DE1258993B - Process for the production of water-soluble organic dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Int. Cl .:

C09b

GERMAN

PATENT OFFICE

EDITORIAL

German class: 22 a -1

Number: 1258 993

File number: C 32803IV c / 22 a

Filing date: May 5, 1964

Opening day: January 18, 1968

Dyes, which are reactive halogen atoms or contain other radicals that carry a pair of binding electrons with hydroxyl groups Materials that can react have become known in large numbers. They serve in particular as reactive dyes for dyeing and printing cellulose material.

Such dyes now need for their practical application, especially in the printing shop, high dye concentrations, which requires very good solubility in water. The solubility but depends on the size and type of the dye molecule, the type of reactive radicals and the Number of solubilizing groups in the dye molecule. Very soluble dyes with a larger number of sulfonic acid or carboxyl groups can generally not be because of insufficient substantivity or lack of aggregation ability does not fix well on the fiber. On the other hand, poorly soluble dyes have the disadvantage that they precipitate out of the printing ink and therefore deliver troubled, uneven prints.

It has now been found that new, highly water-soluble organic dyes are obtained if organic dyes or dye intermediates. which reactive halogen atoms or contain other residues, which take along a pair of binding electrons with hydroxyl groups Materials can react with sulfinic acids, which have at least one more water-solubilizing agent Carry group, or brings their salts to implementation and in the case of the dye intermediates the reaction products obtained by reaction with the missing dye component converted into dyes.

The present process makes it possible to produce dyes with particularly good solubility with regard to their coloring properties, in particular with regard to the shade compared to the underlying starting dyes have no disadvantages.

Process for the preparation of water-soluble
organic dyes

Applicant:

Cassella Farbwerke Mainkur Aktiengesellschaft,

6000 Frankfurt-Fechenheim

Named as inventor:

Dr. Richard Fleischhauer, 6000 Frankfurt;

Dr. Heinz Bender, 6000 Bergen-Enkheim

You can now according to the invention dye intermediates which z. B. as diazo or coupling components for mono-, dis- and polyazo dyes and also reactive ones Halogen atoms or other radicals, which take along a pair of binding electrons can react with materials containing hydroxyl groups, contain, use as starting material. Such compounds can contain, for example: mono-, di- or trihalogenazinyl radicals, e.g. B. a halopyridazine, halopyrimidine or haloquinoxaline radical, but especially a halogenated one 1,3,5-triazinyl radical or halogenated azole radicals, such as halooxazole, haloimidazole, Halothiazole residues.

They can also contain: residues of / i-haloethanesulfonic acids, β- haloethylsulfones or / i-halopropionic acids, and finally residues of α, / i-unsaturated carboxylic acids, such as acrylic acid, / i-chloroacrylic acid, / f-chlorocrotonic acid, propiolic acid. In the case of the halogen-containing radicals, the halogen atoms are substituted by the radical of a sulfinic acid with water-soluble groups;

C - shark

NaS O, R

C - SO ₂ R

(D

- CO - CH ₂ - CH ₂ - Hal
(SO ₂ )

- CO - CH = CH ₂
(- SO ₂ )

Η - SO ₂ IL _co
SO ₂

-CO-CH ₂ -CH ₂ -SO ₂ R

(- SO ₂ -)

(Π) (III)

709 719/385

where R is an organic radical with at least one solubilizing group, e.g. B. a sulfonic acid or carboxyl group.

Sulfinic acids with a solubilizing group are:

Benzoic acid sulfinic acid (2), benzoic acid sulfinic acid (3), benzoic acid sulfinic acid (4), 4-bromobenzoic acid-sulfinic acid- (2),

2-hydroxy-benzoic acid-sulfinic acid- (5), '

2-methyl-4-chlorobenzoic acid-sulfinic acid- (6), cinnamic acid-sulfinic acid- (2),

Hydrocinnamic acid-sulfinic acid- (2), l-hydroxypropane-2-sulfinic acid-3-sulfonic acid,

1,4-dihydroxybutane-2-sulfinic acid-3-sulfonic acid, ethane-l-sulfonic acid-2-sulfinic acid, Propane sulfonic acid sulfinic acid.

However, the reactions can also be carried out with finished dyes which are those listed above contain halogen-containing or unsaturated residues.

The dyes can be of various classes, such as the azo, anthraquinone, phthalocyanine, Belong to nitro, nitroso, azine, thiazine, oxazine, thiazole, stilbene, xanthone, triphenylmethane series.

