JPS6129333B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following formula () By esterifying and hydrolyzing the compound represented by to open the ring, the following formula () is obtained. This invention relates to an improved method for producing a _compound represented by
~100% sulfuric acid or sulfur trioxide under vigorous and thorough mixing at a temperature of 100 to 180 °C, optionally with subsequent addition of water or 1 to 1 molar amount of SO ₃
The method is carried out using ~2-fold equimolar amounts of sulfur trioxide or sulfur trioxide-containing sulfuric acid at a temperature of 10 DEG to 180 DEG C. with subsequent addition of water and intensive thorough mixing. In the above formulas () and (), R is a hydrogen atom or a lower alkyl group, such as a methyl or ethyl group, especially a methyl group, or a nitro group or a chlorine atom or a bromine atom, β-hydroxy- or The β-sulfatoethylsulfonyl group is present at the 5- or 6-position of the benzoxazolone ring or at the 4- or 5-position of the benzole nucleus of aminophenol. 2-Amino-phenol-4-β-sulfatoethylsulfone and -5 by the method according to the invention
The preparation of -β-sulfatoethylsulfone or 5-β-sulfatoethylsulfonyl- and 6-β-sulfatoethylsulfonyl-benzoxazolones is particularly advantageous. The compounds of formula () are suitable as initial products (diazo component) for the preparation of azo dyes. It is known per se to convert compounds of the formula () into compounds of the formula () upon hydrolytic decomposition of the oxazolone ring. However, the previously reported methods require a large excess of sulfuric acid, and the excess sulfuric acid is used during the after-treatment of the esterification product of formula () and during the isolation or further processing of the esterification product to form the dye. Upon preparation, it must be diluted with water, neutralized, and separated from its esterification product or dye. Recovery of sulfuric acid is therefore practically impossible. Moreover, the acids, either as such or in neutralized form, contaminate wastewater as soluble sulfates. Furthermore, the known esterification process has the disadvantage that the compound of formula () is obtained as a solution in sulfuric acid, but this solution is hardly suitable for storage, e.g. for further processing on another day. have. For example, the esterification of compounds of formula () according to DE 1153029 is carried out using 6-fold equimolar amounts of concentrated sulfuric acid. The compound of formula () obtained after diluting the sulfuric acid with much ice and water is isolated as a solid by suction filtration. This is then obtained in a yield of only 67% of theory, residues remain in the mother liquor, and the excess diluted sulfuric acid likewise has to be neutralized in order to be disposed of. Furthermore, the non-isolated products and sodium sulfate significantly contaminate the waste water. Neutralization of excess sulfuric acid with calcium carbonate and the separation of sparingly soluble calcium sulfate, as described in German Patent No. 1153029, Example 2, significantly reduces wastewater, but additionally treats it. In addition, this method has the disadvantage that the gypsum thus obtained has to be disposed of as unusable industrial waste. If aminophenol produced by a known method is diluted with ice and water and then used as is for the production of azo dyes (diazotized and coupled with a so-called coupling component, and optionally metalized), wastewater contamination may occur as well. is very high: the dye produced is isolated by salting out with sodium or potassium chloride, while the sulfates and most of the chlorides remain dissolved. Dyes produced without waste water by evaporative concentration or spray drying of dye solutions obtained without prior separation of sulfates have very weak tinting power and are produced as dye powders containing a high proportion of neutral salts. obtained, which would be of little interest for industrial use. There is therefore a need for an esterification process which is free from these drawbacks and which is virtually completely or only slightly environmentally polluting. According to the present invention, we have found the above-mentioned improved process for preparing compounds of general formula (). The reaction temperature may be between +10°C and 180°C. Temperature adjustment is usually carried out using a cooling or heating jacket in the reaction vessel or simmering machine. The processing time of the reaction mixture in the mixing machine may be from a few minutes to several hours depending on the temperature and the mixing or mixing intensity and the esterification agent used. If sulfuric acid (oleum) containing sulfur trioxide is used in the reaction according to the invention, its content of sulfur trioxide preferably ranges from 15 to 65% by weight, preferably up to 70% by weight.
