DE928902C - Process for the preparation of water-insoluble monoazo dyes - Google Patents

Description

Process for the preparation of water-insoluble monoazo dyes It has been found that valuable water-insoluble monoazo dyes are obtained, if you diazotized cyananilines, the core only by alkyl groups and / or Halogen atoms are substituted with aromatic coupling agents in the p-position to the amino group Amines couples in which one hydrogen atom of the amino group is replaced by an oxalkyl radical and the other hydrogen atom has been replaced by an alkyl or oxalkyl radical, and the components are chosen so that they do not contain any sulfonic acid or carboxylic acid groups contain.

The new water-insoluble monoazo dyes produce clear, lightfast and washfast yellowish orange to bordeaux-red colorations on polyamide and acetate artificial silk fibers. The new dyes are distinguished by the fact that they can be used to achieve the same or almost the same color tones of particular clarity and the same or almost the same lightfastness on the two types of fiber, including scarlet and yellowish red. This distinguishes them in an advantageous manner from the known comparable water-insoluble monoazo dyes which contain a nitro group as a substituent in the diazo component. The monoazo dye known from patent 6q.8768 from diazotized i-amino-2-cyano-q.-nitro-6-chlorobenzene and iN-di-oxäthylamino-3-methylbenzene is the process according to the same azo component and diazotized i-amino-2- cyan-4, 6-dichlorobenzene available dye inferior in the lightfastness of its dyeings on polyamide fibers. Examples i. 15.3 parts of i-amino-3-chloro-4-cyanobenzene are dissolved in 50 cm3 of concentrated hydrochloric acid and 35 parts of 20% sodium nitrite solution are run in with thorough stirring and cooling. When the diazotization is complete, the solution is filtered, partially neutralized (congoviolet) with dilute sodium hydroxide solution or soda solution and combined with a solution of 19.5 parts of iN, N-di-oxethylamino-3-methylbenzene in dilute hydrochloric acid. The coupling, which is already beginning, is completed by adding sodium acetate, with the azo dye separating out as a light red powder. The dye is filtered off and washed neutral. When dry, it forms a light red powder that dissolves in organic solvents such as acetone or alcohol with a red color. It dyes acetate artificial silk and polyamide fibers, finely distributed through suitable additives, in clear yellow-tinged red tones.

2. i3.2 parts of i-amino-2-methyl-4-cyanobenzene are dissolved in 50 cm3 of concentrated hydrochloric acid and 35 parts of 20% sodium nitrite solution are run in while stirring and cooling. After the end of the diazotization, the clear diazo solution is partially neutralized (congoviolet) with dilute sodium hydroxide solution or soda solution and combined with a solution of 20.7 parts of iN-butyl-N-oxäthylamino-3-methylbenzene in dilute hydrochloric acid. The coupling is completed by adding sodium acetate, the azo dye separating out as an orange powder. The dye is filtered off and washed neutral. When dry, it forms a light red powder that dissolves in organic solvents, such as acetone or alcohol, with an orange color. He dyes acetate artificial silk and polyamide fibers in shades of orange, finely dispersed with suitable additives.

3. 21.1 parts of i-amino-2-methyl-4-cyano-6-bromobenzene are 6.9 Share sodium nitrite diazotized in the usual way. The ones with soda or caustic soda partially neutralized diazo solution becomes a hydrochloric acid solution of 19.5 parts i-N, N-Di-oxäthylamino-3-methylbenzene given. By adding sodium acetate it becomes the coupling ended, the dye precipitating in solid form and then filtered off will. The dried azo dye dissolves well in organic solvents, like ethyl acetate, acetone or alcohol, with an orange color and dyes acetate rayon and polyamide fibers, finely divided by dispersants, in shades of orange.

