GB2076421A

GB2076421A - Azo dyestuffs

Info

Publication number: GB2076421A
Application number: GB8113731A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1980-05-08
Filing date: 1981-05-05
Publication date: 1981-12-02
Also published as: IT8148412A0; IT1170952B; ES8303500A1; FR2482121B1; ES8301494A1; ES510880A0; DE3117127A1; FR2482121A1; ES501998A0; GB2076421B; BR8102844A

Abstract

Sulpho-free dis- or polyazo compounds in metal-free or 2:1 metal complex form of formula <IMAGE> in which A1 and A2 are metallised or metallisable groups, X and Y are conventional bridging groups A is <IMAGE> and R3 is alkyl or A together with R3 forms a phenyl ring; R1 is an aromatic or heterocyclic coupling component group, n is at least 2, and Z is a basic or ammonium group. Novel azo compounds in 2:1 metal complex form are of formula II <IMAGE> in which R1, R3, A, Y, X, Z and n are as above defined and Me is a metal and novel azo compounds in metal-free form are of formula VIII <IMAGE> in which R10, R9, r, ring E, ring G and Y' are as defined in the specification and X and Z are as above. These azo compounds are useful in dyeing and printing on cotton, paper and leather.

Description

SPECIFICATION Improvements in or relating to organic compounds The invention relates to sulpho-free dis- or polyazo compounds in metal-free or 2:1 metal complex form. By "2:1 metal complex" is meant a complex of 2 atoms of metal with each dyestuff molecule, even though each metal atom is associated with only one azo group.

According to the invention there is provided a sulpho-free symmetrical or asymmetrical dis- or poly-azo compound of formula I in metal-free or in 2:1 metallisedform

in which each Y independently is a direct bond or a (C1-4) alkylene group or a bridging group of the formula

where the above substituents, marked with a star, are attached to the group Z by the carbon atom which is starred, in which mis 1,2,3or4 and R4 is hydrogen or C14 alkyl; each R, independently is an aromatic or a heterocyclic coupling component group; X is a bridging group or a direct bond; n is at least 2; each Z independently is -N (CH3)2,

in which piss, 1 or 2 and mis as defined above and AO is a conventional non-chromophoric anion; and either 1) each A is

(a) and each R3 independently is (Cr~4) alkyl; and or 2) each A together with R3 and the ethylene group to which A and R3 are attached, forms the group (b)

and the aromatic rings in groups (a) and (b), independently, can be substituted by one or two groups selected from halogen, (C1-4)alkyl and (C1~4)alkoxy, and A1 and A2, for compounds of formula I in metal complex form, form the group -O-Me-O- where Me is copper, cobalt, iron, nickel, manganese or zinc, and for metal-free compounds each A2 independently is hydrogen, C1-4alkoxy or -OH and A1 is-OH with the proviso that, when the compound of formula I is in metal-free form, each A and R2 form the group b) above and R1 is a 1 - phenyl pyrazole, the phenyl group of which is substituted by one group -Y-Z where Y and Z are as defined above.

Preferably when the azo compounds of the invention are in metal-free form A2 is hydrogen.

Preferably X is any one of groups X, to X46 where X, is a direct bond X2 is a straight or branched chain C1~4alkylene and X3 to X46 are as listed below:

where R5 is halogen, C1-4alkyl or (C1-4)alkoxy each R6 independently is halogen,-NH-CH2-CH2- OH or -N(CH2-CH2OH)2 and @ R7 i R7 is a straight or branched chain C14 alkylene group.

Preferably X is Xa where Xa is selected from the groups X1, X5@) X6, X7, X10, X11, X12, X22, X25,) X26, X27, X30, X42 and the groups listed below @ X2'-CH2-,X2"-CH2-CH2-,X2"'-(CH2)3-,X2iv -(CH2)4-,

where each R5a independently is chlorine, methyl or methoxy and each R6ais chlorine,-NH-CH2-CH2OH or-N-(CH2-CH2-OH)2@ More preferably X is Xb where Xb is X1, X7, X11, X12, X27,X2',X2",X14',X19',X19"',X20',X20",X21',X32',X34',X34iv, X34v,X40'orX42.

