CS216606B1 - Azodyes containing the remainder of the citrazine acid in the molecule and method of preparation the same - Google Patents

Abstract

The process serves to prepare novel, citrazinoyl-containing azo dyes of the formula I <IMAGE> where Ar, R, R1, R2 and R3 are each as defined in Claim 1. Said azo dyes are prepared by coupling diazotised aromatic amines of the general formula II <IMAGE> with compounds of the general formula III <IMAGE>

Description

The invention relates to azo dyes containing a residue of citrazic acid in a molecule and to a process for their preparation. The essence of the process is the coupling of diazotized aromatic amines with citrazic acid (2,6-dihydroxypyridine-4-carboxylic acid) at temperatures of 0 to 50 ° C, optionally following substitution of the dyes obtained.

Azo dyes resulting from the coupling of diazotized amines with citrazic acid have not been described. Due to their coloring properties, they have the character of direct, reactive and dispersive dyes and are available in a variety of shades, in particular yellow, orange, red, brown and black. They are suitable for dyeing textile substrates, both natural and synthetic.

Process for preparing azo dyes of the formula I,

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AND

216 606 where it indicates

Ar the rest of diazo components of the benzene or naphthalene series,

R is hydroxyl, alkoxy, wherein alkyl contains 1 to 12 carbon atoms, amino, dialkylamino, wherein alkyl contains 1-16 carbon atoms, alkylamino, wherein alkyl contains 1-16 carbon atoms,

R ^ is hydrogen, sulfo-, hydroxy-, carboxy, halogen,

R _{2 is} hydrogen, sulfo, carboxy, halogen, amino, optionally substituted, nitro, -SO ₂ -CH = CH ₂ ,

R 1 is hydrogen, amino, optionally further substituted with cyanuric chloride, 2-methoxy-4,6-dichlorotrianine, 2,4,5,6-tetrachloropyrimidine, 2,4-difluoro-5-chloropyrimidine, 2,3-dichloroquinoxaline-5-carbonyl chloride chloroacetyl chloride, optionally further substituted by a cyanuric chloride residue in which one Cl atom can be replaced by an aniline sulfo residue, wherein when Ar is a naphthalene series residue, R @ 1 = hydrogen, R @ ₂ = hydrogen, optionally sulfo and R @ 6 = sulfo, According to the invention, the diazotized aromatic amines of general formula (I) are:. II,

wherein R 1 and R ₂ are as defined above and R 2 is hydrogen or amino, they are coupled with a compound of formula HI,

III

Wherein R is as defined above, at a temperature of 0 to 50 ° C and a pH of 3 to 9, optionally, if R ₃ in Formula II is an amino group further substituted by reactive residues, the corresponding reactive compound of formula IV is prepared first,

Z-NH

Sat ₃ h

IV

216 606 where Z is a reactive residue, and this is reacted, before or after coupling with citrazinic acid, with a compound of formula V,

wherein and R 8 are as defined above, optionally further with kycnir chloride.

In addition to the discrete aromatic amines, the active components may be present. benzene and naphthenene series as well as polycyclic and heterocyclic compounds, substituted on the nucleus by halogen, nitro, alkyl, alkoxy, respectively. a solubilizing group such as -SO 3 H, COOH, optionally. derivatives thereof, such as a carboxamide, alkylcarboxamide group.

In the case of aromatic dicmines, the coupling with citric acid is usually preceded by an alkylation. acylation, as a reaction with 2,4-dihalo-6'-pyrrolidino-1,3-oxo-1,3,5-triazine, 2,4,5,6-tetracloxypropylidine, 2,4,6-tri: loir-5-ctaloropropyrimidine, chloroacetyl chloride, 2,3- The compound is then treated with diconium salts of the above-mentioned aromatic heterocyclic amines.

In cases where the resulting dye according to the claim of the Octive Compensation, the functional groups capable of substitution, such as, are present. other substituents, such as suitable cyl, bensoyl, tosyl ctd, and especially the introduction of radicals having reactive centers, can be introduced into the moiety of dyes. They are characteristic of the so-called reactive dyes and have considerable technical significance.

The coupling reaction with citric acid or derivatives thereof can be carried out in solution or in solution.

By way of illustration, some of the types of active components for coupling with acid and its derivatives are shown in the table.

