CH625821A5 - Process for preparing asymmetrical 1:2 chromium complexes containing an azo compound and an azomethine compound - Google Patents

Description

The invention relates to processes for the preparation of 1: 2 chromium complexes in the form of the free acids of the formula I.

mean and A1, A2, A3, X, Y, Z, n, R3 and R4 have the meanings given in claim 2.

4. The method according to claim 1, characterized in

that the free acids of formula I are converted into their salts with N-containing bases. 65

5. Use of the water-insoluble dyes, prepared by the process according to claims 1 and 4, for coloring organic non-textile materials.

A N = N B

Cr

/ W

D-CH «= N

correspond in which e

n + 1

(I)

(H®)

n + 1

{

625 821

4th

A the rest of a carbocyclic diazo component with the rest of a complex-forming hydroxy or carboxy. group in the vicinity of the azo bridge;

B the remainder of a carbocyclic, heterocyclic or open-chain coupling component with the remainder of a complex-forming hydroxyl or amino group adjacent to the azo bridge;

D the remainder of a carbocyclic aldehyde with the remainder of a complex-forming hydroxy group adjacent to the azomethine compound;

E is an optionally substituted aliphatic hydrocarbon with the residue of a complex-forming hydroxyl or caboxy group; and n is the number of car-boxyl and sulfonic acid groups not involved in the formation of the complex.

The compounds of the formula I are prepared by working on 1: 1 chromium complexes of the formula II

A1 hydrogen, hydroxysulfonyl, chlorine, bromine, methyl, methoxy, ethoxy, nitro, methylsulfonyl, ethylsulfonyl,

A3 hydrogen, where

A1 and A2 together can form a fused-on benzene ring optionally substituted by nitro;

R1 is hydrogen, chlorine, bromine, nitro, hydroxysulfonyl, phenylazo optionally substituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro or hydroxysulfonyl or naphthylazo substituted by hydroxysulfonyl;

R2 is hydrogen, chlorine, bromine or nitro, where

R1 and R2 can together form a fused benzene ring;

X-O- or COO-;

Y -O- or -NH-; A- .1

K CILC = C - CONH- \ v

3I I \

-N = N-

IX

Cr

, ©

(II),

25th

R '

CH-

Sulfamoyl, N-mono- or N, N-di-Ci to -Cf-alkyl-substituted sulfamoyl or N-phenylsulfamoyl;

A2 hydrogen, chlorine, nitro or hydrosulfonyl,

AQ in the AQ means azomethine compounds of the formula III

~ \ _3 ^

R

Yr

A

CN

OH

H-D-CH = N-E-H

(III)

or their two individual components, the compounds of the formulas II and III together containing the carboxyl and sulfonic acid groups corresponding to the number n.

The compounds of formula I can be converted into their salts. Cations for the complexes include, for example, alkali, ammonium or substituted ammonium cations, such as sodium, potassium, ammonium, trimethyl, tributyl, dimethyldibenzyl, di-β-hydroxyethyl, β-ethylhexyl, y- {ß- Ethylhexoxy) propyl or i-propoxypropylammonium into consideration.

In particular, the invention relates to processes for the preparation of dyes which are in the form of the free acids of the form Ia or

45

a n + 1

50

R3 is hydrogen, methyl, phenyl or carbamoyl; R4 is hydrogen or phenyl which is optionally substituted by methyl, chlorine or hydroxysulfonyl;

R5 is methyl, methoxy, acethylamino, propionylamino, benzoylamino, N-phenylamino, dimethylamino or diethylamino;

R6 hydrogen or methyl;

R7 is hydrogen or hydroxysulfonyl, where R5 and R6 together can form a fused benzene ring optionally substituted by bromine, amino, hydroxy, phenyloamino, acetyl, propionyl or benzoylamino of the hydroxysulfonyl .;

Z "(Cii2) n '" f "• ■

1 3 CH2C6H5 KH5

(h9)

(Ia)

-CH-

:?

n + 1

(CH ") C00H 2 n1

or -CH-CH CH0-; and

Ah 2 2

m represents the numbers 1, 2 or 3.

Compounds of the formula H-A-NH2 or compounds suitable for the preparation of the compounds of the formula II or

65

in which n has the meaning given above,

-NH.

