CS233731B2 - Processing of water soluble disazo-compounds - Google Patents

Abstract

1. Water-soluble, symmetrical disazo compounds of the general formula (1) see diagramm : EP0076922,P19,F4 in which the formula moieties D, R, X, Y, Z, M and m, occurring twice, are in each case identical to each other and the groups Z are bonded to the benzene nuclei in each case in ortho- or in each case in para-position relative to the ethylenedioxy substituent, and the amino groups -NH- and the groups Z are bonded in the benzene nuclei in each case in meta-position relative to each other and D is the radical of an aromatic diazo component, X denotes a hydrogen atom or a fiber-reactive group which can also have the meaning of the formula member Z defined below, Y is a fluorine atom or a chlorine atom, Z denotes a group of the formula -SO2 -CH=CH2 or -SO2 -CH2 -CH2 -R' in which R' represents a radical which can be eliminated in an aqueous medium under alkaline conditions, or the hydroxy group, M is a hydrogen atom or an alkali metal or the equivalent of an alkaline earth metal, R denotes a hydrogen atom or an alkyl group of 1 to 4 C-atoms and m is the number 1 or 2.

Description

The present invention relates to a process for the production of novel water-soluble disazo compounds, i.e. the technical field of fiber-reactive azo dyes. The novel diso compounds of formula (I) below produced according to the invention are used as dyes.

We have found novel symeeric disazo compounds soluble in water of the general formula 1

to mute ^the 'twice vyskytuujcí symbols D Η X, Ϊ, Z, M and m each have mutually the same meaning and the group Z to the benzene rings are bound always in the ortho-position or in each case in para-position to ethylenf dioKyskupině and amino - The NH- and Z groups on the benzene rings are in each case bonded to one another in the meta-position α

D is the remainder of the aromatic diazo component,

X is a hydrogen atom or, as a fiber-reactive group, 2,3-dichloroquinoxaline-2,4-difluoro-5-chloropyridine-2,4-dichloro-s-triazine,

2-fluoro-4-alkoxy-s-trisinyl having 1 to 4 carbon atoms in the alkoxy moiety, 2-fluoro-4-anino-s-triazinyl or 2-chloro-4-aminnosstrizinyl, both of which are mentioned above is optionally substituted with 1 to 4 carbon atoms, 1 to 4 carbon atoms, aryl and / or 1 to 4 carbon alkyls and all 6 to 10 carbon atoms, all of which are X-reactive to the fiber. bonded to the group D via an amino group of the formula -NR- in which R represents a hydrogen atom or a C1-C4 alkyl group, or X represents a fiber-reactive group Z as defined below or a group of formula -N (R *) ) -2, wherein R is as defined above and Z is as defined below,

Y represents a fluorine atom or a chlorine atom,.

^Z is ^p sku i.nu formula -SO-CH ^ C ^ No ^b about SSO ^ C ^ -CHpsR 'in which

R 'represents an inorganic or organic, alkali-eliminate residue in an aqueous medium or represents a hydroxy group,

M represents a hydrogen atom or an alkali metal such as lithium and in particular sodium or potassium, or an equivalent of an alkaline earth metal such as calcium,

R is hydrogen or C1-C4alkyl and m is 1 or 2.

. When X alone does not represent a fiber-reactive Z group, this X moiety is attached to the D group via an amino group of the formula wherein R is hydrogen or C 1 -C 4 alkyl.

Inorganic or organic radicals R * in the groups? The fiber-reactive SO2-C1-CH2-CHH-sR are, for example, C 1 -C 4 -alkynylphonyloalkyls, such as C 1 -C 4 -alkylalkynyl, C 1 -C 4 -alkyloxy groups, wherein the alkyl groups may be one to the other the same or different from each other and each may contain a carboxy group (of the formula -COOM with M as defined above) or only one of the alkyl groups may contain a carboxy group or a sulH group (of the formula -SO 4 M with M as defined above) such as for example, diethylamino, N, N-methyl-N, N-S, or N, N, N, N, N, N, N, N, N, N, N, N, N, N, N , and preferably a halogen atom such as an atmosphere, a fluorine atom, a chlorine atom or a bromine atom, a thiosulfa group (corresponding to the formula -SO 2 M with M as defined above), a phosphato group (corresponding to the formula -OO ^ M 3, with M as defined above) ), aHonyloxyskpios of the formula -OO ^ NM ^ and es preferably a sulfo group of the formula -OSOy (I and M as defined above).

D is preferably Henylene or naphthyl; an eno group which, in addition to the radical X and the azo group, may contain further substituents customary for azo dyes; such substituents include, in particular: halogen atoms, such as chlorine or bromine, sulfonyl groups, sulfamoyl groups which may be mono- or di-substituted alkyl groups with C 1 to 4 carbon ethers, C 1 -C 4 -phenyl and / or phenylalkyl, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, aryloxy, carboxy, carbamoyl, optionally mono- or disubstituted C1-C4 alkyl, Henyl or C1-C4-phenylalkyl, C1-C4alkyloxycarbonyl and acylamino groups in which they may be acyl C1-4 alkylsilyl, C1-4 alkanoyl or C1-4 alkyl optionally substituted with C1-4 alkyl; on.

Preferably, D is a phenylene group which is optionally substituted by one or two substituents selected from the group consisting of chlorine, bromine, sulfo, C 1 -C 4 alkyl, C 1 -C 4 alkoxy. 4 carbon atoms and carboxy. Likewise, D is a naphthylene group which is substituted by one, two or three sulfo groups.

Further, the lower term optionally used means that the group contains 1 to 4 carbon atoms. Lower alkyl groups which are substituted with an eryl group are preferably phenylethyl and at least benzyl.

Aryl residues are preferably phenyl or naphthyl, wherein the phenyl group may still be substituted by one or two substituents selected from the group consisting of methoxy, ethoxy, methyl, ethyl, chloro, carboxy and sulfo, and the naphthyl group may be may still be substituted by methyl, ethyl, methoxy, ethoxy or carboxy or chlorine and / or one, two or three sulfo groups.

