GB2139643A

GB2139643A - Trisazo dyes

Info

Publication number: GB2139643A
Application number: GB08411626A
Authority: GB
Inventors: Manfred Greve; Helmut Moser; Reinhard Pedrazzi
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1983-05-09
Filing date: 1984-05-08
Publication date: 1984-11-14
Also published as: FR2545829B1; IT1199122B; IT8448161A0; JPH0526830B2; FR2545829A1; GB8411626D0; GB2139643B; CH659252A5; JPS59217762A; HK102289A

Abstract

Compounds in metal-free, 1:1 or 1:2 metal complex form and in free acid or acid addition salt form, of formula I <IMAGE> in which R, T, B, R61, R62, R63 and R64 are hydrogen or organic radicals defined in the Specification, and one R60 is OH the other being NH2. The compounds of formula I are useful as dyestuffs for dyeing textile materials, paper and leather.

Description

SPECIFICATION Improvements in or relating to organic compounds The invention relates to basic sulpho-containing polyazo compounds According to the invention there is provided a compound in metal-free, 1:1 or 1:2 metal complex form and in free acid or addition salt form, of formula I

in which R is hydrogen; C1-4alkyl; C5-6cycloalkyl unsubstituted or substituted by one or two C1-4alkyl groups; phenyl, benzyl or phenyl-ethyl, the phenyl group of the latter three substituents being unsubstituted or substituted by one or two groups selected from methyl, ethyl, methoxy and ethoxy, T is hydrogen; -CN,

-COOR4; -CON(R5)2; -SO2N(R5)2;

B is -A-NH-R2; hydrogen; C1-4alkyl unsubstituted or substituted by a C1-4alkoxy, C2-4alkyl substituted by hydroxy;C5 6cycloalkyl unsubstituted or substituted by one to three C1-4alkyl groups; phenyl C1 3alkyl, the phenyl group of which is unsubstituted or substituted by one to three groups selected from C1 4alkyl, C, 4alkoxy and halogen; -A,-N(R7)2; -A2-N(R8)2R9 A or -N(R7)2; where Xa is-O-, -N(R5) or -S-; R3 is hydrogen, C1-4alkyl, -N(R5)2 or -CON(R5)2; R4 is C1-6alkyl or phenyl-C1-3alkyl; R5 is hydrogen or Cl 4alkyl; or when two R5,5 are present attached to a nitrogen atom both R5's together with the N-atom to which they are attached may form a saturated ring which contains one to three heteroatoms; R6 is Cl 4alkyl; A is C2-8alkylene which may be interrupted by up to two heteroatoms; C2 8alkenylene which may be interrupted by up to two heteroatoms, phenylene or cyclohexylene; A, is C2 8alkylene or C2 8alkenylene; A2 is C, 8alkylene or C2 8alkenylene; R2 is

q is O or 1;; R11 is hydrogen, halogen, NO2, OH, C1-4alkyl or C1-4alkoxy R12 is

-CO(CH2)8-Z, or R2 is hydrogen, a is an integer 1 to 3, R14 is an aliphatic, cycloaliphatic, aromatic or heterocyclic amine group in which the N-atom is attached to the triazinyl ring; R13 has a significance of R14 or is halogen, OH, -N H2, C1 4alkoxy, phenyl or

A3 is a linear or branched C2 6alkylene or NH-CO-CH2- where the starred N-atom is attached to the -NR5 group;; Z is -N(R7)2 or -N(r8)2R9 A# each R7, independently, is hydrogen, C1 6alkyl, C2-6alkyl substituted by an halogen, -OH or -CN group, phenyl(C1-3)alkyl, the phenyl ring of which is unsubstituted or substituted by 1 to 3 groups selected from halogen, C1-4alkyl and C1-4alkoxy; or C5-6cycloalkyl, unsubstituted or substituted by 1 or 3 C1-4alkyl groups; or both R7,s together with the N-atom to which they are attached form a 5- or 6-membered saturated ring which contains one to three heteroatoms (referred to hereafter as the "cyclic significances of R7"); each R8 independently, has one of the non-cyclic significances of R7 except hydrogen and R9 is C1-4alkyl unsubstituted or substituted by phenyl or both R8,s, R9 and the N-atom to which they are attached form a pyridinium group (attached by its N-atom) unsubstituted or substituted by one or two C1-4alkyl groups; or a 5- or 6membered saturated ring which contains 1 to 3 heteroatoms unsubstituted or substituted by one or two C1-4alkyl groups; one R60 is OH and the other R60 is -N H2; R6, is hydrogen, C1-4alkoxy or OH; R62 is hydrogen, halogen, nitro, C1-4alkyl, C1-4alkoxy or OH; R63 has a significance of R62 independently of R62; R64 is hydrogen

-N(R7)2; -N(R8)2R9 Aa; -COY2-Z; -CONH-Y2-,Z; -Y2 Z;NH-CO-Y2-Z; -SO2-NH-Y2-Z or -NHNHCOCH2-Z; Y2 is C, 8alkylene; and Ai is a non-chromophoric anion with the provisos that (i) the number of cationic and protonatable basic groups exceeds the number of sulpho groups present by at least one; (ii) that R64 is in the 3- or 4-position on the phenyl ring to which it is attached (the positions being as indicated).

Preferably with B is -A-NH-R2 then B is-sulpho-free.

In the specification halogen means fluorine, chlorine, bromine or iodine, preferably chlorine.

