DE1001785B - Process for the production of tetrazaporphines - Google Patents

Description

GERMAN

It is known from German patent specification 888 837 that l-amino-3-imino-isoindolenines, preferably in the presence of reducing organic solvents and suitable heavy metal salts, Can produce phthalocyanines in substance and on the fiber.

It has now been found that 2-amino-5-imino-pyrrolenines of the general formula can be obtained in an analogous manner

NH,

Method of manufacture
of tetrazaporphines

R-C3

R '--C

NH

where R is alkyl, cycloalkyl, aralkyl, halogen or H, R 'is alkyl, cycloalkyl, aralkyl or halogen and R + R 'can be members of a cycloalkylene ring, blue-violet or red-violet tetrazaporphine can be obtained under the same conditions.

As 2-amino-5-imino-pyrrolenine derivatives, 3,4-dimethyl, 3-methyl-4-ethyl, S-methyl-cyclohexyl, 3-methyl-4-benzyl-, 3-methyl-4-isopropyl-, 3-chloro-, 3, 4-dichloro- or 3, 4-tetramethylene-2-amino-5-iminopyrrolenine be used.

Heavy metal compounds are all compounds commonly used in the manufacture of phthalocyanines Metals usable. The preferred solvents are those with weakly reducing properties used. Such solvents or solvent mixtures are described in the German patent 888 837.

The tetrazaporphines are produced under the specified conditions at temperatures of about 50 to 150 °. The dyes can also be applied to the fiber e.g. B. be developed by neutral or acidic steaming or by heat treatment alone, it being possible to work according to the dyeing process specified in German patent specification 888 837. The dyeings produced in this way have very good fastness properties.

If a mixture of 1 to 3 mol of the 2-amino-5-imino-pyrrolenine is used as the starting product 3 to 1 mol of any l-amino-3-imino-isoindolenine (according to German Patent 879 100), dyes are obtained which in their constitution between the tetrazaporphines and the phthalocyanines and in the shade compared to the tetrazaporphines to blue are shifted. These dyes can also be used on the

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Dr. Georg Rösch, Leverkusen,

Dr. Helmut Klappert, Cologne-Stammheim,

and Dr. Walther Wolf, Leverkusen,

have been named as inventors

Fiber are produced and result in dyeings of high fastness.

The preparation of the 2-amino-5-imino-pyrrolenines is described in German patent application F 13626 IVb / 12p.

Compared to the previously known processes for the production of tetrazaporphin dyes the inventive method in that it is the preparation of the tetrazaporphin dyes on the Fiber made possible by a brief heat treatment, under conditions in which the fibers are not damaged will.

example 1

42.4 parts by weight of 3,4-dimethyl-2-amino-5-imino-pyrrolenine, prepared according to Example 1 the German patent application F 13626 IVb / 12p, are with

100 parts by weight of the solvent mixture described below made into a paste, then will

Parts by weight of copper chloride solution (118.6 parts by weight of crystallized copper chloride in 1000 parts by weight of aqueous solution) and

Parts by weight of water are stirred in. The mixture is stirred in

Parts by weight of tragacanth thickening (65: 1000) and sets up with water

1000 parts by weight. ^;

This paste is printed on cotton, viscose rayon, rayon or acetate rayon. After your

609 768/2 «

50

400
400

conventional pre-drying at 60 ° is developed the Octamethyltetrazaporphin on the fiber by about _^1/4 hour heating at 100 to 120 °, and fixed, lasting by S to 10 minutes, neutral or acidic vapors in Mather slab can be achieved. In this way, after the usual aftertreatment, beautiful, clear violet prints with excellent fastness properties are obtained.

Instead of the copper chloride solution, equivalent amounts of copper-containing solutions of others can also be used Copper compounds, such as B. those of bromide, sulfate, nitrate, acetate and N-methyl-N-ethanol aminoacetate, be used.

The composition of the solvent mixture used above is as follows: 4 parts by weight of formamide, 5 parts by weight of thiodiglycol, 2.5 parts by weight of diglycol, 7 parts by weight of triisopropanolamine, 5 parts by weight Formylmethylaniline, 5 parts by weight isobutyl alcohol.

Instead of this solvent mixture, you can also use other solvent mixtures or solvents listed in German patent specification 888 837 are used will.