The dyes obtained by the present process are suitable for dyeing animals Fibers such as wool, silk, leather, as well as polyamide fibers and other synthetic fibers, in particular but for dyeing and printing fibers made from natural or regenerated cellulose (Cotton, rayon). In many cases, there is no need to add urea, with in in many cases even deeper colorations or prints can be obtained. The application is generally carried out by the processes customary for reactive dyes, d. H. for example after the steaming process, the thermosetting process, the cold dwell process or the exhaust process.

Compared to dyes that are described in French patents 1,345,490, 1,345,491 and 1,326,676 are described, provide structurally comparable dyes prepared according to the invention more favorable Results of the cold pad process.

example 1

33 kg of 2- (chloropropionylamino) -8-oxynaphthalene-6-sulfonic acid are dissolved in water as the sodium salt. About 22 kg of the disodium salt of benzoic acid-3-sulfinic acid are added to the solution. The mixture is boiled for several hours with initially a weakly acidic reaction and further with neutralization with soda until the starting product can no longer be detected.

The 2 - (β - 3 '- carboxyphenylsulphonylpropionyl) - amino - 8 - oxynaphthalene - 6 - sulphonic acid which is held in place can be obtained as a very readily water-soluble powder by evaporation in vacuo.

The same compound can also be obtained by reacting 2 - (/ ^ - Acroylamino) -8-oxynaphthalene-6-sulfonic acid be won.

22.5 kg of 2-naphthylamine-1-sulfonic acid are diazotized at about 15 to 20 ° C. in the usual way. The diazo suspension is combined with the disodium salt of about 54 kg of 2 - (ß - 3 '- carboxyphenylsulfonylpropionyl) - amino - 8 - oxynaphthalene - 6 - sulfonic acid and the dye formation is completed by adding sodium acetate or sodium bicarbonate, the dye in Solution works.

The dye is deposited by adding sodium chloride, filtered and dried. He's going to be like that a brown-red water-soluble powder obtained and delivers when printing on cotton or viscose rayon after steaming, rinsing, and soapy, vivid scarlet prints of very good ones Authenticity properties.

Dyes of a somewhat more yellowish hue are obtained if the diazo components are used 3-aminobenzenesulfonic acid or 3- or 4-aminobenzoic acid is used.

The dyes can also be prepared in such a way that the applied by coupling the Diazo compound with 2-p'-chloropropionylamino - 8 - oxynaphthalene - 6 - sulfonic acid obtained Reacts monoazo dyes with the disodium salt of benzoic acid-3-sulfinic acid.

Example 2

In a corresponding manner, as in Example 1, paragraphs 1 to 4, indicated, 2- (p'-Chlorpropionylamino) - 5 - oxynaphthalene - 7 - sulfonic acid reacted with the disodium salt of benzoic acid-3-sulfinic acid and the obtained reaction product with the diazo compound of 2-naphthylamine-1-sulfonic acid united. The obtained monoazo dye is an orange colored water-soluble powder and provides vivid reddish orange dyeings on cotton or viscose rayon with very good fastness properties.

Similar, readily soluble, but yellowish orange monoazo dyes are obtained when 3- or 4-aminobenzoic acid or 3-aminobenzenesulfonic acid are used as diazo components.

Example 3

27.9 kg of l-amino-S-ß-chloropropionylaminobenzene-6-sulfonic acid are dissolved as the sodium salt in water and with an initially weakly acidic reaction with the disodium salt of about 20.5 kg of benzoic acid-3-sulfinic acid boiled for several hours, the reaction being kept neutral by adding soda.

The obtained l-amino-3 - (/ j-3'-carboxyphenylsulfonylpropionylamino) - Benzene - 6 - sulfonic acid can be obtained as an easily soluble, almost colorless powder by evaporation in vacuo, or one They can be separated by acidification with hydrochloric acid and salting out with table salt, whereby the "initially Resin or oily product changes into crystalline form after prolonged standing or stirring.

42 kg of the compound (calculated on 100% product) are diazotized at 10 to 20 ° C and in the presence of excess sodium bicarbonate with an aqueous solution of the sodium salt of 14 kg of 5-pyrazolone-3-carboxylic acid combined. The dye is deposited by heating and salting out, filtered and dried. It is a yellow, water-soluble powder and is used in Printing in the presence of urea, soda and alginate thickening on cotton after steaming, Rinsing and soaps greenish yellow prints of very good wet and lightfastness. Used one as coupling component 3-methyl-5-pyr-

azolone, a greenish yellow dye of similar properties is obtained.