Where any symbol appears more than once in a formula unless indicated to the contrary its significances are independent of one another.

Any alkyl, alkylene or alkenylene present is linear or branched unless indicated otherwise. The alkyl group of any alkoxy group is linear or branched unless indicated to the contrary.

Any sulpho group present may be in free acid or salt form. When in salt form the -S03 is balanced by a cation MO+ (where MO+ is a non-chromophoric cation for example Na, KO+ or NH) or by a protonated basic non-cationic group or by a cationic group in the molecule.

Unless otherwise indicated the preferred significance of a variable applies to that variable regardless of where the variable is set forth in the specification.

Any aliphatic amine group is preferably a mono(C1 4alkyl)- or a di(C, 4alkyl)amino group. Each alkyl group independently may be substituted by 1 to 3 substituents independently selected from halogen, phenyl, hydroxy or C5 6cycloalkyl, but is preferably unsubstituted or mono substituted by phenyl or hydroxy, any hydroxy being other than in the a-position.

Any cycloaliphatic amine group present is preferably C5 6cycloalkylamine, the cycloalkyl group of which may be substituted by one or two C, 2alkyl groups.

Any aromatic amine group present is preferably aniline, the phenyl ring of which is unsubstituted or substituted by one to three substituents selected from C, 4alkyl, C, 4alkoxy, halogen, hydroxy and phenoxy.

Any heterocyclic amino present (or 5- or 6-membered heterocyclic ring) is preferably a pyridine, triazine, pyridazine, pyrimidine, or pyrazine group or a group of the formula

(when unsaturated) or a morpholine, pyrrolidine, piperidine, piperazine group (when saturated).

Each group may be substituted by one to three R6 groups; R is preferably R' where R' is methyl, ethyl, unsubstituted phenyl, unsubstituted benzyl or unsubstituted cyclohexyl. More preferably R is R" where R" is methyl or unsubstituted phenyl.

T is preferably T' where T' is hydrogen, CN,

or CON(R5')2 where R3' and R5' are defined below. More preferably T is T" where T" is CN or

where R3" is defined below.

B is preferably B' where B' is -A'-NH-R2', hydrogen -CH3, -C2H5, -C2H4OH, unsubstituted cyclohexyl, benzyl, -(CH2)13N(R7,)2; -(CH2)2-3 N (R6')2Rg' A, where the symbols are defined below. B is more preferably B" where B" is -A"-NN-R2", hydrogen, -CH3, -C2H5, benzyl, (CH2)bN(R,") 2t -(CH2)b N (R8")2R9", where the symbols are defined below and b is 2 or 3.

B is mos preferably B"' where B"' is CH3, C2H5, benzyl, -(CH2)2-3-N(R7")2' -(CH2)2-3-N (R8")2Rg" Ae or A"-NH-R2"'.

Preferably A is A' where A' is C2-8alkylene or unsubstituted phenylene. More preferably A is A" where A" is 1,2-ethylene, 1,3-propylene or unsubstituted meta or para phenylene.

Preferably R2 is R2, where R2' is a group of formula

where the symbols R1,' and R12' are defined below. More preferably R2 is R2" where R2" is

where R11,, and R12" are defined below.

Most preferably R2 is R2"' where R2"' is

Preferably R2 is R3, where R3, is hydrogen, methyl, ethyl, -NH2 or -N(CH3)2. More preferably R3 is R3" where R3" is hydrogen or methyl.

Preferably R5 is R5' where R5, is hydrogen, methyl.or ethyl. Preferably R5' is hydrogen or methyl.

Preferably R6 is R6' where R6' is methyl or ethyl.

Preferably R7 is R7' where R7' is hydrogen, linear or branched C1 6alkyl, unbranched hydroxyC2-3alkyl, benzyl, 2-chloroethyl, 2-cyanoethyl or both R7,s together with the N-atom to which they are attached form an unsubstituted pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine group.

More preferably R7 is R7" where R7" is hydrogen, methyl, ethyl or 2-hydroxyethyl or both R7" s together with the N-atom to which they are attached form an unsubstituted morpholine, piperidine, piperazine or N-methylpiperazine group; Preferably R5 is R8, where R8' is one of the significances of R7, except hydrogen and R9 is R9' where R9' is methyl, ethyl, propyl or benzyl or both R8' 's and R9' together with the N-atom to which they are attached form a pyridinium ring unsubstituted or substituted by one or two methyl groups or a group ss

where Zo is -0-, direct bond, -CH2-;;

More preferably R5 is R8" where R8" is one of the significances of R7" except hydrogen and R9 is R9" where R9,, is -CH3, -C2H5 or benzyl or both R8"s and R9,, together with- the N-atom to which they are attached form a pyridinium ring, unsubstituted or substituted by one or two methyl groups, or is a group P defined above.

Preferably R11 is R11, where R11, is hydrogen, chloro, OH, nitro, methyl or methoxy. More preferably R11 is R11" where R11" is hydrogen, methyl or chloro.

Preferably R,2 is R12, where R12' is

or-CO(CH2)1-2-Z' or hydrogen; More preferably R12 is R12" where R12" is COCH2Z" or

where- R13", R14" and Z" are defined below.

Most preferably R12 is R12"' where R12"' is

where R13"' and R14"' are defined below.

