CS205147B2 - Process for preparing aminoazocompounds - Google Patents

Description

The invention relates to a process for the preparation of aminoazo compounds and in particular to aminoazo compounds containing at least two sulfonic acid groups.

The process according to the invention therefore provides aminoazo compounds having the free formula (I),

Y (I) where is

A monoisulfophenyl optionally substituted with chlorine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or disulfophenyl optionally substituted with methyl, methoxy or chlorine,

Y is hydrogen, methyl, ethyl, or methoxy, provided that when Y is hydrogen, A is not a monosulfophenyl group.

Preferred A groups are, for example, a monosulfophenyl group substituted by a chlorine atom, an alkyl or alkoxy group, in particular from 1 to 4 carbon atoms, and in particular a methyl or methoxy group, and a disulfophenyl group substituted by a methyl, methoxy or chlorine atom.

Particularly preferred groups A are unsubstituted monosulfophenyl or bisulfophienyl and unsubstituted disulfonaphthyl or trisulfonaphthyl.

A preferred class of aminoazo compounds of formula (I) are those wherein A is selected from disulfonaphthyl, trisulfonaphthyl and monosulfophenyl further substituted by one methyl, methoxy, chlorine, or especially sulfo group.

Specific examples of Group A are:

4-sulfophenyl,

2.5-disulfophenyl,

3,5-disulfophenyl, 2,4-disulfophenyl,

2-methyl-1- (1,4-f) -fluoro-phenyl, d-chloro-4-disulfophenyl, S-4-trisulfonaphth-4-yl,

4,6,8-trisuffoinaff-2-yl,

H

NCHfSO.H.

(IV)

4,8-disulfionaphth-2-yl,

5.7-disulfonaphth-2-yl,

6.8-diisulfonaphth-2-yl,

3-sulfolfenyl group,

2-sulfophenyl,

4-methoxy-2-sulfophenyl, 4-methoxy-2,5-disulfophenyl, 4-methyl-2-sulfophenyl.

It is preferred that Y is methoxy and is not particularly methyl.

The aminoazo dyes of the formula I are prepared by reacting an aminoazo compound of the formula II,

AND-

nh _a

Y! Ll>

wherein A and Y are as defined above, with a sulfonating agent.

Examples of a suitable sulfonating agent include chlorosulfonic acid and especially oleum. The process of the invention is conveniently carried out using an excess of 12% to 30% olea at a temperature of 45 to 70 ° C. The reaction time is generally 3 to 12 hours.

In practice, it is often desirable to produce the oleum of the desired concentration in situ, for example by adding the aminoazo compound of formula II to sulfuric acid, for example in the form of a monohydrate, and adding a relatively strong oleate, for example 65%.

The product of the above sulfonation can be isolated by any conventional method, for example by dropping into a large volume of ice water and filtering off the solid product. The solid product may be washed and dried, but optionally wet solids may be used, for example, in further manufacture.

The amino acid compound is characterized in the form of the free acid in the general formula (I), but it is preferable to prepare it in the form of a total or partial salt of the contained acid groups, for example by any reaction of the free acid with a base. Such salts are also obtained when the isolation process described above is carried out in the presence of suitable cations, for example in the presence of metal or ammonium salts which are added to the isolation liquors.

The amino compound of formula II can be prepared by diazotizing an amine of formula III wherein Y is as defined above and hydrolyzing the product thus obtained to remove the sulfomethyl group.

The conditions of the above diazotization and coupling are known per se, for example diazotization can be carried out using a nitrite salt, for example sodium nitrite, in an acidic aqueous medium at a temperature of 0 to 10 ° C and the coupling can be carried out in an aqueous medium of 10 to 30 ° C and at a pH of 4.5 to 5.5.

The hydrolysis can be carried out by heating in an aqueous medium at a temperature of 50 to 100 ° C in the presence of a base such as sodium carbonate or sodium hydroxide.

The N-sulfomethylamine of formula IV can be obtained by reaction of an amine

with an aqueous solution of formaldehyde and with sodium bisulfite at a temperature of 50-80 ° C.