625821

Examples are: diazotizable amines of the benzene or naphthalene series which contain an alkoxy or carboxy group as complex-forming substituents in the o-position to the amino group, in particular for example: 2-aminophenol, 4-chloro-2-aminophenol, 4- or 5-nitro-2-aminophenol, 4,6-dichloro-5 2-aminophenol, 4,6-dinitro-2-aminophenol, 4-methyl-6-nitro-2-aminophenol, 4-chloro-5-nitro-2 -aminoanisole, 4,5-di-chloro-2-aminoanisole, 2-aminobenzoic acid, 4-nitro-2-aminobenzoic acid, 2-aminophenol-4-sulfonic acid, 2-aminophenol-4-sulfonic acid amide, 2-aminophenol4-sulfonic acid methyl amide , 10th

2-aminophenol-4-sulfonic acid phenylamide, 4-chloro-2-aminophe-no-6-sulfonic acid, 4-chloro-2-aminoanisole-5-sulfonic acid methylamide, 4-nitro-2-aminophenol-6-sulfonic acid, 6- Nitro-2-aminophenol4-sulfonic acid, 5-N itro-2-aminoanisole-4-sulfonic acid, l-amino-2-naphthol-4-sulfonic acid, l-amino-6-nitro-2-naph-15 thol-4-sulfonic acid or 2-amino-1-naphthol-5-sulfonic acid.

Compounds of the formula H-B-H or H-K-YH suitable for the preparation of the compounds of the formula II are, for example:

Coupling components of the benzene, naphthalene, pyrazole, pyridine, quinoline or pyrimidine series containing hydroxyl or amino groups and derivatives of 1,3-dicarbonyl compounds, in particular for example:

4-methylphenol, 3,4-dimethylphenol, 4-acetylaminophenol,

4-methyl-3-acetylaminophenol, 3-diethylaminophenol, 4-methyl-25-methyl-3-ethylaminophenol, 3- (o-tolyamino) phenol, 2-naphthylamine, 2-naphthol, 6-bromo-2-naphthol , 5,8-dichloro-l-naphthoI, l-naphthol-5-sulfonic acid, 2-naphthol-6-sulfonic acid, 1-naphthylamine-4- or -5-sulfonic acid, 2-naphthylamine-5- or -6 sulphonic acid, 8-acetylamino-l-naphthol-5-sulfonic acid, 6-phenylamino-30 no-l-naphthol-3-sulfonic acid, 7-amino-l-naphthol-3-sulfonic acid,

3-methyl-5-pyrazolone, l-phenyl-3-methyl-5-pyrazoIon, 1,3-diphenyl-5-pyrazolone, l-phenyl-3-carbäthoxy-5-pyrazolone, 1- (2'-methylphenyl) -3-methyl-5-pyrazolone, l- (4'-chlorophenyl) -3-methyl-5-pyrazolone, 1 - (2 ', 5'-dichlorophenyl) -3-methyl-5-pyra-35 zolon, l -Penyl-3-methyl-5-pyrazolone-4'-carboxylic acid, 1-phenyl-3-methyl-5-pyrazolone-3'- or 4'-sulfonic acid, 1,3-diphenyl-

5-pyrazolone-2'-sulfonic acid, 1- (2'-chlorophenyl) -3-methyl-5-pyrazolone-5'-sulfonic acid, 2,4-dihydroxyquinoline, N-acetoacetyl-cyclohexylamide, N-acetoacetylphenylamide , N-Acetoacetyl-40 (2-chlorophenyl) -amide or N-AcetoacetyI- (4-methyIpehnyl) -amide-2-sulfonic acid.

Suitable starting compounds for those of the formula III are compounds of the formula H-D-CHO or

45

cho are, for example: o-hydroxy aldehydes of the benzene and naphthalene-rich such as 2-hydroxybenzaldehyde, 2-hydroxy-l-naphthalen-dehyde, 3-nitro-2-hydroxybenzaldehyde, 5-nitro-2-hydroxybezaldehyde, 5-bromo 2-hydroxybenzaldehyde, 3,5-dinitro- or 3,5-dichloro-2-hydroxybenzaldehyde, 2-hydroxy-l-naphthaldehyde-3-carboxylic acid, 2-hydroxybenzaldehyde-5-sulfonic acid, 5- (2 ', 5'- Dichlorophenylazo) -2-hydroxybenzaldehyde, 5- (2'-methoxyphe-nylazo) -2-hydroxybenzaldehyde-5'-sulfonic acid or 5- (2'-chlorophenylazo> 2-hydroxybenzaldehyde-5'-sulfonic acid.