Preferably R13 is R13, where R13' is chloro, -OH, -NH2,OCH3,

mono C1-4alkylamino, di-(C1-z)alkylamino, monohydroxy (C2-4)alkylamino, bis-[hydroxy-(C2-4) alkyl]amino

where R21 is unsubstituted C1-12alkyl; or C212alkyl substituted by -OH; or C3-12alkyl interrupted by one to three groups selected from

forms a group of formula

where Y, is a C1-8alkylene or a C3-8alkenylene group Z is -N(R7)2 or -N (R8)2R9 A# R23 is halogen, -OH, -NO2, C1-4alkyl or C1-4alkoxy; R24 is a group -N(R7,)2 or N (R8,)2R91 A or a group -CO-Y2-Z', -NHCO-Y2-Z', -CONH-Y2-Z', -SO2NH-Y2-Z'; -Y2-Z' or -NHNHCOCH2-Z', where Y2 is C1-8alkylene More preferably R,3 is R13" where R13" is

where R2,' is -(CH2)2-3-N(R7")-(CH2)2-3-N(R7")R6' -(CH2)2-3-N(R8")2-(CH2)2-3 -N(R8")2 R6' A# -CH2)2-3-N(R7")-C2H5 -(CH2)2-3-N(R8")2C2H5;

-NHCOCH2-Z" -CH2-CONH-Y2'-Z"; Y2,-Z";

where R5, is methyl or ethyl where Y2, is (C1 4)alkylene.

Most preferably R21 is R21" where R21" is -NHCOCH2-Z", -(CH2)2-3-Z"

where R24' is -N(CH3)2, -N(CH3)3, A@ ; -CONH(CH2)2-3Z", -NHCO(CH2)2-3-Z", -CO (CH2)2-3-Z" or SO2NH(CH2)2-3 Z".

Most preferably R,3 is R13"' where R13"' is

Preferably Z is Z' where Z' is -N(R7')2 or -N(R8,)2 R9' A6.

More preferably Z is Z" where Z" is N(R7")2 or -N(R8")R9" A#. Preferably R,4 is R,4' where R,4' is

More preferably R14 is R14" where R14" is -N(R5")R21".

Most preferably R14 is R14"' where R141,, is

Preferably R62 is R62' where R62, is hydrogen, chloro, nitro, methyl, methoxy or OH; more preferably R62 is R62" where R62" is hydrogen, chloro or methyl, Preferably R61 is R61' where R61' is hydrogen, methoxy or methyl.

Preferably R63 is R63, where R63' is hydrogen, nitro, methoxy, ethoxy, OH, methyl, ethyl or chloro; more preferably R63 is R63" where R63" is hydrogen, OH or methoxy.

Preferred compounds of formula I are of formula I' in metal-free, 1:1 or 1:2 metal complex form and free acid or acid addition salt form,

in which R64, is

N(R7')2' -N(R8')2 R9' A@, -CONH-Y2'-Z', -CO- Y2'-Z',-Y2'-Z', -SO2 NHY2'-Z', -NHCOY2,-Z', NHNYCOCH2-Z'; and the other symbols are as defined above; with the provisos that: (i) the number of cationic and protonatable basic groups exceeds the number of sulpho groups present by at least one; (ii) that R64, is in the 3- or 4-position on the phenyl ring to which it is attached (the positions being as indicated).

More preferred compounds of formula I are of formula I" in metal-free, 1:1 or 1:2 metal complex form

in which the symbols are as defined above, with the provisos that (i) the number of cationic and protonatable basic group exceeds the number of sulpho groups present by at least one; (ii) that the amino group on ring E is in the 3- or 4-position (the positions being as indicated); (iii) that the azo group on ring G is in the 3- or 4-position (the positions being as indicated).

Most preferred compounds of formula I are of formula I"'

in which T", R62", R60, R63", B"', R131,, and R14"' are defined above; with the provisos that (i) the number of cationic and protonatable basic groups exceeds the number of sulpho groups present by at least one; (ii) that the amino group on ring E is in the 3- or 4-position (the positions being as indicated); (iii) that the azo group on ring G is in the 3- or 4-position (the positions being as indicated).

Preferred metallisable groups are -N H2, -OH or -O(C, 4alkyl) which are situated ortho to an azo bridge on a phenyl or a naphthyl group. Metallisation of such groups can be represented as below

in which each A5 independently, is -O- or -NH Mea is a 1:1 or 1:2 metal complex forming metal; both R66'S and R67'S are ortho to each other and together form an aromatic ring system (for example together with the two carbon atoms to which they are attached form a

group).

Preferred compounds of formula I when in metallised form are of formulae Ila to Ilc.

where Ya is -O- or -NH Me is copper, chromium, cobalt, nickel, iron, manganese or zinc for 1:1 metal complexes (Me is preferably copper in this case) or Me is chromium, cobalt, iron or nickel for 1:2 metal complexes (Me is preferably iron in this case); and the other symbols are defined above; with the provisos that (i) in the compounds of formula Ila, llb and llc R64' is in the 3- or 4-position, the naphthyl azo group on ring G is in the 3- or 4-position and the number of cationic and protonatable basic groups present exceeds the number of sulpho groups present; (ii) in the compounds of formula llb the group -O-Me-Ya- is ortho to the naphthyl azo group; and (iii) in the compounds of forula llb and Ic when Ya is -NH- then R60 is OH and when Y,, is -0- then R60 is NH2.