In a corresponding manner, 1-amino-4-chloropropionylaminobenzene-2-sulfonic acid can be used go out and proceed according to paragraphs 1 to 4, then reddish yellow dyes can be obtained.

If the 1-phenyl-3-methyl-5-pyrazolone is used, reddish-tinged yellow dyes are obtained.

Example 4

22.9 kg of l - (/ ^ Chlorpropionylarnino) -3-nitrobenzene are boiled for some time in an aqueous medium with 21 kg of 3-carboxyphenylsulfinic acid (as the disodium salt). After the reaction has ended, the 1 - (/) - 3 '- carboxyphenylsulfonylpropionylamino) -3 - nitrobenzene is reduced with iron and acetic acid to give 1 - (/ ■; - 3' - carboxyphenylsulfonylpropionylamino) -3-aminobenzene. Almost colorless powder with a melting point (decomposition) of about 185 ^C C.

34.8 kg of this amino compound are diazotized in the usual way. The diazo suspension obtained is left in a 24 kg solution to which excess sodium bicarbonate has been added l-NaphthoI-3-sulfonic acid run. After a long time Stirring, the initially gelatinous dye becomes crystalline and can be filtered directly. You get after drying a brick-red water-soluble powder that is applied to cotton when printing in the presence of soda after steaming, rinsing and soaps, vivid red-orange prints of very good quality Provides wet and light fastness. The coupling component used is 3 - methyl - 5 - pyra-zolone or S-pyrazolone-S-carboxylic acid or 1- (2 ', 5'-dichloro - 4 '- sulfophenyl) - 3 - methyl - 5 - pyrazolone, yellow dye powders are obtained, which are in Easily dissolve in water, and prints on cotton that are greenish-tinged yellow with very good wet and lightfastness deliver.

The 3-carboxyphenylsulfinic acid can be replaced by 3- or 4-sulfophenylsulfinic acid.

Example 5

50 kg of the by reaction of l-amino-4- (3'-aminophenylamino) - anthraquinone - 2 - sulfonic acid with / j-chloropropionyl chloride produced dye reacted with the disodium salt of 20.5 kg of 3-carboxyphenylsulfinic acid. One receives after separating and drying a water-soluble dark powder based on cotton or regenerated cellulose printed in the presence of soda and alginate thickening after drying, steaming, Rinsing and soaping produces reddish blue prints of very good wet and lightfastness.

Another very readily soluble dye is obtained if instead of 3-carboxyphenylsulfinic acid the 3- or 4-sulfophenylsulfinic acid is used.

Example 6

One made from 60 kg of copper phthalocyanine and about 600 kg of chlorosulfonic acid at about 115 to 130.degree produced sulfochloride is after separation, pasting with ice water and neutralizing with an aqueous solution of about 20 kg of 2,4-diaminotoluene and after addition of 50 kg of pyridine Stirred at 4 to 6 ° C. for several hours. Then you make alkaline with ammonia, float Cooking, makes strongly alkaline with excess caustic soda and cooks for half an hour. To After cooling, the dye is precipitated with hydrochloric acid, filtered off and washed with salt water containing hydrochloric acid washed. The dye is then redissolved with hot water and sodium hydroxide solution and removed Impurities filtered. To the one with hydrochloric acid

ίο neutralized filtrate is added excess sodium bicarbonate and reacts the dye with p'-chloropropionyl chloride until a sample is no longer is diazotized. The dye can be deposited in good shape with potassium chloride in the heat will. After filtering, it is again mixed with water and at boiling temperature with reacted the disodium salt of about 41 kg of 3-carboxyphenylsulfinic acid, the dye in Solution works. When it cools down, it partially precipitates.

The separation is completed by salting out with potassium chloride.

After filtering and drying, a greenish blue, water-soluble powder is obtained when printing in the presence of soda or sodium bicarbonate and alginate thickening after drying, Steam, rinse and soap on cotton or viscose rayon, wet and lightfast turquoise blue Prints supplies.