4. 15.2 parts of i-amino-2-cyano-5-chlorobenzene are mixed with 6.9 parts of sodium nitrite diazotized in the usual way. The partially neutralized with caustic soda or soda (Congo violet) diazo solution is mixed with a hydrochloric acid solution of 2o.7 g of i-N-butyl-N-oxäthylamino-3-methylbenzene united. The coupling is terminated by blunting with sodium acetate, the The monoazo dye formed is deposited as a light red powder. The dye will filtered off, washed and dried. It dissolves in organic solvents with orange color. Finely distributed by adding dispersing agents, he dyes acetate rayon and polyamide fibers in reddish orange tones.

5. 15.2 parts of i-amino-3-cyano-4-chlorobenzene are mixed with 6.9 parts of sodium nitrite diazotized in the usual way. The diazo solution is made with caustic soda or soda partially neutralized (Congo violet) and with a hydrochloric acid solution of 19.3 Parts of N-butyl-N-oxäthylaminobenzene combined. By adding sodium acetate it becomes the clutch ends. The dye precipitates in solid form. It is filtered off and washed. When dried it is a red powder that turns into organic Dissolves solvents with an orange color. Fine distribution through suitable additives brought, he dyes acetate rayon and polyamide fibers in the same shade of yellow Shades of orange.

6. 27.6 parts of i-amino-2,6-dibromo-4-cyanobenzene are vigorously Stir and cool in one of 100 parts of sulfuric acid and 7 parts of sodium nitrite produced solution of nitrosylsulfuric acid entered. Stir until a sample is clearly soluble in ice water. It is then poured into a lot of ice water. The diazo solution, which has been partially neutralized by adding caustic soda or a solo solution (Congo violet) are combined with a hydrochloric acid solution of 19.5 parts of i-N, N-dioxethyl-amino-3-methylbenzene. The coupling, which is already beginning, is brought to an end by adding sodium acetate. The dye separates out as a red powder. It is filtered off and becomes neutral washed. The dried and powdered dye dissolves in organic Solvents with an orange color and stains, through suitable additives in fine distribution brought in, acetate rayon and polyamide fibers in shades of orange.

