DE1080243B - Process for the production of dyes - Google Patents

Description

GERMAN

It is known from German patent specification 888 837 that 1-amino-3-imino-isoindolenines, preferably in the presence of reducing organic solvents and suitable heavy metal salts, Can produce phthalocyanines. From the German patent specification 1 001 785 it is also known that tetrazaporphines are obtained from 2-amino-5-immo-pyrrolenines under the appropriate conditions can. A particular advantage of this process is that the dyes are derived from the l-amino-3-imino-isoindolenines or 2-Amino-5-imino-pyrrolenines are formed under so mild conditions that they can be obtained from these starting materials on the fiber under conditions which the fiber cannot damage.

It has now been found that dyes of the most varied of hues can be produced under the same conditions can be obtained if instead of the l-amino-3-iminoisoindolenine or 2-Amino-5-imino-pyrrolenine compounds, which in one of their tautomeric forms by the formula

Method of manufacture
of dyes

R ₁ -N-

-NR ₂

H ₂ N-C _Xx

= NH

can be represented in which R ₁ and R _{2 are} hydrogen, acyl, alkyl or aryl groups, mixed with 2-amino-5-imino-pyrrolenines, which may be substituted in the 3- and / or 4-position can, such as B. l-amino-3-imino-isoindolenine, in the presence of metal compounds which can be used for the preparation of metal-containing phthalocyanines, and optionally subjected to a heat treatment in the presence of solvents and reducing agents.

Suitable heterocyclic compounds for the process according to the invention are, for. B. 2,5-diamino-3-phenyl-1,3,4-triazole or the 1,3,4-triazolone-2,5-diimide.

As complex-forming metals or metal compounds, all those are suitable which, for. B. also in the production of metal-containing phthalocyanines can be used. May be mentioned e.g. B. copper, cobalt, nickel, magnesium, Sodium or its salts, such as copper chloride or nickel sulfate.

Suitable solvents for the process according to the invention are preferably those which have weakly reducing properties, such as, for. B. polyhydric alcohols; Glycol and glycerin or reducing acids or their functional derivatives, such as. B. formic acid and formamide or amino hydroxyl compounds, such as the amino alcohols. Other suitable solvents or solvent mixtures are, for. B. in German patent specification 888 837 described. Ge-notifier:

Paint factories Bayer Aktiengesellschaft, Leverkus en-B ayerwerk

Dr. Johannes Eibl and Dr. Manfred Niese,
Cologne-Stammheim,

have been named as inventors

however, chlorobenzene, nitrobenzene or toluene are also suitable.

The production of the new dyes, e.g. B. in the form, of pigments, can be done in such a way that the heterocyclic compounds used as starting material as bases or in the form of their salts with inorganic or organic acids, preferably in Presence of reducing organic solvents or reducing compounds, such as bisulfites of organic ketones, with metals or metal compounds capable of complexing warmed up. Temperatures in the range of 50 to 150 ° C are generally sufficient, but can in some cases it may be expedient to use even higher temperatures. Sometimes it is beneficial to use salts, in particular ammonium salts, of inorganic or organic acids or the acids themselves To inflict reaction. The starting materials can also be applied to the fiber by methods known per se be applied, e.g. B. by padding or printing, and can then by neutral or acidic steaming or developed solely by heat treatment, e.g. B. in the German patent 888 837 can proceed as specified. If desired, one can click on the one to be colored Materials also make reservations in the usual way, e.g. B. by pressing aliphatic beforehand Diamines. The l-amino-3-iminoisoindolenine used as starting material for the production of the new dyes can be obtained by the method of German patent specification 879100, while the 2-amino-5-imino-pyrrolenine e.g. B, can be obtained by the process of German patent specification 1 001 785 can. For the method according to the invention can