Example 7

46.7 kg 1 - [2 ', 4' - dichloro - triazinyl - (Γ, 3 ', 5> 6 '- amino] - 8 - oxynaphthalene - 3,6 - disulfonic acid, prepared in a known manner by reacting 1 mole of l-amino-8-oxynaphthalene-3,6-disulfonic acid with 1 mole of cyanuric chloride at about 0 C in acidic aqueous medium, are dissolved neutrally in water as the sodium salt and acidified with acetic acid. 19 kg of 3-carboxyphenylsulfinic acid as disodium salt are added to the suspension or solution, heated to 40 to 50 C and stirred while neutralizing with soda until everything is in solution has gone. The condensation product obtained can be deposited by salting out with potassium chloride become and forms a pale yellowish colored, water soluble powder.

68.2 kg of the condensation product obtained in this way are dissolved in water and excess sodium bicarbonate solved. A diazo solution prepared from 13.7 kg of 1-aminobenzene-4-carboxylic acid is allowed to do so flow. After the formation of the dye has ended, it is deposited by adding potassium chloride and dried at low temperature. A dark red, water-soluble powder is obtained, that when printing on cotton in the presence of soda, urea and alginate thickening after Steaming, rinsing and soaps deliver vivid, bluish-tinged prints.

The condensation product prepared according to paragraph 1 can be at about 90 to 100 C with a implement another mole of 3-carboxyphenylsulfinic acid, the latter still present in the triazine nucleus Chlorine atom against the 3-carboxyphenylsulfinic acid residue is exchanged.

The alkali salts of this compound are very easily soluble in water and are supplied with the coupling Benzene series diazo compounds, e.g. B. aniline, p-toluidine. 2-aminobenzoic acid, 4-aminobenzoic acid or 4-aminobenzenesulfonic acid. easily soluble

Dyes of a bluish red hue. Shades obtained in the dyes prepared in the same way The following table contains a few more:

Diazo component

Coupling component

4-aminobenzenesulfonic acid

2-naphthylamine-1-sulfonic acid

2-aminobenzoI-sulfonic acid

HO, S

2-aminobenzene
sulfonic acid desg 3-aminobenzene
sulfonic acid desg: 3-aminobenzoic acid desg] 4-aminobenzoic acid the same 2-naphthylamine
1-sulfonic acid the same 2-naphthylamine
1,7-disulfonic acid the same 2-naphthylamine
4,8-disulfonic acid the same 2-naphthylamine
5,7-disulfonic acid the same 2-naphthylamine
1-sulfonic acid the same

the same

HO, S

OH

NH-sulfinyltriazinyl radical

HOOC

/ ^N \

C C-SO,

Cl the same.

like. like. like. like. like.

C C-

Il N

Cl

HO ₃ S

HOOC

C-

Il

SO ₂ - <3

COOH

HOOC

/ ^N \

■ C C-SO ₂

Cl shade on cotton

scarlet

Scarlet Orange Red

Orange red

scarlet

scarlet

Scarlet Scarlet Scarlet

scarlet

scarlet

orange

continuation

Diazo component

Coupling component sulfinyltriazinyl radical

Shade on cotton

3-aminobenzenesulfonic acid

HO ₃ S

4-aminobenzenesulfonic acid

4-aminobenzoic acid

2-naphthylamine-1-sulfonic acid

4,4'-diaminodiphenyl-2,2'-disulfonic acid

OH

like. like. like.

4,4'-diaminodiphenyl-2,2'-disulfonic acid

2-aminobenzoic acid

4-aminobenzoic acid

2-naphthylamine-1-sulfonic acid

4-aminobenzene sulfonic acid

SO ₃ H

SO ₃ H

HO ₃ S

the same

HO, S

OH

the same.

NH-

NH-

CH,

N -

HOOC

C-SO ₂

Cl
the same

the same.

HOOC

C-SO ₂

Cl

<Nn

HOOC

^x c - So ₂ - / \

Ii ² V- /

COOH

SO,

■ C C-SO ₂

N N

ί
Cl

the same.

the same

HOOC

HOOC

Cl

Yellow orange

Reddish orange

Reddish orange

Reddish orange

scarlet

scarlet

orange

Orange red orange

orange

yellow

709 719/385

11

continuation

Diazo component

Coupling component

Sulfinyltriazinyl radical

Shade on cotton

SO ₃ H

NH,

NH,

SO ₃ H

H, C0

HOOC

<Nn

CH,

the same

SO, H

NH,

the same

H ₂ N

HO

HO, S

CC - SO ₂ - <> COOH Orange yellow ι Il
NN
V. HOOC
.Ns I Cl
HOOC
/ ⁿ \ Ta
CC - S0 ₂ - <>
I Il \ / c ⁷ c-so ₂ - <J>
NN Orange yellow I Il
NN
\ / Bluish tint
Red

