PL199311B1 - New derivatives of symmetrical 1,3,5-triazine - Google Patents

Abstract

New compounds have been disclosed, derivatives of symmetrical 1,3,5-triazine, of the general formula shown in the drawing, wherein X 1 and X 2 together or independently of each other represent a hydrogen atom or a sulfone group, and Y represents an N-(e-hydroxyethyl)amino, N,N-di(p- -hydroxyethyl)amino, morpholine, amino, aniline, or an aniline group substituted with a sulfone group, preferably in the meta-, 2- -aminoethylsulfone position. These compounds dye polyamide fibers, wool, polyamide-wool and polyamide-cotton blends blue with a green tint.

Description

Description of the invention

The subject of the invention is novel symmetric 1,3,5-triazine derivatives.

They are known, inter alia, from the textbook "The chemistry of synthetic dyes" ed. Academie Press 1972 New York and London, monochloro- and dichlorotriazine dyes for dyeing cellulose fibers, containing symmetrical 2,4,6-trichloro-1,3,5-trioazine as a reactive system that binds to these fibers.

There are known, from the patent application No. P-337907, symmetric 1,3,5-triazine derivatives of formula I shown in the drawing, in which X represents the N- (e-hydroxyethyl) amino group, N, N-di (e -hydroxyethyl) amino, morpholine, amino, aniline, aniline substituted with a sulfo group, preferably in the meta- position, and Y is hydrogen, chlorine, methyl, methoxy, ethoxy or sulfone.

It has been found that the new symmetric 1,3,5-triazine derivatives of the general formula in which X1 and X2 are together or independently of each other a hydrogen atom or a sulfo group and Y is an N- (e-hydroxyethyl group) ) amine, N, N-di (e-hydroxyethyl) amino, morpholine, amino, aniline, aniline substituted with a sulfonate group, preferably in the meta-, 2-aminoethylsulfone position, dyes polyamide fibers, wool, polyamide-wool blends, polyamide-cotton in blue and blue with a green tint. The dyes obtained with the use of the new compounds are characterized by very good resistance, 6 - 7 on an eight-point scale, to light and high resistance, 5 on a five-point scale, to wet factors.

The new compounds can be prepared by the double condensation of 1-amino-4 (3 'or 4'-aminoanilino) anthraquinone-2-sulfonic acid derivatives such as 1-amino-4 (4'-aminoanilino) anthraquinone-2-sulfonic acid, 1-amino-4 (3'-aminoanilino) anthraquinone-2-sulfonic acid, 1-amino-4 (4'-aminoanilino) anthraquinone-2,3'-disulfonic acid, 1-amino-4 (4'-aminoanilino) ) anthraquinone-2,2'-disulfonic acid, 1-amino-4 (3'-aminoanilino) anthraquinone-2,4'-disulfonic acid, the first condensation being carried out in an aqueous medium at pH 6.5 - 7.5 at temperature 0 - 20 ° C for 1-3 hours, and the second - using the same or different derivatives of 1-amino-4 (3 'or 4'-aminoanilino) anthraquinone-2-sulfonic acid, in the same environment and at the same time pH alone at 35-55 ° C for 1-5 hours. The double condensation product is then condensed with monoethanolamine, diethanolamine, morpholine, aniline, methanilic acid, sulfanilic acid,

2-aminoethylsulfonic acid, in an aqueous medium at a temperature of 85-100 ° C for 1-6 hours. The final product of this condensation is separated from the reaction medium by salting out.

The following non-limiting examples illustrate the subject matter of the invention.

P r z x l a d I.

To a suspension of 3.7 g of cyanuric chloride in 30 g of water, containing 50 g of ice and 0.1 g of dispersant under the trade name Rokacet, a solution of 17.24 g (0.04 mol) of sodium salt of 1-amino-4 (3 ') was added. -aminoanilino) anthraquinone-2-sulfonic acid in 400 g of water, and a condensation reaction was carried out in the temperature range 0-10 ° C while maintaining the pH in the range of 6.5-7.2 by adding 4% sodium hydroxide solution dropwise over 2 hours. The reaction mixture was then heated to about 50 ° C and a second condensation was performed at 45-50 ° C for 3 hours. The 2nd condensation product was condensed with 1.8 g of monoethanolamine in the temperature range 90-95 ° C for 4.5 hours at pH 7.0-7.5 using the maintenance method described above. After

In the 3-th condensation, the reaction mixture was cooled to 60 ° C and the final product was salted out with sodium chloride, cooled to 20 ° C, filtered and dried at 60 ° C.

18.9 g of the compound of the formula shown in the figure were obtained, where X1 and X2 represent hydrogen atoms, and Y - N- (e-hydroxyethyl) amino group. The spectrophotometric analysis of the compound prepared in 50% acetone was as follows:

Xi _max = 603.5 nm si _max = 23,300 dm ³ / mol x cm λ2ma _x = 634.1 nm ε2ma _x = ^{20,700 dm 3} / mol x cm.