Weight%. The process according to the invention is preferably carried out in machines which operate with a summation action - the summation machines mentioned below. The process is carried out by introducing one of the reaction components into a reaction vessel equipped with an intensively working mixing device or into a machine working with a summing action, and gradually adding the second component to it. This can be easily carried out by adding the components to the reactor or by introducing both components simultaneously or as a mixture into the above-mentioned reaction vessel or condenser. Esterification of a compound of formula () with simultaneous hydrolytic ring opening of the oxazolone ring is 92-100
% sulfuric acid at 100 DEG to 180 DEG C., in particular 120 DEG to 160 DEG C. It is particularly advantageous to operate at temperatures between 120 and 160° C. and within a reaction and sintering time of 2 to 20 hours, which in the case of such conditions is particularly suitable for the applied sintering intensities. - This may also depend on the type of machine used. A variation of this process for preparing compounds of formula () from compounds of formula () is to first esterify the compound of formula () in the manner described above and then to
If the esterification is carried out using 100% sulfuric acid at temperatures below 100°C, the reaction temperature in the mixer or mixer must be increased to 100-180°C for hydrolytic ring opening, or the esterification When using fuming sulfuric acid or sulfur trioxide as a oxidizing agent, the hydrolytic ring opening in a mixer or mixer is carried out by gradually adding water in an amount to reach 92-100% sulfuric acid. The temperature should be between 180°C and 180°C. The sulfuric acid used for the reaction with the compound of formula () is preferably used as 95-98% sulfuric acid, as the so-called monohydrate (100% sulfuric acid) or as fuming sulfuric acid. Preferably 1.0 to 1.5− with respect to the molar amount of SO ₃
A double, especially 1.1- to 1.5-fold equimolar amount of esterifying agent is used. During the merging process, inert additives, such as diatomaceous earth, talc or metal powders, can also be added together to improve the merging action or the heat transfer of the merging mixture; During post-treatment or further processing, the sulfuric acid half-ester of the formula () prepared or the dye prepared therefrom can be separated again by simple separation of its aqueous solution. Machines which operate with a mixing action should be understood to be suitable for mixing, dispersing or homogenizing, and which are capable of mixing liquid and solid components with each other under the action of strong forces. In this case, this mixing is usually carried out under high pressure in the following manner. i.e. mechanical parts, such as rolls, disks, etc., moving in parallel or oppositely and expediently running with different speeds.
Rollers, closely intertwined gears and worms are used to mix the components together under high pressure and optionally under the application of shearing forces. 〓
A machine that has a sum function (hereinafter referred to as a sum machine)
Examples include, in addition to the actual mills and extruders themselves, eg saw blade dissolvers, rotor-stator mills, dispergators and roller mills. These machines can operate either discontinuously or continuously and are known in large numbers commercially. Discontinuously operating machines are, for example, double-tank machines, sigmar paddle machines, dispersion machines, Banbury dispersion mixers, etc., and continuously operating machines are For example, Japanese extruders (these are also described in the Ulmanns Encyclopaedia
Chemie, Vol.1 (1951), p.725-727; Ullmanns
Encyclopa¨die der Technischen Chemie, 4.