SO, H

Cl

Diazo component COOH Coupling component hue SO ₃ H H ₂ NA Cl l-naphthol-3-sulfonic acid scarlet NH- ^c Clc> ^N SO ₂ - ( the same HO NH- CO - / \
ΛΛ Bluish red HO ₃ SQ ^) - SO ₃ H the same l- (4'-sulfophenyl) -3-methyl-
5-pyrazolone Reddish yellow the same l- (4'-sulfophenyl) -5-pyrazolone-
3-carboxylic acid Reddish yellow the same l- (2 ', 5'-dichloro-4'-sulfophenyl) -
3-methyl-5-pyrazolone Greenish yellow

13th

Continued 14

Diazo component Cl
I. COOH Coupling component (angry
coupled) hue SO ₃ H
1 SO ₂ - ^ HO
I. H ₂ N - / ^
Y
NH- (~ * 's JX
^H ° ^3S AA (angry
coupled) Bluish red HO the same xV
HO ₃ S ^ _x A Bluish red V-NH ₂
A ^S ° 3H V-NH ₂

- (SO ₂ Cl) ₁ -,
- (SO ₃ H) ₂ _ ₃ the same Intermediate link Cu - phthalocyanine NH ₂
Λ M-NH ₂ the same SO ₃ H NH,
Λ " IJ - NH ₂
T CH ₃ HO ₃ S SO ₃ H

Sulfinyltriazinyl radical

C C-SO ₂ - <>

N N

HOOC

_c /

Cl
the same

the same

Shade on cotton

turquoise

turquoise

turquoise

Primary disazo dyes

1. Diazo component

SO, H

NH ₂

Cl

NH-C

(D

SO,

COOH

2. Diazo component

like (I) coupling component

HO NH,

Shade on cotton

Reddish blue black

15th

continuation

16

1. Diazo component

2. Diazo component

Coupling component

Shade on cotton

SO ₁ H

NH ₂

NH-C

Cl

like (I)

SO ₂

COOH

NH,

/ N-SO ₃ H

NO,

NH,

NO ₂

NH ₂

NO,

(D

(D

(D

like (I)

like (I)

like (I)

like (I)

like (I)

like (I)

HO NH ₂

HO ₃ S

Greenish bluish black

SO, H

HO NH,

HO ₃ S

SO ₃ H

black

the same

the same

NH ₂

OH

NH ₇

NH ₇

NH,

NH ₇

SO, H

black

black

Brick red

Red-brown

orange

Polyazo dyes

Tetrazo component

Coupling components a + b

Reactive diazo component | ** ^Tbton "

^H on cotton

4,4'-diaminodiphenyl-2,2'-disulfonic acid

b)

4,4'-diaminodiphenyl-2,2'-disulfonic acid

4,4'-diaminodiphenylamine-2,3'-disulfonic acid

4,4'-diaminodiphenyl-2,2'-disulfonic acid

H, N OH NH,

angry

a) HO ₃ S

. alkaline SO, H

-S (XH

NH,

NH ₂

H ₉ N OH

Cl-C C-SO,

black

HOOC

angry

a) HO ₃ S

. alkaline.

SO, H (D

black

NH ₇

NH • CH ₂ COOH

Resorcinol < (I)

Dark brown

Resorcinol H ₂ N OH

angry

a) HO ₃ S

, alkaline.

SO, H (I)

(I)

black

H ₇ N OH

HO, S

SO ₃ H

55

Claims (1)

Claim: Process for the production of water-soluble organic dyes, characterized in that that one organic dyes or dye intermediates which are reactive halogen atoms or contain other residues that react with hydroxyl-containing materials while taking along a pair of binding electrons can, with sulfinic acids, which are still min- carry at least one further water-solubilizing group, or their salts for implementation brings and in the case of the dye intermediates the reaction products obtained by reaction converted into dyes with the missing dye component. Documents considered: French patent specifications No. 1326 676,1345 490, 345 491. When the application was announced, a coloring table with explanations was laid out. 709 719/385 1.68 © Bundesdruckerei Berlin