CS258774B1 - 4-Xylylhydrazo derivatives of 3-hydroxy-2-naphthoic acid - Google Patents

Abstract

4-xylylhydrazo derivatives of 3-hydroxy-2- -naphthoic acid of the general formula X, where the methyl groups are in positions 2', 3' or 3',4' and their mutual mixtures with 5 to 95% of the isomer with positions 2', 3' of ethyl groups and 95 to 5% of the isomer with positions 3', 4' of methyl groups are a valuable intermediate dye for the production of so-called hydrazo condensation pigments of red shades.

Description

The invention relates to 4-xylyl hydrazoderivatives of 3-hydroxy-2-naphthoic acid of the general formula X

wherein the methyl groups may be in the 2 ', 3' or 3 ', 4' positions or a mixture of dyes of the formula

X consisting of 5 to 95% isomer with methyl 2 ', 3' and 95 to 5% isomer positions and 3 ', 4 * methyl positions prepared by diazotization of 2,3- and 3,4-xylidines by coupling of the diazonium salts formed with sodium 3-hydroxy-2-naphthoate and isolation of the resulting carboxyhydrazo dyes.

The carboxyhydrazine dyes of the formula I can be used as starting dyes for the production of so-called hydrazocondensation pigments of red shades. The group of analogous azo condensation pigments occupies an important place in modern colorant dyes used mainly for dyeing synthetic materials and fibers in matter. The best known group of such dyes are the pigments of the Swiss Cromophtel palette, with red shades utilizing carboxyazo dyes synthesized from 3-hydroxy-2-naphthoic acid and selected aromatic amines (2-methoxycarbonylaniline for CI Pigment Red 139, 2-methyl-3-chloro-aniline for CI Pigment Red 140, 2-methyl-5-chloroaniline for CI Pigment Red 141, 3-chloroaniline for CI Pigment Red 143, 2,5-dichloroaniline for CI Pigment Red 144-166). High requirements on application properties and stability of azocondensation pigments such as. thermostability, lightfastness and insolubility in organic solvents greatly limit the choice of active azo components and require precise synthesis of both the dyes and the final pigments.

It has now been found that pigments of comparable and in some cases even better application properties than those of C.I. Pigment Red 139-166 (higher color strength and shade brilliance, see table) can be prepared from the subject 4-xylyl hydrazoderivatives of 3-hydroxy-2-naphthoic acid of formula I, using 2,3- and 3,4-xylidines readily available by nitration of 2,3-xylene and reduction of the obtained mixtures of 2,3-dimethyl-1-nitrobenzene and 3,4-dimethyl-1-nitrobenzene. These amino compounds are also economically advantageous, since the manufacturing cost is about 30% of the cost of producing the aromatic amines used for the said C.I. pigments. Pigment Red 139-166. In order to compare the coloristic application properties, the coloristic parameters of pigment C.I. Pigment Red 166 based on 2,5-dichloroaniline and pigments prepared from blends of 2,3- and 3,4-xylidines.

The present invention protects the 3-hydroxy-2-naphthoic acid 4-xylyl hydrazoderivatives of formula (I) wherein the methyl groups may be in the 2 *, 3 'or 3', 4 'positions or a mixture of colorants of formula (I) positions of methyl groups 2 ', 3' and 95 to 5% of the isomer with positions of methyl groups 3, 4 ', which are prepared by treating aqueous mixtures containing mineral acids and 2,3-xylidine or 3,4-xylidine, or a mixture of both amines treatment with nitrites at temperatures of 0 to -10 ° C, followed by the addition of a selected adsorbent, preferably diatomaceous earth or activated carbon or a mixture of both, the system is mixed, the solid is removed by mechanical separation and the resulting solution of diazonium salts is treated with an aqueous solution Sodium 3-hydroxy-2-naphthoate, while maintaining the pH of the reaction mixture in the range of 7-8 by the continuous addition of dilute sodium hydroxide or sodium carbonate solution during the coupling. After coupling, the reaction mixture is acidified with a mineral acid, preferably hydrochloric acid, to a pH of less than 5, the precipitated finely suspended dye is agglomerated by heating the system to 75-95 ° C, the dye is mechanically separated, washed with water and dried. Known indication sensors, such as neutralizing, diazotizing, coupling (US Pat. No. 156,743, US Pat. No. 191,471, US Pat. No. 203,737, US Pat. No. 196,092), and their interconnection with dosing devices can be applied in the individual synthetic steps. for individual reaction components to optimize the interaction of the components and limit the course of side reactions.

It has been found that only the 4-xylyl hydrazoderivatives of 3-hydroxy-2-naphthoic acid of the general formula (I) are formed under the reaction conditions; the content of 4-xylylazoderivatives of 3-hydroxy-2-naphthoic acid has not been demonstrated. The compounds of the above formula I have not been described in the available literature.

The preparation of the 4-xylyl hydrazoderivatives of 3-hydroxy-2-naphthoic acid of the formula I is illustrated in the following examples.

Table

Pigment Amin Coloring Migration in PVC Stability v org. rozpou-; Štědlech in oil (force; shade) in PVC (strength; shade) WHOSE. Pigment Red 2,5-dichloroaniline 100/100 100/100 5 5 Versal red A mixture of 2,3- and 3,4-xylidines 95: 5 72/100; 0.22; 1.9 J 82/100; 1.92; 2.4 J 5 5 Versal red 90:10 mixture of 2,3- and 3,4-xylidines 79/100; 1.52; 4,1 J 95/100; 2.12; 3.0 J 5 5 Versal red 60:40 mixture of 2,3- and 3,4-xylidines 81/100; 1.82; 6.2 J 98/100; 3.12, 4.8 J 5 5

..... yellower

J ..... clearer

Example 1

26.6 g of 2,3-xylidine are stirred in 400 ml of water, 220 ml of 8.7% hydrochloric acid are added, the solution is cooled by adding 150 g of ice and diazotized at -5 to 0 ° C, allowing 90 ml of 15 % sodium nitrite solution. After complete diazotization, the cloudy solution of 2,3-dimethylbenzenediazonium chloride was sclerified with 2 g of diatomaceous earth, the sludge was washed with water and the filtrate was diluted to 2000 ml. A control analysis showed the total molar content of 2,3-dimethylbenzenediazonium chloride in the filtrate.

