CH618967A5 - Process for the preparation of sulphuric acid hemiester compounds - Google Patents

Description

The invention relates to a process for the preparation of compounds of formula II

nh.

(II),

9 ^

s02-ch2-ch2-0s03h

(II).

10th

s02-ch2-ch2-0s03h in which R represents a hydrogen atom, a lower alkyl group, the nitro group or a chlorine or bromine atom and the / 3-sulfatoethylsulfonyl group is in the 4- or 5-position of the benzene nucleus, by esterification and hydrolytic ring cleavage of compounds of formula I.

15

in which R represents a hydrogen atom, a lower alkyl group, the nitro group or a chlorine or bromine atom and the / 3-sulfatoethylsulfonyl group is in the 4- or 5-position of the benzene nucleus, by esterification and hydrolytic ring cleavage of compounds of the formula I.

20th

(I),

s02-ch2-ch2-0h

30th

in which R has the meaning given above and the / 3-hydroxyethylsulfonyl group is in the 5- or 6-position of the benzoxazolone ring, which is characterized in that the reaction is carried out with a 1 to 2 times equimolar amount on mol S03, on 92 to 100% sulfuric acid at a temperature of 100 to 180 ° C with thorough mixing.

The preparation of 2-amino-phenol-4- / 3-sulfatoethylsulfone and -5-ß-sulfatoethylsulfone by the method according to the invention is particularly preferred.

The compounds of formula II are suitable as precursors (diazo components) for the production of azo dyes.

The conversion of compounds of the formula I into compounds of the formula II with hydrolytic splitting of the oxazolone ring is known per se. However, the method described so far requires large excesses of sulfuric acid, which must be diluted with water, neutralized and separated from the esterification product or from the dye either in the working up of the esterification product of the formula II and in its isolation or in its further processing to give dyes. A recovery of the sulfuric acid is practically impossible. The acids also pollute the wastewater as such or in neutralized form as soluble 55 sulfates.

Furthermore, the known esterification process has the disadvantage that the compounds of the formula II are obtained as solutions in sulfuric acid; however, these solutions are not very suitable for storage, for example for subsequent processing.

Thus, the esterification of a compound of the formula I according to DE-PS 1 153 029 takes place with the 6-fold equimolar amount of concentrated sulfuric acid. After diluting the sulfuric acid solution with plenty of ice and water, the compound of formula (II) obtained is isolated in substance by suction (filtering off). It is only 67% of theory. Th. Preserved, the rest remains in the mother liquor, as well as the excess, dilute sulfuric acid, the

3rd

618 967

for wastewater must be neutralized. However, the non-isolable product and the sodium sulfate represent a considerable burden on the wastewater.

A neutralization of the excess sulfuric acid with calcium carbonate and filtration of the sparingly soluble calcium sulfate, as described in Example 2 of the German patent 1 153 029, relieves the waste water, but requires additional work and material expenditure; Furthermore, this method has the disadvantage that the gypsum obtained in this way must be disposed of as unusable industrial waste.

Likewise, the wastewater pollution is very high if the aminophenol prepared by the known method is used directly after the dilution with ice and water to produce an azo dye (diazotization and coupling with the desired coupling component and optionally metallization): the dye produced is salted out with sodium chloride or Potassium chloride isolated, while the sulfate and a large part of the chlorides remain dissolved. A wastewater-free extraction of the dyes by evaporation or spray drying of the resulting dye solutions without prior separation of the sulfate would, however, lead to very weak-colored dye powders containing a high content of neutral salts, which will hardly be of any interest for industrial use.

There was therefore an urgent need for an esterification process which avoids these disadvantages and has practically no or substantially less pollution of the environment.

It has now been found an improved process for converting the abovementioned compounds of the formula (I) into their sulfuric acid semiesters of the formula (II), in which the reaction of a compound of the formula (I) with the 1 to 2-fold equimolar amount, based on mol S03, on 92 to 100% sulfuric acid at a temperature of 100 to 180 ° C with vigorous mixing, preferably in a kneading machine, hereinafter called kneader.