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Table

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In the case of reactive dyes, properties can be changed by introducing an additional reactive center prior to coupling with citrazinic acid, such as

where

Ar is a benzene linker,

X is chlorine, aromatic amine, amino, Cy denotes the s-trlazine cycle

Comparison of the properties of the new dyes prepared according to the invention with the existing yellow marks results in the desired shade of greenish yellow, high spreading and stability on textile substrates.

The economic advantage is predetermined by the use of an intermediate available synthetically from domestic raw materials.

The properties of these yellow dyes can be used to prepare and nuance dyes of other shades such as green, scarlet, olive, etc.

Example 1

17.3 parts by weight of sulfanilic acid were dissolved in 400 ml of water and 40 ml of 2.5N sodium carbonate solution. After cooling to 10 ° C, this solution was mixed with 40 ml of 2.5N sodium nitrite in water and poured into a solution of 100 ml of water and 100 ml of 2.5N hydrochloric acid all at once. After stirring for 10 minutes, any excess nitric acid was blunted with a solution of amidosulfonic acid and the diazonium salt suspension was poured into a solution of 15.5 parts by weight of a portion of citric acid dissolved in 500 ml of water and 50 ml of a 2.5N solution over 15 minutes. sodium carbonate. During the coupling, the mineral acidity was permanently blunted with a 2.5N sodium carbonate solution to a faintly red reaction of indicator papers connected with brilliant yellow. After coupling, the dyes were isolated by acidification and salting with sodium chloride (10 wt%, parts per volume of reaction mixture) in a yield of 22 wt%. parts.

After dyeing by conventional wool and polyamide procedures, a brilliant yellow hue is obtained with good wet fastness and light fastness.

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Example 2

In the same manner as in Example 1, a total of 23.3 parts (17%) of o-aminobernenesulfonic acid (O-aminobernenesulfonic acid) was prepared in a brilliant greenish-yellow hue with good fastness and excellent light fastness.

Table I gives examples of acidic monoazbbrins derived from citrazic acid and wool and polyamide staining.

Table 'I

Ex. Active coopp R Coloring 3 2-oaphthylsoin-6-cellulose fetyselines OH žlul 4 2 nsfty _lsminol> 5 ·· íiaulfetyselioa OH žluí 5 2-oaphthylsoin-4,8-diaulfic acid OH žluí 6 2- (2-O, 4-di-5,7-trifluoromethyl) OH žlul 7 2-naphthylsoio-3,6,81tisulfoic acid OH žlul 8 l-naphthylsoin-6-hydroxy-felines OH žluí 9 1-Sulfonyl-10-sulfonic acid OH žluí 10 ^ оп ^ у ^ оЗш- 8- sulfoky se li na OH žiu!

Example 11

55.2 hrno!;. Part kyannuchloridu was dissolved in 3 <00 The anhydrous acetone with stirring helmets ^d about ²⁰⁰⁰ ° in L ^dy you ^hIL azeotropic ^s to ² ° C · К ^tet ^ Ldáta suspension was during 30 minutes a solution of 56.4 wt. parts of -fenУ · ^β odiamnoaUfoetУ saliva in 500 ml of water and 120 ml of 2.5N sodium uiličitanu. The temperature is maintained at 2 to 3 ° C by external cooling during condensation. The resulting hydrochloric acid is blunted with a soda solution (positive reaction on a brilliant yellow paper coupled). After completion of the condensation, the solution is acidified with 500 ml of 2.5 N hydrochloric acid solution and diazotized by dropwise addition of 120 ml of 2.5 N sodium nitrite solution with vigorous stirring.

46.5 parts by weight of citric acid were dissolved in 300 ml of water and 300 ml of a 2.5N solution of trisotrate and cooled to 5 ° C. To this solution, freshly prepared suspension of the azo salt was added over ³⁰ minutes. The reaction mixture was maintained in alkaline pH by the addition of sodium nitrate solution (on brilliant yellow paper). After completion of coupling, the yellow dye was isolated by salting with sodium chloride (15% w / v solution volume) and acidifying with hydrochloric acid to a slightly acidic reaction. ^p o fll / crawfish dye was pr 15% brine and vacuum ^of uauěeno at ²⁰ ° C.

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Dye dyes - cellulose fibers in conventional ways. brilliant green coloring.

Example 12.