The preferred significance of R3 is methyl and pre ferably R4 is R4a where R4a is hydrogen or methyl.

Preferably mis m' where m' is 2 or3 and preferably p is p' where p' is 0 or 1.

Preferably n is 2.

Preferably R6 is R6a where R6a is defined above.

Preferably Y is Y' where Y' has the significance of Y except that Y' may not be C2+4 alkylene. More pref erablyY is Y" where Y" is -CH2-,-CO-NH-(CH2)m'*-,

were m' is defined above.

Still more preferably, Y is Y"' where Y"' is-CH2-, * * -NH-CO-CH2-or-CO-NH-(CH2)3-.

@ Preferably Z is Z' where Z' is-N(CH3)2,-N(CH3)3A#

where p is as defined above.

Preferably the compounds of formula I are symmetrical; that is, both groupings attached to the bridging groupX are identical.

Preferred sulpho-free dis- or poly-azo compounds of the invention are in metal complex form and are of the formula II

in which R1, R3, A, X, Y, Z and n are above defined and Me is defined above. Preferably Me is copper.

Preferred metallised compounds of formula II are a) offormula Ill

orb) of the formula; IV

or c) of the formula V

or d) of the formula VI

all of which may be symmetrical or asymmetrical, and in which each R8 independently is hydrogen, methyl or -CH2CH20H each Rg independently is hydrogen or Alkoxy each lettered aromatic ring may be further substituted by up to q substituents selected from halogen, C1-4alkyl and C14alkoxy, whereby for rings marked B, q = 1, for rings marked D, q = 2, and for rings marked E, q = 1 when R9 is alkoxy and q = 2 when R9 is hydrogen, by 'halogen' is meant CI or Br, preferably CI, and p, m, Y', Z and Xa are defined above.

The Z-Y'- group in formulae V and VI is preferably located at the 4- or 5- position, more preferably at the 4-position. Preferably rings B, D and E have no substitution. In addition to that shown in the formulae.

Preferably R9 is R9, where R9 is hydrogen or methoxy, more preferably hydrogen. The preferred metal complexes of the invention are those of formulae III to VI above in which, independently, Me is copper, m is m', R4 is R4a, Rg is R9' or hydrogen, p is p', X is Xb, Y is Y" or Y"' and Z is Z', where m', R4a, R9', p', Xb, Y", Y"' and Z' are as defined above.

Of the compounds of formulae Ill-VI, those of formula V are preferred, particularly symmetrical compounds offormulaVa

in which Z', Y"' and Xb are as defined above.

An azo compound in metal complex form of formula II may be produced by metallising a compound of formula VII

in which R1, R3, Y, Z, X, A and n are defined above, and each R10independently is hydrogen or a C14 alkyl group, preferably R10 being R10 where R10 is hydrogen or methyl, with a salt of a metal selected from copper, cobalt, iron, nickel, manganese and zinc two form the 2:1 metal complex.

Further the invention provides metal-free sulphofree, symmetric or asymmetric azo compounds of the formula VIII

where r isO or 1, ring G may be further substituted as defined above whereby q = 1 when r = 1 and q = 2 when r = 0, and in which Rg, ring E, X, Y', Z and R10 are as above defined. These compounds are useful as dyestuffs, and, where r = 1, are also intermediates in the preparation of the azo compounds of the invention in metal complex form.

Preferred metal-free azo compounds of the invention are of formula IX

in which p', R10,, Rg, Y", Z, m', rand Xa are defined above, and R is chlorine, -CH3, C2Hs, OCH3 ar OC2Hs.

More preferred metal-free azo compounds of the invention are symmetrical compounds of formula X1

in which Z', Y"' and Xb are as defined above.

The production of the metal-free azo compounds of formula VIII is carried out by coupling 1 mole of a tetrazo compound formed from a diamine of formula XII

with 2 moles of a coupling component of the formula XIII

in which R,, R10, ring E, ring G, Y' and Z have been defined above.