Compounds of formula I in metal-free form may be prepared by either reacting a diazotised compound of formula Ill

with a compound of the formula IV

in acid medium to form a compound of formula V

followed by reacting the compound of formula V with a diazotised compound of formula IV

in alkali medium; or by reaction a diazotised compound of formula IV with the compound of formula IV to form a compound of formula VII

in acid medium followed by reacting the compound of formula VII with a diazotised compound of formula III in alkali medium. The SO3H groups can be converted to the salt form by known methods.

Coupling to form compounds of formula I can be carried out according to known methods.

Advantageously, coupling is carried out in aqueous (acid, neutral or alkali) medium at a temperature .from - 10"C to room temperature, if necessary in the presence of a coupling accelerator such as pyridine or urea. Alternatively, coupling may be effected in a mixture of solvents, for example, water and an organic solvent.

Metallisation of the compounds of formula I can be achieved by known methods.

The azo compounds of formula I in 1:1 metal complex form may be prepared by metallising compounds of formula I in metal-free form with a metal selected from copper, cobalt, iron, nickel, manganese, chromium and zinc.

The azo compounds of formula I in 1:2 metal complex form may be prepared byxnetallising compounds of formula I in metal-free form with a metal selected from chromium, nickel, cobalt and iron.

Metallisation is carried out advantageously in aqueous medium or a mixture of water and a water-miscible organic solvent, for example acetone, lower alkyl alcohols, dimethylformamide, formamide, glycols or acetic acid at a pH range from 1.0 to 8.0, preferably pH2 to 7. The metallisation process may be carried out at a temperature from room temperature to the boiling point of the reaction medium.

Alternatively, metallisation may be effected in a wholly organic medium (for example dimethylformamide). Advantageously, for instance, cobaltisation may be carried out in the presence of an inorganic nitrite such as lithium, sodium, ammonium or potassium nitrite in the ratio of 2 to 6 moles of nitrite per gram atom of cobalt.

Suitable cobalt-yielding compounds are, for example, cobalt (11 or Co (111) sulphate, acetate, formate or chloride.

Copper-yielding compounds are, for example, cupric sulphate, cupric formate, cupric acetate and cupric chloride.

The nickel-yielding compounds are Ni (II) or NI (III) compounds, such as nickel formate, nickel acetate and nickel sulphate.

Preferred manganese-yielding compounds are Mn (II) compounds and iron-yielding compounds are Fe (II) or Fe (III) compounds. Examples of these and zinc-yielding compounds are manganese, iron and zinc formate, acetate and sulphate.

Preferred chromium-yielding compounds are Cr (II) and Cr (III) formate, acetate and sulphate.

In the compounds of formula I the anions A3 can be any non-chromophoric anions such as those conventional in basic dyestuff chemistry. Suitable anions include chloride, bromide, sulphate, bisulphate, methylsulphate, aminosulphonate, perchlorate, benzenesulphonate, oxalate, maleate, acetate, propionate, lactate, succinate, tartrate, malate, methanesulphonate and benzoate, as well as complex anions, for example, zinc chloride double salts and anions of boric acid, citric acid, glycollic acid, diglycollic acid and adipic acid or addition products of orthoboric acid with polyalcohols with at least one cis diol group present. These anions can be exchanged for each other by ion exchange resins or by reaction with acids or salts (for example via the hydroxide or bicarbonate or according to German Offenlegungsschrift 2,001,748 or 2,001,816).

The azo compounds of formula I are suitably worked up into solid or liquid preparations, for example by granulation or by dissolving in a suitable solvent. The compounds of formula I are suitable for dyeing, padding or printing on fibres, threads or textile materials particularly natural or regenerated cellulose materials for example cotton, or synthetic polyamides or synthetic polyesters in which the acid groups have been modified. Such a polyamide is described in Belgian Patent 706,104 and such a synthetic polyester is described in US Patent 3,379,723.

The azo compounds of formula I may also be applied to base fibres such as hemp, flax, sisal, jute, coir or straw.

The azo compounds of formula I are also used for dyeing, padding or printing fibres, threads or textiles produced therefrom which consist of or contain homo- or mixed polymers of acrylonitrile or a 1,1 -dicyanoethylene.

The textile material is dyed, printed or pad-dyed in accordance with known methods. Acid modified-polyamide is dyed particularly advantageously in an aqueous, neutral or acid medium, at temperatures of 60"C to boiling point or at temperatures above 100"C under pressure.

The textile material may also be dyed by the compounds of formula I in organic solvents, e.g.

in accordance with the directions given in German Offenlegungsschrift 2,437,549.

Cellulose material is mainly dyed by the exhaust process, i.e. from a long or short bath, at room temperature to boiling temperature, optionally under pressure, whereby the ratio of the bath is from 1:1 to 1:100 and preferably from 1:20 to 1:50. If dyeing is effected from a short bath, then the liquor ratio is 1:5 to 1:15. The pH of the dye bath varies between 3 and 10 (for short and long dyebaths). Dyeing preferably takes place in the presence of electrolytes.

Printing may be effected by impregnation with a printing paste produced by known methods.

The dyes of formula I are also suitable for dyeing or printing paper, e.g. for the production of bulk-dyed, sized and unsized paper. The dyestuffs may similarly be used for dyeing paper by the dipping process. The dyeing of paper is effected by known methods.

The dyes of formula I are also suitable for dyeing or printing leather by known methods.

Dyeings with good fastness are obtained on both paper and leather.

Dyeings made with the dyes of formula I on leather have good light fastness properties, good diffusion properties with PVC, good water-, wash and sweat-fastness properties, good fastness to dry cleaning, good fastness to drops of water and good fastness to hard water.

