CS226739B2 - Method of preparing disazo compounds - Google Patents

Abstract

1. A process for the preparation of disazo compounds of the general formula (1) see diagramm : EP0063276,P12,F4 in which R**1 denotes a hydrogen atom, a chlorine or bromine atom or a sulfo group, R**2 is a hydrogen atom or a chlorine or bromine atom, R**3 represents a hydrogen atom, an alkyl group having 1 to 4 C-atoms or an alkoxy group having 1 to 4 C-atoms and R**4 denotes an alkoxy group having 1 to 4 C-atoms and Z**1 and Z**2 are each bonded in the benzene nucleus in the meta- or para-position relative to the azo group and each represents a hydrogen atom, the beta-thiosulfatoethylsulfonyl group, the vinylsulfonyl group or the beta-sulfatoethylsulfonyl group, and Z**1 and Z**2 can be identical to or different from one another, but with the proviso that they do not both represent a hydrogen atom at the same time, and M represents a hydrogen atom or the equivalent of a metal, and the formula moieties R**1 , R**2 , R**3 , R**4 and M are identical to or different from one another and also identical to or different from Z**1 and Z**2 , characterized by that a mixture of two diazotized aromatic amines of the general formulae (2) and (3) see diagramm : EP0063276,P12,F5 see diagramm : EP0063276,P12,F6 in which R**1 , R**2 , R**3 , R**4 , Z**1 and Z**2 have the abovementioned meanings, are reacted with a coupling component of the general formula (4) see diagramm : EP0063276,P12,F7 in which M has the abovementioned meaning, first in a strongly acid range and then in a weakly acid to weakly alkaline range.

Description

The invention relates to the technical field of the synthesis of disazo dyes.

From literature. Disazo compounds are known, consisting of - two diazo components and one divalent coupling component whose divalent. the coupling component is 1-amino-ε-hytooxyyte-disulfonic acid and one or both diazo components contain O-sulfatoethylsulfonyl or vinylsulfonyl groups as reactive to the waves. Produced. with double - sided compilation. of at least one of said atheomic amines comprises one of said fiber-reactive residues, in that at least one of said at least one of said amino-amityphenyl-1-amino-8-hydroxy-3,6-disuffonic acid is present; of these diazocomponents, copied in a strongly acidic pH range with said coupling component, and the obtained mono-compound is coupled with a second diazo component with the addition of a second diazo component. In all these cases, the copolymerization is carried out in succession. In this two-step, step-like copolymer, the first azo-coupling is introduced in the first coupling stage.

- · 3 *

226,739 to the ortho position to the amo group of the coupling component, and then a second is introduced into this monoazo compound. azo group to the -ortho-position relative to the hydroxyl group of the coupling component of such synthesis. double, stepped couplings to produce disazo compounds are known from U.S. Pat. No. 960,534 and from the 'Japanese Published Applications of Sho-43-15229 and U.S.-47-14348.

It has now been found that, surprisingly, such a disazo can be combined with a certain structure and with. very good application-tangential properties .a-p. very good '- permanence also gain ,,. if the diazoal salts of both are reacted in order to synthesize these certain disazasilate compounds. which serve as starting materials and the divalent coupling component - which serves as starting material,. not. step by step - one after the other, but so that the 'coplication' is carried out - in - a mixture of these components with one another »

Accordingly, the present invention relates to a process for the preparation of a compound of formula 1

(4) in which

R ^ represents a hydrogen atom, a chlorine atom or a bromine atom or a sulfo group,

R represents a hydrogen atom or a chlorine atom or a bromine atom,

R ^ is hydrogen, C alky-C s alkyl such as ethyl and preferably methyl, or is C až-C alko alkoxy such as ethoxy, and preferably methoxy, and

R1 is C1-C4alkoxy;

as an ethoxy group and preferably a methoxy group,

- 5 226 739

2

Z and Z are each bonded in the benzene ring at the meta * or para-position to the azo group and each of these symbols represents a hydrogen atom or a β-thiosulfato * ethylsulfonyl group (corresponding to the formula * ei -SOg-CHg-CHg-S-SO2M) wherein M is as defined below) or a vinylsulfonyl group or a 3-8-sulfatoethylsulfonyl group (corresponding to the formula -SOg-CHg-Hg-OSO-M, where M is also as defined below), wherein both Z and Z may be equal or different from each other, with the proviso that both symbols do not simultaneously represent a hydrogen atom, and

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

and the radicals R, R, R, R and M may be the same or different from each other, as well as to the symbols and Z 2 may be the same or different from each other, consisting of a mixture of two diazotized aromatic amines of formulas 2 and 3