In the compounds of the invention the anion AO can be any non-chromophoric anion conventional in basic dyestuff chemistry. Suitable anions include chloride, bromide, sulphate, bisulphate, methylsulphate, aminosulphate, perchlorate, 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 of addition products of orthoboric acid with polyalcohols or cis - polyols. 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 starting compounds of formula VII must have at least four metal complex forming substituents and are for the most part known (with the exception of the metal-free compounds of formula VIII) or can be made by known methods. The diamines offormula Xl and the coupling components XII are known or can be made by known methods. The metallisation process is advantageously carried out by treating 1 mole of azo compounds with a metallising agent containing at least 2 equivalents of metal.

The metallisation is carried out by known methods 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 3.5 to 8.0, preferably pH 5 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 of2 to 6 molsofnitrite per gram atom of cobalt.

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

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

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

Coupling can be effected by known methods preferably in an acid, neutral or alkaline aqueous medium at a temperature of from 0 C to room temperature, if necessary in the presence of a coupling accelerator such as pyridine or urea. Alternatively coupling can be carried out in a mixture of solvents for example water and an organic solvent.

Preferred azo compounds according to the invention are those for which the cationic molecular weight without the metal atom is 400 to 1200, preferably 450 to 1000, more preferably 500 to 950.

The compounds according to the invention are suitably worked up into a solid or liquid preparation for example by granulation or by dissolving in a suitable solvent. The compounds of the invention are suitable for dyeing, padding or printing on textile materials particularly natural or regenerated cellulose materials for example cotton, mercerised cotton, alkali treated cotton, hemp, sisal,jute or flax.

Exhaust dyeing may be carried out from a long or short bath at a temperature from room temperature to the boil, optionally under pressure, at a goods to liquor ratio of 1:1 to 1:100 preferably 1:20 to 1:50. If dyeing is carried out from a short bath the liquor to goods ratio is 1 to 1:15. The pH of the dyebath is generally between 3 and 10.

Exhaust dyeing may be carried out in the presence of added electrolytes, although it is preferable to dye in the absence of added electrolytes. The amount of added electrolyte is usually 0-20 g/l, more usually 0-10 gill, even more usually 0-5 g/l and most usually 0-2 g/l. Preferred electrolytes are alkali metal salts or alkaline earth metal salts, for example sodium chloride or sodium sulphate.

Printing is carried out by impregnation with a printing paste made up of the dyestuff, water, a thickener, optionally an organic acid (forexample acetic acid or formic acid) and optionally an electrolyte, followed by fixation on the fibres. The printing paste is printed by means of a template or roller; and the dyestuff is fixed, for example by steaming at tem peratures around 100"C, optionally with an intermedi- ate drying step. Fixation of the dyestuff can be accomplished by a pad-steam process or a thermofixation process for example a pad-mu I I' process in which the temperature'should not exceed 230"C. The finishing ofthe dyeing or print is carried out by known methods.

The compounds of the invention have a good substantivity on cellulose.

Preferred dyes according to the invention are those having an exhaust quotient under standard conditions as defined below.

The exhaust quotient is defined as the percentage of the dyestuff originally in the bath which exhausts on to a mercerised cotton yarn after 90 minutes at the boil in an electrolyte-free bath with a goods to liquor ratio of 1:20 containing enough dyestuff to produce a '/. standard depth dyeing. Preferably for azo compounds according to the invention the exhaust quotient is in the range 50 to 100%, more preferably 70 to 100%, even more preferably 80 to 100% and most preferably 90 to 100%. The III standard depth is defined according to NORM DIN 54'000 and ISO NORM R 105111959 part 1.

The dyestuffs on cellulose material (e.g. cotton) produce dyeings having good light fastness and wet fastness (for example water fastness, wash fastness, sweat fastness, peroxide fastness and chlorite fastness).

