DE1644219C3 - 2 to 1 metal complex monoazo dyes Process for their preparation and their use - Google Patents

Description

20 acid of the general formula 1 correspond

HOOC

The present invention provides new, valuable,

where Me is a cobalt or chromium sulfonic acid group-free 2: 1 cobalt and chromium atom is, A is a sulfonic acid group-free phe- plex monoazo dyestuff, which in the form of the free Nylene or naphthylene nucleus means that are formed by chlorine, bromine, nitro, methyl, ethyl, methoxy groups or a carboxy group can be substituted, B and C are the same or different 30 and each of the naphthylene, hydroxy or aminonaphthylene type, the acetylamino-naphthylene radical, the l-phenyl-3-methyl-pyrazolon (4) -5-yl radical, its Phenyl nucleus by chlorine or a nitro group may be substituted, or the acetoacetanilide residue as a coupling component, its phenyl nucleus may be substituted by chlorine and or a methyl group, X - O - or - COO - and Y and Y '- O - or - NH - mean, where X, Y and Y 'are each in a position adjacent to the azo groups.

2. Process for the preparation of the dyes of the formula 1 mentioned and defined in claim 1, characterized in that one

a) an Ul chromium complex monoazo dye of the general formula (2)

O = C

N = N-C

HOOC

H ^{1 + 1}

A-N = N-B

[Anion] '' (2)

in which A, B, X and Y have the meanings given in claim 1, with equimolecular amounts a monoazo dye of the general formula 3 capable of complex formation

COOH

(3)
HOOC
in which C and Y 'are those mentioned in claim 1 in which Me is a cobalt or chromium atom, A is a phenylene or naphthylene nucleus which is free from sulfonic acid groups and which is substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy groups or a carboxy group can, B and C are identical or different and each has the naphthylene, hydroxy or aminonaphthylene radical, the acetylamino-naphthylene radical, the l-phenyl-3-methyl-pyrazolon (4) -5-yl radical, whose phenyl nucleus is by chlorine or a nitro group can be substituted, or the acetoacetanilide radical as coupling component, the phenyl nucleus of which can be substituted by chlorine and / or a methyl group, X is —O— or —COO - and Y and Y 'is - O - or - NH - , where X, Y and Y 'are each adjacent to the azo groups.

The present invention further relates to processes for the preparation of these new dyes, the so be carried out that one is either a 1: 1 chromium complex - Monoazo dye of general

65

Formula 2

A-N = N-B

Cr ^{(+ I}

[Anion] '' (2)

where A, B, X and Y have the above meanings, with equimolecular amounts of a monoazo dye capable of complex formation of the general Formula 3

COOH

YH

HOOC

wherein C and Y 'have the above meanings, in the presence of acid-binding agents in aqueous or aqueous-organic medium in the pH range 5.5 to 8.5, preferably at pH 6 and between about 50 and about 100 ° C., preferably between 70 and 85 ° C., or two equivalents of one for complex formation capable monoazo dye of the general formula 3 in the presence of acid-binding agents in an aqueous medium at 80 bic 100 C in the pH range 5.5 to 9.5, preferably at about 6.5, with a Equivalent of a chromium or cobalt releasing agent, such as chromium (! II) hydroxide, chioin (1II) chloride, Chromium (111) acetate, formate or salicylate. Chrome alum, Cobalt sulfate, cobalt acetate or ammoniacal cobalt sulfate solution.

As azo components of the radicals B and C, for example, 2-naphthol, 4-acetamino-1-naphthol, 2-naphthylamine-l-sulfonic acid, l-phenyl-3-methylpyrazolone- (5), 1- (3'- or -4'-nitrophenol) -3-methylpyrazolone - (5), 1 - (3'-chlorophenyi) -3-methyl-pyrazolone - (5), N- acetoacetylaniline, N - acetoacetyl-4-chloroaniline and N-acetoacetyl-S-chloro ^ -aminotoluene called.

