GB1602641A

GB1602641A - Anionic diazo compounds their preparation and use as dyestuffs

Info

Publication number: GB1602641A
Application number: GB9543/78A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1977-03-14
Filing date: 1978-03-10
Publication date: 1981-11-11
Also published as: DE2809476A1; CH628667A5; JPS53112928A; FR2383996A1; IT7848406A0

Abstract

Novel anionic disazo compounds conforming to the formula <IMAGE> where the phenyl ring A, the phenylenic or naphthylenic middle component B and M are each as defined in Claim 1, R3 in compounds of the formula Ib is R3b and (1-4C)alkyl while in compounds of the formula Ic R3 is R3c and an acyl radical -SO2 <IMAGE> in which the ring Z can be further substituted by halogen, (1-4C)alkyl and/or (1-4C)alkoxy, and R4 is (1-6C)alkyl, (1-6C)alkoxy, amino, mono-(1-6C)alkylamino or di-(1-6C)alkylamino, are prepared by alkaline coupling of an appropriate diazotised monoazoamine onto an appropriate phenol containing the radical -NHCOR4 and by subsequent etherification or acylation of a compound of the formula Ia to introduce the radical R3. The compounds of the formula Ia, Ib and Ic are used for dyeing and printing anionic-dyeable substrates; suitable substrates are natural and synthetic polyamides, polyurethanes, cationically-modified polyolefins and leather.

Description

(54) ANIONIC DISAZO COMPOUNDS, ThEIR PREPARATION AND USE AS DYESTUFFS (71) We, SANDOZ LTD., of 35 Lichtstrasse, 4002 Basle, Switzerland, a Swiss Body Corporate, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to anionic disazo compounds, their preparation and use as anionic dyes.

More particularly, the present invention provides compounds of formula I,

in which A is a diazo component radical, B is coupling/diazo component radical of the 1,4-phenylene, 1,4-naphthylene or 5,6,7,8-tetrahydro-1,4-naphthylene series, R3 is hydrogen, (C1-4)alkyl or

wherein ring Z is unsubstituted or monosubstituted by halogen, (C alkyl or (C1-4)alkoxy, and R4 is (C1-6)alkyl, (C1-6)alkoxy, amino, mono(C1-6)alkylamino or di(C1-6)alkylamino, with the proviso that the compounds contain a single water-solubilizing group, which group is a sulpho group and is present in the diazo component radical A, which compounds are in free acid or salt form, and mixtures of compounds of formula I.

Preferably, the diazo component radical A is a diazo component radical of the benzene series.

Preferred compounds of formula I are those of formula Ia, in which

ring A1 is the phenyl radical without the substituents, B1 is a radical of formula (a), (b) or (c)

each of R1 and R2, independently, is hydrogen, (C1-4)alkyl, (C1-4)alkoxy or mono halogen-substituted(C1-4)alkyl, R, is hydrogen, halogen, (C1 < )alkyl, monohalogen-substituted (C1--4) alkyl, (C1-4)alkoxy, mono(C1-6)alkylamino, di(C1-6)alkylamino, alkyl(C1-6) carbonylamino or alkoxy(C1-6)carbonylamino, R6 is hydrogen, halogen, (C1-4)alkyl or (C1-4)alkoxy, R, is hydrogen or methoxy, M is hydrogen or an equivalent of a nonchromophoric cation, and R3 and R4 are as defined above.

By halogen as used herein is meant fluorine, chlorine or bromine.

Any halogen as R, and/or Re is preferably chlorine or bromine, with chlorine being especially preferred.

Any halogen-substituted alkyl as R5 is preferably a fluoro- or chlorosubstituted alkyl, with chlorosubstituted alkyl being especially preferred. Any unsubstituted or substituted alkyl as Rs preferably contains 1 or 2 carbon atoms, more preferably 1 carbon atom. Preferably any alkyl asR5 is unsubstituted, Any alkyl as R6 is preferably methyl or ethyl, with methyl being most preferred.