R ¹ R ³ 228 739 Ί г * \ NH ~ II ² HgN— 2 of ¹ __L π K ² (2) R ⁴ (3)

in which * 1 O Λ Ί O

R ¹ , R, R, R *, Z ^x and Z * have the meanings given above, in reaction with the coupling component of formula 4

(4) in which

M is as defined above, first in a strong acidic medium between pH 3 and 3 and then in a weak acidic to alkaline medium between pH 4 and 8, at temperatures from 0 to ° C

226 739

The reaction is carried out using approximately equimolar possibilities of the starting compounds. In a reaction step carried out in a weakly alkaline medium, portions of the β-sulfatoethyl-8-oloyl groups or groups can be converted to vinylsulfonyl groups.

Mixtures of the two diazotized amines of formulas 2 and 3 are obtained by, for example, each of the two aromatic amines separately diazotized in a customary manner, and then the two diazonium salts with each other. The mixture is mixed and combined with the coupling component or the mixture of both aromatic amines is diazotized together and the mixture of these diazonium salts is then combined with the coupling component.

Initially ongoing. the reaction carried out in a strongly acidic, preferably aqueous, medium is preferably carried out in the pH range between 0 and 3, in particular between 0.5 and 2.5. The temperature of the coupling reaction can be chosen in the range of from 0 ° C to 30 ° C. Preferably, the reaction is carried out at temperatures between 5 and 25 ° C. The pH can be between 4 and 8, preferably the reaction is carried out at a pH of between 4.5 and 7. Also here, the reaction temperature can be chosen between 0 and 30 ° C. Copies are carried out at temperatures between 5 and 25 ° C · ^{228 738}

The process according to the invention can be carried out, for example, as follows:

Aqueous solutions or suspensions or solutions or suspensions of diazonium salts of the two aromatic amines of formulas 2 and 3 are mixed with an aqueous solution or suspension of the coupling component of formula 4 and adjusted to a strongly acidic range if necessary, preferably by adding hydrochloric acid, particularly preferably pH between 0 and 3 ° C The reaction mixture is stirred at a temperature between 0 ° C and 30 ° C, preferably between 5 ° C and 25 ° C, for several hours, such as 4 to 12 hours, and then the pH of the reaction medium is adjusted with an acid binding agent. to a slightly acidic to slightly basic pH range, preferably a pH between 4.5 and 7 is selected. The reaction mixture is stirred at a temperature of mm 2 and 30 ° C, preferably at a temperature of · meei 5 and 25 ° C, several. hours, such as 2 to 6 hours, and then the resulting disazo compound corresponding to formula 1 is isolated in the usual manner.

The acid-binding agents used to treat the weakly acidic to weakly basic medium are preferably salts of weak inorganic or organic acids, such as utiHSite, during the coupling reaction.

- 9 22В 739 in acetic acid * boric acid, or acetic acid, 8 with alkali or alkaline earth metals or using acidic or basic salts of phosphoric acid. Of the alkali metal and alkaline earth metal salts, sodium, potassium and calcium salts are preferred. In particular, sodium carbonate and potassium carbonate, sodium acetate, sodium borate and particularly preferably sodium bicarbonate are used as the acid-binding agents for blunting the strongly acidic pH range.

The isolation of the compounds produced by the process of the invention from the reaction mixtures in which they are synthesized is carried out by generally known methods, such as by precipitation of disazo compounds from the reaction medium with electrolytes such as sodium chloride or potassium chloride or by evaporation of the reaction solution itself. . However, the reaction mixture obtained by synthesis can also be used directly as a liquid preparation, if desired, optionally after concentration and / or with the addition of buffers.

The disazo compounds of the general formula (1) produced by the process according to the invention are dyes with very good fiber reactivity and very good application technical properties which

226 · 739, by analogy with known application and fixation methods, provide on fibrous materials sacrificing hydroxyl groups and / or carboxamidocapsules, blue (navy blue) to bluish black, greenish black, reddish black and pure black coloring and prints with good to with very good constancy. In particular, light fastness, linen fastness, water and polish fastness, acid and alkali fastness, as well as color fastness, seawater fastness and water fastness are particularly important. The dyeing possibilities of the disto compounds produced by the process according to the invention are excellent. Also, the degree of fixation corresponding to the various application processes is extremely high. The fibrous materials which contain hydroxyl groups and which may advantageously be dyed with the compounds produced by the process according to the invention are in particular cellulosic fibrous materials, such as cotton materials. The carboxamide-containing fibrous material is mainly wool and silk and synthetic polyamide fibers such as polyamide 6 or polyamide 6,6 fibers.