The anions in general formula 2 mentioned above are non-complexing Anions, such as nitrate, sulfate, fortnate and acetate ions, but especially chloride ions in Question.

The reaction takes place in water or in mixtures of water with water-miscible organic solvents, such as acetone, ethanol, iso- and n-propanol, isobutanol or ethylene glycol.

The 2: 1 metal complex monoazo dyes obtainable according to the process are obtained by salting out with sodium or potassium chloride or by acidifying their aqueous solution with acetic acid to pH 4.0 to 4.5, the dyes precipitating in the form of their free acids, deposited.

The 1: 1 chromium complex monoazo dye of the aforementioned general formula 2 is obtained by heating to 80 to 115 ° C, preferably to 100 ° C, one Monoazo dye of the general formula 4

A-N = N-B

(41
XY

H H

ίο in the A, B, X and Y the meanings given above have, with equivalent amounts of a chromium donating agent, such as chromium (III) chloride, Chromium (III) acetate or formate, in n-butanol or Ethylene glycol produced. A modification of this process is the reduction of hexavalent Chromium, used as alkali chromate, to trivalent chromium with n-butanol or ethylene glycol in the presence of concentrated hydrochloric acid, the amount of which is such that the molar ratio of alkali dichromate to hydrogen chloride is 1: 4.

Examples of amines, the general formula mentioned for the preparation of MonoazoiarbstolTen dct 4 that can be used are 2-aminophenol. 2 - amino - 4 - methylphenol, 4,6 - dinitro-2-aminophenol. 4- and 5-chloro-2-aminophenol. 1-amino-2-naphthol. 4- and S-nitro-2-aminophenol. Enabling the production of metal complex formation Monoazo dyes of the general hormel 3 takes place in a known manner by diazotizing 2-amino-terephthalic acid, 4-amino-isophthalic acid or a mixture of 2- and 4-aminoisophthalic acid. where the weight fraction of the 2-isomer Can be 20 to 50%, so the mixing ratio should be 1; 4 to 1: 1, and domes in aqueous medium with the azo components described above between about 0 and about 50 C, preferably between 10 and 20 C, in the pH range 6.0 to 10.0. Those in the form of their alkali salts water-soluble monoazo dyes are made from the neutral, aqueous solution by salting out with Sodium chloride deposited, or by acidifying the aqueous solution with hydrochloric acid to pH 2.5 to 3.5 precipitated, the dyes of the general formula 3 being free acids which are very sparingly soluble in water are present.

The monoazo dyes of the general formula 4 capable of forming metal complexes are described in known manner by diazotizing the amines described above and coupling in an aqueous medium with the azo components described above between 0 and 50 ° C, preferably between 10 and 25 ° C, in the pH range 5.0 to 10.0. The water-insoluble monoazo dyes are isolated by simple filtration.

The new 2: 1 chromium complex monoazo dyes are very soluble in water in the form of their alkali salts and are therefore suitable for dyeing and printing fabrics or scrims made of nitrogen-containing materials Fibers of both natural and synthetic

table origin, such as fabrics or scrims made of silk, wool, polyamide or polyurethane fibers. With regard to the nitrogenous materials mentioned, the new dyes are primarily suitable for dyeing wool and polyamide fiber materials.

The new metal complex dyes are used by the dyeing and printing processes generally customary in the art. To the

The dyeing of nitrogen-containing fiber materials, such as wool and polyamide fibers in particular, is used ■ euen metal complex dyes, preferably in the form, which is sparingly soluble in water, in which the

- COOH group is in the free acid form, or in the water-soluble form in which the

- COOH group is present as a potassium, Namum or ammonium salt group, together with a ion-active or nonionic dispersing agent, the weight ratio of the dye to the dispersing agent being 1: 0.1 to -1: 1, η a neutral or weakly acidic one Brought bath of constant or practically constant pH and ^{dyed therein preferably at 70 to 20 0} C in the presence of compounds which are common for dyeing nitrogenous textile materials, such as sodium sulfate, ammonium acetate, quaternary ammonium salts. The pH of the dyebath can also be changed during the dyeing process by adding acids or acidic salts or alkalis or alkaline salts, for example by starting the dyeing process at pH 7.5 and lowering it to 4.0 during the dyeing process.