Any alkoxy as R, and/or Re is preferably methoxy or ethoxy. Any monoalkylamino group as R5 is preferably methyl- or ethylamino, more preferably methyalmino. Any dialkylamino as R5 preferably contains methyl and/or ethyl groups, more preferably methyl groups. The most preferred alkyl(C1-6)carbonylamino as R5 is acetylamino.

Any alkoxy(C1-6)carbonylamino as R5 is preferably methoxy- or ethoxy-carbonylamino.

R5 is preferably R5', where R5' is hydrogen, halogen, (C1-4)alkyl, (C1-1)alkoxy or acetylamino. More preferably, R5 is R5", where R5" is hydrogen, chlorine, (C1-2)alkyl, (C1-2)alkoxy or acetylamino. Even more preferably, R5 is R5"', where R5"' is hydrogen, chlorine, methyl, methoxy or acetylamino, with hydrogen being most preferred.

R6 is preferably R6', where R6' is hydrogen, halogen, (C1-2)alkyl or (C1-2)alkoxy. More preferably, R6 is R6", where R6" is hydrogen, chlorine or methyl, with hydrogen being especially preferred. Preferably, when R5, R5', R5" or R5"' signifies acetylamino, R6 is hydrogen.

When R5 and R6 are both hydrogen, the sulpho group on ring A1 is preferably in the 3- or 4-position. When one of R5 and R6 is hydrogen and the other is other than hydrogen, the two substituents on ring A1 are preferably in the 2,4-, 2,5- or 3,4position, more preferably in the 2,4- or 2,5-position, with the sulpho preferably being in the 2-position when the other substituent is acetylamino. When both of R5 and R6 are other than hydrogen, the three substituents on ring At are preferably in the 2,3,52,4,5- or 2,4,6-positions, with the 2,4,5- and 2,4,6-positions being more preferred and the sulpho group preferably being ortho or para to the azo group.

Any halogen-substituted alkyl as R1 and/or R, is preferably a chlorosubstituted alkyl. Any unsubstituted alkyl or alkoxy or substituted alkyl as R1 and/or R2 preferably contains 1 or 2 carbon atoms, more prefreably 1 carbon atom. Preferably any alkyl as R1 and/or R2 is unsubstituted.

R1 is preferably R1,' where R1 is hydrogen, methyl or methoxy, with methoxy being especially preferred.

R2 is preferably R2', where R2' is hydrogen, methyl or methoxy. More preferably, R2 is R2", where R2", is methyl or methoxy.

R7 is preferably hydrogen.

B or B1 is preferably a radical of formula (a) or (b), in which latter radical R is, as indicated above, preferably hydrogen. More preferably, B, is a radical of formula (a).

Any alkyl radical as Re is preferably methyl or ethyl. When Ra is

any halogen on ring Z is preferably chlorine; any alkyl on ring Z is preferably methyl or ethyl (especially methyl); and any alkoxy on ring Z is preferably methoxy or ethoxy.

R3 is preferably R3', where R3' is hydrogen, methyl, ethyl, phenylsulphonyl or tosyl. More preferably, R3 is R3", where R3" is methyl or ethyl.

Anv alkvl group as R or as a substituent on an amino group as Re preferably contains 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, with methyl being most preferred. Any alkoxy as R4 preferably contains 1 to 4 carbon atoms, with methoxy and ethoxy being most preferred.

Preferably R4 is R4', where R4' is (C1-4)alkyl, (C1-4)alkoxy or unsubstituted amino. More preferably, R, is R4", where R4" is methyl, ethyl, methoxy, ethoxy or amino. Even more preferably, Re is R4"', where R4"' is methyl, methoxy, ethoxy or amino. Most preferably, Re is R4lv, where R4iv is methyl or amino, especially methyl.