The D-carbonates of the compound of the present invention are identical in structure to those of the disazo compounds of formula (1), which have been synthesized according to the conventional and known synthesis stepwise procedure. The two diazonates with the coupling component of formula (4) are initially added by adding the first diazonium salt of the aromatic amine of formula (2) in an acidic medium; then for. addition of an aromatic amine diazonium salt of formula 3 in a weakly acidic to slightly encapsulated medium. Correspondingly, the dyeing properties of the disazo compounds produced by the process of the invention are similar to those of the compounds which have been produced according to the known and conventional sequential coupling procedure and which correspond to the disazo compounds of the general formula (1). disazo compound. This fact could not be assumed. Rather, it was to be expected that a mixture of both diazo components and a coupling component would yield a mixture of disazo compounds, namely a mixture of 4 disazo compounds, one of which would be a compound of Formula 1 and the other would be isomeric to it. wherein the diazo component of formula 3 is coupled in the ortho position to the amino group and the diazo component of formula 2 is coupled in the ortho position to the hydroxyl group as well as two others. These diazo compounds in which both diazo components are always identical, i.e. in one diazo component corresponding to the general formula 2 and the other diazo component corresponding to the general formula 3.

The process of the invention has a contrast. The known and conventional processes for the preparation of the compounds of the formula I have the advantage that they can be carried out. . Both aromatic amines can be diazotized together and can be carried out in the same vessel. The cost of equipment * and working time · for the production of disazo compounds are thus significantly reduced, · which in technical provo brings a considerable advantage ·

Suitably the process according to the * invention are produced ^d isazoslou ^NO Compounds of formula 1 wherein ^R represents ₂ Cl or - 'bromo or sulfo, R is hydrogen, R ^ and R ^ are the OTA same and znameeaaí methoxy or ethoxy and Z * and Z are both the same or different from each other and denote β-thiosullatoethylsulfonyl, O-sulfoethylsulfonyl, or vinyl sulfonyl, both preferably being p-sulfoethylsulfonyl, with Z and Z respectively. * are bound both preferably in the p-position to the azo-. group ·

Particularly preferred is · production 'of the compounds of _{1 2} formula 1 wherein R and R · znameenaí both hydrogen, R Ar' are both same and set a ethoxy, preferably methoxy gr yne and Z * and Z * are 'above vý13

226,739, but preferably both have the same meaning and each represents a β-sulfatoethylsulfonyl group which is preferably bonded in para-position to the azo group.

The following examples are intended to illustrate the invention. Parts refer to parts by weight, percentages. refer to percentages by weight, unless otherwise specified · Parts by volume are in proportion to liter per kilogram ·

He did

70.25 parts of 4-β-β-β-ω-phthalic acid and 85.25 parts of 4-β-β-β-β-ω-thiophenyl-2,5-diethoxyethanoline are introduced. to 675 parts of water and at a temperature of 20 to 22 ° C, the pH is adjusted to 5.3 to 6.0 within one hour with sodium hydrogen carbonate · The anilines dissolve therein · Then 107.5 parts by volume of a 31% aqueous hydrochloric acid solution are added and 475 parts of ice to acidify the solution to congo red and to adjust the temperature to 0-5 ° C. At this temperature diazotization is carried out with 65.5 parts by volume of a 40% aqueous sodium nitrite solution. Then a slight excess of nitrous acid decomposes by adding 0.5 parts of amidosulfonic acid.

228 739 Then, 77.8 parts of 1-amino-.epsilon.-hydroiodonaphthalein-3,6-di-dionic acid are added and the reaction mixture is stirred. 4 to 5 hours at a temperature between 4 and 8 ° C and a pH value between 1 and 2. After this reaction time, 90 minutes are added.

66.7 parts of sodium hydrogen carbonate to adjust the pH of the reaction mixture to 6. The reaction mixture is stirred for about 4-5 hours to complete the formation of the disazo compound. The compound obtained is isolated by drying. of the reaction solution for spraying, to obtain a black powder containing electrolyte (predominantly sodium chloride). The yield was 249 parts of the di-zinc salt of the formula

This compound has very good properties in terms of reactivity to fibers and materials on the materials described in the description, especially on fibrous materials.

15,226,739 of cellulose by the application and fixation methods customary and known for greenish fiber-reactive dyes Black dyes having very good fastnesses, for example those mentioned above.