Fiber-reactive groups X which may be contained in the disazo-entities of the general formula (1) according to the invention are widely known in the literature for fiber-reactive carbocyclic and heterocyclic radicals as well as aliphatic series, but preferably 2,3-dicillin-lithium-carbonyl radicals, 2,4- a difluoro-5-pyridopyrimidyl residue, a 2,4-dicloro-a-eizinyl radical, a 2-cllue-4-alkoxy-s-triaziiyl radical having 1 to 4 carbon atoms in the alkoxy group and 2-cllue-4-eminyl triaziiyl radical in which the amino group may be substituted by C1 -C4 alkyl radicals, aryl radicals and / or C1 -C4 arylalkyl radicals in the alkyl moiety as well as the aforementioned group Z, which are reactive towards the fiber and are bonded to the group D via the aforementioned -NR 1 - group; or the group X is represented, as mentioned above, by the group Z itself, which is reactive to the fiber.

The sulfuaminoniftyl components of the compounds of the invention, which are evident from formula (1), are preferably derived from the following eminaphtholsulfonic acids: from k-emno-8-nef tol-4-disulfonic acid, 1-amino-8-non-tolol-4,6 2-amino-8-naphthol-6-sulfonic acid, 2-ethylamino-6-naphthonic acid, 2-amino-5-difluoro-7-sulfonic acid, 2-ethylamino-5-nitro-sulfonic acid 7-sulfonic acids, 2-8-amino-3-nitro-3,6-difluoroic acid, 2-amino-5-methyl, 7-di-phthalic acid, 2-amino) -8-aoleol-5-phosphonic acid.

The novel disazoalkanes of the general formula (1) can be present both in acid form and in the form of their salts, such as in the form of sulfonic acid salts. Preferred are the compounds in the form of their salts, in particular in the form of alkali metal and alkaline earth metal salts such as sodium salts, potassium salts and calcium salts. These compounds will preferably look in the form of alkali lipid salts for dyeing and printing preferably fibrous materials.

According to the invention, diaazo-compounds of the formula I are produced by the known azo compound of the formula 4:

OH

Y in which

D, M, R, X, Y, and · in mmjí abovementioned meaning ^ 'is reacted in an aqueous medium at a temperature between 20 and 5 ° · C above ^hr for ^d n ^of between 25 · and 3 ° C and s ^{p h} o ^d Note pH of between ² 0 and ⁷ °, preferably between

3.0 e 5.0, in an equivalent amount (i.e. 2 mol of compound of formula 4 per 1 mol of compound of formula 5 below) with a symmetrical diamino compound of formula 5

in which ^:

Z has the same meaning as above, and the Z groups are bonded to the benzene nuclei in ortho- or para-position to the ethylenedioxy group and the amino and Z groups in the benzene rings are always in the meta-position to each other.

In addition to the process according to the invention, the novel disazo compounds of the formula I can also be prepared, for example, by the preparation of a compound of the formula 2 which is previously known and described below, which is described twice as described below.

(2), in which the two occurring symbols M, R, Y, Z and m have the same meaning as previously defined, and the amino groups -NH-, Z and ethylenedioxy are bonded to each other on the benzene rings given for formula 1, coupling with an equivalent (double equimolar) rating of the diazonium compound of the aromatic amine of formula 3

HgH - D - X (3) where

D and X maj above meanings, obvyto MAO-ovi ^d Borne ^to MDs ^at běSSným with ^{b em} in the aqueous medium when the heat-· I between .0 ° C and ⁴⁰ ° C above odně ^h between ⁰ ° C for 1 2 e ⁰ C and at ^{a pH} between ³ and 7.0 ^θ is preferably between ^5.0 and ^6, the fifth

The azo compounds of formula (4), which are used as starting materials in the process of the invention, can be prepared in a conventional manner by coupling a compound of formula (6).

OH

Y in which

M, R, Y and m have the meanings given above (6), with the diazonium amino compound of the above formula (3)

The compounds of formula (2) which are used as starting materials in a further process for the preparation of the compounds of formula (1) are novel compounds, these novel compounds of formula (2) are prepared by reacting a compound of formula (6) with an equivalent amount of diamine. of formula 5 at a temperature of between 5 and 50 ° C, preferably between 10 and 25 ° C, and at a pH of between 3.5 and 7.0, preferably between 4.0 and 5.5, or by the diamino compound of the above general formula of formula 5 reacts with a double molar amount of 2,4,6-trifluoro-s-triazine or 2,4,6-trichloro-s-triazine in an aqueous or aqueous-organic medium / pH at a temperature between -10 ° C and + 15 ° C and at a pH of between 2.5 and 5.5, preferably between 3.0 and 4.5, to give a symmetrical compound of formula 7

O-CH ₂ -CH ₂ -O,

OF

Y

NH— (Ai

Y (7), in which:

each symbol Z and each symbol Z has the same meaning as defined above, ethylenedioxy, groups bonded to benzene nuclei, and condenses in a conventional manner

-NH- and Z groups are each other, this compound of the general formula aminonaphtholsulfonic acid as usual and of the general formula shown for formula 1, for the expert 8

(SO ₃ M) _m (8), in which

M, R, and m have the above meanings, in an equivalent amount (2 mol of the compound of formula 8, not 1 mol of the compound of formula 7)

The hitherto unknown diamine compounds of the general formula 5 are described in DE-OS 31 29 4θ1. these compounds can be prepared by using ethylene glycol bis-aniline ether as the starting material, and this compound is acetylated analogously to known methods to the N, N'-bis-ethyl-amino derivative; to this compound again using chlorosulfonic acid and thionyl chloride, such as described by Houben-Weyl, Methoden der Organischen Chemie, Vol. IX, p. 578 (1955), preferably at a temperature between 40 and 50 ° C, introduce one sulfochloride group in each of the benzene cores, followed by reduction of the sulfochloride groups with an alkali metal sulfite, especially sodium sulfite, in the presence of an alkali metal hydroxide in aqueous solution at a temperature of between 0 and 60 ° C and a pH of between 7 and 10 to sulfinic acids, these groups are then re-ethylated to beta-hydroxyethylsulfonyl derivatives by treatment with ethylene oxide in the presence of aqueous sulfuric acid or ethylene chlorohydrin, for example as described in Belgian patent 747,418. and these are then de-ethylated by treatment with an inorganic acid.

the diaminocompounds having beta-hydroxyethylsulfonyl groups thus obtained correspond to the compounds of formula 5, in which Z is a beta-hydroxyethylsulfonyl group, these beta-hydroxyethylsulfonyl groups can be converted into the Z groups with the meanings indicated for formula 1 in accordance with known methods, e.g. by esterification with a sulfating agent to the corresponding beta-sulfatoethylsulfonyl groups.