Dyeings prepared with dyes of formula I on paper produce a substantially clear spent liquor which is important for environmental reasons. The dyes of formula I have good build-up properties, do not run once applied to paper and are not pH sensitive. Dyeings produced with dyes of formula I have good light fastness and the nuance on exposure for a long time to light fades tone in tone. The dyes of formula I have good wet fastness properties not only for water but also for milk, soap, water, sodium chloride solution, fruit juice, and sweetened mineral water. Further dyeings made with dyes of formula I are fast for alcoholic beverages due to a good alcohol fastness. Further the dyes of formula I have good nuance stability.

The dyes of formula I may be converted into dyeing preparations. Processing into stable liquid or solid dyeing preparations may take place in a generally known manner, advantageously by grinding or granulating or by dissolving in suitable solvents, optionally adding an assistant, e.g.

a stabiliser or dissolving intermediary such as urea. Such preparations may be obtained, for example, as described in French Patent Specification 1,572,030 and 1,581,900 or in accordance with German DOS 2,001,748 and 2,001,816.

Liquid preparations of the compounds of formula I preferably comprise 10 to 30% by weight of a compound of formula I and to 30% of a solubilising agent such as urea, lactic acid or acetic acid, the rest of the composition being water. Solid preparations preferably comprise 20 to 80% dyestuff, 20 to 80% solubilising agent such as urea or Na2SO4 and 2 to 5% water.

In the following Examples all parts and percentages given are by weight and the temperatures given are in degrees Centigrade, unless indicated to the contrary.

Example 1 In 600 parts of water 22.2 parts (0.05 mols) of a compound of the formula 1 a

in hydrochloric acid medium are diazotised with 3.45 parts (0.05 mols) of sodium nitrite at 0-5". To this solution 1 5.9 parts (0.05 mols) of 1 amino-8-hydroxy naphthalene-3,6 disulphonic acid are added dropwise, dissolved in 1 50 parts of water and 3 parts of sodium carbonate. The solution has a pH of 1.5. By the addition of 10 parts of sodium acetate over 1 2 hours the pH is brought to 2.3.The resulting dyestuff is of formula 1 b

22 Parts (0.05 mols) of 2,4 bis-(diethylaminopropylamino)-6-(3'-aminophenylamino)-5-triazine in hydrochloric acid medium are diazotised in aqueous medium with 3.45 parts (0.05 mols) of sodium nitrite at 0-5" and are then added to the compound of formula 1 b in acid medium.

By the addition of 45 parts of a 30% aqueous NaOH solution the pH is brought to 8.5 to 9.

After coupling has finished a dyestuff of the formula 1c

is obtained. This compound 1c dyes paper and leather a black tone.

Example 2 22 Parts (0.05 mols) of 2,4-bis(diethylamino propyl amino)-6-(3'-amino phenylamino)-3triazine in hydrochloric acid medium are diazotised in aqueous medium with 3.45 parts (0.05 mols) of sodium nitrite at 0.5 . This is then added in acid medium to 1-amino-8-hydroxy naphthalene 3,6-disulphonic acid and then 22.2 parts of the compound of formula 1a (from Example 1) are added in alkali medium to produce the compound of formula 2a

This is an isomeric form of the compound 1 c and also dyes paper and leather a black tone.

Both dyes Ic and 2a have good fastness properties.

Examples 3 to 25 Compounds of the formula

in which the symbols are defined in Table 1 can be formed by a method analogous to that of Example 1 or Example 2 from appropriate starting materials. In these Examples the symbols A33-42 and T2, T4 and T5 are as defined below.

A33 is -(CH2)3N(CH3)2

A40 is -NHCOCH2-N(CH3)3 Cl# A41 is -CONH(CH2)3N(CH3)2 A42 is -SO2NH(CH2)2N(C2H5)2.

T2 represents -CN

Table ib Positions Position and sig- of -N = N Position and Ex. nificance on ring significance No. T B of R62 G R60a R60b R63 of R64 3 T4 A33 H 4 OH N H2 H 4-A38 4 T4 do. H 4 NH2 OH H 4-A38 5 T4 do. H 3 OH NH2 H 3-A38 6 T4 do. H 3 NH2 OH H 3-A38 7 T4 do. H 3 OH NH2 H 4-A38 8 T4 do. H 3 NH2 OH H 4-A38 9 T2 A35 H 4 OH N H2 H 3-A38 10 T5 do.H 4 OH N H2 H 3-A38 11 T4 A34 H 4 OH NH2 H 3-A38 12 T4 A35 H 4 OH NH2 H 3-A38 13 T4 A36 H 4 OH NH2 H 3-A38 14 T4 A37 H 4 OH N H2 H 3-A38 15 T4 A35 H 4 OH NH2 H 3-A39 16 T4 do. H 4 OH NH2 H 3-A40 17 T4 do. H 4 OH NH2 H 3-A41 18 T4 do. H 4 OH NH2 H 3-A42 19 T4 A33 OH(4) 3 OH NH2 H 3-A38 20 T4 do. OH(4) 3 OH NH2 H 3-A38 21 T4 do. OH(3) 4 OH NH2 H 3-A38 22 T4 do. OH(3) 4 OH NH2 H 3-A38 23 T4 A35 H 4 NH2 OH OH 3-A42 24 T4 do. H 4 NH2 OH OH 3-A42 25 T4 do.H 4 NH2 -OH OCH3 3-A42 Examples 26 to 28 The following metallised compounds can be formed by metallising the appropriate compounds: Example 26 :1:1 copper complex of Example 20 Example 27 :1:1 copper complex of Example 22 Example 28 : 1:1 copper complex of Example 24.

