diazo component Coupling component metal hue 2-aminophenol-4-ethyl sulfone Acetoacetic anilide Co yellow 2-aminophenol-4-ethyl sulfone Acetoacetic acid-2-methylanilide Co yellow 2-aminophenol-4-ethyl sulfone Acetoacetic acid 4-chloro-2-methylanilide Co yellow 2-aminophenol-4-ethyl sulfone Acetoacetic acid 2,4-dimethylanilide Co yellow 2-aminophenol-4-ethyl sulfone Acetoacetic acid-2-chloroanilide Co yellow 2-aminophenol-4-ethyl sulfone Acetoacetic acid-2,5-dimethoxy-4-chloroanilide Co yellow 4-nitro-2-aminophenol Acetoacetic acid-2-methylanilide Co yellow 4-nitro-2-aminophenol Acetoacetic acid-2-methoxyanilide Co yellow 4-nitro-2-aminophenol Acetoacetic acid 4-chloroanilide Co yellow 4-chloro-2-aminophenol Acetoacetic anilide Co yellow 4-chloro-2-aminophenol Acetoacetic acid-2-methoxyanilide Co yellow 4-chloro-2-aminophenol Acetoacetic acid-2-methylanilide Co yellow 4-chloro-2-aminophenol Acetoacetic acid 2,4-dimethylanilide Co yellow 4-chloro-2-aminophenol Acetoacetic acid-2-chloroanilide Co yellow 4-chloro-2-aminophenol Acetoacetic acid 4-chloro-2-methylanilide Co yellow

Example 13

One carries in 3000 parts of 96% sulfuric acid at 0 to 10 ° 560 parts of N-methylolbromoacetamide and then adds 250 parts of the by diazotization of 2-aminophenol-4-sulfonamide and domes 2-naphthol obtained azo dyes. The mixture is stirred for 4 hours at 0 ° to 10 ° and 8000 parts of ice are applied the end. The precipitated dye is filtered off with suction, washed several times with water and suspended the dye paste in 8,000 parts of water. By adding sodium hydroxide solution, a pH of 7 to 7.5, heated to 60 to 65 ° and a solution of 110 parts of cobalt sulfate is added dropwise within 30 minutes and 30 parts of tartaric acid dissolved in 400 parts of water. By simultaneous dropwise addition of diluted Sodium hydroxide solution ensures that a pH of 7 to 7.5 is maintained in the solution. After 1 hour, the dyestuff which has precipitated out is filtered off with suction and dried at 50 ° to 60 °. You get 810 parts of the reactive dye of the composition

709 720/441

27 O

Il

Br - CH ₂ - C - NH ■

Il

CH, - NH-C-CH, - Br

Na®

SO ₂ NH CH ₂ -NH-C-CH ₂ -Br

CH ₂ -NH-C-CH ₂ -Br

which dyes wool and synthetic superpolyamide fibers with excellent wash fastness in bordeaux colors.

B e i s ρ i e 1 14

25 parts of methylol-a-bromoacrylic acid amide are carried in 250 parts of 96% strength sulfuric acid at 0 to 10 ° and then adds 20 parts of the diazotization of 2-aminophenol-4-ethyl sulfone and kuppein obtained on l-phenyl-S-methyl-S-pyrazolone Dye too. The mixture is then stirred for 24 hours at 10 ° to 20 ° and ice is poured onto 800 parts. After this The dye paste is suspended in 800 parts of water with suction and repeated washing a pH of 7 to 7.5, heated to 90 to 100, ° and leaves a solution of within 30 minutes 10 parts of potassium dichromate and 20 parts of glucose are added dropwise. The mixture is stirred for a further hour at 90 bis 100 ° and a pH of 7 to 7.5, lets cool, sucks off and dries at 50 to 60 °. You get 27 parts of the dye of the composition

OH

Claims (3)

Patent claims: 1. A process for the production of metal-containing azo dyes, characterized in that that one is identical or a mixture of mutually different sulfonic acid and carboxylic acid groups-free Azo dyes of the general formula HY A-N = N-B Il CH, -N —C —R, 40 45 CH ₂ - NH - C - C = CH wherein A is a radical of the benzene or naphthalene series, in which Q is in o-position to Azo group is located, B denotes the remainder of a coupling component in which Y is in the adjacent position represents the azo group, Q represents an —OH, —COOH or —O-alkyl group, Y represents the rest - O -, - NH -, —N-aryl, —N-aroyl and / or - N-arylsulfonyl is, Ri is hydrogen, an alkyl or aryl substituent, R2 is a saturated or unsaturated haloalkyl group, where the halogen can be in a- or / S-position, a vinyl, α-halovinyl, di- or trihalovinyl radical, an a- or / J-alkylvinyl radical or a substituted or unsubstituted α-hydroxymethylene or ^ S-hydroxyethylene radical esterified with an aliphatic or aromatic sulfonic acid and m ' denotes the number 1 or 2, optionally in a mixture with metallizable azo dyes of the general formula which dyes wool and synthetic superpolyamide fibers orange with excellent wash fastness. ? T A-N = N-B (Ha) wherein A, B, Q and Y have the meaning given have treated with chromium or cobalt donating agents in such a way that 1: 2 metal complex dyes develop. 2. Process for the preparation of the after
Claim 1 available metal-containing
substances in modification of the procedure
Claim 1, characterized in that
Colorants of the general formula AnAzo color according to Andaß man A- -N = N B " Me IO A N = N B wherein A, B and Y have the meaning given in claim 1 and X represents the radical —O - and / or - COO -, Me is Cr or Co and K is a cation, in the presence acidic condensing agents with compounds of the general formula HO - CH ₂ - N - C - R ₂
R ₁ (IH) 30th where Ri and R2 are those given in claim 1 Have meaning, converts, while the starting components are free of sulfonic acid and carboxylic acid groups selects and, in the case of demetallization of the dyes used in the form of the metal complexes, the products obtained treated with agents indicating chromium or cobalt in such a way that 1: 2 metal complex dyes develop. 3. A process for the preparation of the metal-containing azo dyes obtainable according to claim 1 in modification of the procedure after arrival 35 40 spoke 1, characterized in that the 1: 1 chromium complex compound of an azo dye the general formula Q HY i
AN = NB- Il CH ₂ -NCR ₂ wherein A, B, Q, Y, Ri, R- and m 'have the meaning given in claim 1, with another metal-free dye of this formula or an azo dye of the general formula Q HY A-N = N-B wherein A, B, Q and Y have the meaning given in claim 1, or that one has the 1: 1 chromium complex compound of an azo dye of the general formula Q HY A-N = N-B with a metal-free azo dye of the general formula HY A-N = N Il CH ₂ - N - C - R ₂
R ₁ converts to the 1: 2 chromium complex compound and thereby the starting components of sulfonic acid and freely chooses carboxylic acid groups. Considered publications:
Announced documents of the Belgian patent No. 579 968. When the application was announced, a coloring table with explanations was laid out. 709 720/441 1.68 © Bundesdruckerei Berlin