909 787/380

the mixing ratios can be varied as required, contains, at the boiling temperature for 1 minute,

by z. B. 1 to 3 moles of the heterocyclic compound. The thickening then takes place in the usual way

fertilize with 3 to 1 mol of the amino-imino-isoindolenine washed out and the coloring soaped at the boil. Man

and / or the 2-amino-5-imino-pyrrolenine used. gets a strong reddish brown color, which is

According to the new process, dyes or 5 marked light fastness properties and very good general fastness properties

Colorings or prints in the most varied of colors.

tones, such as B-. Red-brown, black-brown, yellow-brown b) Varying the quantitative ratio of triazole and

or different shades of gray or different shades of olive, isoindolenine, by adding 20 g of 2 ₎ 5-diamino-3-phenyl-

obtained which have excellent fastness properties. 1,3,4-triazole and 20 g of l-amino-3-imino-isoindolenine

lo, you get brown-yellow prints, the very good ones

Example 1 have light and general fastness properties.

c) Apply 10 g of amino-imino-isoindolenine and 30 g

1OS g of l-amino-3-imino-isoindolenine and 35 g of 2,5-di-2,5-amino-3-phenyl-1,3,4-triazole, you get olive

amino-3-phenyl-1,3,4-triazole are mixed with 35 g of anhydrous yellow prints.

Oxalic acid, 20 g ammonium phosphate and 27 g CuCl ₂ in 15 Instead of the solution given in Example 4, a)

1500 ecm of dimethylformamide 3 to 5 hours to 130 to medium mixture, other solvent-

Heated to 135 ° C. After a while, a brown down mixture of z. B. used the following components

knock out. The mixture is suctioned hot and the are: methyl diglycol, dimethylformamide, phenoxy

Washed precipitate with a little dimethylformamide. ethanol, methanol, triethanolamine or triethylene

The residue is dissolved in 5 ° / _o hydrochloric acid for 1 hour at ao glycol. If you put the dye mixtures without the

40 to 50 ° C stirred, suction filtered and washed neutral. Addition of the thickener, so you can with the

The same measure is repeated with soda solution. solutions obtained tissue in a manner known per se

Finally, the precipitate will pad with 11 water.

Boiled for 1 hour, then vacuumed and dried. It example 5
a red-brown powder is obtained. Yield 95g. 25th

In example 4, the copper chloride solution is replaced

Example 2 40 g of a 16.5 ° / ₀ aqueous nickel chloride solution

so in the case of example 4, a) a print is obtained

16.7 g of l-amino-3-imino-isoindolenine, 17.5 g of 2,5-di- a deep neutral brown shade, in the case of the amino-3-phenyl-l, 3,4-triazole, 3 g of anhydrous oxalic acid, 30 Example 4, b) a yellowish brown shade and im 5 g of ammonium phosphate and 3 g of nickel chloride (water trap of Example 4, c) an olive shade that free) will all have excellent fastness properties with 150 ecm nitrobenzene for 4 hours to 130.

heated to 160 ° C. The suctioned product is, as in

Example 1 described, treated. It becomes a yellow-brown example 6

Pigment received. Yield 18.1g. 35

If in example 4, c) the amino-immo-iso-

Example 3 indolenine by a corresponding amount of the 5-phenyl

amino-imino-isoindolenine, the ammonium lactate solution

20.8 g l-amino-3-imino-isoindolenine, 31.1 g of 2,5-di- through 30 g of lactic acid (80 ° / ₀ ig), and the copper chloride amino-3-phenyl-l, 3,4-triazole, 2 ecm of formic acid, 3 g of 40 g of a 16.5% strength nickel chloride solution, this gives nickel chloride (anhydrous) and 200 ecm of chlorobenzene are refluxed for 3 hours in the case of Example 4, a). The chlorobenzene tinted brown shade. If the same process is carried out using steam and the residue, modification in Example 4, b), one as described in Example 1, worked up. A dark olive yellow shade and, in the case of Example 4, c), red-brown pigment are obtained. Yield 16.3g. 45 an olive yellow shade, which is also excellent

