JPS6115067B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula ()

[Formula] By esterifying the compound represented by the general formula ()

In order to produce the aminophenol-sulfuric acid half-ester compound represented by the formula, this reaction is carried out from 92 to
100% sulfuric acid, sulfur trioxide, or 1- to 2.2-fold equimolar amount of sulfuric acid containing sulfur trioxide (SO ₃
The present invention relates to an improved method characterized in that it is carried out in a washing machine using In the general formulas () and (), R is a hydrogen atom,
Lower alkoxy groups (e.g. methoxy or ethoxy groups, especially methoxy groups), lower alkyl groups (e.g. methyl- or ethyl-groups, especially methyl groups), nitro groups or chloro- or bromine atoms (of which especially the bromine atom)
and β-hydroxy- or β-sulfato-ethylsulfonyl group refers to the 4- or 5-hydroxy group of the benzene ring.
- Exists in position. According to the method according to the invention, the following compounds, such as 2-amino-phenol-4-β-sulfatoethylsulfone, 2-amino-phenol-5-β
-sulfatoethylsulfone, 2-amino-4-
Methyl-5-β-sulfatoethylsulfonyl-
Phenol, 2-amino-4-methoxy-5-β
Particular preference is given to producing -sulfatoethylsulfonyl-phenol. Compounds of formula () are suitable as initial products (diazo component) for producing azo dyes. Methods for converting compounds of formula () into compounds of formula () are known per se. However, the previously reported methods require a large excess of sulfuric acid, which is used during the post-treatment of the esterified product of formula () and during its isolation or further processing to form a dye. It must then be diluted with water, neutralized and optionally separated from the dye. Recovery of sulfuric acid is therefore practically impossible. Moreover, this acid contaminates wastewater in its pure form or in neutralized form as soluble sulfate. The known esterification process also has the disadvantage that the compound of formula () is obtained as a solution in sulfuric acid. This solution is hardly suitable, for example, for storage for subsequent processing. The esterification of the compound of formula () is carried out, for example, in Example 5 of German Patent No. 953103 using concentrated sulfuric acid in a 6-fold molar amount. After diluting the sulfuric acid solution with a large amount of ice and water, the amino group is diazotized, and the resulting diazonium compound is neutralized with a large excess of sulfuric acid to form neutral sodium sulfate, and then coupled with a coupling component. It is made into an azo dye and then chromated. The resulting chromium complex dye is salted out using sodium chloride, separated in this way from the large amount of sulphate ballast, and then taken off. However, large amounts of the sodium sulfate present in the mother liquor and the sodium chloride which is additionally added for salting out are introduced into the waste water. German Patent No. 1012010 Specification Examples 1 to 4
and the methods described in Examples 1 to 4 and 6 of German Patent No. 1 126 542 are similarly processed. Neutralize excess sulfuric acid using calcium carbonate,
Removal of sparingly soluble calcium sulfate (as described for example in DE 953 103, Example 3) significantly reduces wastewater pollution, but requires additional handling and equipment costs. shall be.
Furthermore, this method has the disadvantage that the resulting gypsum must be deposited as unusable industrial waste. Furthermore, from Example 2 of German Patent Application No. 1443877, the corresponding sulfuric acid half ester of formula () is prepared by using a compound of formula () in a 3 to 4 times equimolar amount of amidosulfonic acid in pyridine. It is well known that it can be changed to Although this means that the amount of esterifying agent conventionally used in excess can be significantly reduced, the pyridine used must be thoroughly distilled off afterwards under reduced pressure. Nevertheless, approximately one quarter of the pyridine used in this case still reaches the mother liquor when the sulfuric acid half ester is further processed to give the dye. Therefore, the pyridine must be removed from the mother liquor in some way before this wastewater reaches the drain. An urgent problem therefore arises which requires an esterification process which avoids the above-mentioned disadvantages and which, in fact, does not pollute the environment at all or hardly pollutes it at all. Now, the present inventor has esterified the compound represented by the above general formula () to form the corresponding sulfuric acid half ester represented by the general formula (), and the compound represented by the general formula () is 92% to 100%