Edition, Vol. 2 (1972), p. 23, 292-299. ]. The work-up of the reaction product of formula () after esterification and hydrolytic ring opening in the reaction vessel is carried out in the manner customary and customary to those skilled in the art. This work-up is advantageously carried out in such a way that the reaction product is dissolved in water and the solution is neutralized at the same time. This neutralization is preferably carried out using sodium bicarbonate or sodium carbonate. The neutral or completely slightly acidic solution is then evaporated to dryness or spray-dried, optionally after the above-mentioned inert additives have been separated off, for example by filtration or centrifugation. In this way, for example, upon neutralization with the abovementioned sodium salts, a compound of formula () is obtained in the form of its sodium salt. Potassium bicarbonate or potassium carbonate can likewise be used for neutralization. Another possibility for working up the reaction product is to dissolve the hydrate in water and then neutralize it with calcium carbonate, filter off the formed and precipitated calcium sulfate and add it to the liquid. Sodium oxalate or oxalic acid and sodium carbonate or sodium bicarbonate are added and the solution is separated from the precipitate formed in a conventional manner, for example by filtration or centrifugation, and then spray-dried. In the case of this new esterification process, the amount of gypsum formed is significantly lower than in the previously known processes. However, the outstanding and important advantage of the esterification process according to the invention for preparing aminophenol compounds of the formula () is that no work-up of the final product is necessary. That is, the reaction product is obtained from the washing machine as a powder, as brittle or small lumps, or as a plastic material. And the products can be easily stored and transported in these forms. Therefore, the product can be used for a simple further treatment without waste water and which is environmentally friendly, i.e. the following formula () (In the formula, R has the above-mentioned meaning, and the β-sulfatoethylsulfonyl group is the 4-position or 5-position of the diazo component.
K is a residue of a coupling component,
Furthermore, it is possible to produce fiber-reactive azo dyes represented by (which may contain an azo group) as well as metal complex dyes thereof. This is because the products of formula () obtained by the esterification process according to the invention are obtained with a degree of esterification of 95-100% and in high yields and, surprisingly, in higher quality than in the case of the known process. This is because it will be done. Therefore, the products obtained by the esterification process according to the invention exhibit excellent quality and even high shade of dyeings and prints on cellulose fiber materials formed using azo dyes and their metal complex compounds, and It can be obtained in high yield calculated from the starting compound (). When 1 to 1.5 mol of the esterifying agent is used per 1 mol of the compound of formula (), the hydrate is usually obtained as a powder at temperatures below 50°C, and 1.5 mol of the esterifying agent is used per 1 mol of the compound of formula (). When ~2.0 mol is used, the hydrate is obtained as a powder or plastic. The esterification product obtained by this method can preferably be stored in containers and transported as a powder without any problems, so that subsequent processing, for example to produce dyestuffs, is temporally and spatially dependent on the esterification. It can be done without. Post-treatment for producing azo dyes involves diazotizing the hydrate in an aqueous Congoic acid solution, and optionally adding more acid depending on the amount of esterifying agent used in the esterification step. This can be canceled partially or completely. The diazotization is carried out in a known and customary manner, and is similarly coupled with the coupling component of the following formula H--K, in which K has the above-mentioned meaning, after adjusting the appropriate PH-value. ) dyes can be formed. In a further preferred manner, metal complex compounds, in particular copper, cobalt or chromium complex dyes, can be prepared using metal donor agents in the same reaction medium. Since the dyes prepared in this way have a relatively low content of sulfates resulting from esterification, the dyes are precipitated by salting out with sodium chloride or potassium chloride and are then precipitated without separation, preferably in a weakly acidic solution. The to neutral dye solution can be directly evaporated or subjected to spray drying. A dye powder of excellent quality and purity and strong tinting strength is thus obtained in very good yields, which corresponds in its properties to the products prepared by known methods, but which, in general, Degree of esterification of β-hydroxyethylsulfonyl group, formula ()
The content of the dye or its metal complex compound, the tinting power,
It is superior to the latter in terms of water solubility and dye yield. Because of the good dye solubility, the dye solution obtained can be used directly for dyeing purposes, optionally after additionally concentrating it to a smaller volume. Therefore, the present invention relates to the simple production of fiber-reactive azo dyes using the compound of formula () obtained by the esterification method according to the present method, and its feature is that the reaction Product (〓
diazotization product) directly as a diazo component, optionally dissolved in neutral water, diazotized by a conventional method, and adjusted to an appropriate pH for azo coupling.
After adjustment to the desired value, it is coupled with a coupling component and the azo dye thus obtained is isolated without prior isolation, optionally metallized and then by spray drying or evaporative concentration. The examples given below are intended to illustrate the subject matter of the invention. Note that the relationship between parts by weight and parts by volume shown in the examples corresponds to the relationship between kg. Example 1 (a) One summation arm has a speed of 29 revolutions/min, the other summation arm has a speed of 21 revolutions/min.