Compounds of the formula 2 obtained according to the invention can be used as kopdační ^components recited the cells for in the mites ^to u, i.e. with REA ^ the mixture obtained in the synthesis, or ^C o oeziizolaci for the production of azo compounds, in particular for producing disazo compound of the formula 1 according to the invention . The isolation of the compounds of formula (2) from their reaction solutions is carried out in a customary manner known to the person skilled in the art, by salting out with electrolytes such as sodium chloride or potassium chloride, or by spray drying.

Disazo compounds of formula (I) produced by the process of the invention are also and isolated by generally known methods, such as salting out of the reaction medium with electrolytes such as sodium chloride or potassium chloride, or evaporation, such as spray drying. directly as a liquid dye preparation, the solution formed by the detergent compound of the invention, optionally after addition of buffers or / or after optionally thickening.

The disazo compounds of the invention possess valuable dye properties which, due to the presence of the Z residues and possibly the adjacent X residues, are reactive to the fibers. These novel compounds are used as dyes, preferably for dyeing (in general) materials containing hydroxy, amino or carboxamido groups. Accordingly, the present invention also relates to the supply of compounds of the formula I for dyeing and printing such cuts, or for dyeing and printing such ogatrials by conventional methods using dyes of the compounds of formula 1. Preferably, these materials are used in the form of fiber fibers, in particular in the form of textile fibers.

The hydroxyl-containing material is natural or synthetic material^jtydroutygroups, such as^toice vlátoiita ^ e^and^ e ^ i ^^^^y z crluloz^with or from her CD^GE Not to produce products^bo polyvinyl alcohols, cellular storage theaters are cotton, but also other filaments such as flax, hemp, jute and frame fibers, or regenerated cellulose fibers, such as e.g.^kland^d biuitaita stata and vlskzozové^hit is the same^tolike paper.

The carboxamido-containing groups are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal fibers, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyaoid-4.

By means of the distzoelectric compounds according to the invention, a dyeing with a very good dye yield is obtained, for example, on the cellulose fibers by the pulling-out process using a variety of alkalis as additives from a long bath. The compounds of formula I dye cellulosic fibers using known methods, also with excellent dye yields, which can be fixed with alkali as additives by dwelling at a temperature of about 10 ° C, steaming or dry heat.

Pooooí obvyklýc taskařs ^h ^ t ^P u ^p Ostu for C ^ u ^ ov vlátoa ^1, I ^ ^to about Jeto pink, napřínad pooooí printing with a printing paste containing sodium eeшUhiδitanu Uydró ^g, paint ^^ 1 ^ 1 ^ acetate or other binding agent acid, and subsequent steaming at a temperature of 101 DEG Ю3 ° C, the ^knots of pottatěněto ma ^ e ^ iálu or dvoirfázově, napřínad printing with a neutral Neto s ^ of tysebu thousandth ^p Asta β successors fixation either vesním ^t and ^kt of after-eten ^ o oetartalu .

a hot alkaline bath containing an electrolyte or an overnight alkaline bath with an electrolyte content and a delay, steaming or dry heat treatment of the overnight material will also produce color-intensive prints with good contour status and a bright white pool. Rwaita printing is little dependent on fixation conditions. Therefore, these prints exhibit a very satisfactory amount of shades.

For application-related reasons, particularly preferred compounds of the formula I are those which contain, as a Z-residue, reactive towards the filaments with a tert-sulfonyl-sulfonyl group, as well as those dyes which contain the heterocyclic reactive radicals X described in the description. -NR-.

The dyeings and prints obtained using the compounds of formula (1) on cellulose fibrous materials have very good stability; of these, it is necessary to emphasize in particular the most important constraints on production and use, such as light stability, · stability in linen, for example at 60 ° C or 95 ° C, acid and alkaline in washboard, water and seawater , dyed, alkaline and acidic perspiration, pleating, ironing and abrasion.

The polyamide fibers are usually dyeed from an acidic medium. Thus, for example, acetic acid, acetic acid and ammonium acetate or sodium acetate can be added to the dye bath to achieve the desired pH. The addition of the usual leveling aids, for example based on the reaction product of cyanochloride with a triple molar amount of aminobenzene- and / or thininiatalentulphonic acid or on the basis of a reaction product of a fatty amine such as stearylamine, for example with alkylene oxide, is recommended ethylene oxide. Dyeing can be carried out usually ^p s te ^p lot ^and CH from ⁶⁰ to 1 ° 5 ° ^C, preferably · ^p s in ^y t, and ^h cheer procedure at boiling temperature teavicí ^lά harvest ^or the ^TBE in the establishment of a ^p racujícím · a " tlateu at te ^{Lot P} ch to 12 ° C.

The following examples serve to illustrate the invention. The parts referenced in these examples are thicker parts, percentages represent percentages of fertilizers unless otherwise indicated. The parts are parts by volume in a ratio of kg to liter.

The compounds described in these examples by the formula are given in the form of free acids. In general, these compounds are prepared and isolated in the form of their sodium or potassium salts and are also used as dyes for their salts. Likewise, the starting compounds and components mentioned in the following examples, in particular in the table summarized form, in the free acid form, can be used in the synthesis as such or in the form of their salts, preferably in the form of alkali metal salts, as in the form of sodium salts or potassium salts.

Example 1

To an aqueous solution of 46.7 parts of 1- (4,6-Uicalor t-triazin-2- ^yl ltmino) -8-3,6-nittol Uitulfonov ^E k / NY-sowed at -Temperature 1 ° and ^{15 C p} and ^d s ^h o note ^pH 2.5 ^p s ^d and neutral solution of 31.1 parts of ^ethylene-y Koo bi8- (4-tminio22ЬitttstUfaaoettalsuUl'onilfennl) ether at 15 ° parts of water. The pH of the reaction mixture was maintained at 6.0 with sodium carbonate throughout the reaction. This condensation reaction can be monitored by thin-layer chromatography. product of formula (given in free acid form)

Thus, it can be characterized as a double-coupled coupling component for the production of a purifying compound, characterized by a chromatic chromatographic comparison with a starting material and optionally by-products, as well as its functions as divalent coupling components.

After completion of the reaction, the condensation product is precipitated with sodium chloride, filtered off, washed with a 1% aqueous sodium chloride solution and optionally dried. In this way, the sodium salt of the compound of the above formula is isolated, which can be used as a coupling component for the production of red, particularly brilliantly red disazo compounds with very good properties of dye reactive dyes.