The cation of the sulpho group in the compounds of formula I and the non chromophoric cation M of the compounds of formula Ia may be any conventional cation for anionic dyestuffs. Examples of such cations are alkali metal cations such as sodium, lithium or potassium, or unsubstituted or substituted ammonium cations of formula N$(R,)4, where each Re, independently, is hydrogen, (C1-4)alkyl or 2-, 3-, or 4-hydroxy(C2-4)alkyl, with the proviso that at least one Re is other than hydroxyalkyl. Examples of such ammonium cations are ammonium, mono-, di-, triand tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium.

Further preferred compounds according to the invention are those of formula Ia wherein (i) B1 is a radical of formula (a) or (b), R5 is R5', R6 is R6', R7 is hydrogen, R1 is R1' and R2 is R2', especially those where the sulpho group on ring A1 and any substituents as R5' and/or R6' are in the above-indicated preferred positions.

(ii) B1 is a radical of formula (a) and all other variables are as given under (i).

(iii) B1 is radical of formula (a), R5 is R5' R6 is R6', R1 is R1', R2 is R2', R3 is R3' and R4 is R4', especially those where the sulpho group on ring A1 and any substituents as R5 and/or R6' are in the above-indicated preferred positions.

(iv) B1 is a radical of formula (a), R, is R5', Re is R6", with the proviso that when R5" is acetylamino, R6" is hydrogen, Re is methoxy, Re is 2', R3 is R3' and R4 is R4", especially those where the sulpho group on ring A1 and any substituents as R5" and/or R6" are in the above-indicated preferred positions.

(v) B1 is a radical of formula (a), R5 is R5"', R6 is R6", with the proviso that when R5"' is acetylamino, R6" is hydrogen, R1 is methoxy, R2 is R2", R3 is R,' and Re is R4", especially those where the sulpho group on ring A1 and any substituents as R5"' and/or R6" are in the above indicated preferred positions.

(vi) All variables are as defined in (v) with the exception that R6 is Re".

(vii) All variables are as defined in (v) with the exception that Ra is R3" and Re is R4"' (viii) All variables are as defined in (v) with the exception that R, is R3" and R is R4iv.

(ix) All variables are as defined in (v) with the exception that Re is R3", R4 is methyl and both Re and Re are hydrogen.

The present invention also provides a process for the production of compounds of formula I and mixtures thereof, comprising a) coupling the diazotized amine of formula II, A-N=N-B-NH2 II wherein A and B are as defined above, or a mixture thereof, with a phenol of formula III,

wherein Re is as defined above, or a mixture thereof5 under alkaline conditions, to produce a compound of formula Ix,

wherein A, B and Re are as defined above, or a mixture thereof, or b) etherifying or acylating a compound of formula Ix or a mixture thereof, to form a compound of formula I wherein Re is other than hydrogen.

The coupling reaction in process variant a) may be effected in accordance with known methods. Diazotization to produce the starting materials thereof may also be carried out in conventional manner.

The etherification or acylation of process variant b) may be effected in known manner. Suitably, the etherification is carried out employing the corresponding dialkylsulphate. The reaction is suitably carried out in aqueous alkaline medium, the preferred pH value being from 9 to 10. The reaction temperature is suitably from 30 to 90"C, more preferably from 60 to 800 C.

Acylation is suitably effected employing the corresponding sulphonylchloride.

The reaction mixture is suitably aqueous which is made alkaline with soda, the preferred pH being from 8 to 10. The reaction temperature is suitably between 30 and 90"C, preferably between 60 and 70"C.

The compounds of formula I obtained may be isolated in accordance with conventional methods.

In general, as a result of the reaction conditions ,compounds of formula I are obtained which are in the salt form, which compounds may be converted into the free acid forms in accordance with known methods.

The compounds of formula II and III are either known or may be prepared in accordance with known methods from readily available starting materials, for example, compounds of formula II may be obtained by coupling the diazonium compound to the amine A-NH,, in acid medium, with an amine B-NH,.