56.4 wt. part mfeunrlenliaimnasUfolkreeliny was dissolved in 1000 m of water and

150 m of 2.5 N sodium bicarbonate solution. After added :! 1 g Kcortamolu NNO reaction mixture was externally cooled with ice to a temperature of 2-3 DEG ^{C., and} introduced Otom 55.2 wt. % of fine crystalline cyanturide. The resulting acid was escalated by the addition of an additional soda solution so that the pH of the reaction mixture was about 10. When, after about 1 hour, the solids passed from the reaction mixture to the solution, a solution of 51.9 parts by weight of sulfamic acid dissolved in 500 ml was added. water, and 150 m of 2.5N soda solution. The temperature of the reaction mixture was then raised to 40 ° C and maintained at this temperature for 90 minutes. The dead acidity was simultaneously blunted with a soda solution.

After completion of the reaction, the solution was acidified by the addition of 500 m of 2.5 N hydrochloric acid solution, cooled to 5 ° C and phasototized by dropwise addition of 120 m of 2.5 ^N sodium nitrite solution.

46.5 wt. Parts oitrazinové acid were dissolved in 300 m. Of water and 300 m of 2.5N ^u ^ 1 ^: L l ^Cl; The mixture was cooled to 10 ° C. The diazonium salt solution was added to the Whem solution for 30 minutes. By the addition of sodium bicarbonate solution, the reaction mixture was kept permanently oscillating to a brilliant yellow reaction. Upon completion of the copying, the solution was acidified to pH 2-4 with hydrochloric acid and salted with solid sodium chloride (15% v / v). ^E stain ° flltrovan% 2C washed with brine and dried ^p s 60 ° C. ^The dye on the cellulose fibers shows a brilliant greenish-yellow hue when dyeed by conventional methods.

Ex ^ mv ^ rea ch ^P ro dyes cellulose, animáfl.in and ^p oly £ im.d ^s and trains ^{on the} early reactive groups are listed in 'Table II.

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Table II

P5ÍKL. Color part of milk Reactive article Coloring 13 3 "tMnoo4" Sslff-1 "feoylazo-3" -piperidine ^-2'- h ^ OTo- ⁶ -one- ⁴ -carboxylic acid ^2- théophyll-, β-iiCxLfr-O 2 - triazine greenish  žiuE 14 a. 3-Amino-4-sulfo-1-phenylazo-3 / * * -pyridin-2-hydroxy-6-one-4- -carboxylic acid 2,4,5,6 ^^^^^ - pyrimdin greenish bileE 15 Dec 3-tminoo4 sslfo-ϊ-feolltzf ~ 3 '- * / / pyridine ^{-2-hydroxy-Hydroxy -} 6 -one ⁴ - - ^ ^ carb x ^^^ oic acid 2,4,6-Trifluoro-4- - Chlorine pyrr greenish yellow 16 3 ^{- 4} tminoo --slfffl ^- feoyltzf ^- 3-p-idin- ² '-H ^ ojo! ^- '-one- ^4' -carboxylic acid 2,3-Dichloro-octanoic acid N -carbonyl chloride Greenish yellow 17 ^3-4 tminoo --slfo feolltzf-L-3 '- ^py rid ⁱ n-2' -hydroxy ^{- '-one-4'} carboxylic acid cЫ.fracetylchlfrid Greenish yellow

Example 18 •

2 ⁸ . ¹ part by weight of the aminofertyl-4-ethyl-ethylsulfone sol ester was dissolved in 300 m of water, 100 mL of 2.5N hydrochloric acid was added, cooled to 5 ° C and diazotized by adding 40 mL of 2.5N sodium nitrite with vigorous stirring. The diazonium salt solution was then within 20 minutes. when dripping into a solution of 15.5 wt. parts of citrazic acid dissolved in 100 mL of water and 100 m of 2.5N soda solution. After an additional 30 minutes of stirring, the dye was isolated by adding 70 'pots, parts of sodium chloride and acidifying the reaction slurry with concentrated hydrochloric acid for a positive reaction to Koingo papers.

After filtering the precipitated small yellow crystals, turn solution 2 (% brine and dry) to obtain 35 parts by weight of the dye. By standard dyeing method, it produces a brilliant green-yellow hue on the cotton material.

Example 19

31.1 wt. part of a 4-m 2 ester . about ^{Al 3-n} amnofe lL- ² '-H ^ ^ HRO ytylsulfonu treated as in Example 18. The' isolation. 34 parts by weight of dye were obtained which dyeed cotton with a red-yellow hue.

