CS202513B2 - Method of preparing aminoazo compounds - Google Patents

Abstract

New aminated azo cpds. have, as the free acid, formula (I) (where Y is H, Me, Et or OMe; Z is H, Me, OMe, SO3H or COOH; n is 0 or 1; P-contg. gp. is m- or p-to azo link). They are prepd. by reacting cpds. (I) not contg. SO3H with a sulphonating agent, and are used as intermediates in the prepn. of polyazo dyes in which NH2 in formula (I) is replaced by -N=NE (where E is residue of coupling component). The polyazo (esp. diazo) dyes are used to colour natural and synthetic polyamides and also, esp., natural and regenerated cellulosic material. They can be used together with dispense dyes to colour cellulosic-polyester blends from a single bath. Compared with corresponding dyes not contg. SO3H on the benzene ring with the Y gp. the dyes give stronger, brighter dyeings of high tinctorial intensity the dyeings have good fastness to wet treatment and often to light.

Description

(54) A method for preparing aminoazo compounds

The invention relates to aminoazo compounds, in particular aminoazo compounds having a phosphoric acid group and at least one sulfonic acid group.

The process according to the invention produces aminoazo compounds which are in the form of the free acid. The formula (I) is a compound of formula (I).

(I) where n is zero or the number 1,

Z is hydrogen, methyl, metho ^, sulfo · SO ^H or carboxy

COOH, ’

Y is a hydrogen atom, a methyl group, an ethyl group or a methoxy group, and a group of the formula ## STR2 ## in the meta or para position to the azo group.

Preferred are aminoazo compounds of formula I having one or more of the following meanings:

a) n is zero,

b) Z represents a hydrogen atom,

c) Y is hydrogen or methyl. group 'and ‘

d) the group of the formula (6) is in the meta position to the azo group.

Examples of aminoazo compounds of formula 1 include: 4-amino-6-methooy-333-sulfo-1,1'-azobenzene-3'-phosphonic acid, 4-anino-6-methyl-3,6'-disslfo-1,1 '-a-btnzen-3 * "fo.sron OA · acid-amine N-J 6 * - ^d with ^{UF O-,} * ¹ * -azobtnzenoЗ -fos ^of acid ^and of ky8eli-and ^4-aoinoo6- Imtho: 1'-6'-diisulfo-1,1'-azobenzenesen-3'-phosphonic acid, 4-amino-6-methyl-2'-sulfon-6'-carbo: χf-1,1'-azobenzenesen-3 ^, -phosphonic acid ,. ⁴ -aoiho ^about З-Su of ^{S-6'-carboxy-1, 1 '}-to-btnzen-3'f ^of osfonooá acid.

4-Amino-6-mithol · fZ-sulfo-b'-mtho-o-1,1'-azobenzene-1'-phosponic acid, and in particular 4-aminooZzSuUf'o-1,1 '- azobenzene-3 ^/ · -fo8: Oonic acid a.

4-Amino-6-methyl-3-8sulfonyl. 1 * -S-benzo-3 * -phosphonic acid.

According to the process of the invention, the compounds of formula (1) are prepared by reacting an amino compound of formula (1).

(II) wherein n, Z and Y are as defined above, with a sulfonating agent. · '

Examples of sulfonating agents suitable for the process of the present invention are chlorofluoronic acid and especially oleum. The process according to the invention may be effected using oleum nactoytku ^{12-3 0%} at 45 toploto ^Y7 and ⁰ ° C. Reaction ^y RH ^and zpravtola 3-12 Todina.

In practice, it is common practice to prepare the oleum of the desired in situ concentration by, for example, adding the aminoazo compound of formula (11) to the sulfuric acid. For example to the monohydrate and the addition of relatively concentrated oleate, for example 65% olea.

The product of the aforesaid salt may be isolated by any means, for example by introducing into a large volume of ice water and filtering off the solid product. The solid was. It can be washed and optionally dried, but in many cases a wet solid is used, for example for further production.

The amine azo compounds have the free acid form of the general formula 1, but it is recalled that they can be obtained in the form of total or partial salts of the direct acidic groups, for example by any known method, such as reaction of the free acid with bases, e.g. with ammonia. . Such sooi are also obtained if the UT _e uOora described insulation. It is carried out in the presence of suitable cations, such as metal salts or ammonium salts, which are added to the solutions from which the dye is to be isolated.

The amino compounds of formula (11) may be obtained by riazotation of an amine of formula (111)

d-N-uulfootthyrroleo dome of general formula 1V (111)

(IV) wherein η, Y and Z are as defined above and by hydrolysis of the product thus obtained to remove the eulfomethyl group.