Example 2

To an aqueous solution of 46.7 parts of 1- (4,6-dichloro-s-triazin-2-yl-amino) -8-naetole-3,6-dieulfonic acid at a temperature of 10-15 ° C and a pH of 2 5 ří.d ^{p o} n u ^! ^ n ^{d, and} LN 32 ^the organic ^solution, 7-duo ethyleoglykol'bis "(4-emioo-2-beta-LF ⁰ thiosulfetoethyl ^sυ oylfeoyl) ether in 200 parts water. The pH of the reaction mixture was adjusted to 6.0. This condensation reaction can be monitored by thin-layer chromathography. Reaction product of formula (given as free acid)

which can be used as a compound according to the invention as a double-coupled coupling component for the production of sausages, can be characterized by chromatography (thin-layer chromatography) with the starting material and possible by-products, as well as its functions as divalent coupling components .

After completion of the condensation reaction, the compound of the invention is salted out with sodium chloride, filtered and washed with 20% aqueous sodium chloride solution and optionally dried. In this way, the sodium salt of the compound of the above formula is isolated, which can be used as a coupling component for the production of red, especially brilliantly red, disazosulfonates having very good color fastnesses.

Example 3

To an aqueous solution having a pH of 3.5 38.7 parts of 2- (4,6-dichllr-s-trtaz0n2 - ytamiol) -5-otftl ^{L-7 L-l} lul onlvé acid at 1 ^0-15 C was added ^and the neutral solution of 31.1 parts ethyleIn> lyktl-bis- (4-tminol22beea зulfatoethylsulflOylfeoyl) ether in 150 parts water. The reaction mixture was adjusted to pH 6.0 by addition of sodium carbonate and maintained at that pH throughout the reaction. The condensation reaction can be monitored by thin film condensation. Reaction product (shown as free acid)

which can be used as a compound of the invention as a double-coupled coupling component for the production of distillation, can be characterized by chromatography (thin-layer chromatorraphia) by comparison with the starting material and possible by-products, as well as its functions as divalent coupling components.

After completion of the reaction, the compound of the invention is salted out with sodium chloride, filtered and washed with aqueous sodium chloride solution and optionally dried. In this way a sodium salt of a compound of the above formula is obtained, which can be used as a coupling component to produce orange-colored disazo compounds with very good fiber-reactive dye properties,

Example 4

A solution of pH 6.8 of 31.1 parts of ethylene glycol-bls- (4-amino) 2-beta-sulfatoethylsulfonylphenyl) ether in 100 parts of water is stirred at 5 ° C into a suspension of 18.8 parts of cyanuric chloride in 30 parts of water and 30 parts ice. Until the reaction is complete, the temperature of the reaction mixture is maintained at 5 ° C and the pH is maintained at 3.0 to 3.5 ° C. A clear solution of this condensation product is then added to a pH 6.8 solution of 25.3 parts of 2-N of methyl-amino-5-naphthol-7-sulfonic acid, the reaction mixture is adjusted to pH 6.0, heated to 60 ° C and maintained at this temperature for 2 hours. The condensation reaction can be monitored by thin layer chromatography. Reaction product of formula (depicted in free acid form)

which can be used as a compound of the invention as a double-coupled coupling component to produce disazo compounds can thus be characterized by chromatographic comparison (thin layer chromatography) with the starting material and possible by-products as well as its function as a divalent coupling component.

Upon completion of the reaction, the compound of the invention may be isolated in a conventional manner, such as that described in the preceding example, and further processed to reaction products (disazo compounds).

Naturally, further processing is also possible using a solution obtained by synthesis, i.e. without intermediate insulation. Using this compound as coupling component, orange to red disazo compounds having very good fiber-reactive dye properties can be obtained by reaction with other conventional diazo components.

Example 5

To a solution of pH 6.9 31.1 parts of ethylene glycol bis- (4-amino-2-beta-8-sulfatoethylsulfonylphenyl) ether in 75 parts of water at 5 ° C was added dropwise with good stirring 13.6 parts of cyanurfluoride while the pH is maintained between 3.0 and 3.5 with sodium bicarbonate. After stirring for 10 minutes, a suspension of pH 6.7 of 23.9 parts of 2-amino-5-naphthol-7-sulfonic acid in 150 parts of water was added to the clear solution. The reaction mixture is then adjusted to pH 5.5 and stirred at this pH for about 2 hours at about 20 ° C and then for one hour at 50 ° C. This condensation reaction can be monitored by thin layer chromatography. Reaction product of formula (depicted in free acid form)

The compound of the present invention, as a double-half coupling component for the production of di-carbonates, can be used as a compound of the present invention by chromatography. and thin layer) by comparison with the starting material and possible byproducts, as well as its function as binder coupling components. The compound of the invention is isolated in a customary manner, for example according to the data contained in the above examples. This compound can also be further processed without intermediate isolation in the form of the resulting reaction solution, to produce orange-colored disazo compounds by coupling twice as much as the diazo component. The di-compounds thus obtained according to the invention are disclosed in FIG. very good fiber-reactive dye properties.

Example 6

To a solution of pH 6.9 of 31.1 parts of ethylene glycol-bis- (2-amino-4-beta "8ulfatoethylsulfonylfenyl) ether in 75 says ^ ch water ^for at 5 ° C under stirring piHtope ^13, 6 ^to Dito yanurfluorSdu wherein the pH of the reaction mixture is maintained between 3.0 and 3.5 using sodium hydrogen nitrate. After stirring for 15 minutes, a suspension of pH 6.7 of 31.9 parts of 1-amine-8-biphenyl-6,6-bisulfonic acid in 60 parts of water was added to this solution. Ta.to reaction mixture was stirred at ^{pH 5.5 h} Odnoo most expensive ^ 2 hours in ¹ s ^{p p} te ture ^{of 20} ° C and ^{p h} o Otom one-yne at 5 ⁰ ° C. Condensing ^the rea tion may with OVA ^{d l} e ^t ^ AflII chromatography on thin layer. Reaction product (shown in free acid form)

SO ₃ H SO ₃ H can be used as a compound according to vinal as a double-copolymerizable coupling component for the production of distososololeyey and can therefore be characterized by chromatography (chro ^2O2-8 ^ thin layer) by comparison with the starting material and possible by-products as well as its functions as a divalent coupling component. This compound is isolated in an aqueous manner and, after reaction with conventional diazo components, provides a red disazo compound with very good properties of the dye-reactive dyes.