The new dyes show a variety of shades, such as purple, green, orange, yellow, brown and gray shades. They have an excellent affinity for textile fabrics or scrims made of nitrogen-containing natural or synthetic fiber materials, especially woven fabrics or Made of wool or polyamide fibers. The new metal complex dyes are also very resistant to alkalis and have good solubility in water. Dyeing on wool and polyamide fibers with the new dyes are characterized by good lightfastness and wetfastness properties.

Compared to known 1: 2 chromium and cobalt complex monoazo dyes very similar constitution, which also contain a carboxyl group and in German patents 1049 515 and 1,074,786 and in the journal "Helvetica Chimica Acta" 45 (1962), on p. 1027, are described the new dyes have an unexpectedly higher color strength on polyamide goods in the exhaust process and much better light and white fastness. Another well-known, constitutionally also comparable 1: 2 chromium complex monoazo disperse dye containing carboxyl groups from the Swiss patent specification 384 108 has been compared even as unsuitable for the dyes according to the invention proven for dyeing polyamide goods using a common exhaust process, whereas with the new dyes strong, uniform colorations can be obtained.

example 1

39.6 parts by weight (0.1 mol) of the 1: 1 chromium complex dye the formula

Cr ^{1 +} »

Cl "

33.6 parts by weight (0.1 mol) HZ '^' - dicarboxyphenylr-azoj-2-naphthol 55.0 parts by weight (0.4 moles) of crystallized sodium acetate, 1000 parts by weight of water and 500 parts by weight of ethanol are refluxed for 8 hours with stirring. After cooling down the 2: 1 chromium complex monoazo dye formed is allowed to rise to room temperature Salted out 150 parts by weight of sodium chloride and filtered off. The wet one The filter residue is dissolved in 500 parts of water and the dye is precipitated with 50 parts by weight of glacial acetic acid, filtered off and dried. The black dye results in essi>; - acidic on wool and polyamide fibers Bad gray dyeings with very good light and wet fastness properties. The dye obtained corresponds to the formula

H ⁺

Example 2

42.5 parts by weight (0.1 mole) of the 1: 1 chromium complex dye the formula

33.6 parts by weight (0.1 mole) of 1- (2 ', 5'-dicarboxyphenyl'-azo) -2-naphthol and 55.0 parts by weight (0.4 mol) of crystallized sodium acetate are in a mixture of 1000 parts by weight of water and 500 parts by weight of ethanol for 4 hours with stirring on Refluxed. After half of the liquid volume has been distilled off, 50 parts by weight are added

Glacial acetic acid added, filtered and dried. The obtained dye of the formula

O ₂ N

H ^H

COOH

on wool and polyamide fibers from an acetic acid bath produces bluish-tinted red dyeings with very good light- and wet fastness properties.

Example 3

30.0 parts by weight (0.1 mol) chromium (III) chloride hexahydrate are dissolved in 50ö weight parts of water and 14.0 parts by weight (0.35 mol) of sodium hydroxide in 25 parts by weight of water with stirring and heating to 6O ⁰ C To this was added fresh

precipitated chromium (III) hydroxide is given to 73 parts by weight (0.2 mol) of 4- (2 ', 5'-dicarboxyphenyl-l'-azo) -3-methyl-l-phenyl-pyraz, olone-5, heated to reflux with stirring and, when the mixture began to boil, 7.0 parts by weight (0.12 mol) of glacial acetic acid were added. After 12 hours of boiling, the chroming is complete. The dye is made by adding 50 parts by weight Precipitated glacial acetic acid, filtered and dried. The brown-yellow dye gives on wool and

to polyamide fibers from acetic acid bath yellow dyeings with good light and wet fastness properties. The dye obtained corresponds to the formula

20th

25th

30th

IV

example

39.6 parts by weight (Ο, ϊ mol) of the 1: 1 chromium complex monoazo dye the formula

