DE745413C - Process for the preparation of monoazo dyes - Google Patents

Description

Process for the preparation of monoazo dyes In the French patent specification 8 [0 512 and in the British patent specification 517 918, inter alia, dyes have been described which have the general formula correspond. R denotes the radical of a diazotizable amine, x is hydrogen or alky 1 (this term also denotes substituted alkyl, for example substituted by an OH group, and also higher alkyl), y is alkylene or allylidene. It has been described there that these dyes can be obtained by allowing polybasic, in particular dibasic, carboxylic acids to act on aminoazo dyes which contain an alkyl group substituted by at least one hydroxyl group and bonded to an N atom in such a way that the OH -Group is esterified and an acidic group capable of salt formation is present. These dyes can also be prepared in such a way that coupling-capable amines of the general formula where x denotes hydrogen, alkyl or oxyalkyl, treated with the basic carboxylic acids in such a way that acidic esters are formed and any diazo compounds can then act on them.

It has now been found that the new dyes, which can be obtained by introducing the remainder of the chlorosulfoacetic acid into the dyes of the general formula where R is the radical of a diazotizable amine free of sulfonic acid groups and -x is hydrogen, alkyl or substituted alkyl, also have very valuable properties, in that their alkali salts, which also include the salts of ammonium, are particularly good It is soluble in water and has a drawability on acetate rayon which is considerably better than the four dyes of the British patent = J%% J9.

The new dyes can be prepared in such a way that one can rely on azo dyes of the general formula (1Z and x have the meanings already given), expediently in the presence of an organic solvent, allowing sulfochloroacetic acid to act.

One can also proceed in such a way that one can rely on coupling-capable amines of the general formula in which x has the meaning already given, sulfochloroacetic acid act 1ä and lets free diazo compounds act on the condensation compounds formed by sulfonic acid groups.

The new dyes contain the Chlorstilfoessigsätire probably bonded like an ester and should therefore correspond to the general formula (R and 1 have the same meaning as above). It turned out to be. it is advantageous to use more than the calculated amount of Chlorsulfoessigsätire for the esterification of a hydroxyl group. In the case of intermediate compounds or dyes which contain more than one hydroxyl group, by suitable choice of the amount of chlorosulfoacetic acid, compounds can be prepared in which all hydroxyl groups are esterified or free hydroxyl groups are still present, whereby the drawability of the dyes can be influenced as desired.

These dyes form salts, and especially the salts of alkalis, which also includes the salts of ammonium, are easily soluble in water. They can be used to dye acetyl cellulose, especially acetate rayon will. They can also be used in certain cases to dye animal fibers, such as wool and silk. They color this fiber, acetyl cellulose or animal fibers, depending on the nature of the underlying stains, non-esterified dyes, in yellow, red, brown and blue tones. the the new dyes underlying for ver. Turn coming not esterified Dyes result from the lists of diazotization and diazotization given below Coupling components.

If the new dyes are to be prepared from coupling components which have already been treated with chlorosulphoacetic acid, these are, as already mentioned, by the action of stilfochloroacetic acid on couplable amines of the general formula obtain. Uni @ eting is best done by heating these compounds directly or in organic solvents with the chlorosulfoacetic acid.

This implementation can include can be made at the following bases: N-Methvl-N-oxväthylaminobenzol, N-thv @ - oxyätliylaminobenzol, N-Methoxyätliyl-XT-oxyiitbylaminoWnzol, S-n-propyl-N-ooxyethylaminobenzene, i \ -1lethyl - \ - oxypropylaminobenzene, N-isopropyl-N-oxäthvlaininobenzol, N-ii-Butyl-N-oxäthylaminobenzol, N-Isobtityl-N-oxätliylaminobenzol, N-n-Amyl-N-oxätlivJaininobenzol, N-at @ y @ - @ - @, - oxy -;, - chierpropylaininobenzol, N @ ety @ - @ - oxätliylaininobenzol. Of the Benzolkem can be substituted by methyl or alkoxy groups, where but care must be taken that the p-position to the substituted amino group is still contains a hydrogen atom which can be exchanged for a diazo radical. So there are coming also suitable N-substitution compounds of i-amino-3-methyl- or -2-methoxy-5-methylbenzene in question, e.g. B. i-N-n-propyl-N-oxäthylamino, -3-methylben; -zene and i-1 \ T-n-butyl-N-oxäthylamino-3-methylbenzene, I-amino-3-acetylaminobenzene also reads N-substitution compounds "e.g. N - ethyl - N - oxäthylamino - 3 - acetylamino-6-methox3 # benzene and i-N-n-butyliU-oxäthy lamino-2-methoxy-5-acetylamino benzene, as well as i-N-n-propyl- \ T-o @ xäthylaminoy-methoxy-5-methylbenzäl.