The compounds of formula I and mixtures thereof are useful for dyeing or printing anionic dyeable substrates. Suitable substrates include natural and synthetic polyamides, leather and basic-modified polyolefins or polyurethanes. Especially suitable are textile substrates consisting of or comprising natural and synthetic polyamides, such as wool or silk, and particularly nylon. The dyestuffs may advantageously be used for carpet printing.

The compounds of formula I, or mixtures thereof, may be employed as such or may be used in the form of liquid or solid preparations. The preparation of stable liquid, for example concentrated aqueous preparations, or solid preparations, may be carried out in accordance with conventional methods, for example by dissolving in suitable solvents, optionally with the addition of conventional additives such as solubilizing agents, for example urea, or by grinding or granulating. Such preparations may be obtained in accordance with the procedure described in French Patents 1,572,030 and 1,581,900.

Further, the compounds of formula I, or mixtures thereof, may be made up into preparations which are dispersible in cold water. Such dispersions may be prepared, for example, by grinding the dye wet or dry in the presence of one or more conventional anionic dispersing agents and optionally in the presence of other conventional additives, with subsequent spray-drying. The preparations so obtained are fincly dispersed in cold water and are thus easy to handle.

Dyeing may be carried out in accordance with known methods, for example pad dyeing or exhaust dyeing, especially the latter as the compounds of formula I and mixtures thereof build-up from a neutral dye bath. Furthermore, the compounds of formula I and mixtures thereof are also useful for use in the "space-dyeing" process.

The compounds of formula I and mixtures thereof are well soluble in water, build-up well, migrate well and give even dyeings, especially on stripy nylon. The dyeings obtained, especially those made with compounds where Re is other than hydrogen, possess notable light-fastness. Furthermore, the compounds of formula I and their mixtures give dyeings which have notable general fastness, such as wetfastness, especially wash-, milling- and sweat-fastness.

The compounds of formula I and mixtures thereof are suitable for combining with other dyes having neutral build-up, whereby dyeings having the above-mentioned advantageous properties are obtained. Further, such dyeings do not exhibit catalytic fading.

The following Examples further serve to illustrate the invention. In the Examples, all parts are by weight and all degrees are in degrees Centigrade.

EXAMPLE 1.

33.7 Parts of an azo dye obtained by diazotizing 1-aminobenzene-4-sulfonic acid followed by coupling under acid conditions with l-amino-2,5-dimethoxybenzene are dissolved with heating in 200 parts water and 12.5 parts of an approximately 25% ammonia solution and are then mixed with 6.9 parts sodium nitrite dissolved in 25 parts water. The nitrite-containing aminoazo dyestuff solution is added dropwise, over the period of 30 minutes, to a reaction vessel containing 28 parts of 30% hydrochloric acid, 40 parts water and 50 parts ice. After stirring for 1 hour, 2.76 parts sodium nitrite dissolved in 10 parts water and 11.5 parts 30% hydrochloric aad are added thereto and the solution is stirred for 18 hours, after which time diazotization is complete.

15.1 parts 3-acetylamino-1-hydroxybenzene are stirred in 100 parts water with 1 part sodium carbonate at a pH value of 9.5. The diazonium solution obtained as described above is added dropwise thereto from a compression pump over the period of 30 minutes, the pH of the solution being maintained at a value of 9.5 by the addition of 27 parts sodium carbonate. After a further 15 minutes the coupling is complete. The precipitated dyestuff is isolated by filtering. The filtercake is dissolved at 80" (pH 9.5) with water to a volume of 750 parts by volume and mixed over a period of 30 minutes with 12 parts diethylsulphate. During the 30 minutes the pH is maintained at 9.5 by the dropwise addition of a 30 /, sodium hydroxide solution and the temperature is held at 80 , after which time the etherification is then complete.

The precipitated dyestuff which is isolated by filtration followed by drying is a brown powder and corresponds to the formula

The dyestuff which gives a red colour when dissolved in hot water gives even dyeings on wool, silk and synthetic polyamides of brilliant yellowish-red shades which have good light- and wet-fastness. The dyestuff also has good build-up from a neutral bath.