% sulfuric acid, sulfur trioxide or a 1- to 2.2-fold equimolar amount (relative to the number of moles of SO ₃ ) of sulfuric acid containing sulfur trioxide in a machine operating with a summation action. We have found an improvement method that consists of implementing. As machines which operate with a harmonizing effect, it is to be understood that they are suitable for mixing, dispersing or homogenizing and 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 original mills and extruders themselves, eg saw blade stirrers (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 wafers include, for example, double tank type wafers, sigmar paddle type wafers, dispersion wafers, Panbury dispersion mixers, etc.; is, for example, a Japanese extruder;
Ulmanns Encyclopadie der Technischen
Chemie, Vol.1 (1951), p.725-727; Ullmanns
Encyclopa¨die der Technischen Chemie, 4.
Edition, Vol. 2 (1972), p. 23, 292-299. ]. The process can be carried out by first charging one of the reaction components into a machine operating with a summation action and then adding the second component thereto, or alternatively by introducing both components simultaneously or in a mixture into a machine. It is easily done as follows. The sulfuric acid used in this reaction is concentrated sulfuric acid (96%)
Preference is given to using it as a so-called monohydrate (100% sulfuric acid) or as fuming sulfuric acid. Furthermore, in order to esterify the compound represented by the formula (), an equimolar amount of 1 to 2.2 times, particularly preferably 1.0 to 1.5 times, particularly 1.1 to 1.5 times the molar number of SO ₃ is used. Preference is given to using esterifying agents. The reaction temperature can be from 10°C to 160°C, preferably the reaction is carried out using sulfuric acid or oleum or sulfur trioxide in a sludge machine at a temperature of 100° to 140°C. Temperature control is usually achieved by means of a cooling jacket or a heating jacket on the machine. 〓The processing time of the reaction mixture in the machine is determined by the temperature and 〓
It takes several minutes to several hours depending on the strength of the mixture and the esterification agent used. 100~ conveniently
operating at a temperature of 140° C. with a reaction time of 5 minutes to 6 hours and a summation time that is particularly applicable in such conditions; this also depends on the summation strength of the machine used. It can depend on the type. During the merging process, inert additives are added, such as diatomaceous earth, to improve the merging action or the heat transfer of the merging mixture.
Talc or metal powders can also be added together, and these additives can be added to the sulfuric acid half ester of the formula () prepared or the dye prepared therefrom to its aqueous solution during post-treatment or further processing of the hydrate. can be separated again by simple filtration. The work-up of the reaction product after esterification in the machine is carried out in the customary manner 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 post-treatment of the hydrate is to neutralize the hydrate with calcium carbonate after dissolving it in water, sucking off the formed and precipitated calcium sulfate, and adding sodium oxalate or oxalic acid and carbonic acid to the liquid. Sodium or sodium bicarbonate is 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 is that no further treatment 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. The product can be used for easy wastewater-free and environmentally satisfactory further processing, i.e.