The compounds of Examples 3, 4, 9 to 19 and 21 to 28 are black and the compounds of Examples 5 to 8 and 20 are greenish-black.

Application Example A 70 Parts of chemically bleached sulphite cellulose obtained from pinewood and 30 parts of chemically bleached sulphite cellulose obtained from birchwood are ground in 2000 parts of water in a Hollander. 0.12 Parts of the dyestuff from Example 1 of formula 1c are sprinkled into this pulp. Paper is produced from this pulp after mixing for 20 minutes. The absorbent paper which is obtained in this manner is dyed in a black tone. The waste water is practically colourless.

Application Example B 0.5 Parts of the dyestuff from Example 1 of formula 1 c are added to 100 parts of chemically bleached sulphite cellulose which have been ground in a Hollander with 2000 parts of water Sizing takes place after thorough mixing for 15 minutes. The paper which is produced from this material has a black tone and good light- and wet-fastnesses.

Application Example C An absorbent length of unsized paper is drawn at 40 to 50 C through a dyestuff solution having the following composition: 0.5 Parts of the dyestuff from Example 1 0.5 Parts of starch and 99.0 Parts of water.

The excess dyestuff solution is squeezed out through two rollers. The dried length of paper is dyed in a black tone.

Application Example D 100 Parts freshly tanned and neutralised chrome leather are agitated for 30 minutes in a vessel with a dyebath of 250 parts water at 55 C and 0.5 parts of the dyestuff of Example 1, and then treated in the same bath for 30 minutes with 2 parts of an anionic fatty liquor based on sulphonated train oil. The leather is then dried and prepared in the normal way, giving a leather evenly dyed in a black tone.

Other low affinity vegetable-tanned leathers can similarly be dyed by known methods.

Application Example E 2 Parts of the dyestuff of Example 1 are dissolved in 4000 parts demineralised water at 40 C.

100 parts of a prewetted cotton textile substrate are added, and the bath is raised to boiling point over 30 minutes and held at the boil for 1 hour. After rinsing and drying, a black dyeing is obtained having good light- and wet-fastnesses. The dye exhausts practically totally and the waste water is almost colourless.

The dyestuffs of any of the other Examples 2 to 28 may be used in place of the compound of Example 1 any one of Application Examples A to C. The dyes so used may be in the form of solid or liquid preparations.

Claims

1. A compound in metal-free, 1:1 or 1:2 metal complex form and in free acid or acid addition salt form, of formula I

in which R is hydrogen: C14alkyl; C56cycloalkyl unsubstituted or substituted by one or two C1-4alkyl groups; phenyl, benzyl or phenyl-ethyl, the phenyl group of the latter three substituents being unsubstituted or substituted by one or two groups selected from methyl, ethyl, methoxy and ethyoxy, T is hydrogen; -CN,

-COOR4; -CON(Rs)2; -SO2N(R5)2;

B is -A-NH-R2; hydrogen;C1 4alkyl unsubstituted or substituted by a C1 4alkoxy, C24alkyl substituted by hydroxy; C56cycoalkyí unsubstituted or substituted by one to three C1 4alkyl groups; phenyl C1 3alkyl, the phenyl group of which is unsubstituted or substituted by one to three groups selected from C1 4alkyl, C1 4alkoxy and halogen; -A1-N(R7)2; -A2-N (R8)2R9 A or -N(R7)2); where X, is -O-, -N(R5) or -S-; R3 is hydrogen, C1 4alkyl, -N(R5)2 or -CON(R5)2; R4 is C1-6alkyl or phenyl-Cl 3alkyl; R5 is hydrogen or C1 4alkyl; or when two R5,sare present attached to a nitrogen atom both R5,s together with the N-atom to which they are attached may form a saturated ring which contains one to three heteroatoms; R6 is C1-4alkyl; A is C28alkylene which may be interrupted by up to two heteroatoms; C28alkenylene which may be interrupted by up to two heteroatoms, phenylene or cyclohexylene; A1 is C28alkylene or C28alkenylene;; A2 is C1-8alkylene or C28alkenylene;

q is 0 or 1; R1, is hydrogen, halogen, NO2, OH, C1-4alkyl or C1 4alkoxy

-CO(CH2,-Z, or R2 is hydrogen, a is an integer 1 to 3, R14 is an aliphatic, cycloaliphatic, aromatic or heterocyclic amine group in which the N-atom is attached to the triazinyl ring; R,3 has a significance of R14 or is halogen, OH, -NH2, C1-4alkoxy, phenyl or

A@ is a linear or branched C@@@alkvlene or -NH-CO-CH@- where the starred N-atom is attached to the -NR5 group;; Z is -N(R7)2 or -N (R8)2Rg Ae each R7, independently, is hydrogen, C1-6alkyl, C2-6alkyl substituted by an halogen, -OH or -CN group, phenyl(C1-3)alkyl, the phenyl ring of which is unsubstituted or substituted by 1 to 3 groups selected from halogen, C1-4alkyl and C1 4alkoxy; or C5-6cycloalkyl, unsubstituted or substituted by 1 or 3 C1-4alkyl groups; or both R7,s together with the N-atom to which they are attached form a 5- or 6-membered saturated ring which contains one to three heteroatoms (referred to hereafter as the "cyclic significances of R7");; each R8 independently, has one of the non-cyclic significances of R7 except hydrogen and R9 is C1-4alkyl unsubstituted or substituted by phenyl or both R8,s, R9 and the N-atom to which they are attached form a pyridinium group (attached by its N-atom) unsubstituted or substituted by one or two C1-4alkyl groups; or a 5- or 6membered saturated ring which contains 1 to 3 heteroatoms unsubstituted or substituted by one or two C1-4alkyl groups; one R60 is OH and the other R60 is -N H2; R61 is hydrogen, C1 4alkoxy or OH; R62 is hydrogen, halogen, nitro, C1 4alkyl, C1 4alkoxy or OH; R63 has a significance of R62 independently of R62; R64 is hydrogen