Have authenticity properties,
Example 4

Example 7

a) 10 g of 2,5-diamino-3-phenyl-l, 3,4-triazole and 30 g

l-Amino-3-imino-isoindolenine with a solution 50 Carry out the process of Example 4 by

Medium mixture, consisting of 150 g of formamide, 36 g of tri-man the 2,5-diamino-3-phenyl-l, 3,4-triazole through the

isopropanolamine, 30 g of thiodiglycol, 35 g of diglycol and the corresponding amount of 2,5-diamino-1,3,4-triazole replaced,

10 g of an emulsifier based on aryl polyglycol ether are obtained in the case of Example 4, a) dark brown

made into a paste. A dark brown-yellow dispersion is formed. Discoloration, in the case of Example 4, b) gray-brown

This mixture is now 55 colorations at normal temperature and olive-gray in the case of Example 4, c)

in 500 g of a common wheat starch-tragacanth coloration.

Thickening stirred in. Then 40 g of copper are replaced. The copper chloride solution is replaced by 40 g of a

ferchloridlösung (about 12 _^0/0 strength, based on CuCl ₂ · 2H ₂ O), about lo.ö ^ aqueous nickel chloride solution, we obtain similar

40 g of a 60% ammonium lactate solution and 124 g borrowed, but slightly greener shades,
Water entered. This mixture is stirred until 60

a largely homogeneous printing paste is obtained. Example 8

In the film or machine impression, this paste is on

Natural or regenerated cellulose fibers are applied. In example 4, the l-amino-3-imino-iso-iso- and carefully dried at elevated temperature (about 40 to indolenine by 5-phenyl-amino-imino-isoindolenine and 80 ° C.). The development of the dye takes place 65 the 2,5-diamino-3-phenyl-l, 3,4-triazole by either neutral or acidic amount of 2-amino-5-imino-3,4-dimethyl- 1,3,4-steaming at 100 ° C. or by 4 to 8 minutes long triazole and the ammonium lactate solution by heating 30 g milk-dry to 125 to 140 ° C. acid (80 ^J / ₀ ig) is obtained in the case of the example 4, a)

The dyed fibers are then in a bath, the dark brown colorations, in the case of Example 4, b)

5 g of oxalic acid and 5 g of formic acid per liter of water

game 4, c) olive yellow colorations that have good fastness properties.

If the copper chloride solution is replaced by 40 g of an approximately 16.5% nickel chloride solution, one obtains similar, but slightly more yellowish or greener shades.

It is of course possible, apart from the proportions of the isoindolenines given in the examples and other triazoles to use, in which mixed tones then arise, z. B. gray to almost black or dull blue-gray or blue-green hues.

Example 9

A textile fabric made of natural or regenerated cellulose is printed with a paste consisting of 9 parts by weight of diethylenetriamine, triethylenetetramine or aminoethanol or another primary or diprimary amine, 60 parts by weight of a customary thickening of wheat starch - tragacanth and British gum and 31 parts of water, and after that Drying with a solution consisting of 3 parts by weight of 3-phenyl-2,5-diamino-l, 3,4-triazole, 1 part by weight of l-amino-3-imino-isoindolenine, 15 parts by weight of a mixture of solvents mentioned in Example 4, 4 parts by weight of copper chloride solution (about 12%, based on CuCl ₂ • 2H ₂ O), 63 parts by weight of water and 4 parts by weight of ammonium lactate (60 ° / ₀ ig), padded, dried in the manner described in Example 4 and developed. A colorless (white) reservation is obtained on a red-brown background. "30

Example 10

8 parts by weight of an equimolecular mixture consisting of the diazo compound of 4-chloro-2-toluidine and N-methyl-m-sulfoanthranilic acid with / S-oxynaphthoic acid-o-ethoxyanilide, are with 1.5 parts by weight of sodium hydroxide solution (32%), 5 parts by weight of ethyl alcohol, 7 parts by weight Water, 6 parts by weight of diethylenetriamine, ■ 60 parts by weight of those described in the previous example Thickening and 12.5 parts by weight of water mixed together, on tissue made from native or regenerated Cellulose printed and padded with the padding solution described in the previous example, dried, with Developed neutral water vapor and, as described in Example 4, post-treated. You get scarlet ones Reserve effects on a red-brown background.