These intermediate compounds form compounds that are readily soluble in water. They also easily dissolve in dilute mineral acids and water in the form of theirs Alkali and alkaline earth salts.

If you put these compounds in neutral or weakly acidic means Reacts with diazo compounds, dyes are obtained which, especially in the form their alkali salts or ammonium salts, are soluble in water. As bases, their diazo compounds are used, the commonly used aromatic amines and are suitable especially those which contain a nitro group in the p-position to the amino group, z. B. i-Amino, 4-nitrob, enzene, i-Amino 2-chloro-4-nitrobenzene, i-Amino-2-metho @ xy-4.-nitrob, enzene, i-Amino-d.-nitrobenzene-2-methyl sulfone, i-amino-2, 4- dinitrobenzene, i-amino-2, 4.-dinitro-6-cyanobenzod, i-amino, -2, 4-dinitro - 6 - halobenzene, i - amino, 2, 4. - dinitrobenzene - 6 - methylsulfone and i-amino-2-cyano-4-nitro-6-halobenzenes. Example i 165 parts of i-N-ethyl-N-oxäthylaminobenzene are toluene in 100 parts by volume solved. The solution is treated with 260 parts of sulfochloroacetic acid and the mixture then heated to boiling for 1 hour while stirring. That which boils away with the toluene Esterification @ water is collected separately, while the excess toluene flows back into the reaction flask: "'# ar, h completed reaction is the Toluene distilled off and the residue dissolved in 2ooo parts of water. The watery one optionally filtered solution is now mixed in the usual way with the diazo solution of 138 parts of i-amino - .. l.-nitrobenzene combined and the mineral acid with sodium acetate dulled. The dye is filtered off with suction, slurried again in water, with Ammonia made exactly neutral, suction filtered again and under reduced pressure dried.

A scarlet powder is obtained in a yield of 80 to 90 ° / Q, which dissolves very well in water and dyes acetate artificial silk from a neutral Glauber's salt bath in scarlet shades. A similar procedure is followed when using i-amino-2-chloro-4. nitrobenzene or i-amino-2-cyano-.I-nitrobenzene as diazo components, giving red and reddish-tinged violet dyes. If i-amino-2-nitrobenzene is used, an orange dye is produced, while aniline or i-amino-2-chlorobenzene gives yellow dye. EXAMPLE 2 226 parts of sulfochloroacetic acid are added to the solution of 195 parts by weight of i-dioxäthylainino-3-methylbenzene in 100 parts by volume of toluene and the mixture is heated to the boil for one hour while stirring. To. When the reaction is complete, 400 parts of water are added to the mixture, complete dissolution taking place.

This is separated from the toluene and allowed to flow in in the presence of ice the sulfuric acid diazo solution from 163 parts of i-amino-2-cy an-4-nitrobenzene coupled. Then 26oo parts by weight of 30 ° Iaiger sodium hydroxide solution are added dropwise neutralized, the dye filtered off with suction, washed with salt and reduced under reduced pressure Print dried.

250 parts of a dark powder are obtained, which easily dissolves in water dissolves and Acetatkunstsei.de from neutral Glauber's salt bath in full purple tones colors. A blue-violet dye is obtained by using i-amino-2-cyano-4-nitro-6-chlorobenzene as a diazo compound.