In the following Table 1, further dye stuffs of the formula

which are obtained in analogy with the procedure described in Example 1 are given.

The significances for D, R1, R2, R3, R4 are indicated and the dye-shades on polyamide is indicated under column J, whereby a signifies orange, b signifies scarlet red, c signifies yellowish-red, d signifies brownish-red and e signifies yellowish-orance. TABLE 1

Example Position of No. D R1 R2 R3 R4 NHCOR4 group J 2 4-sulphophenyl OCH3 OCH3 C2H5 CH3 2 c 3 do. do. CH3 do. do. 2 a 4 do. do. do. do. do. 3 a 5 do. do. OCH3 CH3 do. 3 c 6 do. do. H C2H5 do. 3 c 7 do. H H do. do. 3 a 8 do. OCH3 H H do. 2 c 9 do. do. OCH3 tosyl do. 3 b 10 do. do. do. phenyl- do. 3 b sulphonyl 11 do. do. do. C2H5 NH2 3 b 12 do. CH3 CH3 do. CH3 3 a 13 3-sulphophenyl OCH3 OCH3 do. do. 3 c 14 do. do. do. do. do. 2 b 15 do. do. CH3 CH3 do. 3 a 16 do. do. OCH3 do. do. 3 c 17 do. do. do. C2H5 C2H5 3 c 18 do. do. CH3 CH3 OCH3 2 a TABLE 1 (Continued)

Example Position of No. D R1 R2 R3 R4 NHCOR4 group J 19 3-sulphophenyl CH3 CH3 H CH3 3 a 20 do. H H C2H5 do. 3 a 21 do. OCH3 OCH3 do. NH2 3 c 22 4-acetylamino-2-sulphophenyl do. do. C2H5 CH3 3 d 23 do. do. CH3 CH3 do. 3 b 24 5-acetylamino-2-sulphophenyl do. do. do. do. 3 a 25 2-methyl-4-sulphophenyl do. do. C2H5 do. 3 b 26 do. do. do. do. do. 2 a 27 do. do. OCH3 n-C4H9 do. 3 b 28 2-methyl-5-sulphophenyl do. CH3 C2H5 do. 3 b 29 do. do. do. CH3 do. 2 a 30 4-methyl-2-sulphophenyl do. do. do. do. 2 a 31 2-ethyl-4-sulphophenyl CH3 do. do. do. 2 a 32 2,4-dimethyl-6-sulphophenyl OCH3 do. do. do. 3 a 33 do. do. do. do. do. 2 e 34 do. do. do. phenyl- NH2 3 a sulphonyl 35 2-methoxy-5-sulphophenyl do. do. CH3 CH3 3 b TABLE 1 (Continued)

Example Position of No. D R1 R2 R3 R4 NHCOR4 group J 36 2-methoxy-5-sulphophenyl OCH3 CH3 CH3 CH3 2 a 37 do. do. OCH3 C2H5 OC2H5 2 a 38 2-ethoxy-5-sulphophenyl do. do. CH3 CH3 2 b 39 4-chloro-2-sulphophenyl do. do. do. do. 3 b 40 do. do. do. do. do. 2 b 41 do. CH3 CH3 do. NH2 3 a 42 do. OCH3 OCH3 tosyl CH3 3 b 43 2-chloro-5-sulphophenyl do. do. C2H5 do. 3 b 44 do. do. do. do. do. 2 b 45 do. do. CH3 CH3 OCH3 2 a 46 do. do. do. do. CH3 3 a 47 5-chloro-4-methyl-2-sulphophenyl do. do. do. do. 3 b 48 do. do. OCH3 C2H5 do. 3 c 49 2,5-dichloro-4-sulphophenyl do. CH3 do. do. 3 b 50 do. do. OCH3 do. do. 3 b In the following Table 2 further dyestuffs of formula

The significances of D, B,, B, and Rl are given, whereby (Y) as B, signifies 1,4naphthylene and (Z) as B, signifies 5,6,7,8-tetrahydro-1,4-naphthylene. As in Table 1, the dye shade on polyamide is indicated under column J, whereby the letters a to e have the same meanings as given above.