The dyestuffs of the invention and their preparatins can be usedforthe bulk dyeing of sized or unsized paper. Dyeing of paper can also be carried out by dipping, in known manner. The waste effluent of the bulk paper producing process is practically colourless or only slightly coloured by the dyestuffs of the invention, and this is an important factor in prevention of water contamination. The dyes do not run after dyeing on paper nor on the whole are they pH sensitive. The dyeings made on paper with the dyes of the invention show good light fastness and even after long exposure to light mixtures of the dyestuffs remain tone in tone. Further the nuance stability (of the individual dyestuff) is good.

The dyed paper has good wet fastness not only with respectto water but also with respect to milk, fruit juice, sweetened mineral water and alcoholic drinks.

The azo compounds of the invention can be incorporated into dyeing preparations. The process for preparing a stable liquid preparation of the dyestuffs of the invention is known and is for example carried out by dissolving the dye in a suitable solvent system, if necessary in the presence of an auxiliary agent such as a stabiliser. This is described in French Patent 1,572,030. Alternatively the dyestuffs of the invention can be granulated according to known methods.

The dyestuffs according to the invention can also be used to dye, pad or print fibres, yarns or textiles consisting of or comprising acid-modified polyamide or polyester fibrins. Acid-modified polyamide is described in US Patent3,039,990 and acid-modified polyester is described in Belgian Patent 549179 and US Patent2 893816.

Dyeing of these textiles can be carried out under conditions suitable for basic dyestuffs, advantageously in acid or neutral aqueous baths preferably in a goods to liquor ratio of 1:3 to 1:80 and at a temperature of 60"C to 100 C or under pressure above 100 C.

Dyeing may be carried out in the presence of a conventional auxiliary agent for example dodecyldimethylbenzylammonium chloride as a retarder, the adduct of stearyl alcohol with 50 mols ethylene oxide as a non-ionic auxiliary agent or benzyloxypropionitrile as an accelerator, A further use of the dyestuffs according to the invention is to print or dye leather which can be accomplished by known methods.

In dyeing leather, basic dyeable polyamide or basic dyeable polyester the above mentioned preferences regarding the exhaustquotient or the molecular weight (when dyeing or printing on cellulose) do not necessarily apply.

The invention will now be illustrated with reference to the following Examples in which all temperatures are in degrees Centigrade and all parts and percentages are by weight unless indicated to the contrary.

Example 1 24.4 Parts of dianisidine base is tetraazotised conventionally in dilute hydrochloric acid and is coupled with 65 parts of the coupling component of the formula a)

at a pH of 4.

34.4 Parts of the resulting red dyestuff is dissolved or suspended in a mixture of 400 parts dimethylformamide, 42 parts diethanolamine and 13.3 parts copper acetate and the mixture is stirred for 4 hours art 90".

The reaction product is reduced to half its volume in a rotary evaporator and the resultant solution is precipitated in 3000 parts of acetone. A red copper dyestuff of the formula

is produced.

The dyestuff has a good substantivity and good fastness properties on cotton and paper.

Example 2 10.9 Parts of o - aminophenol is diazotised conven optionally in dilute hydrochloric acid and coupled at a pH of 3 to 4 with 3 - pyridinium - 6 - pyridone. After coupling the brown dyestuff suspension is filtered at pH 9, washed and dried. The resulting compound of formula (b)

dissolves in dilute acetic acid to give an orange colour.

9.5 Parts of dyestuff (b) is dissolved at room temperature in 92 parts of 92% sulphuric acid. At a temperature of 20-25 1.34 parts formaldehyde (in the Form of a 37% solution) is added dropwise to the mixture. The reaction mixture is stirred for six hours and is poured into 1000 parts of acetone under ice cooling. The orange suspension contains a product formula -

after anion exchange in acetic acid, and is filtered under suction and washed with acetone.

9.1 Parts of the compound of formula c) is stirred in 100 parts of water at 60 C and a pH of 4.

6.25 Parts of copper sulphate dissolved in 30 parts of water is added dropwise to the reaction mixture, and the pH of the mixture is held between 4 and 5 by the addition of sodium acetate. The reaction mixture is allowed to react for seven hours, is poured into 1000 parts acetone and the rest ining dyestuff is filtered and purified according to known methods, to give after anion exchange a dyestuffofformula

which dyes cotton and paper a brown red shade with good substantivity and good fastness properties.