Suitable starting compounds for those of the formula III are compounds of the formula HE-NH2 or HX-Z-NH2 are, for example, aliphatic amines which contain a complex-forming hydroxyl or carboxylic acid group in the 2- or 3-position to the amino group, such as l-aminoethanol 2,1-aminopro-panol-2, l-aminopropanol-3,3-amino-3-methylbutanol-l, 2-

Amino acetic acid, 2-aminopropionic acid, 3-aminopropionic acid, 2-amino-3-hydroxypropionic acid, 2-amino-3-phenylpropionic acid, 2-aminobutyric acid, amino succinic acid or 2-aminoglutaric acid.

The 1: 2 chromium complexes are prepared starting from the 1: 1 chromium complexes of the azo compounds, which can be obtained by known processes.

The reaction of the 1: 1 chromium complexes with the azome-thin compounds or their individual components is expediently carried out in aqueous solution or suspension, optionally with the addition of organic solvents, for example alcohols or carboxamides. The 1: 2 complex formation takes place, for example, in the weakly acidic to alkaline range, preferably at pH 6 to 9 and at elevated temperature, for example from 50 ° C. to the boiling point.

The resulting 1: 2 complexes can be isolated by acidification, salting out with alkali salts or evaporation; water-soluble complex salts are obtained. To produce water-insoluble, organophilic dyes, the complexes can be precipitated from aqueous solution with suitable N-containing bases, which provide the cations.

Longer-chain alkyl or cycloalkylamines with preferably 6 to 16 carbon atoms, such as 2-ethylhexylamine, di- (2-ethylhexyl) amine, 3- (2'-ethylhexoxy), are preferably used as N-containing bases for the preparation of these solvent dyes ) -propylamine, dodecylamine, isotridecylamine, oleylamine, dicylclohexylamine, N, N'-diphenylguanidine, N, N'-di- (2-methylphenyl) guanidine, phenylbiguanide, 4-chlorophenylbiguanide or (2-M ethylphenyl> biguanide.

The dyes are suitable for dyeing or printing natural or synthetic nitrogen-containing materials, such as wool, polyamide or polyurethane fibers.

The water-soluble, but soluble in organic solvents color salts with amine bases can be used for coloring organic liquids, resins or lacquers, wood stains or ballpoint pen pastes, for coloring anodically oxidized aluminum or as spinning dyes, for example for the production of colored cellulose ester or polyamide fibers.

Of particular technical importance are dyes whose anion of the formula Ib or Ic

50

55

(Cl)

65

(Ib)

625 821

6

A

-N = N K

-N = N

A

(le)

corresponds in which m is the numbers 0, 1 or 2 and K1 is a radical of the formula and A1, A2, A3, X, Y, Z, R3 and R4 have the meanings given.

R3 is preferably methyl and R4 is phenyl optionally substituted by methyl, chlorine and / or hydroxysulfonyl.

Preferred for:

A1 hydroxysulfonyl, chlorine or nitro,

A2 hydrogen, chlorine, nitro or hydroxysulfonyl,

A1 and A3 together form a condensed benzene ring optionally substituted by nitro and

Z -CH2-, -CH2CH2-j -CH- or

CH,

J

-CH-CH ^ -.

t c:

CH,

D

In the following examples, parts and percentages are by weight unless otherwise noted.

The formulas belonging to the examples are shown on the drawing sheets. Example and formula numbers match.

example 1

22 parts of 5-phenylazo-2-hydroxybenzaldehyde-4'-sulfonic acid are stirred in 300 parts of water and after adding

6.4 parts of aminoacetic acid to pH with aqueous sodium hydroxide solution

7.5 posed. Heating to 70 ° C. gives an orange solution, into which 35 parts of the 1: 1 chromium complex compound of the azo dye 5-nitro-2-aminophenol - 2 naphthylamine-5-sulfonic acid are gradually introduced while stirring. The original pH is maintained by further addition of sodium hydroxide solution.