The temperature can generally be regulated by means of the cooling or heating jacket of the reaction vessel or the kneader. The treatment time of the reaction mixture in the kneader can, depending on the temperature and mixture or Kneading intensity and the esterification agent used, from a few minutes to several hours.

The process is generally carried out in a simple manner either by placing one of the reaction components in the reaction vessel provided with an intensively working mixing device or in the kneading machine and gradually adding the second component to it, or alternatively adding both feeds this reaction vessel or the kneader simultaneously or as a mixture.

The esterification of the compound of formula (I) with simultaneous hydrolytic cleavage of the oxazolone ring takes place in such a way that it is carried out using 92 to 100% strength sulfuric acid at a temperature of 100 to 180 ° C., preferably at 120 to 160 ° C. . It is particularly advantageous to work at a temperature between 120 and 160 ° C. within a reaction and kneading time of 2 to 20 hours, which in these conditions depends in particular on the kneading intensity used, which in turn can depend on the type of machine.

The sulfuric acid used in the reactions with the compounds of formula (i) is preferably used as 95 to 98% sulfuric acid, as a so-called monohydrate (100% sulfuric acid) or as oleum. It is preferred to use the 1.0- to 1.5-fold, in particular the 1.1- to 1.5-fold equimolar amount, based on mol S03, of esterifying agent.

In order to improve the kneading action or the heat transfer in the kneading mixture during the kneading process, additions of inert additives, such as diatomaceous earth, talc or metal powder, can also be processed, which are then processed or processed further from the kneaded material of the sulfuric acid semi-ester of the formula (II) prepared. or a dye produced therefrom can be separated off again by simply filtering off from aqueous solution.

Machines that work with kneading action are to be understood as those that are suitable for mixing, dispersing or homogenizing and that can process liquid / solid components with a high force. Here, the processing (kneading) under high pressure takes place in the usual way in such a way that parts of the machine running in the same direction or in opposite directions, preferably running at different speeds, such as rollers, disks, rollers, closely intermeshing gears and worms, undermine the components Mix high pressure, if necessary using shear forces. Such machines with a 20 kneading action, hereinafter referred to as kneaders, are in addition to the actual kneaders and extruders themselves, for example, sawtooth stirrers (dissolvers), rotor stator mills, dispersers and roller mills. These machines can work discontinuously as well as continuously; a large number of them are known in 25 commercially available forms. Discontinuously working kneaders are, for example, double-bowl kneaders, such as Sigma paddle kneaders, dispersion kneaders, dispersion die kneaders, continuously working kneaders, for example kneading extruders (see also Ulimann's Encyclopedia of Technical Chemistry, Vol. 1 (1951), pages 725-727; Ullmann der Technischen Chemie, 4th edition, Vol. 2 (1972), pages 23 and 292-299).

The reaction mixture of the formula (II) can be worked up after the esterification and hydrolytic ring cleavage in the reaction vessel (kneader) in a manner customary and customary for the person skilled in the art. This is advantageously done by dissolving the reaction material in water with simultaneous neutralization of the solution. The neutralization is preferably carried out with sodium bicarbonate or sodium carbonate. The neutral or very weak acidic solution is then evaporated to dryness or spray-dried, if appropriate after separating off the inert additive mentioned above, for example by filtration or centrifugation. In this way, the compound of the formula (II) is obtained in the form of its sodium salt, for example in the case of neutralization 45 with the abovementioned sodium salts. Accordingly, potassium bicarbonate or potassium carbonate can be used for neutralization. A further possibility of working up the reaction material (kneaded material) is that after dissolving in water it is neutralized with calcium carbonate, the precipitated calcium sulfate formed is filtered off with suction and the filtrate is treated with sodium oxalate or oxalic acid and sodium carbonate or bicarbo-nate, which Solution from the precipitate formed in a conventional manner, for example by filtering or centrifuging, separating and then spray-drying. This new esterification process produces much smaller amounts of gypsum than the previously known processes.