-N(R7)2; -N (R8)2Rg Ae; -COY2-Z; -CONH-Y2-Z; -Y2 Z; NH-CO-Y2-Z; -SO2-NH-Y2-Z or -NHNHCOCH2-Z; Y2 is C18alkylene; and AD is a non-chromophoric anion with the provisos that (i) the number of cationic and protonatable basic groups exceeds the number of sulpho groups present by at least one; (ii) that R64 is in the 3- or 4-position on the phenyl ring to which it is attached (the positions being as indicated).

2. A compound according to Claim 1 in which R is R' where R' is methyl, ethyl, unsubstituted phenyl, unsubstituted benzyl or unsubstituted cyclohexyl.

3. A compound according to Claim 1 in which R is R" where R" is methyl or unsubstituted phenyl.

4. A compound according to any one of the preceding claims in which T is T' where T' is hydrogen, CN;

where R3, is hydrogen, methyl, ethyl, -NH2 or N(CH3)2 and R5, is hydrogen, methyl or ethyl.

5. A compound according to Claim 4 in which T is T" where T" is CN or

where R3" is hydrogen or methyl.

6. A compound according to any one of the preceding claims in which B is B' where B' is A'-NH-R2', hydrogen, -CH3, -C2 H5, -C2K4OH, unsubstituted cyclohexyl, benzyl, -(CH2)13N(R7,) -(CH2)2 3N (R8,)2R8,A, where A' is C28alkylene or unsubstituted phenylene, R7' is hydrogen, linear or branched C16alkyl, unbranched hydroxyC2 3alkyl, benzyl, 2chloroethyl, 2-cyanoethyl or both R7's together with the N-atom to which they are attached form an unsubstituted pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine group;; R5, is one of the significances of R7, except hydrogen and R9' is methyl, ethyl, propyl or benzyl or both R8's and Rg' together with the N-atom to which they are attached form a pyridinium ring unsubstituted or substituted by one or two methyl groups or a group P

where Zo is -0-, direct bond, -CH2-; -NH-, -NR5, -N(R6)2 A, -SO2-, -SO-, -S-, and R2, is a group of formula

q is defined in Claim 1; R1,' is hydrogen, chloro, OH, nitro, methyl or methoxy; R12, is

or -CO(CH2)1-2-Z' or hydrogen; ; R13' is chloro, OH, -N H2, OCH3,

mono C1-4alkylamino, di(C1-2)alkylamino, monohydroxy(C2-4)alkylamino,bis-[hydroxy(C1-4) alkyl]amino or

Z' is -N(R7,)2or N(R8')2R 99' Ae;

where R21 is unsubstituted C1-12alkyl; or C2-12alkyl substituted by -OH; or C3-12alkyl interrupted by one to three groups selected from -N(R7)- and -N(R8)2 A#; -NHCOCH2-Z; -CH2CONH-Y1-Z; -Y1-Z;

forms a group of formula

where Y1 is a C1 8alkylene or a C3-8alkenylene group Z is -N(R7)2 or -N(R8)2 R9 A R23 is halogen, -OH, -NO2, C1-4alkyl or C1 4alkoxy; R24 is a group -N(R7,)2 or -N (R6')2R9' A@ or a group -CO-Y2-Z', -NHCO-Y2-Z', , -CONH-Y2-Z', -SO2NH-Y2-Z';-Y2-Z' or -NHNHCOCH2-Z' where Y2 is C1-8alkylene.

7. A compound according to Claim 6 in which B is B" where B" is -A"-NH-R2", hydrogen, -CH3, -C2H5, benzyl; -(CH2)bN(R7")2; and -(CH2)bN( R8")2R9" A where b is 2 or 3; A" is 1,2-ethylene, 1,3-propylene or unsubstituted meta or para phenylene; R7" is hydrogen, methyl, ethyl or 2-hydroxyethyl or both R7" is together with the N-atom to which they are attached form an unsubstituted morpholine, piperidine, piperazine or Nmethylpiperazine group; R8" is one of the significances of R7" except hydrogen and R8,, is -CH3, -C2Hs or benzyl or both R8"s and R8,, together with the N-atom to which they are attached form a pyridinium ring unsubstituted or substituted by one or two methyl groups or is a group P defined in Claim 6;; R2" is

where q is defined in Claim 1; R11" is hydrogen, methyl or chloro; R12" is COCH2Z" or

Z" is N(R7,1)2 or - N(R8")2R9" A

R21' is -(CH2)2-3-N(R7")-(CH2)2-3-N(R7")R6' -(CH2)2-3-N(R8")2-(CH2)2-3 -N(R8")2 R6' A@ -(CH2)2-3-N(R7")-C2H5 -(CH2)2-3-N(R8")2-C2H5;

-NHCOCH2-Z" -CH2-CONH-Y2'-Z"; Y2'-Z";

where R6, is methyl or ethyl, R24 is defined in Claim 6, and Y2, is (C1 4)alkylene.