Example 3 Dianisidine is coupled with 3 - pyridinium - 6 pyridone by a known method (see German Offen iegungschrift 2,627,680).

15.2 Parts of the resulting known dyestuff is dissolved in 200 parts dimethylformamide and 25.2 parts of diethanolamine and to the solution 8 parts of copper acetate is added. The mixture is warmed over 6 hours to 80 with stirring. The reaction mixture is concentrated in a rotary evaporator then precipitated in 3000 parts of acetone. The brown suspension is filtered under suction and the solid material is dried.

The resultant dyestuff is of the formula

which dyes cotton and paper a brown-violet shade.

Example 4 26.7 Parts of a diazo component, produced conventionally by chloromethylation of ortho - nitroanisole, quaternising with trimethylamine and reducing the nitro group to an amino group (by the Be' champs reaction) and diazotised in a dilute hydrochloric acid, is coupled with 20.6 parts of diacetic acid dianiside at a pH of 4 to 6. The yellow dyestuff is isolated and dried.

8.9 Parts of the yellow dyestuff is dissolved in 120 parts of dimethylformamide and 12.6 parts of diethanolamine and the solution is mixed with 4 parts of copper acetate. The mixture is stirred for 7 hours at 90 and the reaction volume is then reduced in a rotary evaporator and poured into 3000 parts acetone. The brown suspension is filtered and the solidified mass is washed with acetone and dried to give a dyestuff of the formula

which dyes cotton and paper a yellow shade and has good fastness properties. The dyestuff also has a good substantivity on both paper and cotton.

Example 5 81 Parts of a compound of the formula d)

(described in Swiss patent 329) is dissolved in 1000 parts of dimethylformamide and 126 parts of diethanolamine, mixed with 40 parts copper acetate and stirred for 4 hours at 900. According to the method of Example 1 a dyestuff of the formula

is produced, which dyes cotton and paper a blue shade and has good fastness properties. The dyestuff has a good substantivity on both substrates.

Examples 6-31 By following the procedure of Example 1, with suitable choice of starting materials, symmetrical compounds of formula:

may be produced, in which Z, Y, R9, X, Me and the position of the group Z-Y- are listed in Table I, and the anion is any conventional non-chromophoric anion.

Groups X are designated as defined above, groups Z are designated as follows:

cN A 1 N(CH3)2 Z7 no A9 4 CH3 Z2 AO -N(CH2)3 - AT 2 N (CH3 ) 3 As z ~ Ae Z3 N(CH3) 2 A CH2 CH2C}f20H (3 (CN3) 2 A(3 2 -N 0/=\ As cH2-N(cN3)2 210 -N(CH3)2 A(3 25 2± CH2 P (CH2) 3NN2 Z"a CH3 -a Zll a technical 26 N/ CH3 mixture of Z4 Z8 \H) above and groups are designated as follows: : Y, -CH2- V2-NH-CO-CH2- Y3 -SO2-NH-CH2-CH2 Y4 -SO2-NH-(CH2)-3 Y5 -CO-NH-CH2-CH2 V6 -CO-NHCH22 Table I position Example No. Z Y Z-Y- R9 Me X 6 Z1 Y4 4- H Cu X1 7 Z, V6 4- H Cu X1 8 Z1 V6 4- H Ni X1 9 Z2 V1 5- H Ni X1 10 Z2 V2 4- H Co X1 11 Z2 V2 4 H Ni X1 12 Z2 V3 4 H Cu X7 13 Z2 V4 4- H Fe X11 14 Z2 Y5 4- H Zn X,2 15 Z2 V6 5- H Mn X27 16 Z3 Y, 4 H Cu X2 17 Z4 Y2 4- H Cu X14, 18 Z5 Y2 4- H Cu X2" 19 Z6 Y2 4- H Cu X20 20 Z7 Y2 4- H Cu X19"' 21 Z6 V2 4- H Cu X19' 22 Z9 Y2 4- H Cu X20" 23 Z10 Y2 4- H Cu X32' 24 Z11 Y2 4- H Cu X34iv 25 Z4 V2 4- H Cu X34' 26 Z4 Y2 4- H Cu X2, 27 Z4 Y2 4 H Cu X42 28 Z2 V1 5- OCH3 Cu X1 29 Z2 V2 4 OCH3 Cu X34 30 Z2 V2 4- OCH3 Cu X39' 31 Z2 V2 4 OCH3 Cu X40' The compounds of Examples 6-31 give reddishyellow to bluish-red dyeings on cotton or paper.