Example 7

The 17.3 parts of the sulfonylbenzoyl is diazoitized in an aqueous solution in the usual manner and 74.1 parts of the compound according to the invention (Example 1) are added, for example in the form of an aqueous suspension. The pH of the coupling mixture was then adjusted to between 6.0 and 6.5 with sodium aluminate and maintained throughout the coupling reaction. After completion of the reaction with the distosyl salt, the vin is isolated by hanging with sodium chloride.

2.337.31 or by spray drying. A dark red powder is obtained which, in addition to the electrolyte, contains an alkali metal salt of the compound of the following formula, predominantly sodium salt, of the compound of formula

This disazosloučeninn of the invention has very good dye properties and dyes .As \ £ gybarvov; cÍJai and printing processes customary for reactive dyes fibrous' cellulose materials in the presence of an alkali such as sodium bicarbonate, sodium carbonate or sodium hydroxide aqueous solution .. ^ ¹ in full of bright red shades with very. good stability, use and production, in particular with very good wet stability and very good stability. iiíš světlin

Example 1 a d 8

30.3 parts of 2-naphthylamino-1,5-disulfonic acid are diazotized in an aqueous solution in the usual manner. 80.3 parts of the compound of the invention (coupling component) described in Example 2 are then added to the suspension of the palzonium compound, the pH of the coupling mixture is adjusted to 6.0-6.5 with sodium carbonate and the coupling reaction is completed by stirring for several hours. range of values рЯ _а

The disazo compound of the invention is salted out with sodium chloride, filtered off with suction, dried and ground. A red powder is obtained which, in addition to the electrolyte, contains an alkali metal salt of a compound of the following formula, a predominant sodium salt of the formula

This disazo compound of the invention exhibits very good dyeing properties and dyes using brilliant red shades of cellulose fibrous materials such as cotton using the dyeing and printing methods customary for reactive dyes. These dyeings and prints have very good fastnesses in use and manufacture, in particular very good wet fastnesses and fastnesses to light.

Example 9

38.3 parts of 2-naphthylamine-1,5,7-trisulfonic acid is diazotized in a conventional manner. 69.8 parts of the compound of the invention (coupling component) of Example 3 are added to the aqueous solution of the diazonium compound with stirring and the pH of the coupling mixture is adjusted to 5.5 with sodium carbonate. After stirring for several hours at this pH, the coupling reaction is terminated. The disazo compound of the invention is salted out with sodium chloride, filtered off, washed with aqueous sodium chloride solution, dried and ground. A red powder is obtained which, in addition to the electrolyte, contains an alkali metal salt of the compound of the following formula, predominantly a sodium salt of the formula

SO3H OH

This disazosloučeninB has as colorant very good properties and colors using various staining and printing methods customary for reactive dyes in the presence of alkali such uhličitmu sotoého, hydrogennhMčitenu sodium ^é him or ^originally it sodium hydroxide ^eh o cedulózové materials in bright orange shades having particular good light fastness and very good wet fastness.

Example 1C

20.3 parts of 4-amino-thiol-3-sulfonic acid are diazotized in water in the usual manner, and 71.2 parts of the compound of the invention (coupling component) described in Example 4 are added from the mixing by stirring. the sodium carbonate was adjusted to between 6.0 and 6.5 and maintained in this range until the coupling reaction was complete.

The disazo compound of the invention is isolated by spray drying or salting with sodium chloride. A red powder is obtained which, in addition to the electrolyte, contains an alkali metal salt of a compound of the following formula, predominantly a sodium salt of the formula

This compound of the present invention exhibits very good wavelet reactive dye properties and dyes the materials described herein, in particular cellulosic fibrous maaerials, by the dyeing and ticking methods customary for fiber-reactive dyes, such as in alkaloids such as sodium carbonate or aqueous carbonate. sodium hydroxide, in scarlet red shades. The dyeings and prints obtained using the disazo compound of the present invention exhibit very good stability in use and manufacture, in particular very good light fastness and very good wet fastness.

Example 11

The production of the disazo compound according to the invention is carried out as described above. In Example 9, however, the coupling component used therein in Example 3 is replaced by the equivalent amount of the compound of the invention described in Example 5 '(copolymer) in the coupling reaction. Upon completion of the coupling reaction and conventional work-up, the salt of the compound of the following formula is obtained as the sodium salt of the compound of formula o-ch ₂

SO ₃ H ^H0 3 ^S

-CH2-CH2-OSO3H

O-CH ₂

SO3H

This disazo compound according to

SO ₃ H ^H0 3 ^S to the invention shows very good properties even: rviv fiber-reactivity and providing for mattriálech mentioned in the description, such as in particular cellulose fiber materials, for example cotton application and fixing methods customary for reactive dyestuffs vlálmům dyeings with prints in bright orange shades with very good wet fastnesses and good light fastnesses.

Example 12

9.3 parts of aniline are diazotized in water in a conventional manner. To the aqueous solution of the diazonium compound is then added 77 parts of the compound of the invention (coupling component) described in Example 6, and the coupling reaction is carried out at pH 6.0. The disazo compound is then isolated as usual. by a method such as salting out with sodium chloride, filtering off and washing the product with an aqueous sodium chloride solution. After drying and grinding a red powder is obtained which contains, in addition to the electrolyte, a sodium salt of the compound of the formula

I 1

SO ₃ H SO ₃ H

This compound showed a casing very good properties and dyes coloring and tiskařslými processes customary for reactive baurriva and conventional fixing methods fibrous maaeri ^a l ^y z oelu ^{e Ozy,} I ^OZ cottonseed ^ in jasnýc ^h red speedily removal of the ^ i ^d giants stability in use and production, especially with very good wet stability and good light fastness.

Example 13

18.7 parts of 1-amino-4-methylbenzze-2-sulfonic acid are dissolved in 150 parts of water with the addition of sodium carbonate at pH 6.8 and 20 parts of 5N are added to this solution.

4 sodium nitrite solution. The suspension obtained is mixed into a mixture of 30 parts of 31% hydrochloric acid and 100 parts of ice. The reaction mixture was stirred for an additional 1 hour and then the excess nitrous acid was quenched with amidosulfonic acid. An aqueous suspension of 46.7 parts of 1- (4, 6-chloro-s-triazin-2-ylthio) -8-oaftol-4,6-di8Ufonic acid, pH 3.5 cooled to 5 ° C, was then added to the reaction mixture. Noc: 2 ° C. This reaction is ^p rov ^and di- when -teplotě Ю ° C and at ^pH 5.5.

