DE1247513B - Process for the production of dyes - Google Patents

Description

Process for the production of dyes In the German patent specification 863 056 is the manufacture of condensation products from caprolactim-O-alkyl ethers with compounds which carry an active methylene group described. These condensation products represent colorless to at most pale yellow compounds.

It has now been found that deeply colored condensation products which represent valuable new dyes, if you get from naphthostyril and amide halides, imide halides or derived from its core substitution products Lactim-O-alkyl ethers with compounds that contain an active methylene group, implements.

The condensation takes place with great probability with the formation of a C = C double bond according to the following scheme: Hal HN-C I \ Hal (S3 \ / I: amide halide C N = C-Hal + H2C FiN-C (activated) I: -2H-Hal II: imide halide II: -H-Hal N = CO-alkyl III: -alkyl-OH (bu III: lactim-0-alkyl ether Suitable starting materials derived from substituted naphthostyriles and having an amide halide, imide halide and lactim-O-alkyl ether structure are in particular those which have alkoxy groups, in particular in the 5- or 6-position, and also with chlorine, bromine or fluorine in the 5-, 6-position or 8-position and are ring-substituted with alkyl, carboxylic acid ester, carboxamide, sulfonic acid amide or cyano groups.

Suitable compounds with an active methylene group are, for example Malonic acid esters and malonic acid amides or nitriles, acetylacetone, acetoacetic esters, Cyanoacetate, barbituric acid and theirs Derivatives, pyrazolones, 3-hydroxy-thionaphthenes, 2-oxy-3-naphthoic acid arylides, acetoacetic acid arylides or nitroalkanes.

The reaction is preferably carried out in an inert anhydrous Solution or Diluents such as benzene, toluene, xylene, chlorobenzenes, nitrobenzenes, Dimethyl sulfoxide or dimethyl, formamide.

In view of the great responsiveness of the starting products used amide halides, imide halides and lactim-O-alkyl ethers derived from naphthostyril and the associated difficulty of realizing it is not necessarily so necessary, use these in isolated form, but you can, for example, special the amide or imide halides also in the form of their formation mixtures, as they are in the Condensation of naphthostyril or its core substitution products with halides of phosphorus or sulfur, for example phosphorus pentachloride, phosphorus pentabromide, Phosphorus oxychloride, sulfuryl chloride or thionyl chloride arise, use. the The latter condensation is preferably carried out in an inert organic solvent made, and the resulting reaction mixture can immediately used for the further reaction with the compound with an active methylene group will.

Furthermore, it is usually possible to use the amide halides or imide halides to be formed only as an intermediate and in this case according to a one-pot process immediately the naphthostyril and the compound with an active methylene group in the presence of halides of phosphorus or sulfur, for example phosphorus oxychloride, condensation in a suitable inert organic solvent.

The dyes obtained by the process according to the invention are suitable for dyeing a wide variety of materials, especially for dyeing and printing of those based on polyesters, e.g. B. polyethylene glycol terephthalates.

Example 1 A suspension of 23 g of naphthostyrilamide chloride in 150 ccm of anhydrous chlorobenzene is first heated until the occurring The evolution of hydrogen chloride has ended, and then with a solution of 18 g of 6-methoxy-3-hydroxythionaphthene in 100 cc of absolute chlorobenzene are added. Under The reaction product separates in the form of a strong evolution of hydrogen chloride of red-brown crystals, which are isolated by suction and after washing with Benzene, methanol and water dries. This gives a dye which is in organic solvents with an intense red color and dissolves after recrystallization from chlorobenzene has a melting point of 278 to 279 ° C. The solution color of the The dye obtained in concentrated sulfuric acid is red.

The dye is suitable for dyeing polyester materials Based on polyethylene glycol terephthalates using the high-temperature dyeing process.

This gives red dyeings with good fastness properties.