An outstanding and significant advantage of the esterification process according to the invention for the preparation of the 60 aminophenol compounds of the formula (II) is, however, that the end product does not have to be worked up at all. The reaction products emerge from the kneaders in the form of powders or crumbly or small chunks or as a plastic mass; in this form they can be easily stored and transported. They are therefore easy, wastewater-free and environmentally friendly processing to fiber-reactive azo dyes of the formula (IV)

618 967

4th

oh in which R has the abovementioned meaning and the / 3-suI-fatoethylsulfonyl group is in the 4- or 5-position of the diazo component and K represents the rest of a coupling component, which may also contain an azo group, in particular to metal complex compounds of these dyes, possible. This is because the process products of the formula (II) obtained by the esterification process according to the invention are obtained with a degree of esterification of 95-100% and in high yield, but surprisingly, but also in a higher quality than by known processes. Accordingly, the metal complex dyes obtainable from the process products of the esterification process according to the invention are of excellent quality and high purity of the nuances of the dyeings and prints produced with them on cellulose fiber materials and, moreover, are calculated in high yield, calculated on the starting compound of the formula (I) above, receive.

When using 1 to 1.5 moles of esterifying agent per mole of compound of formula (I), the kneadable material is usually obtained as a powder below 50 ° C., when using 1.5 to 2 moles of esterifying agent per mole of compound of formula (I) Powder or in plastic form. The kneaded material obtained in accordance with the process can be stored and transported without problems, preferably as a powder, in barrels, so that the further processing, for example to give dyes, can be carried out regardless of the time and place of the esterification.

In the further processing to azo dyes, the kneadable material can be diazotized in an aqueous, conga-acidic solution, it being possible, depending on the amount of esterification agent used in the esterification process, to partially or completely dispense with further addition of acid. The diazotization is expediently carried out in a known and customary manner, as is the subsequent coupling with a coupling component of the formula HK, in which K has the meaning mentioned above, after setting a corresponding pH to form a dye of the abovementioned formula (IV), which in turn can advantageously be converted into a metal complex compound, in particular a copper, cobalt or chromium complex dye, in the same reaction medium using a metal-donating agent.

Because of the relatively low content of sulfate from the esterification in the dye solution thus prepared, it is not necessary to separate the dyes by salting out with sodium chloride or potassium chloride and then to filter them off, but the weakly acidic to neutral dye solutions can advantageously be evaporated to dryness or evaporated Submit spray drying.

In this way very strong dye dye powders are obtained in very good yield with excellent quality and purity, the properties of which correspond to those of the products prepared in a known manner, but these generally correspond to the degree of esterification of the / 3-hydroxyethylsulfonyl group and the dye content of the formula (IV ) or its metal complex compound, the color strength, the solubility in water and the dye yield.

Because of the good solubility in dyestuffs, the dyestuff solutions obtained can also be used directly for dyeing purposes, if appropriate after additional concentration to a smaller volume.

s Fiber-reactive azo dyes can thus be prepared in a simplified manner using the process products of the formula (II) obtained in the esterification process according to the invention, by using the reaction material (kneading material) directly as a diazo component, optionally dissolved in water, diazotized by customary processes, after adjustment couples a pH value corresponding to the azo coupling with a coupling component, metallizes the azo dye thus obtained, if necessary without prior isolation, and then isolates it by spray drying or evaporation. 15 The following examples serve to explain the subject matter of the invention. The parts by weight stated in them relate to the parts by volume (parts by space) like the kilogram to the liter.