Commercially available dispersions - Japanese machines (e.g.
Werner & Pfleiderer, Stuttgart
6-(β) as a dry powder in
-Hydroxyethylsulfonyl)-benzoxazolone (94.4%) (3866 parts by weight) was charged in advance and heated to 110-120°C using a heating jacket. 98% sulfuric acid within 10 minutes while running the machine
Inject 1900 parts by weight and leave the reaction mixture for about 14 hours.
Process at 140-150°C while running the Japanese machine.
Initial foam formation is suppressed by adding small amounts of commercially available silicone defoamers. A dark pasty composition formed which first putty-like and then crystallized on cooling to room temperature, and then a greenish-gray powder formed. Next, remove it from the Japanese machine. 4960 parts by weight of 2-amino-1-hydroxy-5-(β-sulfatoethylsulfonyl)-benzole (86%) was obtained as a powder, corresponding to 95.7% of the theoretical yield. (b) Add 2.0 parts by weight of the hydrate to about 0.7 parts by weight of sodium hydrogen carbonate.
At the same time, add parts by weight little by little into a mixture consisting of 8 parts by volume of water and 2 parts by weight of ice.
Stir at 5°C. The aqueous solution thus obtained has a PH value of approximately 4.5 and is clarified by filtration and evaporated to dryness under reduced pressure at 60-65°C. After grinding, in addition to 9% by weight of sodium sulfate, the following formula 2.1 parts by weight of a yellowish white powder was obtained containing the pure compound represented by in the form of its sodium salt. Example 2 Commercial dispersion - 6-(β-hydroxyethylsulfonyl) as a dry powder in a machine
3866 parts by weight of benzoxazolone (94.4%) was charged in advance. 65% within 20 minutes while operating the machine
Flow in 1607 parts by weight of fuming sulfuric acid. The temperature is maintained below 100°C using a cooling jacket. After 2 hours, mainly the following formula A putty-like reaction composition containing the compound represented by is heated to 125 DEG -130 DEG C. by steam jacket heating. 250 parts by weight of water are added dropwise over the course of 2 hours and foam formation is suppressed with a silicone antifoam agent. After adding water, the reaction temperature is increased to 145-155°C and the composition is left at this temperature with the machine running for 20 hours. It is then cooled to room temperature, during which the contents of the machine harden and turn into a powder. 5100 parts by weight of 2-amino-1-hydroxy-5-(β-sulfatoethylsulfonyl)-benzole (81%) are obtained, with a degree of esterification of 96%. Examples 3 to 7 If carried out in a manner analogous to that described in Examples 1 or 2, the starting compounds listed in Examples 3 to 7 of the table below produce the following in high purity, high degree of esterification and high yield. The corresponding nitric acid half ester of the stated formula (final product) was obtained. This sulfuric acid half ester compound can be reacted in a known manner, for example analogous to that described in Examples 8 to 18 below, primarily for the preparation of fiber-active azo dyes and their metal complex compounds.

【table】

[Table] Example 8 69 parts by weight of the hydrate produced under Example 1a was added to 300 parts by weight of water.
part by volume and 150 parts by weight of ice and diazotized with 40.1 parts by volume of 5N sodium nitrite. The small excess of nitrous acid is destroyed after the diazotization reaction by post-stirring for 15 minutes with a small amount of amidosulfonic acid. The yellow diazonium salt solution is water
1-Amino-8-hydroxy- in 300 parts by volume
76 parts by weight of 4,6-disulfonic acid (84%) are placed in a solution made neutral. Adjust the pH to 6-7 with water-free sodium carbonate and hold until the end of the coupling (diazonium salts are no longer detected). Crystalline copper sulfate is then added, and the pH is adjusted to 4.5-5.0 using 50 parts by weight of crystalline sodium acetate and sodium carbonate. The reaction solution was heated to 1 at room temperature.