Example 2

42.4 parts by weight of 3,4-dimethyl-2-amino-5-imino-pyrrolenine (produced according to Example 1 of German patent application F 13626 IVb / 12p) are with

100 parts by weight of the solvent mixture mentioned in Example 1 made into a paste, and on it

50 parts by weight of nickel chloride solution (165 parts by weight of crystalline nickel chloride in 1000 parts by weight aqueous solution) and

400 parts by weight of water are stirred in. The mixture is stirred in

400 parts by weight of tragacanth thickening (65: 1000) and set up with water and rayon obtained beautiful clear purple prints with excellent fastness properties.

If, instead of the nickel chloride solution, the corresponding amounts of copper or cobalt salt solutions are used, in this way, dyes of a similar shade and very good fastness properties are produced on the fiber.

Example 4

If a according to Example 1 is prepared from 51.4 parts by weight of 3,4-tetramethylene-2-amino-5-imino-pyrrolenine ( printing paste produced according to example 3 of German patent application F 13626 IVb / 12p) is used, in this way, clear, bluish violet tones on the vegetable fiber or synthetic fiber have excellent fastness properties generated.

Example 5

31.8 parts by weight of 3, 4-dimethyl-2-amino-5-imino-pyrrolenine and

12.5 parts by weight of l-amino-3-imino-isoindolenine (manufactured according to the German patent specification 879 100) with

100 parts by weight of the solvent mixture mentioned in Example 1 made into a paste, on it

50 parts by weight of copper chloride (118.6: 1000) and 400 Parts by weight of water are stirred in. The mixture is stirred in

400 parts by weight of tragacanth thickening (65: 1000) and set up with water

1000 parts by weight.

This paste is printed on cotton, viscose rayon and rayon. After the usual pre-drying at 60 ° is achieved by subsequent neutral or acid steaming or by dry heat treatment a clear violet-blue dye obtained on the fiber with excellent fastness properties.

1000 parts by weight.

This paste is used with the instructions given in Example 1 on cotton, viscose rayon, Spun rayon or acetate rayon beautiful clear reddish purple prints with excellent fastness properties obtain.

Instead of the nickel chloride solution, 25.5 parts by weight of N-methyl-ethanol-aminoacetic acid nickel can also be used or equivalent amounts of other nickel compounds can be used.

Example 3

47.2 parts by weight of 3-ethyl-4-methyl- (or 3-methyl-4-ethyl) -2 - amino - 5 - imino - pyrrolenine (prepared according to example 2 of German patent application F13626 IVb / 12p) are used with

100 parts by weight of the solvent mixture mentioned in Example 1 to be made into a paste

50 parts by weight of nickel chloride solution (165 parts by weight of crystalline nickel chloride in 1000 parts by weight aqueous solution) and

400 parts by weight of water are stirred in. The mixture is stirred in

400 parts by weight of tragacanth thickening (65: 1000) and set up with water

40

Example 6

If, as indicated in Example 5, a printing paste is made from: 10.6 parts by weight of 3,4-dimethyl-2-amino-5-iminopyrrolenine and 37.5 parts by weight of 1-amino-3-imino-isoindolenine and 50 parts by weight of copper chloride solution (118.6: 1000) made and printed on cotton, a clear red-tinged blue is developed by steaming or heating.

Example 7

If, as indicated in Example 5, a printing paste composed of 21.2 parts by weight of 3,4-dimethyl-2-amino-5-iminopyrrolenine and 25 parts by weight of 7- (or 4-) aza-1-amino-2-imino-isoindolenine (according to German patent specification 879100) and 50 parts by weight of copper chloride solution (118.6: 1000) made and printed on cotton, in this way a clear, true color is developed through steaming or heating, which in the clay between one Purple and a reddish blue.

60

1000 parts by weight.

This paste is used to apply the instructions given in Example 1 to cotton and viscose rayon

Example 8

47 parts by weight of 3-ethyl-4-methyl- (or 3-methyl-4-ethyl) -2-amino-5-imino-pyrrolenine (prepared according to Example 2 of German patent application F 13626 IVb / 12p) are with 200 parts by weight of one Solvent mixture of the composition below made into a paste and stirred in 428 parts by weight of water. Solution of 200 parts by weight of N-Methyläthanol-aminoessigsaurem copper and 55 parts by weight of 50 ° / ₀ acetic acid the mixture is stirred in a 10%.