20 Example 1

a) In a commercially available dispersion kneader (for example from Werner & Pfleiderer, Stuttgart-Feuerbach), one kneading arm of which ran at a speed of 29 rpm and the other of which kneading arm ran at 21 rpm, 25 3866 parts by weight of 6- (ß -Hydroxyäthylsulfonyl) -benzoxazolon (94.4%) presented as a dry powder and heated to 110-120 ° C by means of jacket heating. Then 1900 parts by weight of 98% sulfuric acid were allowed to flow in with the machine running within 10 minutes, and the reaction mixture was worked in the running kneader at 140-150 ° C. for about 14 hours. Initial foam formation was suppressed by the dropwise addition of a small amount of a commercially available silicone defoamer. A dark, pulp-like mass formed which, when cooled to room temperature, initially became putty-like, then crystalline and finally gave a greenish-gray powder. The kneader was then emptied. 4960 parts by weight of 2-amino-l-hydroxy-5 - (/ 3-sulfatoethyIsulfonyl) benzene (86% strength) were obtained as powder, corresponding to a theoretical yield of 95.7%. 40 b) 2.0 parts by weight of the kneaded material were stirred into a mixture of 8 parts by volume of water and 2 parts by weight of ice with the simultaneous addition in portions of about 0.7 part by weight of sodium bicarbonate at 0 to 5 ° C. The pH of the aqueous solution thus obtained was about 4.5; It was clarified by filtration and evaporated in vacuo at 60 to 65 ° C dryness. After grinding, 2.1 parts by weight of a yellowish-white powder are obtained which, in addition to 9% by weight sodium sulfate, the pure compound of the formula oh ch2-ch2-oso3h

60

contained in the form of their sodium salt.

Examples 2-6 If the procedure is analogous to that described in Example 1-65, the starting compounds given in Table Examples 2 to 6 below are obtained in high purity and with a high degree of esterification and in high yield and the corresponding sulfuric acid semiesters

5

618 967

of the formulas given below (end products). These sulfuric acid half-ester compounds can be reacted in a known manner, for example in a manner analogous to that described in Examples 7 to 17 below, especially for the production of fiber-reactive azo dyes and their metal complex compounds.

End product

CHo-0oS i 2 2

ch0 I * ■ 0s03h oh

Ar ch2-o2s-v5

ch.,

I *

0s03h nh,

Cl

example

Output connection

1 4

/ v "H

çh2 "2

ch0

i ^

Oh

V

-o-s t ch.

JÓT "

cho-0os t, 22 'C1

ch_

f> H

s02-ch2-ch2-0h oh

-r-A-a

I.

s02-ch2-ch2-0s03h

O NH

s02-ch2-ch2-0h oh jrNH2

s02-ch2-ch2-0s03h r \

s02-ch2-ch2-0h oh

° 2N '^ r ^ yNH2

V

S02-CH2-CH2-0 £ 03H

618 967

6

Example 7

69 parts by weight of the kneaded material prepared in Example la were dissolved in a mixture of 300 parts by volume of water and 150 parts by weight of ice and diazotized with 40.1 parts by volume of 5N sodium nitrite solution. A slight excess of nitrite was destroyed after stirring for 15 minutes with a little amidosulfonic acid after the diazotization reaction. The yellow diazonium salt solution was added to a neutralized solution of 76 parts by weight of l-amino-8-hydroxy-4,6-disulphonic acid (84%) in 300 parts by volume of water. A pH of 6 to 7 was adjusted with anhydrous sodium carbonate and held until the coupling was complete (no more diazonium salt detectable). 50 parts by weight of crystallized copper sulfate were then added, and a pH of 4.5 to 5.0 was set with 50 parts by weight of crystallized sodium acetate and with sodium carbonate. The reaction solution was stirred at room temperature for 1 hour, then clarified with the addition of 10 parts by weight of diatomaceous earth and evaporated at 50 to 60 ° C.