The dyestuff of Example 1 and the dyestuffs of Tables 1 and 2, which are all in the sodium salt form may, depending on the reaction and isolation conditions, be obtained in the free acid form or in other salt forms, for example those salt forms indicated as significances for M in the description hereinbefore.

TABLE 2

Example Position of No. D B2 R3 R4 NHCOR4 group J 51 4-sulphophenyl (Y) C2H5 CH3 3 a 51 do. (Y) CH3 do. 3 a 52 3-sulphophenyl (Y) C2H5 do. 3 a 54 do. (Y) do. NH2 2 a 55 4-sulphophenyl (Y) phenyl- CH2 3 a sulphonyl 56 4-acetylamino-2-sulphophenyl (Y) C2H5 do. 3 b 57 2-chloro-5-sulphophenyl (Y) CH3 C2H5 2 a 58 do. (Y) do. CH3 3 a 59 4-sulphophenyl (Z) C2H5 do. 3 c 60 3-sulphophenyl (Z) H do. 2 c APPLICATION EXAMPLE A.

100 Parts of pre-wetted synthetic polyamide, for example nylon 66, are entered at 40 into a dyebath consisting of 4000 parts of water, 10 parts of anhydrous sodium sulphate and 2 parts of the dyestuff from Example 1.

The dye liquor is heated over the course of 30 minutes to boiling temperature and kept at this temperature for 1 hour. 4 Parts of glacial acetic acid are then added thereto and dyeing is completed with heating for a further 30 minutes at boiling temperature. During dyeing, the water that evaporates is continuously replaced. The yellowish-red dyed nylon cloth is then removed from the liquor, rinsed with water and dried. Wool may also be dyed by the same process.

Dyeings may be made in the same manner using the dyestuffs of Examples 2-60, or mixtures of two or more of the dyestuffs of Examples 1 to 60.

The dyeings have notable wet and light fastness.

APPLICATION EXAMPLE B.

Polyamide is printed with a printing paste containing: 30 parts dyestuff of Example 1 50 parts urea 50 parts solubilizing agent (e.g. thiodiethylene glycol) 290 parts water 500 parts suitable thickening agent (e.g. based on carob bean gum) 20 parts acid donating agent (e.g. ammonium tartrate) 60 parts thiourea.

The printed textile goods are steamed.for 40 minutes at 102O (saturated steam), rinsed cold, subsequently washed at 600 with a dilute solution of a conventional detergent and rinsed again with cold water. A yellowish-red print having notable light and wet fastness is obtained.

In analogous manner printing pastes may be made employing the dyestuffs of Examples 2-60 or mixtures of two or more of the dyestuffs of Examples 1-60.

Such pastes may be employed for printing in accordance with the above given procedure.

WHAT WE CLAIM IS: 1. A compound of formula I,

in which A is a diazo component radical, B is a coupling/diazo component radical of the 1,4-phenylene, 1,4-naphthylene or 5,6,7,8-tetrahydro- 1,4-naphthylene series, Rs is hydrogen, (C1-4)alkyl or

wherein ring Z is unsubstituted or monosubstituted by halogen, (C1-4) alkyl or (C1-4)alkoxy, and Re is (C,e)alkyl, (C1~6)alkoxy, amino, mono(Cse)alkylamino or di ( C1~6) alkylamino, with the proviso that the compound contains a single water-solubilizing group, which group is a sulpho group and is present in the diazo component radical A1, which compound is in free acid or salt form, or a mixture of compounds of formula I.

2. A compound or mixture according to Claim 1, in which the diazo component radical A is a diazo component radical of the benzene series.