Examples - 2 to 21

In the following Examples 2 to 21, which are summarized in tabular form, further disazo compounds corresponding to formula 1 are described which can be prepared in a uniform form by the process of the invention by reaction of a mixture of the corresponding diazotized amines of formulas 2 and 3. 1-amino-8-hydroxy-3,6-disulfonic acid as a divalent coupling component, for example, analogously to the procedure described in Example 1. The compounds of formula 1 - shown in the table by the formula are described in free acid form. These compounds were obtained as the corresponding sodium salts by the procedure of Example 1. They are fiber-reactive dyes with good application properties and good fastness, which dye, for example, cellulosic fibrous materials in the shades shown in the table for each example.

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Claims (6)

THE INVENTION OF THE INVENTION 226 739 A process for the preparation of disazo compounds of the general formula 1 (1) in which it represents a hydrogen atom, a chlorine atom or a bromine atom or a sulfo group, it represents a hydrogen atom or a chlorine atom or a bromine atom; represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms C 4 -C 4 alkoxy or C 1 -C 4 alkoxy; and 27 226. 739-4 is alkoxy and 1 to 4 atoms. carbon, i 2 Z * and Z are bonded in the benzene ring at the meta- or para-position to the azo group and each of these. is hydrogen, O-thiosulfatoethylsulfonyl, vinylsulfonyl or β-sulfatoethylsulfonyl, wherein Z * and Z * are both the same or different from each other, but both of which are not hydrogen, and M is hydrogen or a metal equivalent and ^{b sition} *, R ² "R ^3, R and M are not equal ^b mutually 1 2 rozdíl.n ^é and also to the radical ^Z * and Z ² are the ^same as or different from each other Ebo, vyznaačjící in that the mixture of two diazotovaných aromatic amines of the general, formulas 2 and 3 28 22В 739 (3) in which 1 2 3 4 R ^x , R, R, R 1, Z ^x and Z have the meanings given above, in reaction with a coupling component of formula (4): M is as defined above, in the pH range between 0 and 3 and then in the pH range between 4 and 8, at temperatures from 0 to 30 ° C. is as defined in point 1, characterized in that ae and two of the aromatized amines of general formula 226 739 сн ~ г OSOýí SO _? -CH, I for ₂ OSO ₃ M in which M is as defined in point 1, coupled with a compound of formula 4 as defined and defined in point 1; Process according to one of Claims 1 to 6, characterized in that compounds of formulas 2, 3 or 4 are used as starting materials in which M np OA-O is hydrogen or potassium and R, R, R, R * , 2 ^х and Z have the meanings given in points 1 to 6. Printed by Moravian Printing Works, plant 12, Leninova 21, Olomouc Price: 2, <0 К 6 s - 29 226 739 2. A process according to item 1 for the preparation of compounds of the formula 1 in which R @ 1 represents chlorine or bromine • 2 G @ 3 or sulio, R @ 2 is hydrogen, R @ 2 and R @ 3 have the same meanings and are methoxy 12 or ethoxy, Z and Z are the same or different from each other and are 3-thiosulfatoethylsulfonyl, O-sulfatoethylsulfonyl or vinylsulfonyl and M is as defined in point 1, characterized in that compounds of formulas 2 are used as starting materials , 3 and 4, wherein R 1, R 2, R ⁴ , R ⁴ , and Z ^fc and M are as defined above. 3. The process of item 1 for producing compounds Wherein R @ 1 and R @ ⁴ are both hydrogen, R @ ⁴ and R @ ⁴ are both the same and are methoxy or ethoxy, Z and Z are the same or different from each other and are O-thiosulfatoethylsulfonyl or O; -sulphatoethylsulphonyl or vinylsulphonyl; and M is as defined in claim 1, characterized in that compounds of formulas 2, 3 and 4 are used as starting materials in which R 1, R 2, R ⁴ , Z ⁴ and Z ² and M are as defined above. 226 739 4. A process according to 1, 2 or 3 for the manufacture of compounds of formula 1 wherein R, R, R, R ⁴ and M have the meanings given in 1, 2 or 3 and Z ¹ and Z are both the same and are O-sulfatoethylsulfonyl, characterized in that compounds of formulas 2, 3 and 4 are used as starting materials in which R ¹ , R ² , R ⁴ , R ⁴ , Z ¹ , Z ² and M are as defined above. A process according to item 2, 3 or 4 for producing compounds of formula 1, wherein R, R, R, R *, 1 2 Z and Z and M. have the meanings given in point 2, 3 or 4, 1 2 and the substituents Z and Z are bound always in the para position к azo group, characterized in that as the starting compounds of Formulas 2, 3 and 4, in which R ^1, R ^2, R ^3, R ^4, Z ¹ , Z ² and M are as defined above, wherein Z and Z in formulas 2 and 3 are each bound Р-У in position k to azo group. 6. The process of item 1 for producing a compound of formula