CS196340B2 - Method of preparing aromatic amines - Google Patents

Abstract

The aromatic amines correspond to the formula: <IMAGE> in which R<1> and R<2> have the meanings given in Claim 1. They are prepared by reacting a corresponding aminophosphonic acid, which contains no sulpho group, with a sulphonating agent. Novel azo dyestuffs, which contain one or more radicals of a diazotised amine of the formula I, are obtained from these amines by diazotising and coupling with a coupling component. The novel azo dyestuffs are particularly suitable for dyeing textiles.

Description

The present invention relates to a process for the preparation of aromatic amines containing a phosphonic acid group having the general formula I,

wherein R ¹ represents a hydrogen atom or a methoxy group.

For steric and directive effects, compounds of formula 1 with an R ¹ group in the ortho or para position to the amino group are considered preferred and the SO 3 H group is also generally in the ortho or para position to the NH 2 group.

Examples of preferred aromatic amines of formula I are given

5-methoxy-4-amino-o-2-phosphonobenzenesulfonic acid a

5-methoxy-2-amino44-phosphonobenzenesulfonic acid and particularly preferred aromatic amines are

2-Amino-4-fo'sphonobenzenesulfonic acid and 2-methoxy-3'amino-5-phosphonobenzenesulfonic acid.

According to the invention the aromatic amine of Formula I are prepared by reacting aminophosphonic acid of the formula II ·, phi ⁴

(U) wherein R 1 is as defined above, with a sulfonating agent.

Any sulfonating agent may be used. and under any conditions that are suitable for the desired sulfonation. For example, olefin can be used as the sulfonating agent at temperatures selected in direct dependence on its concentration, for example, for 20% oleum, sulfonae can be carried out at a temperature of 140-180 ° C.

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with phosphorus trichloride in the presence of a Friedel-Crafts type catalyst, followed by hydrolysis and oxidation to form a phosphonic acid which is then nitrated and reduced to the aminophosphonic acid of formula II. · Or, in the case where R ¹ is methoxy, may have · a compound of formula III to react with phosphorus pentasulfide P2S5, the product is hydrolyzed, nitrated and reduced to amino phosphonic acid of formula II wherein R1 · methoxy.

The aromatic amine of formula (I) prepared by the process of the invention can be isolated by any conventional method, for example, the sulfonation mixture can be diluted with water and the precipitated product is filtered off and washed with water.

The aromatic amines of formula I are valuable intermediates, for example, in the preparation of dyes containing a phosphonic acid group. Such dyes are generally well soluble in water due to the presence of phosphonic and sulfonic acid groups. They can generally be used for coloring textile materials which can be dyed with dye by solubilized anionic groups, such as natural and synthetic polyamide materials such as wool, silk, polyhexamethylenadipamide and polycaproimide, but particularly textile materials of natural and regenerated cellulose fibers such as is, for example, cotton, flax, viscose rayon; in the case of cellulosic textile materials, the dyes are preferably fixed to the fibers by baking at a temperature of 95 to 205 ° C in the presence of carbodiimides such as cyanamide, dicyandiamide, for example as described in British Patent Specification No. 1,411,306.

The amines of the formula I can be used for the preparation of dyes in a variety of ways. For example, they can be reacted with dyes having dichlorotriazinyl groups to introduce substituted phenylamino groups into the triazine core. They are particularly suitable for the preparation of diazonium salts which can be coupled with a variety of coupling components for the preparation of diazonium salts.

Ki? wSjšS ^ ™ in one or polyazoPříklad ii ^nl ynУ ^edpřSd s ^and 440 ^m 1o ^{and D!} ^^ ^{f en} ? ^{y! phospho} new ky ^ysel toy Sé? ⁰ - ^{1 1} ьП ° ^U ^ ncentrovrné alkyl ^- and the mixture is kept for R ° ^6% H01 Lote 160 ° C. Sulfonate ^p Nismes ΐ- ° ^вР 'mala · d _{of 1000 an ID} and _profiles л · / · Λ ^{_T, and} U is the pouTujfe ^ i ^ ^ eSVJ lfPi.ivl 30ttLjřáhn-NIL. yield of more than 90% monosulfonated meta-aminophenylphosphonic acid. The product probably has a formula

Example 2

173 parts of meta-aminophenylphosphonic acid are added in portions to 720 parts of stirred 20% oleate, and when stirring is complete, the mixture is maintained at 160 ° C for one hour. The sulfonation mixture is cooled to 80 ^Oi C and slowly poured into 1000 parts of ice and the resulting mixture was heated at reflux for six hours and then allowed to cool to room temperature. The mixture was stirred with 100 parts of sodium chloride for three hours and filtered to give a monosulfonated meta-aminophenylphosphonic acid in more than 90% yield.

The product probably has a formula

Example 1 a d 3

203 parts of 3-amino-4-methoxyphenylphosphonic acid is added in portions to 720 parts of stirred 20% oleate, and when stirring is complete, the mixture is maintained at 150 ° C for one hour. The sulfonation mixture was cooled to 80 ° C and poured slowly into 1000 parts ice and the resulting mixture was refluxed for 6 hours before allowing to cool to room temperature. The mixture was stirred with 100 parts of sodium chloride for up to 196340 for three hours, filtered to give the monosulfonated compound in a yield of more than 20%.

The product probably has a formula

Claims (1)

A process for the preparation of aromatic amines of the general formula I, OF THE INVENTION to react an aminophosphonic acid of formula II, R ¹ NH _Z ^Ρ0 ΗΖ, (II) wherein R 1 is as defined above, with a sulfonating agent. wherein R @ ¹ represents a hydrogen atom or a methoxy group, characterized in that it is reacted