The residue was ground; 240 parts by weight of a blue-black dye powder were obtained, 63 percent by weight of the dye of the formula

Cu ch „-0os I *

CH0

I z

OSOsNa

S03Na n =

ho3s h-co-ch-

so3h ch2-ch2-0s03h

., 50 parts by weight of chrome alum was added to the present solution without intermediate isolation and the pH was adjusted to 5.3 to 5.7 with crystallized sodium acetate. The reaction mixture was then boiled under reflux for about 10 to 15 hours until there was no longer any metal-free dye in the chromatogram. The solution of the resulting 1: 2 chromium complex dye was clarified with the addition of 10 parts by weight of diatomaceous earth and then spray-dried. A blue-black dye-20 powder was obtained which, using the dyeing and printing processes customary and known for reactive dyes and in the presence of alkaline agents on cellulose fiber materials, gave strong, clear, navy-blue prints and dyeings of very good light and wet fastness properties.

25th

Examples 9 to 17 Furthermore, as can be seen from the table examples below, the metal complex dyes indicated below can be prepared from the compounds of the formula (II) obtained according to the process in a manner according to the invention without intermediate isolation of the diazo component. If the procedure described in Example 7 or 8 is used analogously, the sulfato compounds 35 of the formula (II) given below, where the compounds (A) and (B) were the compounds of the following formulas. In the presence of alkaline agents on cotton and other cellulose fiber materials, this dye provides strong, navy blue dyeings and prints of very good light and wet fastnesses in the usual dyeing methods known for reactive dyes.

A dye powder of the same dye content and of the same good quality is obtained if the clarified dye solution obtained in the preparation is spray-dried instead of being evaporated.

Example 8

70 parts by weight of the kneaded material of the compound from Example 2 prepared in analogy to Example la were dissolved and diazotized as described in Example 7. The solution of the diazonium salt was coupled with 136.5 parts by weight of 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid (53% strength) at a pH of 6 to 7. The resulting azo dye, which in the form of the free acid has the formula

OH

nh,

s02-ch2-ch2-0s03h

.A "'

2 i

45

(A)

ch2-ch2-0s03h (B)

are first diazotized, then coupled in the usual way with the corresponding coupling component specified in the example, then converted into the corresponding metal complex compound by treatment with a copper-, co-balt- or chromium-releasing metallizing agent and the dye obtained in this way isolated by evaporation or spray drying With these dyes (dye powder-55 vern) on cotton, strong, lightfast and wet-fast dyeings and prints are obtained in the shades specified in the examples.

7

618 967

Example compound coupling component of formula II

metal

Color on cotton

10th

11

12

13

14

15

16

17th

(A)

(B)

(A)

(A)

(B)

(B)

(A)

(B)

(A)

-m

H03s so3h ho

1 ^

• cooh so3h oh nh-co-ch, I I

H03s so3h

copper

copper

copper

chrome

Cobalt blue tint. Red yellow tinge. brown

Copper red violet brown

Copper purple

Copper bordeaux

Copper yellow gray black

Claims (7)

618 967 2. The method according to claim 1, characterized in that one carries out the esterification with 1.1 to 1.5 times the molar amount, based on mol S03, of the esterification agent. 2nd PATENT CLAIMS 1. Process for the preparation of compounds of formula II r nh. (I). s02-ch2-ch2-0h in which the / 3-hydroxyethyl isulfonyl group is in the 5- or 6-position of the benzoxazolone ring, characterized in that the reaction is carried out using a 1- to 2-fold equi-molar amount, based on mol S03, on 92 to 100% sulfuric acid at a temperature of 100 to 180 ° C with thorough mixing. 3. The method according to claim 1, characterized in that one carries out the implementation at 120 to 160 ° C. 4. The method according to claim 1, characterized in that one carries out the implementation in a kneading machine. 5. The method according to claim 1, characterized in that one carries out the implementation in a continuously working kneader. 6. The method according to claim 1, characterized in that one produces a product in the form of a kneaded material. 7. Use of the kneaded material produced by the process according to claim 6 as a diazo component for the production of metal complex azo dyes.