The addition of the azomethine compound to the 1: 1 chromium complex compound can be followed by thin layer chromatography.

When the 1: 2 complex formation is complete, the mixture is salted out with 50 parts of potassium chloride and 100 parts of sodium chloride, suction filtered after cooling and dried. 83 parts of a dye complex salt are obtained, the monoanion of which corresponds to Formula 1. The dye dyes wool and synthetic polyamides in yellowish shades of green with very good light and wet fastness properties.

The following complexes, characterized by the starting materials, are obtained analogously:

example

hue

example

hue

example

hue

2nd

olive

4th

olive green

6

brown

3rd

olive green

5

yellow

7

olive brown

8th

violet

Example 9

140 parts of the 1: 1 chromium complex compound of the azo dye l-amino-2-naphthol-4-sulfonic acid - l-phenyl-3-methyl-5-pyrazolone-3'-sulfonic acid and 16.5 parts 2-aminoethanol are in 100 parts Water dissolved at 65 ° C. 32 parts of salicylaldehyde are added with stirring and a pH of 8.5 is established by adding aqueous sodium hydroxide solution. The mixture is stirred at 65 to 75 ° C until the thin layer chromatographic control indicates the completion of the 1: 2 complex formation. After neutralization with acetic acid, 400 parts of sodium chloride are added and the precipitated dye is isolated by filtration.

After drying, 240 parts of a dye are obtained, the complex monoanion of which corresponds to Formula 9. The dyeings obtained on wool or synthetic polyamides are red and have good light and wet fastness properties.

At

colour

At

colour

At

Color play on wool play on wool play on wool

10th

red

14

yellow

18th

greenish

11

red

15

green

blue

12

red

16

blue-gray

19th

blue

13

red

17th

blue

20th

olive

Example 21

47 parts of the 1: 1-chromium complex compound of the azo dye 1-amino-2-naphthol-4-sulfonic acid - 1-phenyl-3-methyl-pyrazolone-5 are stirred in a mixture of 200 parts of ethanol and 150 parts of water and adjusted by adjusting a pH of 7.2 dissolved in aqueous sodium hydroxide solution at 60 ° C. 16.5 parts of X-nitrosalicylaldehyde (3/5 isomer mixture) and 8 parts of aminoacetic acid are added and the pH is maintained at 7.2 by further addition of sodium hydroxide solution. After the formation of the 1: 2 complex has ended, a solution of 38 parts of 3- (2'-ethylhexoxy) propylamine-1 and 15 parts of acetic acid in 150 parts of water is left stirring and stirring at 40 ° C.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

7

625 821

then evaporate the organic solvent. The alcohol with pure red color and can be filtered to produce red precipitated amine salt of the 1: 2 chromium complex, ballpoint pen paste can be used.

washed with water and dried. It dissolves in benzylal

At

N-base

At

N-base

At

N-base game

Hue match

Hue match

hue

22

Dicyclo-

24th

Diphenyl

25th

Dodecyl

hexylamine

guanidine

amine

orange

yellow

green

23

3- (2'-ethyl

hexoxy) -pro-

pylamine-1

blue

8 sheets of drawings

Claims (6)