Examples 32-41 By following the procedure of Example 3, with suitable choice of starting materials, symmetrical compounds of the formula

may be obtained, in which X and Me is given in Table II, Z has any of the significances Z4-Z8 or Z11 defined above, as shown in Table II, and AO is any conventional non-chromophoric anion.

Table II Example No. X Me Z 32 X1 Ni Z4 33 X7 Co Z4 34 X11 Fe Z4 35 X14 Cu Z7 36 X19' Cu Z11 37 X21' Cu Z5 38 X27 Cu Z8 39 X34 Cu Z.6 40 X40' Cu Z4 41 X42 Cu Z4 The dyestuffs of Examples 32-41 dye cotton and paper in red-brown shades.

Examples 42-51 By following the procedure of Example 4, with suitable choice of starting materials, symmetrical compounds of formula

are obtained, in which Z, Y, Me, X and the positions of Z-Y- are as given in Table III.

Table III position Example No. X Me Z Y Z-Y42 X, Ni Z2 Y. 543 X7 Cu Z1 Y1 544 X11 Cu Z2 Y2 445 X14 Co Z3 V2 4-46 X19' Fe Z1 Y4 447 X21' Cu Z2 Y4 448 X27 Cu Z, Y3 549 X34' Cu Z1 V6 450 X40' Cu Z2 Y5 451 X42 Cu Z2 Y1 5 The dyestuffs of Examples 42-51 give yellow dyeings on cotton and paper.

Examples 52-61 By following the procedure of Example 5, with suitable choice of starting materials, symmetrical compounds of formula

may be obtained, in which X, Me, Z and m are as shown in Table IV and A#is a conventional anion.

Table IV Example No. X ME Z m 52 X2' CU Z2 2 53 X7 CU Z3 3 54 X11 CO Z4 3 55 X;4 Fe Z1 3 56 X19' Ni Z5 2 57 X'2, Cu Z6 2 58 X27 Cu Z2 3 59 X34 CU Z, 3 60 X'40 Cu Z1 3 61 X42 Cu Z, 3 The dyestuffs of Examples 52-61 give bluish-red to blue dyeings on cotton and paper.

Example 62 34.6 Parts of a diamine of the formula

is stirred into 2000 parts of water at 0 to 1057 57 parts of 30% aqueous HCI and 13.8 parts of sodium nitrite and tetraazotised in known manner. A bright yellow tetraazo suspension is obtained.

65 Parts of a coupling component of the formula

(made by a known method) is dissolved in 400 parts of water and 40 parts of a 30% aqueous sodium hydroxide solution and is added to the tetraazo solution at 7 to 100. The pH rises from 1.5 to about 4.0 and a dark brown highly viscous dyestuff solution is produced. The pH of the solution is broughtto about 12 at a temperature of 7-10 by adding about 40 parts of a 30% aqueous sodium hydroxide solution. The solution changes to a yellow large grained suspension.

The filtered dyestuff is then dissolved in acetic acid/water solution at 50 and then precipitated in acetone. A yellow water-soluble dyestuff powder results of the formula

The dyestuff has an exhaust quotient of about 90% and gives yellow dyeings on cotton, having good fastness properties.