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Example 20 parts by weight · 4-sulfo-2 amlnofanyl 4iydro ^f ^ ethyl sulfone was dissolved in 500 m of water and cooled to 2 ° C. While stirring, 18.4 parts by weight of finely divided cyarudechoride were introduced. Carefully add 2.5N solution. The sodium suspension was maintained at about pH 3. The condensation was terminated after 1 hour and then a solution of 18.6 parts by weight of m-phenlene lineate acid in 100 ml of water and 40 mL of 2.5N sodium carbonate solution was added. The temperature of the solution was raised to 40 ° C and run. condensation was accelerated by the addition of another sodium citrate solution so that the pH was about 10 ° C. After the reaction was completed, the solution was cooled to 10 ° C with ice, rinsed with 100 ° C. Of 2.5N hydrochloric acid solution and diazotized by dropwise addition of 40 mL of 2.5N sodium nitrite solution. The diazonium salt solution is then introduced into the solution with stirring

15,5 hmo. parts of citrazic acid dissolved in 200 m of water, and 150 ml of 2.5N sodium carbonate solution. The dye formed was precipitated from the solution by acidification with hydrochloric acid and salting out 15% sodium chloride (by volume). The dye colors the cellulose fibers with a greenish-yellow brilliant shade.

Example 21 <

14,3 hmoo. parts of 4-dlor-2-am.m) phenol were dissolved at 60 ° C in 400 m of water and 1 ⁰⁰ ° ^{2 L,} 5 ^N hydrochloric tyseliny. After cooling from outside ^{to 10} ° C, tulle amiitophenol was added dropwise to a solution of 6.9 wt. part of sodium nitrite in 30 mL of water. The diazonium salt solution was sclerified by stirring with 2 g carboxylate and after filtering the tulle for 30 minutes while dropping into a 15.5 pot solution of citrazic acid dissolved in 200 mL of water and 120 mL of 2.5 N while stirring. of sodium citrate solution. The resulting dye was isolated by adding 50wt. Parts of sodium chloride and acidifying the reaction slurry with concentrated hydrochloric acid for a positive reaction to Congo red, filtering, washing with 15% brine, and drying at 110 ° C. Yield 35 parts by weight of dye.

After coloring on wool. fiber with simultaneous chrome metallization provides a rich red hue with good wet fastness and light fastness.

Example 22

Of the 15.4 wt%, 4-nitro-2-minophenol was the same as in Example 21. 31 parts by weight of dye were obtained, dyeing the wool fibers with a slightly more bluish shade than in the previous example. _t ·

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Claims (2)

OF THE INVENTION Azo dyes containing a residue of citrazic acid in a molecule of formula (I) wherein (I) is a label Ar the rest of diazokomponeniy benzene or naphthalene series, R is hydroxyl, alkoxy, wherein alkyl contains 1 to 12 carbon atoms, amino, dialkylamino, wherein alkyl contains 1 to 16 carbon atoms, alkylamino, wherein alkyl contains 1 to 16 carbon atoms, R ^ is hydrogen, sulfo-, hydroxy-, carboxy, halogen, R 8 is hydrogen, sulfo-, carboxy, halogen, amino optionally substituted, nitro, -SOg-CH = CH ₂ , R 2 is hydrogen, amino, optionally further substituted with a reactive residue of cyanuric chloride, 2-methoxy-1,6-diclorthriazine, 2,4,5,6-tetrachloropyrimidine, 2,4-difluoro-5-chloropyrimidine, 2,3-dichloroquinoxaline-5 -carbonyl chloride, chloroethyl ester, optionally further substituted by a cyanuric chloride residue in which one chlorine atom can be replaced by an aniline sulfo acid residue, and wherein when Ar is a naphthalene series residue is R ^ = hydrogen, Rg = hydrogen, optionally sulfo and Ry = sulfo group. 2. A process for the preparation of azo dyes according to claim 1, characterized in that the diazotized aromatic amines of the general formula II (II) are coupled with a compound of the general formula III when R1 and R8 are as defined above and R1 is hydrogen or amino. (III) wherein R is as defined above, at a temperature of 0 to 50 ° C and a pH of 3 to 9, optionally, 216606 znsčí If R in formula II an amino group further substituted with the reactive moieties, are prepared by first odpovíddjící reactive diazo compound of formula IV (IV) wherein Z is a reactive residue, and this reacts kopuu.aaí before or after nd, with alkyl ^0E a citrazine line, with a compound of formula V wherein R 6 and R 8 are as defined above, optionally further with cyanuric chloride. Printed by Moravian Printing Works, plant 12, Leninova 21, Oloipouc