In these dyes there is an Ow group of the dioxäthylamino group acylated%. But if the i-Dioxäthylamino-3-methy lb, enzol is esterified with 37o Parts of sulfo-chloroacetic acid and if you work otherwise as indicated, you get Dyes in which the two O H groups of the dioxäthy 1-amino group are esterified are. Example 3 195 parts by weight of i-diethylamine-3-methylbenzene are used in 100 parts by volume of toluene are dissolved, and the solution is after 226 parts of sulfochloroacetic acid were added, heated to boiling for 1 hour with stirring. The toluene will then distilled off under reduced pressure, the residue in 400 parts by volume Dissolved methanol and, if necessary, filtered the solution. In this solution is now with external cooling by adding the diazo solution of i-amino-2-evan-4, 6-dinitrobenzene coupled at -io °. The diazo solution is obtained by adding 2o8 parts 1 Ainino-2-cyan-.1. 6-dinitrobenzene in the solution prepared in the usual way of 69 parts of sodium nitrite - in 1,000 parts of concentrated sulfuric acid at 30 ° diazotized. After the coupling has ended, the methyl alcoholic suspension is stirred in a mixture of 4,000 parts by weight of ice and 4,000 parts by weight of water, sucked remove the dye, stir it in water to form a suspension, neutralize with Ammonia, sucks it off again and dries it at a lower temperature under a reduced temperature Pressure.

The dye dissolves in warm water with a blue color and stains Acetate rayon from neutral bath in the presence of sodium sulfate in lively blue tones.

If you use larger amounts of sulfochloroacetic acid, z. B. about 35o Parts, both hydroxyl groups of i-Dioxäthylainino-3-Metliyibenzols are complete esterified.

A similar dye is produced if, instead of i-dioxäthylainino-3-methylbenzene, i-oxäthylainino-3-methylbenzene is esterified with sulfochloroacetic acid and the ester is coupled with the diazo compound. Example q. 314 parts of the insoluble azo dye, which is obtained by coupling 1-i @ T - <@ ethyl-N-oxäthylaminobenzene with i-diazo-4-nitrobenzene, are dissolved in 1,000 parts of toluene, and the solution is in the presence of 260 parts Sulfochloroacetic acid heated to boiling for 1 hour with stirring. The water of esterification boiling away with the toluene is collected separately, while the excess toluene is returned to the reaction mixture. After the reaction has ended, the toluene is distilled off and the remaining dye is neutralized with ammonia in the presence of a little water. A scarlet powder is obtained which has the same properties as the dye obtained according to Example i. . Example 5 193 parts of zi \ T -: @ thyl-Nn -; - oxybuty @ aminobenzene (obtainable by condensation of all 3-clilorbutanol with Äthvlatninobetizol, K1); 1.40 to 145 ° j are dissolved in logo parts of Solventnaplitha and with 26o parts sulfochloroacetic acid Esterified at i io to i12 'for i hour. The precipitated ester is dissolved by adding 300o parts of water. After the solvent naphtha has been separated off, the solution is treated with a diazo solution which was obtained in the customary manner by diazotizing 173 parts of 1 alnillo-2-chloro-4-nitrobenzene. To terminate the coupling, it is blunted with sodium acetate, the dye is suction filtered, suspended in a little water and neutralized with ammonia.

After the repeated suction and drying, the result is a dark one Powder that dissolves in warm water and acetate rayon from neutral bath in The presence of sodium sulfate colors in full ruby red tones.

Claims (2)

PATENT CLAIMS: i. Process for the preparation of monoazo dyes, characterized in that dyes of the general formula where R is the residue of a diazotized atom free of sulfonic acid groups and x is hydrogen or alkyl or substituted alkyl, esterified with chlorosulfoacetic acid. 2. Modification of the process of claim i, characterized in that there are esters of coupling-rich amines of the formula in which x has the meaning given above, and chlorosulfoacetic acid couples with any desired fully sulfonic acid group-free diazo compounds. In order to distinguish the subject of the application from the prior art, the following publications were taken into account in the granting process: French patent specifications No. 86_5 36 ?, 840.512.