In many cases, for example when Y is methyl or methoxy, the aminoazo compound of formula II can be prepared directly by coupling the diazonium salt of the amine of formula Ш with an amine

NHj,

The amino compounds of the formula I are valuable intermediates in particular for the preparation of dyes, especially in the preparation of a diazonium salt which can be coupled with a wide variety of coupling components.

The invention therefore also relates to dyes which, in the form of the free acid, correspond to the general formula V,

A - NH2 (III) by coupling with N - sulfomethylamine of formula IV, wherein A - and Y are as defined above - and E represents a residue, the coupling components.

The method according to the invention is illustrated by the following examples in which all parts are by weight - and the weight / volume ratio corresponds to kg / L

Example 1

Preparation of 4-amino-6-methyl-2 ', 3 ^<, 5'-trisulfo · -Ι, Γ-azobenzene

126.5 parts of aniline-2,5disuffonové acid is diazotized by reaction with sodium nitrite and HCl at 0 ° C, the diazonium sulphonyl -se coupled with 53.5 parts of ^1-3 methylaniline in acidic medium and takto- obtained compound was filtered and dried.

parts of 4-amino-t · methyl-2 ^{<5 <-disulffot} apos t -azobenzenu thus obtained was added DO- · 90 parts of sulfuric -acid monohydrate in 30 -minut for -míchání while the temperature allow to rise to a maximum of 50 ° C. Within two hours, to the mixture was added 70 parts of 65% oleum ^1, wherein the reaction temperature by cooling outside - is maintained at 50 ° C. The mixture was stirred at 50-60 ° C for 24 hours, then poured into 400 parts of ice water and filtered. The filter residue is suspended in 500 parts of water, 20% added

Example Amiinoazo compound

4-Ymin-6-methyl-3 ', 5'--disullo ^t l, ^t l -azobenzen

2- (4 ^t phthalimidophosphonothioate <lfenylazo 6'-methyl] naphthalene-3,6,8 - tris = ulfonová acid

2- (4‘-Amino-6‘-methylphenyazonaphthalene-4,8-disulfonic acid)

2- (6-Amino-O-methylphenylazo) naphthalene-4,6,8-trisulfonic acid

2- (β-amino-N-methylphenylazo) -naphthalene-6,8-disulfonic acid

2- (4 ^{<-amiιnΌt6 <tm-e} · methyl phenylazo Jnaf talen5,7-disulfonic acid

2- (4‘-amino-6-methyl-4-enylazo) naphthalene-5,7-disulfonic acid

4-Amino-6-Inethoxy-2 ', 5 ^L disullf-t, Γt-α-benzene

4-Amino-6-methyl · 2 &apos;, 4 & apos ^; -disullo: -t, benzothiazole

2- (4‘tamino-6‘-methoxyphenylazo) naphthalene-3,6,8-r isulfonic acid

2- (4‘-Amino-2,4-disulphonic acid 6,8-disulonic acid)

2- (4‘-Aminophenyl lazo) naphthalene-4,8-disulfonic acid

2- (4'-enyl amiinO'f Lazo) naatalend-disulfonic acid, ¹ new

4-ymΊl · D4 ‘, 6‘-dimethyl-3‘tlulfo-t, Γ-azobenzene

4-amínOt6 methylt2 -sullo ^t-t &apos; azobenzene

4tamino-4'-methoxy-6-meΐhylt2'-sulfo-l, l ^<tyzobeln'ze n · w / v sodium chloride - filtruje- mixture at a temperature of 0- 10 ° C and the filter residue is dried.

Example - 2

Preparation of 4-Amino-6-methyl-3,4-disulfo-1,1-benzobenzene

Diazotized is coupled to

The 3-methylamine in an acidic medium and the compound thus obtained are dried.

parts of the 4-amino-6-methyl-4'-sulfonyl, β-yzobeine zene thus obtained are added to 90 parts of sulfuric acid [specific gravity 1.84] over an hour with stirring, maintaining the temperature of the mixture below 55 ° C . 70 parts of 65% oil were added to the mixture over one and a half hours while maintaining the reaction temperature at 55-65 ° C. The mixture was stirred for 14 hours at 55-65 ° C and then poured into 400 parts ice water. The mixture is filtered, the filter residue is washed with water (150 parts) and dried.