The conditions of the above diazotization and coupling are known per se; The diazotection 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 at a pH of 4.5 to 5.5 and at a temperature of 10 to 30 ° C.

The hydrolysis can be carried out by heating in an aqueous medium to, for example, 50 to 100 ° C in the presence of a base, for example a carbonate or sodium hydroxide.

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

with an aqueous solution of formaldehyde and sodium sulfite 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 obtained directly by coupling the diazonium salt of the amine of formula III with an amine of formula

The amino compound of formula (I) is a valuable intermediate for the preparation of dyes, and in particular disazo dyes, which have the formula -V in the form of the free acid.

(V) wherein E represents the remainder of the coupling component.

The dyes of formula (V) may be prepared by diazotization of an aminoazo compound of formula (I) and coupling with a coupling moiety which contains the residue E.

The process according to the invention is illustrated by the following examples in which parts are by weight.

Example 1

Preparation of 4-ат1по-Ззаи11 * о-1,1 * -azobenzene-3 * -phosphoric acid

100 parts of 3зEminobenzelephosphonic acid with? diazotized by reaction with sodium nitrite and hydrochloric acid at 0 ° C and coupled to 120 parts of N-3-methylphenylene. The compound thus obtained is hydrolyzed by heating to a temperature of 95-100 ° C in 1000 parts of 2N aqueous sodium hydroxide.

110.8 parts of 4-Amino-1,1'-azobenzene-zinc phosphate thus obtained are added to the

252 parts of phosphoric acid (monohydrate) are stirred for 15 minutes while the temperature is allowed to rise to a maximum of 50 ° C. Add 90 parts - 65% olea to the mixture over 90 minutes while maintaining the reaction temperature at 50 ° C by outdoor cooling. The solution was stirred for ^t hour at 5 ^ture EP ⁰ ° ^C and ^the APE ^d M ^{1 d é} í ^profiles an ice-water. ^R in its capacity ^{to 168} e výsoH BDC]. ^y amoxrného chloride, stirred for 30 minutes and filtered. The filter residue is washed with 200 parts of a 10% (w / v) aqueous ammonium chloride solution and then dried.

Example 2 ..

Preparation of 4-Jmino-t-butyl-Z-zinc-1,1'-aztblnzen-3 * -f08fontic acid

The diazotized 3-aminobutyric acid is coupled to 3-methylphosphoric acid in an acidic medium and the compound thus obtained is hydrolyzed in an alkaline medium at a temperature of 95-100 ° C. -

36.8 parts of the thus obtained 4-and ^ ii ^ (^ - ^ i ^ - ^] ^ eeth ^'1 l'1,1' -azobenzen - ^ - phosphonic acid is added to 90 parts of sulfuric acid (specific hmoonost 1.84) over 30 minutes míchtáií while maintaining the batch temperature at 50 ° C až'55 outdoor cooling. Add 60 parts of 65% oleum it to ^the SME of the SL-průb ^of hu 9 ⁰ min ^price is maintained reaWní ^ mperature 50 and ⁵⁵ ° C. a solution of ^e was stirred for 10 hours at - 50 to 55 ° C and then dropped into 400 dííůiddové water. the product precipitated and! ^ 1 ^^ ι, washed with 20 parts of 10% (w / v) aqueous ammonium chloride solution and then dried.

P Peak-1 and d - 3.

Preparation of 4 'aoinоtЗ-motlyl-3,6'-Зdвu1fo-1,1'-phosphonic acid

The diazotized zinc-4-sulfulfobenzophosphonic acid is coupled to 3 zoel / hl in an acidic medium. ,

The 33.7 parts of 4-amino-3-isotyl-6'-sulfonyl-1,1'-asbestosone _0- phonic acid thus prepared is added to 90 parts of sulfuric acid (specific gravity 1.84) over a period of half an hour - while maintaining the temperature of the mixture by outdoor cooling at 55 ° C. To the mixture - add 80 Iddu ⁶ 5% oleum at a temperature of 55 ° C and ^'65 ° C ⁽⁴ °, ²⁰ and 20 klových portions) at intervals of 10 and a half hours and stirring was continued for 6 hours at 55 to 65 ° C after the last addition. The solution was dropped into 500 parts of ice water, 15% (wt / wt) sodium chloride was added and the mixture was filtered. The filter residue is washed with 10 parts of aqueous sodium chloride solution and dried. .

In the table below, further compounds of the formula I according to the invention (listed in column 3) are obtained which are obtained by the use of suitable aminoazo compounds. (listed in column 2), as described in Example 1, 2 or 3.

Example

Aminoazosloučenina

New compound

No.