The produced compound dyed polyamide fibers and wool blue.

P r z x l a d II.

A solution of 17.24 g (0.04 mol) of sodium salt of 1-amino-4 (3'-aminoanilino) anthraquinone was added to a suspension of 3.7 g of cyanuric chloride in 30 g of water, containing 50 g of ice and 0.1 g of Rokacet. -2-sulfonic acid in 400 g of water and a condensation reaction in the temperature range 0-10 ° C

The mixture was kept at a pH of 6.5 - 7.2 as in Example 1 by the dropwise addition of a 4% sodium hydroxide solution over 2 hours. The reaction mixture was then heated to approximately 50 ° C and a second condensation was performed at 45-50 ° C for 3 hours at pH 6.5-7.2 using the same method as above. The 2nd condensation product was condensed with 3.15 g of N, N-diethanolamine in the temperature range 90-95 ° C for 4.5 hours at pH 7.0-7.5, using the same method as described above. The next step was as in example 1.

19.3 g of the compound of the formula shown in the figure were obtained, where X1 and X2 represent hydrogen atoms, and Y - N, N-di (e-hydroxyethyl) amino group. The spectrophotometric analysis of the compound prepared in 50% acetone was as follows:

Xi _max = 600.6 nm si _max = 23,000 dm ³ / mol x cm λ _2π3Χ = 634.1 nm ε2 _m a _x = 23,250 dm ³ / mol x cm.

The produced compound dyed polyamide fibers and wool blue.

P r x l a d III.

A solution of 17.24 g (0.04 mol) of sodium salt of 1-amino-4 (3'-aminoanilino) anthraquinone was added to a suspension of 3.7 g of cyanuric chloride in 30 g of water, containing 50 g of ice and 0.1 g of Rokacet. -2-sulfonic acid in 400 g of water and a condensation reaction in the temperature range 0-10 ° C at pH 6.5-7.2 maintained as in Example 1 for 2 hours. The reaction mixture was then heated to about 50 ° C and a second condensation was performed at 45-50 ° C for 3 hours. The product of the 2nd condensation was condensed with 5.2 g of sulphanilic acid in the temperature range 90

- 95 ° C during 4.5 hours at pH 7.0-7.5 maintained by the method of Example I. The following was followed as in Example I.

20.1 g of the compound of the formula shown in the figure were obtained, where X1 and X2 were hydrogen and Y - an anilino group substituted in the para-sulfo position. The spectrophotometric analysis of the compound prepared in 50% acetone was as follows:

Xi _max = 600.6 nm si _max = 23050 dm ³ / mol x cm λ _2π3Χ = 634.1 nm ε2ma _x = ^{23,200 dm 3} / mol x cm.

The produced compound dyed polyamide fibers and wool blue.

P r x l a d IV.

A solution of 21.32 g (0.04 mol) of 1-amino-4 (3'-aminoanilino) anthraquinone acid sodium salt was added to a suspension of 3.7 g of cyanuric chloride in 30 g of water, containing 50 g of ice and 0.1 g of Rokacet. -2,4'-disulfonic acid in 300 g of water and carried out a condensation reaction in the temperature range 0-10 ° C while maintaining the pH in the range 6.5-7.2 as in Example 1 for 2 hours. The reaction mixture was then heated to about 50 ° C and a second condensation was performed in a temperature range of 45

- 50 ° C during 3 hours. The product of the 2nd condensation was condensed with 2.79 g of aniline in the temperature range 90-95 ° C for 4.5 hours at pH 7.0-7.5 controlled as in Example I. The next steps were as in Example I.

24.0 g of the compound of the formula shown in the drawing were obtained, where X1 and X2 represented sulfo groups and Y - anilino group. The results of the spectrophotometric analysis of the produced compound in water were as follows:

λ _Π3Χ = 610.0 nm and: _max = 21,000 dm ³ / mol x cm.

The produced compound dyed polyamide fibers and wool blue.

P r z k ł a d V.

A solution of 8.62 g (0.02 mol) of 1-amino-4 (4'-aminoanilino) anthraquinone acid sodium salt was added to a suspension of 3.7 g of cyanuric chloride in 30 g of water, containing 50 g of ice and 0.1 g of Rokacet. -2-sulfonic acid in 200 g of water and a condensation reaction in the temperature range 0-10 ° C at pH 6.5-7.2 maintained as in Example 1 for 2 hours. Then a solution of 10.66 g (0.02 mol) of 1-amino-4 (3'-aminoaniline) anthraquinone-2,4'-disulfonic acid sodium salt in 200 g of water was added dropwise and the reaction mixture was heated to 45-50 ° C. and held at this temperature at pH 6.5-7.2 for 3 hours. The product of the 2nd condensation was condensed with 2.79 g of aniline in the temperature range 90-95 ° C for 4.5 hours at pH 7.0-7.5 maintained at the same level as in Example 1. The following procedure was followed as in example I.