It is possible to produce fiber-reactive azo dyes of the formula, especially metal complex compounds thereof. Furthermore, in the above formula, R has the above-mentioned meaning, and the β-sulfatoethylsulfonyl group is the 4-
or at the 5-position, where K is a residue of a coupling component and may further contain an azo group. These facts indicate that the product of formula () obtained by the esterification method of the present invention has a degree of esterification of 95 to 100% and a high yield, and surprisingly, is higher than that obtained by the known method. By obtaining high quality. The metal complex dyes obtained from the products of the esterification process according to the invention are therefore of outstanding quality and exhibit a high degree of purity of color in the dyeings and prints on the cellulose fiber materials produced with them. , and can be obtained in high yield calculated from the starting compound of the above formula (). 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, and 1.5 to 2.2 mol of the esterifying agent is used per 1 mol of the compound of formula (). In some cases, it is obtained as a powder or plastic. The hydrate obtained by this method can be stored in storage tanks and transported without problems, preferably as a powder;
The further processing, for example for producing dyestuffs, can thus be carried out both in time and in location independently of the esterification. For further processing to produce the dye, the hydrate is diazotized as an aqueous Congo acid solution. Depending on the case, depending on the amount of esterifying agent used in the esterification step, further addition of acid can be partially or completely omitted. Diazotization is carried out in a known and customary manner, by coupling a coupling component of the formula HK (where K has the meaning given above) and, after adjusting a suitable pH value, in exactly the same manner. , a dye represented by the above formula () can be formed. The dyes can further advantageously be converted into metal complex dyes, in particular steel, cobalt or chromium complex dyes, using metal donors in the same reaction medium. The dye solution produced in this way has a relatively low content of sulfate derived from esterification, so
It is not necessary to precipitate the dye by salting out with sodium chloride or potassium chloride and then remove it; the weakly acidic to neutral dye solution can be conveniently evaporated to dryness or spray-dried as is. . A highly tinting dye powder is thus obtained with excellent quality and purity in very good yields. In terms of its properties, this dye corresponds to the products prepared by known methods, but in general the degree of esterification of the β-hydroxyethylsulfonyl group, the content of the dye of the formula () or its metal complex compounds,
It is superior to the latter in terms of coloring power, water solubility and dye yield. Since the dye has good solubility, the dye solution obtained can be used as is or, if necessary, after being concentrated to a smaller volume for dyeing purposes. The present invention therefore also relates to a simple process for producing fiber-reactive azo dyes by using the product of formula () obtained by the esterification process according to the invention, which is characterized by: The hydrate is used as it is as a diazo component, optionally dissolved in water, and then diazotized by a conventional method.Then, after adjusting the pH value to a value suitable for azo coupling, it is coupled with a coupling component.
The azo dye obtained is not isolated beforehand, but is optionally metalized and then isolated 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) Commercially available dispersion machine (e.g. Wuerner & Buchreiderer, Stutsgart-Heuer-Batsch) - one of the dispersion arms has a speed of 29 revolutions per minute and the other has a speed of 21 revolutions per minute. operates with - in 2-amino-1-hydroxy-
2657 parts by weight of 4-(β-hydroxyethylsulfonyl)benzole (98%) are first introduced in the form of a dry powder. Then 65% while operating the machine
1285 parts by weight of fuming sulfuric acid (which contains 65 parts by weight of SO ₃ and 35 parts by weight of H ₂ SO ₄ in 100 parts by weight of oleum) are added within 15 minutes. The reaction mixture is then mixed for a further hour in a machine operating at 120-140°C. After that, take out the Japanese food from the Japanese machine. Thus 2-amino-1-hydroxy-4-
3743 parts by weight of (β-sulfatoethylsulfonyl)-benzole (93%), corresponding to 98% of theory, are obtained as a light gray powder. (b) 2.0 parts by weight of the hydrate are stirred sequentially into a mixture consisting of 8 parts by volume of water and 2 parts by weight of ice at 0 to 5°C with the simultaneous addition of about 0.75 parts by weight of sodium bicarbonate. The pH value of the resulting aqueous solution is 5.0
Or it will be 5.4. The solution is clarified by filtration and evaporated to dryness under vacuum at 40-50°C. After grinding, 2.1 parts by weight of powder are obtained. This is the following formula in addition to 9% by weight of sodium sulfate.