37.6 g of 3-hydroxy-2-naphthoic acid are added to the 411 ml of water, added

83.6 ml of a 9.1% sodium hydroxide solution and the mixture is heated to 60-70 ° C until dissolved. The turbid solution is sclerified with 1 g of diatomaceous earth, the sludges are washed with water and the filtrate is diluted to a volume of 580 ml. A control analysis showed the total molar content of sodium 3-hydroxy-2-naphthoate to be 2 to 5% lower than the found molar content of 2,3-dimethylbenzenediazonium chloride.

A solution of 2,3-dimethylbenzenediazonium chloride is continuously added to the sodium 3-hydroxy-2-naphthoate solution while maintaining the pH of the reaction mixture at 7.0 to 8.0 by adding a total of 40 ml of 9.1% sodium hydroxide solution simultaneously. After coupling, the reaction mixture is acidified with 37 ml of 8.7% hydrochloric acid, the system is heated to 95 ° C, the solid is filtered off and the cake is washed with water until the acid and chloride ions in the filtrate are lost. After drying at 80 ° C, 65 g of 4- (2 ', 3'-xylylhydrazo) -3-hydroxy-2-naphthoic acid are obtained, which can be used directly for the preparation of disazo pigments. The dried sample obtained hydrazobarviva (150 ° C, 3 hours) was subjected to elemental analysis and found: 71.44% C, 5.04% H, 8.72% N. If the molecular formula ^C i9 ^H I6 ^N ° 2 3 3 ^e theory. content! 71.24% C, 5.03% H, 8.75% N. Melting point (Kofler):

280 ° C (dec.).

Example 2

A mixture of 13.3 g of 2,3-xylidine and 13.3 g of 3,4-xylidine is used for diazotization, the further preparation including coupling and dye isolation being the same as in Example 1. 65.0 g of a mixture of 4- (2 ', 3'-xylylhydrazo) -3-hydroxy-2-naphthoic acid and 4- (3', 4'-xylylhydrazo) -3-hydroxy-2-naphthoic acid in a 1: 1 ratio; the mixture is suitable for the preparation of disazopigments.

Example 3

26.6 g of 3,4-xylidine are stirred in 400 ml of water, 220 ml of 8.7% hydrochloric acid are added. the solution is cooled by adding 150 g of ice and diazotized at -5 to 0 ° C by admitting 90 ml of a 15% sodium nitrite solution using an automatic metering device connected to a diazotizing sensor (according to US Pat. No. 156,743) indicating the presence of nitrous acid during diazotation. The sensor signal is converted to a unified current signal by a two-wire INPAL 75 converter. The use of the sensor ensures an optimal diazotization process with a constant minimum excess of nitrous acid in the reaction mixture during and after the diazotization. The turbid solution of 3,4-dimethylbenzenediazonium chloride obtained is sclerified with 2 g of diatomaceous earth and 0.5 g of carboraffin, the slurries are washed with water and the filtrate is diluted to 2000 ml. Control analysis revealed the total molar content of 3,4-methylbenzenediazonium chloride in the filtrate.

37.6 g of 3-hydroxy-2-naphthoic acid are added to the 411 ml of water, added

83.6 ml of a 9.1% sodium hydroxide solution and the mixture is heated to 60-70 ° C until dissolved. The turbid solution is sclerified with 1 g of diatomaceous earth, the sludges are washed with water and the filtrate is diluted to a volume of 580 ml. A control analysis showed the total molar content of sodium 3-hydroxy-2-naphthoate, which should be 2 to 5% lower than the molar content of 3,4-dimethylbenzenedlazonium chloride found.

A solution of 3,4-dimethylbenzenediazonium chloride is added to the sodium 3-hydroxy-2-naphthoate solution using an automatic metering device, indicating the diazonium ions by means of a gold scraped electrode (AO No. 196 092), maintaining the pH of the reaction mixture at 7.4 to 7.8 by simultaneous admission of a 9.1% sodium hydroxide solution, the dosage of which is automatically controlled by connection to a glass electrode; total consumption of hydroxide solution is 40 ml. After coupling, the reaction mixture is acidified with 37 ml of 8.7% hydrochloric acid, the system is heated to 95 ° C, the suspension is filtered and the cake is washed until the acid and chloride ions in the filtrate are lost. After drying at 80-90 ° C, 65 g of 4- (3 ', 4'-xylylhydrazo) -3-hydroxy-2-naphthoic acid are obtained which can be used directly for the preparation of disazopigments. A dried sample of the obtained hydrazo dye (150 ° C, 3 h) was subjected to elemental analysis and found: 71.10% C, 5.015% H, 8.77% N. For a summary formula ^c 19 ^H ig ^N 2 ° 3 ^theoretical · ° content % H, 5.03;% N, 8.75.

Claims (1)

3-hydroxy-2-naphthoic acid 4-xylylhydroxy derivatives of the general formula I wherein the methyl groups are in the 2 ', 3' or 3 ', 4' positions and mixtures thereof consisting of 5 to 95% isomer with the 2 ', 3' methyl positions 95 to 5 S isomer with 3, 4 * methyl positions.