3. A compound or mixture according to Claim 1, in which the compound of formula I is one of formula Ia,

in which ring A1 is the phenyl radical without the substituents, B1 is a radical of formula (a), (b) or (c)

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

APPLICATION EXAMPLE B.

Polyamide is printed with a printing paste containing:

30 parts dyestuff of Example 1

50 parts urea

50 parts solubilizing agent (e.g. thiodiethylene glycol)

290 parts water

500 parts suitable thickening agent (e.g. based on carob bean gum)

20 parts acid donating agent (e.g. ammonium tartrate)

60 parts thiourea.

The printed textile goods are steamed.for 40 minutes at 102O (saturated steam), rinsed cold, subsequently washed at 600 with a dilute solution of a conventional detergent and rinsed again with cold water. A yellowish-red print having notable light and wet fastness is obtained.

In analogous manner printing pastes may be made employing the dyestuffs of Examples 2-60 or mixtures of two or more of the dyestuffs of Examples 1-60.

Such pastes may be employed for printing in accordance with the above given procedure.

WHAT WE CLAIM IS: 1. A compound of formula I,

in which A is a diazo component radical, B is a coupling/diazo component radical of the 1,4-phenylene, 1,4-naphthylene or 5,6,7,8-tetrahydro- 1,4-naphthylene series, Rs is hydrogen, (C1-4)alkyl or

wherein ring Z is unsubstituted or monosubstituted by halogen, (C1-4) alkyl or (C1-4)alkoxy, and Re is (C,e)alkyl, (C1~6)alkoxy, amino, mono(Cse)alkylamino or di ( C1~6) alkylamino, with the proviso that the compound contains a single water-solubilizing group, which group is a sulpho group and is present in the diazo component radical A1, which compound is in free acid or salt form, or a mixture of compounds of formula I.
2. A compound or mixture according to Claim 1, in which the diazo component radical A is a diazo component radical of the benzene series.
3. A compound or mixture according to Claim 1, in which the compound of formula I is one of formula Ia,

in which ring A1 is the phenyl radical without the substituents, B1 is a radical of formula (a), (b) or (c)

each of R1 and R2, independently, is hydrogen, (C1-4)alkyl, (C1-4)alkoxy or mono halogen-substitued(C1-4)alkyl, R5 is hydrogen, halogen, (C1-4)alkyl, monohalogen-substituted(C1-4)alkyl, (C1-4)alkoxy, mono(C1-6)alkylamino, di(C1-6)alkylamino, alkyl(C1-6) carbonylamino or alkoxy(C1-6)carbonylamino, Re is hydrogen, halogen, (C1-4)alkyl or (C1)alkoxy, R,is hydrogen or methoxy, M is hydrogen or an equivalent of a nonchromophoric cation, and R3 and R4 are as defined in Claim 1.
4. A compound or mixture according to Claim, 3, in which R5 is hydrogen, halogen, (C1-4)alkyl, (C1-4)alkoxy or acetylamino.
5. A compound or mixture according to Claims 3 or 4, in which R6 is hydrogen, halogen, (C1-2)alkyl or (C1-2)alkoxy.
6. A compound or mixture according to any one of Claims 3 to 5, in which R1 is hydrogen, methyl or methoxy and R2 is methyl or methoxy.
7. A compound or mixture according to any one of Claims 3 to 6 in which B7 is hydrogen.
8. A compound or mixture according to any one of Claims 3 to 7, in which B, is a radical of formula (a).
9. A compound or mixture according to any one of the preceding claims, in which B, is hydrogen, methyl, ethyl, phenylsulphonyl or tosyl.
10. A compound or mixture according to any one of the preceding claims in which R4 is (C1-4)alkyl, (C1-4)alkoxy or unsubstituted amino.
11. A compound or mixture according to Claims 3, wherein B1 is B1' where B1' is a radical of formula (a), R1 is methoxy, R2 is hydrogen, methyl or methoxy, R3 is hydrogen, methyl, ethyl, phenylsulphonyl or tosyl, R4 is methyl, ethyl, methoxy, ethoxy or amino, R5 is hydrogen, chlorine, (C1-2)alkyl, (C1-2)alkoxy or acetylamino and R6 is hydrogen, chlorine or methyl, with the proviso that when R5 is acetylamino, R6 is hydrogen.
12. A compound or mixture according to Claim 11, in which when R5 and R6 are both hydrogen, the sulpho group on ring A1 is in the 3- or 4-position, when one of R5 and R6 is hydrogen and the other is other than hydrogen the two substituents on ring A1 are in the 2,4-or 2,5-positions, and when both of R5 and R6 are other than hydrogen, the 3 substituents are in the 2,4,5- or 2,4,6-positions.
13. A compound or mixture according to Claim 11 or 12, in which R2 is methyl or methoxy and R5 is hydrogen, chlorine, methyl, methoxy or acetylamino.
14. A compound or mixture according to any one of Claims 11 to 13, in which R3 is methyl or ethyl.
15. A compound or mixture according to Claims 11 to 14, in which R4 is methyl, methoxy, ethoxy or amino.
16. A compound or mixture according to any one of Claims 11 to 15, in which R4 is methyl or amino.
17. A compound or mixture according to any one of Claims 11 to 16, in which R4 is methyl and R5 and R6 are both hydrogen.
18. A compound of formula