Example 11

If the nickel chloride solution given in Example 5 is replaced by a cobalt salt solution, such as. B. cobalt chloride, Cobalt sulfate or a complex compound of cobalt salts with amino acids, such as. B. Sarcosine, so receives brown to pale yellow discolorations.

Example 12

If the nickel chloride solution given in Example 5 is replaced by an iron salt solution, such as. B. ferrous sulfate or iron (III) sulfate, yellow-brown to pale yellow colorations are obtained.

Example 13

Is used in Example 6 instead of 5-phenyl-amino-3-imino-isoindolenine 5-methoxy-l-amino-3-imino-isoindolenine or S-acetyl-l-amino-S-iminoisoindolenine, red-brown to brown-yellow colorations are obtained when using copper salts and with Use of nickel salts for deep brown to yellow-brown colorations.

Example 14

Is used in Example 6 instead of 5-phenyl-amino-3-immQ'isoindolenine a 3,4-dialkyI-2-amino-5-imineQ-pyrrolenine the formula

NH

R ₁ -C

in which a) R ₁ and R ₂ each represent a methyl group or b) R ₁ and R ₂ each represent an ethyl group or c) R _{1 represents} a methyl and R _{2 represents} an ethyl group, then when using the in the Examples 5, 11 and 12 described nickel, cobalt or iron salts red-brown to light brown colorations.

Example 15

Is used in Example 6 instead of 5-phenyl-amino-3-imino-isoindolenine the Bz-aza-1-amino-3-imino-isoindolenine, red-brown to pale brown is obtained Shades.

Example 16

Is used in Example 7 instead of 2,5-diamino-1,3,4-triazole following connections:

a) 2,5-diamino-3- (2-chlorophenyl) -1, 3,4-triazole,

b) 2,5-diamino-3- (2-nitrophenyl) -1, 3,4-triazole,

c) 2,5-diamino-3- (4-carboxyphenyl) -1, 3,4-triazole,

d) 2,5-diamino-3- (4-sulfonamidophenyl) -1, 3,4-triazole,

e) 2,5-diamino-3-benzenesulfon-l, 3,4-triazole,

in this way brown to olive-yellow shades are obtained.
Example 17

If in Example 4 the l-amino-3-imino-isoindolenine is replaced by the corresponding amount of 5-phenyl-amino-3-imino-isoindolenine or 5-methoxy-1-amino-3-imino-isoindolenine or S-acetylamino-1-amino-S-imino-isoindolenine or by the pyrrolenines given in Example 14 and that given in Example 4 is replaced 2,5-diamino-3-phenyl-1,3,4-triazole by corresponding amounts of the triazoles given in Example 16 is obtained under the conditions given in Example 4, brown to pale yellow dyes that have very good fastness properties own.

If instead of the copper salt specified in Example 4, corresponding amounts of cobalt, nickel or Iron salts, you get similar shades.

60

Claims (1)

Claim: Process for the preparation of dyes in bulk or on the fiber, characterized in that compounds which, in one of their tautomeric forms, are represented by the formula R ₁ -N- -NO, , C = NH 7 ° can be represented in which R _x and R ₂ stand for hydrogen, acyl, alkyl or aryl groups, in a mixture with 2-amino-5-imino-pyrrolenines, which may be substituted in the 3- and / or 4-position can, such as B. l-Amino-3-imino-isoindolemne, in the presence of metal compounds used for the production of metal-containing phthalocyanines can be, and optionally in the presence of solvents and reducing agents subjected to a heat treatment. A coloring table was displayed when the application was announced.