Is used in the above example instead of the isolated naphthostyrilamide chloride after several hours of condensation from 17 g of naphthostyril with 21 g of phosphorus pentachloride suspension obtained in 150 cc of anhydrous chlorobenzene at 50 ° C and works in then, as indicated above, one arrives at the same thing as well Dye.

Example 2 19 g of the lactim O-methyl ether derived from naphthostyril are heated together with 18 g of 6-methoxy-3-hydroxy-thionaphthene in 150 ccm of dimethylformamide 30 Minutes to 145 ° C and then pour the reaction mixture into water.

After suctioning off the precipitate that has separated out, thoroughly Subsequent washing and drying at 80 ° C. are also obtained in this way as in Example 1, paragraph 1, described dye.

Example 3 A suspension of 23 g of naphthostyrilamide chloride is as described in the example, with 19.4 g of 6-ethoxy-3-hydroxy-thionaphthene up to Completion of the evolution of hydrogen chloride which occurs condenses. After the same Working up, as indicated in Example 1, gives a red dye which has a melting point of 267 ° C after recrystallization from chlorobenzene.

The dye dyes polyester material using the high temperature dyeing process in yellowish red tones.

Example 4 17 g of naphthostyril, 21 g of phosphorus pentachloride and 18 g 6-Methoxy-3-hydroxy-thionaphthene is dissolved in 150 cc of phosphorus oxychloride for 16 hours stirred at 50 ° C. Customary work-up also gives a good yield to the red dye described in Example 1.

Example 5 22.5 g of naphthostyrilamide chloride in 100 cc of anhydrous Xylene heated to 100 ° C for 15 minutes.

The solution is then mixed with a solution of 17.5 g of 1-phenyl-3-methyl-pyrazolon- (5) 100ccm of anhydrous xylene are added and the mixture is kept at 100.degree. C. for a further 15 minutes. The color of the reaction mixture appears with a strong evolution of hydrogen chloride to deep red-brown. The solvent used is then removed by steam distillation driven off and the precipitate which separates out in the residue is filtered off with suction and dried. This gives a brown dye, the fibers of polyethylene glycol terephthalate dyes in golden yellow to orange tones with good fastness properties.

The following table shows the color shades obtained on polyester materials of other dyes which can be prepared according to the invention and which are formed during the condensation of naphthostyrilamide chloride or imide chloride with the specified compound with an active methylene group. hue Starting product of the according to the invention can be prepared with an active methylene group Dye 4-methyl-6-chloro-3-hydroxy thionaphthen .. red-violet 4-methyl-5, 7-dichloro-3-hydroxy bila. Blue violet 2,1-naphthoxy-thiophene ........ black brown 9-chloro-a, ßnaphthoxy-tbiophen .. red-violet 2-hydroxy-naphthalene-3-carbon acid anilide red 2-hydroxy-naphthalene-3-carbon acid-a-naphthylamide bluish-tinted red Acetoacetic acid-o-anisidide ....... yellow Indoxyl ...................... reddish blue continuation hue Starting product of the invention can be prepared with an active methylene group Dye 1-chloro- + hydroxy-naphthalene ... red Anthron blue-violet Nitromethane yellow

Claims (3)

Claims: 1. Process for the production of dyes, thereby characterized in that one of naphthostyril and its core substitution products derived amide halides, inud halides or lactim-0-alkyl ethers with compounds, which contain an active methylene group, converts. 2. Further development of the method according to claim 1, characterized in that that he in the case of using from naphthostyril and its core substitution products derived amide halides or imide halides these without intermediate isolation in the form of the reaction mixtures used in the implementation of naphthostyril and its nuclear substitution products with halides of phosphorus or sulfur, preferably in the presence of an inert, anhydrous organic solvent, have been received. 3. Further development of the method according to claims 1 and 2, characterized in that in the case of using from naphthostyril or amide halides or imide halides derived from its core substitution products Mixtures of naphthostyl or its core substitution products and compounds, containing active methylene groups in the presence of halides of phosphorus or the sulfur, preferably in an inert, anhydrous solvent.