in which M is hydrogen or a non-chromophoric cation.
19. A compound of formula

in which M is hydrogen or a non-chromophoric cation.
20. A compound of formula

in which M is hydrogen or a non-chromophoric cation.
21. A compound of formula

in which M is hydrogen or a non-chromophoric cation.
22. A compound of formula

in which M is hydrogen or a non-chromophoric cation.
23. A compound of formula I as defined in Claim 1, or a mixture thereof, in which A is sulphophenyl optionally substituted by one or two substituents selected from the group consisting of halogen, (C1-@)alkyl and (C1-4)alkoxy, or sulpho phenyl monosubstituted by mono(C, ) alkylamino, di(C1-6)alkylamino, alkyl(Cl -ti) carbonylamino or alkoxy(C1-6) carbonylamino, B is a radical of formula (a) defined in Claim 3, 1,4-naphthylene or 5,6,7,8 tetrahydro-1,4-napthylene and R3 and R4 are as defined in Claim 1 which compound is in free acid or salt form.
24. A compound according to any one of Claims 1, 2 or 23, which is in the sodium salt form.
25. A compound according to any one of Claims 3 to 22, in which M is sodium.
26. A compound according to any one of Examples 2, 3, 6 to 12, 14 or 16 to 6U
27. A process for the production of a compound of formula I, or a mixture thereof.

as defined in Claim 1, comprising a) coupling the diazotized amine of formula II, A-N=N-B-NH2 wherein A and B are as defined in Claim 1, or a mixture thereof, with a phenol of formula III,

wherein Re is as defined in Claim 1, or a mixture thereof, under alkaline conditions, to produce a compound of formula Ix,

wherein A, B and R4 are as defined in Claim 1, or a mixture thereof, or b) etherifying or acylating a compound of formula Ix or a mixture thereof, to form a compound of formula I wherein R, is other than hydrogen.
28. A process for the production of a compound of formula I or a mixture thereof, as defined in Claim 1, substantially as hereinbefore described with reference to any one of Examples 1 to 60.
29. A compound of formula I or a mixture thereof, whenever prepared by a process according to Claim 27 or Claim 28.
30. A process for dyeing or printing anionic dyeable substrates, comprising employing a compound or mixture according to any one of Claims 1 to 26 or 29, as dyestuff.
31. A process according to Claim 30, in which the substrate consists of r:r comprises natural or synthetic polyamides, leather, basic-modified polyolefins or polyurethanes.
32. A process for dyeing or printing anionic dyeable substrates, substantially as hereinbefore described with reference to Application Example A or B.
33. Dyed or printed substrates, whenever obtained by a process according to any one of Claims 30 to 32.