The dye obtained corresponds to the formula

45

CV

36.8 Gewichisteite {0.1 Mtrf) 4 ^ 2 ', 5 -Dkarhoxypbenyl- l'-azo) -3-methyl-l-rAenyl-pyrazoton-5 and 5Γ Gewichisteile crystallized sodium acetate are in IQQO Gcwicbtsteea water «ad SOO Gewrcbtsteäen ethanol outer stirring Räckflaß heated after 7 Stuadea the reaction is complete, the Vohaaea wad Dorch DestSation anf half verramdert ead of 2: l-ChroH & ompterfartetoff with SQ parts by weight of glacial acetic acid aasgefällt the SCTE dye gives aaf WoBe and polyamide fibers dv ^ dgräne dyeings having very good Loves and Nafiecbtkilling.

COOH

The nacbsteheaden TabeSea eethalten more games of 2: l-Cteonv aod KobahkompleuBoee rbs after dee m Examples 1 b beschrkbeaen method hergeste be & l.

ίο

Table 1

1: 1 chromium complex
monoazofarbstolT Amine (A) Azo component (B) Melallfreicr Hue on Wool Polyamide fiber Serial 4-nitro-2-aminophenol 2-naphthol Monoazo tolT
Amine = 2-amino- Brown Brown No. 4,6-E> initro-2-amino- 2-naphthoi terephthalic acid Brown gray-brown phenol Azo component (C) 5 4-chloro-2-aminophenol l-phenyl-3-methyl-
pyrazolone-5 2-naphthol Red Red 6th 4-chloro-2-aminophenol 2-naphthol 2-naphthol violet violet 4-Nii: ro-2-aminophenol l-phenyl-3-methyl-
pyrazoion-5 red-brown red-brown 7th 5-Ni '.: Ro-2-aminophenol 2-naphthylamine
1-sulfonic acid 2-naphthol green green 8th 5-Nii ro-2-aminophenoI 2-naphthol 2-naphthol green green 9 4-nitro-2-aminophenol 2-naphthol 2-naphthol Brown Brown 10 Acetoacctanuid 11th 4,6-dinitro-2-amino- 2-naphthol Acetoacetanilide brown olive brown olive 12th phenol l-phenyl-3-methyl- 4-nitro-2-aminophenol 2-naphthol pyrazolone-5 Brown Brown 13th 4-nitro-2-aminophenol l-pheny '.- 3-methyl- l-phenyl-3-methyl- orange orange pyrazolone-5 pyrazoion-5 14th 5-nitro-2-aminopheno5 l-phenyl-3-methyl- Acetoacetanilide Red Red 15th pyrazolone-5 l-phenyl-3-methyl- 5-nitro-2-aminophenol l-phenyl-3-methyl- pyrazolone-5 Red Red 16 pyrazolone-5 l-phenyl-3-methyl- 4-chloro-2-aminopheno1 l-phenyl-3-methyl- pyrazolone-5 orange orange 17th pyrazolone-5 l- (4'-nitrophenyl) 4-nitro-2-aminophenol l-phenyl-3-methyl- 3-methyl-pyrazolone-5 yellow-orange geiborange 18th pyrazolone-5 l- (4'-nitrophenyl) 5-nitro-2-anjinophenol 2-naphthol 3-methyl-pyrazolone-5 green green 19th H4'-nitrophenyl) 4-nitro-2-aminophenol 2-naphthol 3-methyl-pyrazolone-5 Brown Brown 20th l- (4-nitrophenyl) 4,6-dinitro-2-amino- 2-naphthol 3-methyl-pyrazolone-5 brown olive brown olive 21 phenol M4'-nitrophenyl) 4,6-I3ioitro-2-amino- 2-naphthol 3-rnelhy! -Pyrazolone-5 Gray Gray 22nd phenol l- (4'-nitrophenyl) 4-nitro-2-aminophenol 2-naphthol 3-methyl-pyrazotone-5 Gray Gray 23 4-acetamino 2-aminophenol 2-naphthol 1-naphthol violet violet 24 4-acetamino 5-N! Tro-2-aminophenol 2-naphthoi 1-naphthol Gray Gray 25th 4-acetamino 4-chloro-2-aminopheno 2-naphthol 1-naphthol blue blue 26th 4-acetamino 4-Ch ΙθΓ-2-ammopheno l-phenyl-3-methyl- i-naphthol Brown Brown 27 pyrazolone-5 4-acetamino 4-nitro-2-aminopheno! l-pheayl-3-raeäthyl- I-naphthol Brown shower 28 PyrazoIon-5 4-acoamino 5-nitro-2-arainophenol l-l ^ rayl-3-niethyl- 1-naphthol bordo bordo 29 pyrazolone-5 4-acetamino 1-naphthol 30th 4-acetamino 1-naphthol