625 821 2nd PATENT CLAIMS 1. Process for the preparation of asymmetrical 1 ^ chromium complexes containing an azo and an azomethine compound, which in the form of the free acids of the formula I A — N = N ■ 1/ Cr D -CH ~ = N- n + 1 (H ) (I) n + 1 correspond in the 15th A the remainder of a carbocyclic diazo component with the remainder of a complex-forming hydroxyl or carboxy group adjacent to the azo bridge; B the remainder of a carbocyclic, heterocyclic or open-chain coupling component with the remainder of a complex-forming hydroxyl or amino group adjacent to the azo bridge; D the remainder of a carbocyclic aldehyde with the remainder of a complex-forming hydroxy group adjacent to the azomethine compound; 25th E is an optionally substituted aliphatic hydrocarbon residue with the residue of a complex-forming hydroxyl or carboxy group; and n is the number of car-boxyl and sulfonic acid groups not involved in the complex formation 30 mean, characterized in that 1: 1 chromium complex of the formula II correspond in which n has the meaning given in claim 1, A! Hydrogen, hydroxysulfonyl, chlorine, bromine, methyl, methoxy, ethoxy, nitro, methylsulfonyl, ethylsulfonyl, sulfamoyl, N-mono- or N, N-di-Ci to -Gi-alkyl-substituted sulfamoyl or N-phenylsulfamoyl; A2 is hydrogen, chlorine, nitro or hydroxysulfonyl; A3 hydrogen, where A1 and A3 together can form a fused-on benzene ring optionally substituted by nitro; R1 is hydrogen, chlorine, bromine, nitro, hydroxysulfonyl, phenylazo optionally substituted by chlorine, bromine, methyl, methoxy, ethoxy, nitro or hydrosulfonyl or naphthylazo substituted by hydroxysulfonyl; R2 is hydrogen, chlorine, bromine or nitro, where R1 and R2 can together form a fused benzene ring; X-O- or-COO-; Y-O-or-NH-; "1 k ck3ç = Ç - conh-w A-N-N-B V Cr (II), 35 te in which A © denotes an anion, azomethine compounds of the formula III 40 H-D-CH = N-E-H (III) attached, the compounds of the formulas II and III together containing the number n corresponding carboxyl and sulfonic acid groups. 45 2. The method according to claim 1, characterized in that that dyes are produced in the form of the free acids of the formula Ia N = N-K W ~ R2 CH = H Z © n + 1 R3 is hydrogen, methyl, phenyl or carbamoyl; R4 is hydrogen or phenyl which is optionally substituted by methyl, chlorine or hydroxysulfonyl; R5 is methyl, methoxy, acetylamino, propionylamino, benzoylamino, N-phenylamino, dimethylamino or diethylamino; R6 is hydrogen or methyl; R7 is hydrogen or hydrosulfonyl, where R5 and R6 together can form a fused benzene ring optionally substituted by bromine, amino, hydroxy, phenylamino, acetyl, propionyl or benzoylamino or hydroxysulfonyl; (Ia) - (cv_v i, -CH-, -ÇH- (h®) : H2C6H5 n + 1 -CH-, -CH- or LH ^ (CH „) COOH 6 5 1 -CH-CH "CH" -: and I 2 2 ' ch3 ni mean the numbers 1, 2 or 3. 3rd 625 821 3. The method according to claim 1, characterized in that one produces dyes in the form of the free acids of the formula e CH = N-Z n + 1 (h *) +1 n + 1 or ^ n + 1 (H*) n + 1 40 correspond in which m is the numbers 0, 1 or 2; and K1 is a radical of the formula or 6. Process for the preparation of asymmetrical 1 ^ chromium complexes containing an azo and an azomethine compound which are in the form of the free acids of the formula I A-N-N-B 1/ Cr 1\ D-CH = N-E (H®) (I) n + 1 20th 25th 30th correspond in the A the remainder of a carbocyclic diazo component with the remainder of a complex-forming hydroxyl or carboxy group adjacent to the azo bridge; B remainder of a carbocyclic, heterocyclic or open-chain coupling component with the remainder of a complex-forming hydroxy or amino group adjacent to the azo bridge; D the remainder of a carbocyclic aldehyde with the remainder of a complex-forming hydroxy group adjacent to the azomethine compound; E is an optionally substituted aliphatic hydrocarbon residue with the residue of a complex-forming hydroxyl or carbon group; and n is the number of car-boxyl and sulfonic acid groups not involved in the complex formation, characterized in that 1: 1-chromium complexes of the formula II A-N-N-B \ // Cr (II), e in which A © denotes an anion, the two individual components of azomethine compounds of the formula III H-D-CH = N-E-H (III) accumulates, the compounds of formulas II and III together containing the number n corresponding carboxyl and sulfonic acid groups. 7. The method according to claim 6, characterized in that the free acids of the formula I are converted into their salts with N-containing bases. 8. Use of the water-insoluble dyes, prepared by the process according to claims 6 and 7, for coloring organic non-textile materials. 55