Contains the pure compound of the formula in the form of its sodium salt. Example 2 63.7 parts by weight of the hydrate prepared according to Example 1(a) were dissolved in a mixture consisting of 300 parts by volume of water and 100 parts by weight of ice, and diazotized using 40.1 parts by volume of 5N-sodium nitrite solution. become A small excess of nitrous acid is decomposed using a small amount of amidosulfonic acid after the diazotization reaction. This was then added with powdered 1-(4'-sulfophenyl)-3-methyl-pyrazolone-(5) (98%) 51.8
Add parts by weight. Until the coupling reaction is complete (diazonium salt test is negative), approximately 17 parts by weight of water-free sodium carbonate is used to
Adjust to 6.5 and keep. Then crystallized copper sulfate 50
The pH value is adjusted to 4.5 to 5.0 using 50 parts by weight of crystallized sodium acetate and about 14 parts by weight of water-free sodium carbonate. The reaction solution was stirred at room temperature for 3 hours, then clarified and
Evaporate and concentrate at 60℃. Grind the residue. Thus the yellow-brown dye powder
202 parts by weight are obtained. This is the following formula This corresponds to 66% by weight of the dye represented by This produces colors which have very good light and wet fastness on cotton and other cellulosic fiber materials in the presence of alkaline-acting agents using customary and known dyeing methods for reactive dyes. Provides deep, vivid yellow printing or dyeing. In preparing the dye powder, if the resulting clear dye solution is spray-dried instead of evaporative concentration, dye powders of similar dye content and equally good quality are obtained. Example 3 63.7 parts by weight of the hydrate prepared according to Example 1(a) are dissolved and diazotized as described in Example 2. The diazonium salt solution was diluted with 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid (53
%) at a pH value of 6 to 7 using 136.5 parts by weight. The resulting azo dye - which in free acid form has the following formula: Corresponding to - was prepared as a solution without intermediate isolation, and 50 parts by weight of chromium alum was added to it,
Adjust the pH to 5.3 to 5.7 using crystallized sodium acetate. The reaction mixture is then boiled under reflux for about 10 hours until metal-free dye is no longer visible in the chromatogram. The resulting 1:2-chromium complex-dye solution is clarified with the addition of 10 parts by weight of diatomaceous earth and then spray-dried. A blue-black dye powder is thus obtained. It produces a deep marine blue color with very good light and wet fastness on cellulose fiber materials in the presence of alkaline-acting agents using customary and known dyeing methods for reactive dyes. Provide printing or dyeing. Example 4 63.7 parts by weight of the hydrate prepared according to Example 1(a) are diazotized according to Example 2. The diazonium salt solution was diluted with 2-aminonaphthalene-5-sulfonic acid (98.4
%) with a pH value of 5 to 6 using 45.3 parts by weight. The dye produced - which in free acid form has the following formula: Cobalt sulfate crystallized in a solution of -28.1
Add parts by weight. crystallized sodium acetate 40
Parts by weight are then used to adjust the pH value to 5.0 to 5.5 using water-free sodium carbonate. The reaction solution is stirred for 1 hour at room temperature until no metal-free dye is anymore visible in the chromatogram. The resulting 1:2-cobalt complex dye solution was poured into diatomaceous earth.
Clarify with addition of 10 parts by weight and then spray dry. A black dye powder is thus obtained. This provides deep black prints or dyeings with very good light and wet fastness on cellulose fiber materials using dyeing processes customary and known for reactive dyes. Example 5 2-Amino-1-hydroxy- in Example 1(a)
Example 1(a) except that 2657 parts by weight of 4-(β-hydroxyethylsulfonyl)-benzole was replaced by an equimolar amount of 2-amino-1-hydroxy-5-(β-hydroxyethylsulfonyl)-benzole. Similarly, when operated as described in 2-amino-
1-Hydroxy-5-(β-sulfatoethylsulfonyl)-benzole is obtained in powder form in equally good yields and with a degree of esterification of 98-99%. In the same manner as described in Example 1(b), 2-
Amino-1-hydroxy-5-(β-sulfatoethylsulfonyl)-benzole can be isolated in the form of its alkali salt. Example 6 2-Amino-1-hydroxy-4-(β-hydroxyethylsulfonyl)-
2216 parts by weight of benzole (98%) are first introduced in the form of a dry powder. 100 to this while operating the machine
% sulfuric acid ("monohydrate") are added within 20 minutes. Adjust the reaction temperature using a heating jacket.
Increase the temperature to 130°C and heat the mixture at 130-140°C for a further 6
If it is running for hours, leave it in the machine. After that
Remove the Japanese food from the Japanese machine. Thus 69.6% 2-amino-1-hydroxy-
4166 parts by weight of 4-(β-sulfatoethylsulfonyl)-benzole are obtained. Esterification degree is 97%
become. Examples 2 to 4 of the products thus produced
It can be used in the preparation of reactive dyes in a similar manner to that described in . Example 7 Commercially available, continuously operating machine (e.g.
BUSS-KO (Japan machine, type PR46 from BUSS AG, Basel/Switzerland) - which operates at 27 revolutions/min - in the form of dry powder via a metering worm.
Amino-1-hydroxy-4-(β-hydroxyethylsulfonyl)-benzole (98%) 16.0
65% oleum via g/min and metering pump 6.2
Add ml/min simultaneously. 〓Maintain the washer at a temperature of 130 to 140°C using a steam heating jacket.
The resulting hydrate contains 77.6% by weight of 2-amino-1-hydroxy-4-(β-sulfatoethylsulfonyl)-benzole (molecular weight 297). This degree of esterification amounts to 97-98%. The hydrates obtained can be further processed to give reactive dyes in a manner similar to that described in Examples 2 to 4. Examples 8 to 12 When treated in a manner similar to that described in Examples 1, 6 or 7, the starting compounds described in Examples 8 to 12 of the following table can be obtained with high purity, high degree of esterification and high yield. The corresponding sulfuric acid half ester is obtained, having the structural formula (final product) shown below. The sulfuric acid half ester compounds can be used in a manner known per se, for example as described in Examples 2 to 4, in particular for the preparation of fiber-reactive azo dyes and their metal complexes.