8. A compound according to Claim 6 or Claim 7 in which 8 is B"' where B"' is CH3, C2H5, benzyl, -(CH2)2-3-N(R7")'2, -(CH2)2-3-N(R8")2R9 A# or -A"-NH-R2"'; where A", R7" and Rs" are defined in Claim 7; R2"' is

R21" is NHCOCH2-Z", -(CH2)2-3-Z",

where R24' is -N(CH3) 2, -N (CH3)3 AB ; -CONH(CH2)23Z", -NHCO (CH2)23-Z", -CO (CH2)2 3-Z", or SO2NH(CH2)2-3 Z"; and Z" is defined in Claim 7.

9. A compound according to any one of the preceding claims in which R62 is R62' where R62, is hydrogen, chloro, nitro, methyl, methoxy or OH; R61 is R61' where R61' is hydrogen, methoxy or methyl; and R63 is R63, where R63' is hydrogen, nitro, methoxy, ethoxy, OH, methyl, ethyl or chloro.

10. A compound according to any one of the preceding claims in which R64 is R64, where R64, is

N-(R7,)2, -N (R8')2 R9' A7, -CONH-Y2'-Z', -CO-Y2'-Z, -Y2,-Z', -SO2NHY2'-Z-, -NHCOY2'-- Z', NHNHCOCH2-Z; where R7,, R8,, Rg' and Z', are defined in Claim 6 and Y2, is defined in Claim 7.

11. A compound according to Claim 1 in metal-free, 1:1 or 1:2 metal complex form or in free acid or acid addition salt form, of formula I'

in which R' is defined in Claim 2; T' is defined in Claim 4; B' is defined in Claim 6; R60 is defined in Claim 1; R64' is defined in Claim 10; and R61', R62' and R63' are defined in Claim 9; with the provisos that: (i) the number of cationic and protonatable basic groups exceeds the number of sulpho groups present by at least one; (ii) that R64' is in the 3- or 4-position on the phenyl ring to which it is attached (the positions being as indicated),

12.A compound according to Claim 1, in metal-free, 1:1 or 1:2 metal complex form or in acid free or acid addition salt form, of formula I"

in which R62" is hydrogen, chloro or methyl; R63" is hydrogen, OH or methoxy; R80 is defined in Claim 1; R" is defined in Claim 3; T" is defined in Claim 5, B", R,3" and R14" are defined in Claim 7; with the provisos that: (i) the number of cationic and protonatable basic groups exceeds the number of sulpho groups present by at least one; (ii) that the amino group on ring E is in the 3- or 4-position (the positions being as indicated; (iii) that the azo group on ring G is in the 3- or 4-position (the positions being as indicated).

13. A compound according to Claim 1, in metal-free, 1:1 or 1:2 metal complex form or in free acid or acid addition salt form, of formula I"'

in which T" is defined in Claim 5; R62" is defined in Claim 12; R60 is defined in Claim 1; B"', R13"' and R14"' are defined in Claim 8; with the provisos that (i) the number of cationic and protonatable basic groups exceeds the number of sulpho groups present by at least one; (ii) that the amino group on ring E is in the 3- or 4-position (the positions being as indicated); (iii) that the azo group on ring G is in the 3- or 4-position (the positions being as indicated).

14. A compound according to Claim 1, in 1:1 or 1:2 metal complex form and in free acid or acid addition salt form, of formula Ila to llc

in which R' is defined in Claim 2; T' is defined in Claim 4; B' is defined in Claim 6; R62, is defined in Claim 9; R60 is defined in Claim 1; R63, is defined in Claim 9; R64, is defined in Claim 10; Ya is -O- or -NH-; Me is copper, chromium, cobalt, nickel, iron, manganese or zinc when in 1:1 metal complex form or Me is chromium, cobalt, iron or nickel when in 1:2 metal complex form; with the provisos that: (i) in the compounds of formula Ila, llb and llc R64, is in the 3- or 4-position, the naphthyl azo group on ring G is in the 3- or 4-position and the number of cationic and protonatable basic groups present exceeds the number of sulpho groups present; (ii) in the compounds of formula llb the group -O-Me-Ya to the naphthyl azo group; and (iii) in the compounds of formula llb and llc when V, is -NH- then R60 is OH and when V, is -0- then R60 is NH2.

15. A process for preparing a compound according to Claim 1 comprising (1) reacting a diazotised compound of formula Ill

with a compound of the formula IV

in acid medium to form a compound of formula V

followed by reacting the compound of formula V with a diazotised compound of formula VI

in alkali medium, and optionally metallising the resulting product; or (2) reacting a diazotised compound of formula VI with the compound of formula IV to form a compound of formula VII

in acid medium followed by reacting the compound of formula VII with a diazotised compound of formula III in alkali medium; and optionally metallising the resulting product.

1 6. A process for dyeing a substrate comprising applying to that substrate a compound of formula I defined in Claim 1.

1 7. A compound of formula I defined in Claim substantially as herein described with reference to any one of Examples 1 to 28.

18. A process according to Claim 1 6 substantially as herein described with reference to any one of Application Examples A to E.

1 9. Textile material to which a compound of formula I defined in Claim 1 has been applied.

20. Paper or leather to which a compound of formula I defined in Claim 1 has been applied.