Then the reaction solution was 31.1 parts of SIIS eth Len ^^ ^^ ly ^ <^ o-bis-4 ^ ^{<^} ^ imine 2-ta-be-sulfatoethylaulfonylfenyl) ether in 150 parts of water, adjusted to pH 6.8. Value SM ^ i at ^P ^^ Toh Ravi N-NEM sodýfa to ^pH 5.5. JaknHe ^'CZK rea the temperature remains at 2 ⁰ ° C ^to on6tantní values heated mixture ^P s ^{pH 5} 5 ^ST E Jeto hocHnu ^T emperature on 5 ⁰ ° C.

The reaction mixture was cooled to room temperature and the reaction product was precipitated by the addition of sodium chloride. After drying and grinding, a dark red powder is obtained which, in addition to the electrolyte, contains a salt of the compound of the following formula, predominantly the sodium salt of the compound of the formula

In the presence of alkali to this disazo achieved using conventional dyeing and Hslcařských procedures yl ^ knitych Nátr ^ lechi ce ^l u ^l oz ^y clear ^{and 'red} warning ^and color with excellent fastness to use and during manufacture, especially with very good wet fastness properties and with very good light fastness.

Examples 14 to 34

The following examples summarized in the table below illustrate other disazo compounds according to the invention which correspond to the general formula (1) using their starting materials. These compounds can be prepared from the appropriate starting materials by the process of the invention, for example by the methods described in Examples 7 to 13 above.

These disazosloučenlny invention mm, it is also very good properties of reactive dyestuffs fibers and dyed using the application and fixing methods customary in the art, particularly by methods customary for dyes which are fiber-reactivity, materials Uve e ^{d descriptions for} j ^and for zejmtoa VL threads chaffing against ^ m ^ r ^ ly from ^p řírodní regenerate ce ^l u3.ozy ⁱⁿ color strength and permanent shades that are always given in the table.

as d ω '>> N th >О> Μ H Φ P 3 Ci ИН as X Φ X> O U

Ф x: p

Φ

x>

AND

o H and X3

I kO

MCM d • Y N

Honor • A

Ch -P

I <0

HsJ

O

H

WHAT

O

N

Honor atl

AI

H m • A H 3 O i β and φ <P H X) p tf and Φ O H X) <P O and H Al cm 3 >> AND no H O H 00 a and • A 5 φ El P H 01 Φ Ch >> O Φ AND + -P X! P x_z P Φ and Φ

AND

'>} O '>> '>> and d > d ω φ O Ф > > H > and h 01 Cl φ φ •AND Ф ю XJ <P Ю

>> ø> o> N d ati Ch o t

H and >> X! -P Φ O M- -p X_Z O Ch and Φ w H x: •AND 3 P X) O φ and t H O H O P >> AI Φ d í >> XJ φ H and <A 00 <M i r4 Cl >> Φ O d H and O >> •AND «Ρ xl and H P O 3 φ and W

'>> d

IU

K>

Whose Φ x: and P 66 Φ <P H H 2 >> AND m d AND m 1 ω O • H ® •AND x> P H X) AND φ & | H X) and rA O 1 O O -M Μ- «Η Al >> ι H >> H 0 3 H 00 d WHAT M and •AND H and Φ H and « Ř φ H >? x: 1 CM P Φ £ P O P φ AND P Φ

Ό XJ • H •AND 14 Ch O O H 5 Λ H O <P C Whose 3 3 d and and O >> >> AI Al

H XO O > P O and O O d ao <P H 3 l W O O •AND ^d and XJ •AND •AND AND H with X) Φ O no and m >> and AI

O H č

Ή> O

TS X? Ό Ό Ό XJ •AND •AND • H Ή •AND •AND Ch AND and Whose Whose O O O O O O H H H rH H H Λ XI X! xí X1 xs AT O O O ϋ O Whose Ch Whose 14 and and 3 3 3 3 3 2 and and and and and and O O OJ honors я 0 AND? >> Al á> £ >> Al >> AI

H XO O > P O <H and O O d Sa and r-A ao 3 and w O O •AND and J and X? •AND •AND and H 1 and Ό Φ O n and xT i IN

i ai and • A H

Φ

H xo H O H XO O > O >> O > P O -P Af p O <H and <P ^ A d O O O XO O O and <H 3 > and <H and H and O and H what 3 ao d ao 3 and tn O and O and O O O •AND d O <A O •AND d 3 XJ •AND d H d XJ • Α AND and H •AND 3 AND and H and X Φ and O3 and X) Φ O * O O and O - O and m >? AND X) t m >> and Al OJ ! · - and Al

and

Η

O P <P d

oO i d • A toethylsulfolylphenyl) ethe:

O d •AND O H d XO xo XO Φ and •AND > and > and > O CM H O H O Ch O > » Φ d >> d O d and l Al d O O x: O H O O H •AND >) <P p <P x: Vi Ά O O XO H AI H φ H O H H d O > •AND 3 and 3 and 3 3 •AND d •AND O d XO O and O M O O H •AND d d O > and Μ- t and and and Φ Ό O O AND O <3 ι 'O O H X? 5 μ- O «А 3 o d <V | H Whose O d O ¹ d • A 1н O and d •AND 2 d d • A ι d with H •AND 3 H AND H H •AND r4 P •AND H •AND O and O x: H H Φ XI H Φ Φ H Φ H xB -P O i AND O 3 •AND O ϋ •AND O and •AND O ♦ A > and m and and O d >> and and >> and d >> d O and M- m- and O Al rO O AI n O AI O d

lT \

AO

CM οχ o CM

h сб X

X rH Φ ř »> rH if >> (0 X 1 P 0] φ • rd x P 1 40 rd 3 > O li • rd Μ Φ Й > * X Φ rd p 45 60 Φ

> N

O rd

WHAT

O

N «• rd 43 >>

>

о

I co • rd X

I> 5 rd £

x P φ • rd

Й O q fp <K

t rd

O íd

AND

LÍX

I o a • H в сб

I (XJ

I ií \

<6 a

I (XJ

MS)

d H Λ Ή> h fl

O

H

CO M KJ ω S t

Λ P Φ X (XI

I o a • rl §

s • rd rd

Ф

Λ> O d o r r-d 3 CO • rd

AND

O P <B l <ω X P rd ω r ~> «0 rd <0 1 >> • rd Λ and X P ω 1 φ rd X rd O 1 >> Λ4 (XI q >> 1 O rd O ^ d Ы and rd q • rd 3 φ 0 WHAT rd β rd s> 1 > » X P P Φ 1 Ф