The table below lists further diazo and azo components which, when coupled according to the procedure given in the preceding examples, give dyes of similar properties. Diazo components Azo components shade Acetate rayon I polyamide fiber i-Amino-3-chloro-N-ethyl-N-oxäthyl-orange orange 4-cyanobenzene aminobenzene likewise. iN-Butyl-N-oxäthyl- scarlet scarlet red amino-3-methylbenzene The same. iN-Butyl-N-oxäthyl- - bluish-tinted red amino-2-methoxy- 5-methylbenzene Diazo components Azo components shade Acetate rayon I polyamide fiber i-Amino-3-chloro-iN, N-di-oxethyl-amino-scarlet scarlet red 4-cyanobenzene 3-methylbenzene i-Amino-2,6-dibromo- iN-butyl-N-oxäthyl- - bluish-tinted red 4-cyanobenzene amino-2-methoxy- 5-methylbenzene Likewise. iN-Butyl-N-oxäthyl- - yellowish tinted red amino-3-methylbenzene i-Amino-2, 4-dibröm- i-INT, N-Di-oxäthyl-amino- yellowish-reddish- 4-cyanobenzene 3-methylbenzene orange orange like iN-butyl-N-oxäthyl- like yellowish- aminobenzene red like. N-ethyl-N-oxäthyl- like. like. aminobenzene i-Amino-2-methyl- iL \ T, N-Di-oxäthyl-amino- orange reddish- 4-cyano-6-bromobenzene 3-methylbenzene orange the same. iN-butyl-N-oxäthyl- - reddish- amino-3-methylbenzene orange The same. N-Ethyl-N-oxäthyl- yellowish orange aminobenzene orange like. N, N-Di-oxäthyl-amino- like. like. benzene i-Amino-2-methyl-N-butyl-N-oxäthyl- like. 4-cyano-6-bromobenzene aminobenzene same. iN-butyl-N-oxäthyl- like. red amino-2-methoxy- 5-methylbenzene i-Amino-3-chloro- iN-butyl-N-oxäthyl- - bluish- 4-cyano-6-bromobenzene amino-3-methylbenzene red the same. N, N-Di-oxäthyl-amino- orange yellowish- benzene red the same. N-Ethyl-N-oxäthyl- scarlet red desgl. aminobenzene same. N-butyl-N-oxäthyl- like. red aminobenzene the same. IN, N-Di-oxäthyl-amino- like bluish cast- 3-methylbenzene red Likewise. iN-Butyl-N-oxäthylamino- - bororo red 2-methoxy-5-methylbenzene r-An-ino-2,6-dichloro-iN-butyl-N-oxäthyl- - strong 4-cyanobenzene, amino-3-methylbenzene, yellowish red the same. iN, N-Di-oxäthyl- strong amino-3-methylbenzene reddish orange yellowish red the same. iN-Butyl-N-oxäthylamino- - bluish- 2-methoxy-5-methylbenzene red the same. N-butyl-N-oxäthyl- strong yellow- - aminobenzene pungent orange the same. N, N-Di-oxäthyl-amino- orange - benzene i-Amino-2-cyano-N-butyl-N-oxäthyl- orange orange 5-chlorobenzene aminobenzoI Diazo components Azo components Acetate rayon Color I polyamide fiber z-Amino-2-cyano- zN-Butyl-N-oxäthylamino- reddish- reddish- 5-chlorobenzene 3-methylbenzene orange orange Likewise rN-Butyl-N-oxäthylamino- - red 2-methoxy-5-methylbenzene The same. N, N-Di-oxäthyl-amino-orange orange benzene like. N-ethyl-N-oxäthyl- like. like. aminobenzene like. ZN, N-Di-oxäthyl-amino- like. like. 3-methylbenzene. z-Amino-4-chloro- iN-butyl-N-oxäthyl- - yellowish- 5-cyanobenzene amino-3-methylbenzene orange the same. N, N-Di-oxäthyl-anüno- yellowish tinged- desgl. ° Benzene orange desgl. N-Ethyl-N-oxäthyl- desgl_ desgl. a.minobenzol like. N-butyl-N-oxäthyl- like. like. aminobenzene like. ZN, N-Di-oxäthyl-amino- like. like. 5-methylbenzene the same. iN-butyl-N-oxäthyl- orange reddish- . amino-2-methoxy-orange _ 5-methylbenzene r-Anino-2-methyl- N-Ethyl-N-oxäthyl- yellowish- yellowish- 4-cyanobenzene aminobenzene orange orange the same. zN, N-Di-oxäthyl-amino- - orange 3-methylbenzene the same. zN-Butyl-N-oxäthylamino- - bluish- -, 2-methoxy-5-methylbenzene scarlet Likewise. iN-butyl-N-oxäthyl- orange orange amino-3-methylbenzene like. N, N-Di-oxäthyl-amino- like. like. benzene the same. N-butyl-N-oxäthyl- yellowish- desgl. aminobenzene orange i Amino-2, 3, 4-trichloro-N-Ethyl-N-oxäthyl- - bluish- 6-cyanobenzene - aminobenzene red Likewise. iN-Butyl-N-oxäthyl- - red amino-3-methylbenzene the same. zN-Butyl-N-oxäthylamino- - red-violet 2-methoxy-5-methylbenzene

Claims (1)

PATENT CLAIM: Process for the preparation of water-insoluble monoazo dyes, characterized in that diazotized cyananilines, which are only substituted in the nucleus by alkyl groups and / or halogen atoms, with aromatic amines coupling in the p-position to the amino group, in which one hydrogen atom of the amino group is replaced by an oxalkyl radical and the other hydrogen atom is replaced by an alkyl or oxyalkyl radical, couples and thereby chooses the components so that they contain no sulfonic acid or carboxylic acid groups. Cited references: U.S. Patent No. 2,432,393; German patent specification No. 648 768.