【table】

[Table] The degree of esterification in Examples 8 to 12 is 97 to 97, respectively.
Become 99%. Examples 13 to 29 Furthermore, as is clear from the examples in the following table, the following metals can be obtained without any intermediate isolation according to the process according to the invention from the compounds of the general formula ( Complex dyes can be produced. That is, the processing methods described in Examples 2 to 4 are advantageously utilized as follows. The following sulfate compounds - in which compounds (A) and (B) have the following formula:

【formula】

-, which means [formula], is first diazotized, then coupled in a conventional manner using the corresponding coupling component shown in the example, and treated with a suitable metal donor to obtain the metal shown in the example. The dyestuff formed is isolated by conversion to the corresponding metal complex compound and by evaporative concentration or spray drying to obtain a dyestuff powder. This dye is a reactive dye that is commonly used in conventional printing processes.
or dyeing - providing a dark, light-fast and wet-fast print or dyeing on cotton in the respective shades indicated in the following examples, according to the method.

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 General formula () [Formula] (In the formula, R means a hydrogen atom, a lower alkoxy group, a lower alkyl group, a nitro group, or a chloro or bromine atom, and a β-hydroxyethylsulfonyl group is existing at the 4- or 5-position of the benzene ring) is esterified to form a compound represented by the general formula () [Formula] (wherein R has the above-mentioned meaning, and the β-sulfatoethylsulfonyl group is (Existing at the 4- or 5-position of the benzene ring.) To produce a compound represented by A process for the production of half-esters as described above, characterized in that it is carried out in a machine operating with summing action using double equimolar amounts (relative to the number of moles of SO ₃ ). 2 Esterification using esterifying agent 1,1- or)
Claim 1 consisting of carrying out using a 1.5-fold equimolar amount (relative to the number of moles of SO ₃ )
The method described in section. 3. A method according to claim 1 or 2, comprising using about 65% oleum as the esterifying agent. 4. The method according to any one of claims 1 to 3, which comprises carrying out the reaction at 100 to 140°C. 5. The method according to any one of claims 1 to 4, which comprises carrying out the reaction in a continuous machine. 6. The method according to any one of claims 1 to 5, which comprises esterifying a compound represented by the following formula [formula] to form a compound represented by the following formula [formula]. 7. The method according to any one of claims 1 to 5, which comprises esterifying a compound represented by the following formula [formula] to form a compound represented by the following formula [formula]. 8 A compound represented by the following formula [formula] (wherein R is a methyl or methoxy group) is esterified to form a compound represented by the following formula [formula] (wherein R has the above-mentioned meaning) A method according to any one of claims 1 to 5, which comprises preparing a compound.