With this solution, cotton, rayon rayon becomes

or padded rayon and the violet dye is developed through neutral or acidic steaming.

Composition of the solvent used: 250 parts by weight of formamide,
250 parts by weight of diglycol monomethyl ether,
360 parts by weight of triisopropanolamine,

40 parts by weight of a polyethylene glycol based emulsifier and
100 parts by weight of phenoxyethanol

IO

1000 parts by weight.

Example 9

In 40 parts by volume of formamide were 4.92 parts by weight of 3, 4-dimethyl-2-amino-5-imino-pyrrolenine _^(4/100 mol) prepared according to Example 1 of German Patent Application F 13626 IV b / crystalline 12p and 1.7 parts by weight. Copper chloride ( ¹ Z ₁₀₀ mol) entered with stirring and heated to 90 to 100 ° for 1 to 2 hours. The copper octamethyl-tetrazaporphin separates out in a good yield as a dark purple crystal. Precipitate is filtered off with suction while hot, washed with methanol and dried. The dye can be recrystallized from boiling dichlorobenzene and has very good fastness properties. Its solution color in concentrated sulfuric acid is blue. When the solution is poured into water, purple flakes separate out.

Instead of the bases, equivalent amounts of the chlorine or bromine hydrates, the nitrates or any other can be used other salts can be used.

If, in the above example, the copper chloride is replaced by the equivalent amount of a nickel or cobalt salt, the corresponding nickel or cobalt tetrazaporphine is obtained in this way. The latter are also purple Pigments, but of a slightly redder shade.

Instead of formamide, dimethylformamide or the solvent mixture given in Example 1 can also be used in the reaction be used.

Example 10

From 40 parts by volume of formamide, 5.48 parts by weight of 3-ethyl-4-methyl- (or 3-methyl-4-ethyl) -2-amino-5-iminopyrrolenine according to Example 2 of German patent application F 13626 IVb / 12p ( _^4/100 mole) and 2.9 parts by weight crystalline. Nickel chloride is obtained as in Example 9 with a good yield of nickel tetramethyl-tetraethyl-tetrazaporphine. This pigment dye has a slightly more bluish tint than the octamethyl dye.

The corresponding copper and cobalt dyes can be used in the same way with copper or cobalt salts getting produced.

Example 11

If, as indicated in Example 9, 5.96 parts by weight of 3,4-tetramethylene-2-amino-5-imino-pynolenin are used according to Example 3 of German patent application F 13626 IVb / 12p, 1.70 parts by weight are obtained Copper chloride is the corresponding copper tetrazaporphin and with 2.9 parts by weight of crystalline. Cobalt chloride the corresponding Cobalt tetrazaporphine.

Example 12

If, as indicated in Example 9, 3.69 parts by weight of 3,4-dimethyl-2-amino-5-imino-pyrrolenine are used according to Example 1 of German patent application F 13626 IVb / 12p and 1.45 parts by weight of l-amino-3-imino-isoindolenine (manufactured according to German patent specification 879100), a clear blue-violet one is obtained Pigment dye. The mixing ratio between the 2-amino-5-imino-pyrrolenines and the 1-amino-3-imino-isoindolenines can be varied here in any way, obtaining pigment dyes that lie in hue between purple, blue and green.

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Claims (2)

PATENT CLAIMS: 1. A process for the production of tetrazaporphines in bulk or on the fiber, characterized in that that 1 to 4 moles of 2-amino-5-imino-pyrrolenines of the general formula NH, NH where R is alkyl, cycloalkyl, aralkyl, halogen or H, R 'is alkyl, cycloalkyl, aralkyl or halogen and R + R 'can be members of a cycloalkylene ring, with 3 to OMoI of a l-amino-3-imino-isoindolenine, preferably in the presence of weakly reducing organic solvents and heavy metals or heavy metal compounds, subjected to a heat treatment. 2. The method according to claim 1, characterized in that the development of the dyes on the fiber by neutral and acidic steaming. Considered publications:
German patent specification No. 908 288. © 609 768/261 1.57