Examples 63-91 By following the procedure of Example 62 with suitable choice of starting materials, symmetrical metal-free compounds of formula

may be obtained, in which Z, Y, Rg, R, X and the position of Z-V- are as shown in Table V Table V position Example No.Z Y Z-Y- R9 R X 63 Z4 V2 4- H H X, 64 Z4 Y2 4 H H X;4 65 Z4 Yz 4- H H X11 66 Z4 Y2 4- H H X27 67 Z4 Yz 4- H H X34' 68 Z4 Y2 4- H H X21' 69 Z4 Y2 5- H H X21' 70 Z4 Y2 5 - H H X;4 71 Z4 Y2 5 - H H X2,4 72 Z4 V2 5 H OCH3 X, 73 Z2 Y, 5- H OCH3 X, 74 Z1 Y4 4- H OCH3 X1 75 Z2 Y. 5- H H X;;4 76 Z2 Z2 Y, 5- H H X11 77 Z2 Y2 4 - H H X7 78 Z2 V2 4 - H H X42 79 Z2 Y2 4- H H X39' 80 Z2 Y2 4- H H X40' 81 Z, Y6 4- H OCH3 X, 82 Z3 Y3 4- H H X7 83 Z5 Y5 4- H H X2' 84 Z6 V1 4 H H X2" 85 Z9 V2 4- H H Xr2 86 Z10 Y1 4- H H X19"' 87 Z2 Y2 4 OCH3 H X20' 88 Z4 Y2 4- OCH3 H X20" 89 Z2 V2 5 - OCH3 H X32" 90 Z4 Y2 4 OCH3 OCH3 X34 91 Z2 V2 4- H H X34 The compound of Example 73 may be made into a stable liquid preparation by dissolving 10 parts of the dyestuff in a mixture of 45 parts glacial acetic acid and 45 parts water at 40-60 . The dyestuffs of Examples 63-91 dye cotton and paper in yellow to reddish-yellow shades.

Application Example A 70 Parts of a chemically bleached sulphite cellulose (from conifer wood) and 30 parts of a chemically bleached sulphite cellulose (from birch wood) is ground in a Hollander in 2000 parts of water 0.2 Parts of the dyestuff of Example 1 or 62 is added to this mass. After 20 minutes of mixing paper is produced from this mass. The absorbent paper so produced is dyed red or yellow and the backwater is practically colourless.

Application Example B 0.5 Parts of the dyestuff of Example 1 or 62 is dissolved in 100 parts of hot water and cooled to room temperature. The solution is added to 100 parts of chemically bleached sulphite cellulose, which has been ground in a Hollanderwith 2000 parts of water.

After 15 minutes mixing, the mixture is sized. Paper produced from the mass is a red or yellow shade of medium intensity with good wet fastness properties.

Application Example C An absorbent paper web of unsized paper is dyed at 40 to 50 with the following dyestuff solution: 0.5 parts of a dyestuff of Example 1 or 62 0.5 parts starch 99.0 parts water.

The surplus dyestuff solution is pressed out bet ween two rollers. The dried paper web is dyed a red or yellow shade.

Application Example D 2 Parts of the dyestuff of Example 1 or 62 is dissol ved in 4000 parts of softened water at 40 in a bath and 100 parts of resin-finished cotton fabric is added to the bath, which is heated over30 minutes to boil ing. The bath is maintained at this temperature for one hour and topped up with water from time to time. The dyeing is then taken from the bath, washed with water and dried. The dyestuff exhausts practically completely onto the fibres and the spent dyebath is practically colourless. The dyeing produced is a red or yellow shade with good light fastness and good wet fastness properties.

Application Example E Acid modified polyamide fibres are immersed at 20 at a goods to liquor ratio of 1:80 in an aqueous bath containing 3.6 g/l potassium dihydrogen phosphate 0.7 gll disodium hydrogen phosphate, 1 g/l of auxiliary agent (for example the reaction product of a phenol with excess ethylene oxide) and 0.15 gli of the dyestuff of Example 1 or 62.

The bath is heated for about 30 minutes to boiling and is maintained at this temperature for a further 60 minutes. After washing and drying a red or yellow dyeing is produced with good fastness properties.

Acid modified polyester material and acid modified polyamide material may also be dyed by similar methods.