4-amino-6'-sulfo-1,1'-azobenzene-3'-phosphonic acid

4-amino-6-ethyl-1,1'-azobenzene-3'-phosphonic acid

4-amino-6-methoxy-1,1'-azobenzene-3'-phospho-. new acid

4-Amino-6-methoxy-6'-sulfo-1,1'-azobenzene-3'-phosphonic acid

4-amino-6'-carboxy-1,1'-azobenzene-3'-phosphonic acid

4-Amino-6-methyl-6'-carboxy-1,1'-azobenzene-3'-phosphonic acid

4-Amino-6-methoxy-6'-carboxy-1,1'-azobenzene-3'-phosphonic acid

4-Amino-6-methyl-6'-methoxy-1,1'-azobenzene-3'-phosphonic acid

4-Amino-6-ethyl-6'-methoxy-1,1'-azobenzene-3'-phosphonic acid

4-amino-1,1'-azobenzene-4'-phosphonic acid

4-amino-6-methyl-1,1'-azobenzene-4'-phosphonic acid

4-amino-6-ethyl-1,1'-azobenzene-4'-phosphonic acid

4-amino-6-methoxy-1,1'-azobenzene-4'-phosphonic acid

4-amino-6'-methyl-1,1'-azobenzene-3'-phosphonic acid

4-amino-3,6'-disulfo-1,1'-azobenzene-3'-phosphonic acid 4-amino-6-ethyl-3-sulfo-1,1'-azobenzene-3'-phosphonic acid 4-amino 6-methoxy-3-sulfo-1,1'-azobenzene-3'-phosphonic acid 4-amino-6-methoxy-3 ', 6'-disulfo-1,1-azobenzene-3 ^? -phosphonic acid 4-amino-3-sulfo-6'-carboxy-1,1-azobenzene-3-phosphonic acid 4-amino-6-methyl-3-8ulfo-6'-carboxy-1,1'-azobenzene- 3'-phosphonic acid 4-amino-6-methoxy-3-sulfo-6'-carboxy-1,1'-azobenzene-3'-phosphonic acid 4-amino-6-methyl-3-sulfo-6'-methoxy - 1,1'-azobenzene-3'-phosphonic acid 4-amino-6-ethyl-3-8-sulfo-6'-methoxy-1,1'-azobenzene-3'-phosphonic acid 4-amino-3-sulfo- 1,1'-azobenzene-4-phosphonic acid 4-amino-6-methyl-3-sulfo-1,1'-azobenzene-4'-phosphonic acid 4-amino-6-ethyl-3-sulfo-1,1 '-azobenzene-4'-phosphonic acid 4-amino-6-methoxy-3-sulfo-1,1'-azobenzene-4'-phosphonic acid 4-amino-6'-methyl-3-sulfo-1,1 * -azobenzene-3 * -phosphonic acid

Claims (6)

SUBJECT OF THE INVENTION A process for the preparation of aminoazo compounds which, in free acid form, correspond to the general formula I (I) wherein n is zero or the number 1, Z is hydrogen, methyl, methoxy, sulfo SO4H or carboxy COOH, Y is hydrogen, methyl, ethyl or methoxy, and the group HgO4P-CCHgJn- is in the meta or para position to the azo group; (II) characterized in that an aminoazo compound of formula (I) is reacted; wherein n, Z and Y are as defined above, with a sulfonating agent. 2. A process according to item 1 for the preparation of aminoazo compounds of formula I wherein n is zero and Z, Y is as defined in item 1, which is reacted with an amino compound of formula II wherein n is zero and Z and Y have as defined in 1 with a sulphonating agent. 3. A process according to Claims 1 and 2 for the preparation of amino compounds of formula I wherein Z is hydrogen and n and Ϊ are as defined in clause 1, characterized in that an amino compound of formula II is reacted where Z is hydrogen and n and Ϊ have as defined in point 1 with a sulphonating agent. . Fourth ^{p are the methods} ccording ^b ODU ^1-3 for ^{EXAMPLE beta.} rave aminoazooloučenin ^b ecného of formula ^I wherein ^Ϊ represents a hydrogen atom or a methyl group ana Z is as defined in claim 1, characterized TM reacting aminoazo formula II, wherein Y represents a hydrogen atom or a methyl group, and Z is as defined in item 1, is sulfonated with the composition. 5. A process according to claim 1 for the preparation of 4-amino-1,1'-azsbenzene-3 * -phosoonic acids, characterized in that 4-amino-1,1'-azsbenzene-Z ^from phosphonic acid is reacted. an acid with a sulfonating agent. 6. Method according to claim 1 for preparing 4-aminis6 miteylyЗзsulfo-1,1'-a2sbeozto OosSonové-3'-ester, characterized by reacting 4-aminoo2- _I mtthy-1,1' -azobenieti -'- Sosonic Acid with Sulfurizing Agent.