TJ • H li o 3 rd li a &

AND

01 1 r-s rd rd 3 >? 1 WHAT q w 1 0) • rl (β Ή X P rd F Φ >> rd X q O 1 O M <l «Η >> 1 rd H O 3 60 d (0 d -d rd φ 0 > » rd 0 X2 > » 1 P Φ X Φ X P ч-z O P Φ 1 P φ

• rd li o rd x o • rd li o rd x o li s Л4

<6 d • H rd 1 Φ 1 rd 10 ^r ď XO O P Sl O P > o ^ d <0 q φ OJ Λ O and > d <H 1 O 1 rd ll \ and oo 3 1 O 1 WHAT сб O <H O H and and rd d Ό • rl • rd 3 d 1 rd 0 what 0 O Φ ti 1 <0 WHAT 1 r- 1 > » <\ 1 1 1 -M

R • rl li

O rd X

O li a

*

Д4

d 4 ι Φ d of- n • rd 00 ι <0 1 O n rd and d 3 AND O d ⁿ Φ • rd 1 φ • d t • h and C, ι • rl q w 1 1 rd if ι N rd and. 0 rd rd Й 0 • rl >> Ή q Φ O (0 d Φ O and- >> 3 O (0 and X Ό AND φ 0) rd Ή φ n rd rd F Oj rd rl WITH | q SJ >> x: if X >> X >> M AND X >> rl ΧΌ X • η d X O P r-s λι O q | x O q > » ;> л N φ 1 1 O 1 o> d ¹ λ ι φ ι O d · 00 X) 'OJ • ο- what q 'OJ * d rd q d -E * d M q rd > ι • rd > i — 1 í — I N ÚJ> rd L_J O ι O 1 if O O ι ř >> 0 O 1 >> «6 N H ι «Η d P d d X «6 d <n ^xf • rd C; φ m rd • r4 rd AND • rl O ι O rd O and + ' if ó '« ι 3 tSJ 3 O 0) 0 0h O X <H O φ p · ' O ο d 1 0 rd d P ι rd d 1 • Γ-- _Ί , M d ι • rd AND • rl If rd 3 • r | Φ (XI 3 • H n Ή C3 L < X 0 O >> 0 0 M Θ | с: 'Л 0 P ι Λ rd 1 1 Λ ι d AND (0 F • d> C0 ι ι q | X (XI X AND 'o  η V O AND vO O N O ι O « φ - AT 1 1 r- 1 N ι · - 1 d a · a ι ι N

CM M · ux ΛΙ <XI XI (XI

(4-aainol Enri) ^_ 1-amino-8-Nal tol- cyanuric ethyleneglycol-bis- red

- (beta-sulfatoethyl) -3,6-diaulfonic acid - (- amino-2-beta-sulfasulfonic acid Oethylethylsulfonylphenyl) Dethrr rCU Example 2,4,6-halo-s- ethylene glycol derivative- color number diazo component and component -triazine-bis- arylether shade on cellulose

no x: X3 1 P 1 -p 0 Ф 0 Ф <P ~ <P H H H H 3 & i η a 1 Ф Ю I Ф 0 «И • H 0 <H P H ΌΡΗ 2 & ¹ X h r-ι ό я 1 o o I o CM <P M (\ l <P 1 r-4 >> · H O Я 1 НОЯ Я CT í M 0 no • H rH 1 я · Ρ Η § 2 >> 0 >> н 0 я 1 ** >> 1 ρ Ф я μ · φ O 1 P Ρ ο Φ 1 Ρ

> O P

> o

<4 Я

O

&

Ф> Я

Ф Ю

Η χβ ο > • Ρ ο <Ρ я 0 ο я <Ρ 1 Η 00 я 1 00 ο нЧ я Ό • Η 1 6 <0 0 1 ’Φ 1

• H Я O

H Л o

O H Ρ φ

Ž ст ž

Φ 1 ή Η Η я > 9 ст я ст 1 φ • Η 0 «Η Ό • Ρ Η 1 Φ > 9 Η Ό я ο 1 Ο СМ <Η >> 1 Η Η ο 3 ад я ОТ я • Η Η φ Η а 0 £ ρ >> AND Ρ φ Χ3 • Μ- φ Я Ρ ο Ρ ω ι Ρ φ

Η χο ο > Ρ ο «Ρ 8 я ο <Ρ 1 Η 00 2 1 1 от 0 ο • Η Я 1 я Ό • č .ρ 1 Η а Ό φ 0 ст 1 m > 9 »- AND Λί

0 • č я Η • č 1 φ Η 1 0 1 ι φ « ι 1 0 Η ο я ο а Η Η > 9 Η <Η 0 1 • Η α 1 CD 1 >> > » 1 Λ1 >> 1 Η • Η я 6 · .- < χπ Ь AND 1 я О χ: XJ Η X? Η я я ο 0 а > О 1 OJ 43 H -Ρ Ρ > 9 ΧΒ Ρ > 1 χο 0 0 я Η 0 ο я H 1 1 H н 1 φ φ Ρ > φ Ρ > 1 Η Η >> Η α Η я Я Ф я ο ο <Ρ ο ο «Η ο 0 «Η я > 9 ο * н я • H Ф ОТ ст Η Ρ Ρ 0 я Ρ 0 я Ρ я 1 φ 0 1 Ф N N >> • н >> 0 0 α ο 0 я ο Φ ο <Ρ CXJ Η Ш я Λ то я AND? <Ρ <Ρ <Ρ <Η 1 <Ρ ό <Η ο 1 я O • H Φ 1 • č φ Η Η СМ Η Η (IN Η 1 Η 1 <й я 0 t <♦ 4 ti Л 'Л LCX н <Η я я 1 3 Я 1 3 Μ * я <η Η • No AND m H P ф ο Λ ст Η СО ОТ Η Λ 0 1 ст 1 я N 43 1 я and ^r o ¹ Ο см 0 я 1 AND >) t AND 1 а ο Η ο 0 0 1 O ст ОТ я я 1 > 9 Η 0 Я 0 я 0 я Η я > 9 я 1 • č and Я 1 . ₄ • и О я 5Í 6 • Ρ ο • Ρ ο Ύ -Ρ ο 1 Η • Η χ: • Ρ <η я φ • H OJ O В ’н • н 0 Φ Ή φ <Ρ я φ Ή я φ а • Ρ а v — X Ρ N Θ я CD Н н 'СО F Ό Η X » Η • Η Ό Η • Η 0 0 φ 0 1 1 я 0 1 • H н я • гЧ > ΓΊ 2 1 я а 1 я 6 > 9 1 ο 1 '43 0 φ 1 43 а > J ОТ я о ι ω 43 η 0 43 Λ 0 .Μ <м -Ρ - 1 1 Ό · - 1 (C 1 1 0 я