21.9 g of the compound of the formula shown in the drawing were obtained, where X1 was a hydrogen atom, X2 was a sulfo group and Y was an anilino group. The results of the spectrophotometric analysis of the produced compound in water were as follows:

λ _Π3Χ = 620.0 nm ε _Π3Χ = ^{19650 dm 3} / mol x cm.

The produced compound dyed polyamide fibers and wool a blue with a green shade.

PL 199 311 B1

P r x l a d VI.

A solution of 8.62 g (0.02 mol) of 1-amino-4 (3'-aminoanilino) anthraquinone acid sodium salt was added to a suspension of 3.7 g of cyanuric chloride in 30 g of water, containing 50 g of ice and 0.1 g of Rokacet. -2-sulfonic acid in 200 g of water and a condensation reaction in the temperature range 0-10 ° C at pH 6.5-7.2 maintained as in Example 1 for 2 hours. Then a solution of 10.66 g (0.02 mol) of 1-amino-4 (4'-aminoanilino) anthraquinone-2,3'-disulfonic acid sodium salt in 200 g of water was added dropwise and the reaction mixture was heated to 45-50 ° C. and held at this temperature at pH 6.5-7.2 for 3 hours. The product of the 2nd condensation was condensed with 2.79 g of aniline in the temperature range 90-95 ° C for 4.5 hours at pH 7.0-7.5 maintained at the same level as in Example 1. The following procedure was followed as in example I.

21.8 g of a compound of the formula shown in the drawing were obtained, where X1 was a hydrogen atom, X2 was a sulfo group and Y was an anilino group. The results of the spectrophotometric analysis of the produced compound in water were as follows:

X _max = 625.0 nm s _max = 19450 dm ³ / mol x cm.

The produced compound dyed polyamide fibers and wool a blue with a green shade.

Further Examples VII-XVII in which the procedure was analogous to those in Examples 1-6 are shown in the table. The table shows the substrates for the 1st, 2nd and 3rd condensation, the results of the spectrophotometric analysis of the product in water, and the color of the product to dye polyamide fibers and wool.

T a b e l a

Example No. Component of condensation The results of the spectrophotometric analysis Colour coloring first second third [nm] Smax [dm ³ / mol x cm] 1 2 3 4 5 6 7 VII 1-amino-4 (4'-amino- acid) anilino) anthraquinone-2- -sulfone 1-amino-4 (4'-amino- acid) anilino) anthraquinone-2- -sulfone aniline 620 17200 blue with a shade of green VIII 1-amino-4 (4'-aminoanilino) anthraquinone-2,3'-disulfonic acid 1-amino-4 (4'-aminoanilino) anthraquinone-2,3'-disulfonic acid aniline 615 21100 blue with a shade of green IX 1-amino-4 (4'-aminoanilino) anthraquinone-2,2'-disulfonic acid 1-amino-4 (4'-aminoanilino) anthraquinone-2,3'-disulfonic acid aniline 630 23,000 blue with a shade of green X 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- -sulfone 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- -disulfone aniline 600 23800 blue XI 1-amino-4 (4'-amino- acid) anilino) anthraquinone-2- -sulfone 1-amino-4 (4'-aminoanilino) anthraquinone-2,3'-disulfonic acid aniline 620 17400 blue with a shade of green XII 1-amino-4 (4'-amino- acid) anilino) anthraquinone-2- -sulfone 1-amino-4 (4'-aminoanilino) anthraquinone-2,2'-disulfonic acid aniline 620 19500 blue with a shade of green XIII 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- sulfonic 1-amino-4 (4'-aminoanilino) anthraquinone-2,2'-disulfonic acid aniline 625 20,000 blue with a shade of green XIV 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- -sulfone 1-amino-4 (3'-aminoanilino) anthraquinone-2,4'-disulfonic acid aniline 625 19100 blue XV 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- -sulfone 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- -sulfone morpho- rope 618.8 19600 blue

PL 199 311 B1 cont. table

1 2 3 4 5 6 7 XVI 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- sulfonic 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- -sulfone acid methanil new 612.7 19900 blue XVII 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- -sulfone 1-amino-4 (3'-amino- acid) anilino) anthraquinone-2- -sulfone acid 2- -amino- ethyl- sulfo- new 605.3 20300 blue

Patent claim

Claims (1)

New compounds, derivatives of symmetric 1,3,5-triazine, of the general formula shown in the figure, in which X1 and X2 are together or independently of each other a hydrogen atom or a sulfone group, and Y is an N- (e-hydroxyethyl) amino group N, N-di (e-hydroxyethyl) amino, morpholino, amino, aniline, aniline substituted with a sulfonate group, preferably in the meta, 2-aminoethylsulfonate position.