Continued 12

Lrd.
No.

1: 1 chromium complex monoazo dye

Amine (A!

4-nitro-2-aminophenol 2-naphthol 5-nitro-2-aminophenol 2-naphthol 4-chloro-2-aminophenol 4-chloro-2-aminophenol 4-nitro-2-aminophenol 5-nitro-2-aminophenol Metal-free monoazo dye

Amine = 4-amino isophthalic acid

2-naphthol l-phenyl-3-methyl-

pyrazolone-5 2-naphthol

2-naphthol 2-naphthol
2-naphthol
2-naphthol
2-naphthol

l-Pheny! -3-me »hyl-

pyrazolone-5
l-phenyl-3-methyl-

pyrazolone-5

Brown Green

brown gray purple red

Brown Green

(Continuation)

Serial No.

1: 1 chromium complex monoazo dye

4-nitro-2-aminophenol

4,6-dinitro-2-amino-

phenol
4-nitro-2-aminophenol 5-nitro-2-aminophenol

Azo components (B)

2-naphthol 2-naphthol

l-phenyl-3-methyl-

pyrazolon-5 l-phenyl-3-methyl-

pyrazolone-5

Tabel

Symmetrical 2: 1 metal complex dyes

Metal-free Monoazo dye Amine = mixture of

2- and 4-aminoisophthalic

acid Azo component (C)

2-naphthol 2-naphthol

2-naphthol 2-naphthol

Hue on

Wool

brown brown

Polyamide fiber

brown brown

Serial No.

Amine

41

42 43 44 45

46

47
48

49
50

2-amino-terephthalic acid

2-amino-terephthalic acid 2-amino-terephthalic acid 2-amino-terephthalic acid 2-amino-terephthalic acid

2-Amino-terephthalic acid 2-Ammo * erephthalic acid 2-Aiamo-terephthalic column

2-araino-terephthalic saddle hthalic acid

2-naphthol

2-naphthol 4-acetamir »o-1 -naphthol
4-acetamino- 1-naphthol l-phenyl-3-methyl-

pyrazolone-5 l-phenyl-3-methyl pyrazolone-5 ^ 4'-nitrophen> 1h3-methyl-

pyrazolone-5 m4'-nitrophenyl) -3-methyl-

pyrazolone-5 -Acstoacetylaniline I-acetoacetylane

brown orange green bordo olive yellow

Claims (1)

Patent claims: 1, 2: 1 metal complex monoazo dyes that in the form of the free acid of the general formula 1 A-N = N-B O = C H ^{1 +} ' U) have meanings, in the presence of acid-binding agents in an aqueous or aqueous-organic medium in the pH range 5.5 to 8.5 between about 50 and about 10O ⁰ C, or b) two equivalents of a monoazoi agent capable of complex formation of the general Formula 3 in the presence of acid-binding agents in an aqueous medium at 80 to 100 ° C. in the pH range 5.5 to 9.5 with an equivalent of a chromium or cobalt donating center; - msetzL 3. Use of those mentioned in claim 1 and defined or the one according to claim? compounds produced for dyeing textile materials made of nitrogen-containing natural or synthetic fiber materials.