The following table gives additional examples of novel compounds prepared by the process of the invention (the name is in - column 3), which are prepared by - sulfonation of the appropriate - α 'aminoazo compounds - (listed in column 2) as described in Example 1 or 2.

New compound

4-Amino-6-methyl-3,3 ‘, 5'-trisulfo-1'-thiazobenzene

2- (4 ^<i tamiinot6'tmιethyl0enyl yzo) -naphthalene Talon -3,3 - 6,8-teitrasuufoinová acid

2- ^(έ 4'taminιOt6 ^tmethyl! 0enylazo- jnaftalen-3 ', 4,8-tгl · sul0onová acid

2 '- Amino-G-methyl-phenylazo) .naatalen 3 ^<, 4,6,8 - etrasul0onová acid

2- (4-thiamin-6-methylthenyl) phenyl) naphthylene3 ‘, 6,8-trisulfonic acid

2- (4-yminot6 ^<~ 10enylazo methyl) naphthalen-3 ', 5,7-trisulfonic to Lina YSE 2- (4'-amino-6'tethy lfenylazo- Jnaf naphthalen-3', 5,7-trisuffoinová acid 4TA amino-6-methoxy-2 ', 3,5'-trilulfo [thi] azobenzene

4-Methyl-6-methyl-2R, 3,4'-trisullo-1'-azobenzene

2- (4'-6-Ymin ^{<tmethoxyfenylazo)} llafУalent3,3 ', 6,8-tetrasulfonic acid

2- (4'-Aminophenylazo] naphthalene-3 ', 6' - ( ₁ '- ₁ ') - isulfonic acid

2- (β-aminophenylazo) naphthalen-4-yl-trisulfonic acid

2- (4‘-Aminophenylazo) naphthalenium-3,5,5-tris-uphonic acid

4-.ymino.-4 ', ^6-t -dimethylt3,3'disulfO' t, l t ^έ -azobenzen;

4-Amino-6-methyl-2 ', 3-diiulfo-1,1'-benzobenzene

4tamiΏO-4'-methoxy-6-methyl-2 ', 3-dis ulfo ^1-L, L-azobenzene

Example Aminoazo compound

New compound

4-amino-4'-chloro-6-methyl-3 ^, -sulfo-1,1'-

-azobenaeira

4-Amino-6-ethyl-2 ', 5'-disulfo-1,1'-azobenzene

4-amino-4 ^{<-chloro-6-methyl-3,3-disulfo1,1'} агоЬеп2 & п

4-Amino-6-ethyl-2 ', 3,5'-trisulfo-1,1'-benzo

Claims (5)

OBJECT OF THE INVENTION What is claimed is: 1. A process for the preparation of aminoazo compounds of formula (I): EMI2.0 wherein: is A monosulfophenyl optionally substituted with chlorine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, or disulfophenyl phenyl optionally substituted with methyl, methoxy or chlorine, Y is hydrogen, methyl, ethyl, or methoxy, provided that when Y is hydrogen, A is not a monosulfophenyl group. characterized in that the aminoazo compound of formula (II), wherein A and Y are as defined above, is reacted with a sulfoulating compound. agent. 2. The process of claim 1, wherein A is monosulfophenyl or disulfophenyl and Y is as defined in point 1. 3. A process according to claim 1, wherein A is disulfonaphthyl or trisulfonaphthyl and Y is as defined in point 1. 4. A process according to claim 1, wherein A is disulfonaphthyl, trisulfonaphthyl or sulfophenyl, further substituted by one methyl, methoxy, chlorine or sulfo group, Y is as defined in point 1. . 5. A process according to any one of Claims 1 to 5 wherein Y is methyl and A is as defined in 1 to 4.