Claims (10)

A process for the manufacture of nibVcC water-dispersed disazo compounds of general formula 1 ¢), in which the O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O, O P o y o o o o o o o o o o o o o o oy o ou ^era ”Uolsoc to crOylcniioxytgroup and amino group -NH- and group P joou o oo o to ecnocnsoá jaioa o o o o about half a meta a Dwelling aromatic radiocosmetics, X is a hydrogen atom or as a group of cactic γCi-olefin onamethylenes, c, 2,4-difluoro-5-chloroforiloyl, 2,4-dichloro-s-chlorophenyl _< c, 2-tert-4-olo C 1 -C 4 -carbonyl of the alkoxy moiety, 2-fluoro-4-thiaminothiocrityl or 2-chloro-4-thiaminotrityl, respectively, each of which has an alkyl of 4 or more in each case. up to 4 carbon atoms, or residual or total alkyl residues of 1 to 4 carbon atoms and aoyls containing 6 to 10 carbon atoms, all of which are X-chain-containing cetivatives which are present in the group D over the amine group, which R is an oxygen atom or an alkyl group having from 1 to 4 carbon atoms, or an X symbol as a heating product ο ^^^^ OCi or a group O is oconam or a group in the case of N (R); R has an ц ^ влС o ^ onEm and P has an uoc ieic ocou ^, Y on the fluorine atom or on the carbon atom, on ^the other hand on -S ° 2-C ^H = C ^H 2 or on o-oec -Β ^ -Ο ^^ Η ^ Η ² oc kteoé R * o onamous dwellings, which are alkaline in any environment or onamycin, It has a hydrogen atom or an alkali metal or alkaline earth metal eluent, R amino a vodo nbbo alkyl by a duplication of 1 edd ato u o u u and a sham number 1 or 2, in which the octool is intended to treat the decoction 4 OH Y in which D, M, R, X, Y and m are as defined above, reacted in an aqueous medium at a temperature between 20 and 50 ° C and at a pH between 2.0 and 7.0 in an equivalent amount with a symmetrical diamino compound of formula 5 wherein the symbols Z have the same meaning as above, and the Z groups are bonded to the benzene nuclei always in the ortho position or always in the para position to the ethylenedioxy group, and the amino and Z groups are bonded to the benzene nuclei each in the meta position. 2. The process of claim 1, wherein the corresponding compounds of formulas 4 and 5 are used as starting materials to form compounds of formula 1 wherein D is a phenylene group optionally substituted with a substituent selected from the group consisting of halogen, sulfo, sulfamoyl; (C 1 -C 4) alkyl, phenyl, and / or (C 1 -C 4) phenylalkyl, mono- or di-substituted sulfamoyl; (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy, aryloxy, carboxy, carbamoyl; C 1 -C 4 alkyl, phenyl or / and C 1 -C 4 phenylalkyl mono- or disubstituted carbamoyl; (C 1 -C 4) alkoxycarbonyl, (C 1 -C 4) alkanoylamino, (C 1 -C 4) arylalkanoylamino, and optionally C 1 -C 4 -alkyl, substituted with a aryl group; 3. A process according to claim 1, wherein the corresponding compounds of formulas 4 and 5 are used as starting materials to produce compounds of formula 1 wherein D is a non-phthylene group optionally substituted by one, two or three sulfo groups; and chlorine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, C 1 -C 4 alkanoylamino or benzoylamino. 4. A process according to claim 1, wherein the corresponding compounds of formulas 4 and 5 are used as starting materials to form compounds of formula 1 wherein D is a phenylene group optionally substituted by one or two substituents selected from the group consisting of: The group consisting of chlorine, bromine, sulfo, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms and carboxy. 5. A process according to claim 1, wherein the corresponding compounds of formulas 4 and 5 are used as starting materials to form compounds of formula 1 in which D is a naphthylene group which is substituted with one, two or three sulfo groups. 6. Method according to one of claims 1 to 5, characterized in that starting from the corresponding compounds of formulas 4 and 5, to give compounds of formula 1, wherein X represents the amino group -NR ⁿ - bonded to group D 2,3-dichloroquinoxalinecarbonyl radical, 2,4-difluoro-5-chloropyrimidyl radical, 2,4-dichloro-s-triazinyl radical, 2-chloro-4-alkoxy-s-triazinyl radical having 1 to 4 carbon atoms in the alkoxy group , 2-fluoro-4-amino-s-triazinyl or 2-chloro-4-amino-s-triazinyl or 2-fluoro or 2-chloro-4-amino-s-triazinyl, each of which contains an amino group substituted with C 1 -C 4 alkyl, aryl and / or C 1 -C 4 arylalkyl, and R ^M is hydrogen or C 1 -C 4 alkyl. Process according to one of Claims 1 to 6, characterized in that the corresponding compounds of the general formulas (4) and (5) are used as starting materials to give compounds of the general formula: 1 wherein Z is a vinylsulfonyl group or a beta-sulfatoethylsulfonyl group. Process according to one of Claims 1 to 6, characterized in that the corresponding compounds of the general formulas (4) and (5) are used as starting materials to give compounds of the general formula: 1 in which Z and X are both. a vinylsulfonyl group or preferably a beta-sulfatoethylsulfonyl group. 9. A process according to any one of claims 1 to 7, wherein the corresponding compounds of formulas 4 and 5 are used as starting materials to produce compounds of formula 1 wherein X is hydrogen. 10. A process according to claim 1, wherein the corresponding compounds of formulas 4 and 5 are used as starting materials to produce compounds of formula 1 wherein Z is beta-hydroxyethylsulfonyl or vinylsulfonyl or beta-sulfatoethylsulfonyl.