After-stir for an hour, then add 10 parts by weight of diatomaceous earth to clarify and evaporate at 50-60°C. The residue was ground to obtain 240 parts by weight of a blue-black dye powder, which had the following formula: Contains 63% by weight of the dye represented by This dye is a well-known conventional dyeing method for reactive dyes on cotton and other cellulosic fiber materials in the presence of alkaline agents, giving a very good sun- and wet-fast dyeing of dark navy blue and Provide printing. If the clarified dye solution obtained during production was spray-dried instead of evaporative concentration, dye powders of good quality with similar dye contents were obtained. Example 9 A hydrate of the compound of Example 2, prepared analogously to Example 1a, was dissolved and diazotized as described in Example 8. A solution of diazonium salt is diluted with 1-acetylamino-8-
Coupled with 136.5 parts by weight of hydroxynaphtaryline-3,6-disulfonic acid (53%) at a pH value of 6-7. The following formula in free acid form: Without intermediate isolation, 50 parts by weight of chromium alum is added to the solution of the obtained azo dye represented by , and the pH is adjusted to 5.3 to 5.7 with crystalline sodium acetate.
The reaction mixture is then boiled under reflux for about 10 hours until no metal-free dye can be detected in the chromatogram anymore. The resulting solution of the 1:2-chromium complex dye is clarified with the addition of 10 parts by weight of diatomaceous earth and then spray-dried. A blue-black dye powder is obtained, which can be dyed using conventional and known dyeing and printing methods for reactive dyes.
In the presence of alkaline agents, it provided deep, clear navy blue prints and dyeings with very good sunlight and wet fastness on cellulose fiber materials. Examples 10 to 18 As is further evident from the examples in the table below, in the process according to the invention the metal complex dyes described below can be prepared as such from the compounds of formula () obtained by the process without intermediate isolation of the diazo component. can be manufactured. Thus, starting from the usual use of the process described in Examples 8 or 9, a sulfato compound of the formula () described below, in which compounds (A) and (B) are compounds of the formula - is first diazotized and then coupled in the usual manner with the corresponding coupling components mentioned in the examples, then transformed into the corresponding metal complex compound by treatment with a copper-, cobalt- or chromium-donating metallizing agent and evaporated. The dyestuff thus obtained was isolated by concentration or spray-drying, and with this dyestuff (dye powder) intense sunlight- and wet-fast dyeings and prints were obtained on cotton in the tones described in the examples. .

【table】

【table】

Claims (1)

[Claims] 1. The following formula () (In the formula, R means a hydrogen atom, a lower alkyl group, a nitro group, a chlorine atom, or a bromine atom, and the β-hydroxyethylsulfonyl group is present at the 5- or 6-position of the benzoxazolone ring.) The following formula () can be obtained by esterification and hydrolysis to open the ring. (In the formula, R has the above-mentioned meaning, and the β-sulfatoethylsulfonyl group is the 4- or 5-
When producing a compound represented _by
~ 100% sulfuric acid, optionally with subsequent addition of water, under vigorous and thorough mixing at a temperature of 100 to 180 °C or in a 1 to 2-fold equimolar amount to the molar amount of SO ₃ . A process for the preparation of the above-mentioned compounds, which is carried out using sulfuric acid containing sulfur oxide or sulfur trioxide at a temperature of 10 to 180° C. with subsequent addition of water and intensive and thorough mixing. 2. The method according to claim 1, wherein the reaction is carried out using sulfuric acid or sulfur trioxide or sulfur trioxide containing sulfur trioxide in an amount of 1.1 to 1.5 times the molar amount of _SO3 . 3. The method according to claim 1 or 2, wherein the reaction is carried out at 120 to 160°C. 4. A process according to any one of claims 1 to 3, wherein the reaction is carried out in a machine operating with a summation effect. 5. The method according to any one of claims 1 to 4, wherein the reaction is carried out in a washing machine that operates continuously.