Similarly good dyeings can be obtained in Application Examples A-E by substituting an equivalent quantities of a liquid preparation of the dyestuff or a granular preparation of the dyestuff for the pure dyestuff.

Application Example F 1000 parts of freshly tanned and neutralised chrome grain leather are soaked in a bath of 250 parts water and 0.5 parts of the dyestuff of Example 1 or 62 for 30 minutes at 55 , then treated in the same bath for 30 minutes with 2 parts of an anionic fat liquor based on sulphonated train oil, then dried and finished in conventional manner. A leather evenly dyed in red or yellow shade, is obtained.

Calf suede leather, chrome-vegetable tanned sheepskin and box cowhide leather can also be dyed by known methods.

The dyestuffs of Examples 2-61 and 63-91 can be used according to the Application Examples A-F with similarly good results.

Claims

1. A sulpho-free symmetrical or asymmetrical dis- or polyazo compound of formula I in metal-free or in 2:1 metallised form

in which each Y independently is a direct bond or a (C,~4) alkylene group or a bridging group of the formula

where the above substituents, marked with a star, are attached to the group Z by the carbon atom which is starred, in which mis 1,2,3 or4 and R4 is hydrogen or C,4alkyl; teach R, independently is an aromatic or a heterocyclic coupling component group; X is a bridging group or a direct bond; n is at least 2; each Z independently is-N(CH3)2,

in which p is 1 or 2 and m is as defined above and Nazis a conventional non-chromophoric anion; and either 1) each A is

(a)and each R3 independently is (C1~4)alkyl;; and or 2) each A together with R3 and the ethylene group to which A and R3 are attached, forms the group (b)

and the aromatic rings in groups (a) and (b), independently, can be substituted by one or two groups selected from halogen, (C,~4)alkyl and (C14)aIkoxy, and A, and A2, for compounds offormulal in metal complex form, form the group4-Me-O-where Me is copper, cobalt, iron, nickel, manganese or zinc, and for metalfree compounds each A2 independently is hydrogen, C14alkoxy or-OH and A1 is-OH with the proviso that, when the compound of formula I is in metal-free form, each A and R3 form the group b) above and R, is a 1-phenyl pyrazole, the phenyl group of which is substituted by one group -Y-Z where Y and Z are as defined above.

2. Acompound as claimed in Claim 1 in which X is any one of groups X, to X46 where X, is a direct bond X2 is a straight or branched chain C,~4alkylene and X3to X46 are as listed below:

where R5 is halogen, C14alkyl or (C1-4)alkoxy each R6 independently is halogen, -NH-CH2-CH2OH or -N(CH2-CH2-OH)2 and R, is a straight or branched chain C1-4alkylene group.

3. A compound as claimed in Claim 2 in which X is Xa where Xa is selected from the groups X1, X5, X6, X7,X10,X11,X12,X22,X25,X26,X27,X30,X42(defined in Claim 2) and the groups X2'-CH2-, X2"-CH2-CH2-, X2"'-(CH2)3-,X2iv-CH2)4-,

X34'CO-NH-(CH2)2-NH-CO,X34" -CO-NH-(CH2)3-NH-CO

-NH-CO-, X39'-CH=CH-CO-NH-, and X40'-CH2-CH2-CO-NH-, where each R5a independently is chlorine, methyl or methoxy and each R6a is chlorine, -NH-CH2-CH2-OH or-N-(CH2CH2-OH)2.

4. A compound as claimed in Claim 3 in which X is Xb where Xb is X1, X7, X11, X12, X27, X2', X2", X14', X19', X19"' X20', X20", X21', X32', X34', X34iv, X34v, X40' or X42, as defined in Claim 2 or Claim 3.

5. A compound as claimed in any one of the preceding claims in which both groupings attached to the bridging group X are identical.

6. A compound as claimed in Claim 1 in2:1 metal complex form of formula II

in which R1, R3, A, Y, X, Z, n and Me are defined in Claim 1.

7. A compound as claimed in Claim 6 in which the metal is copper.

8. A compound as claimed in Claim 6 or Claim 7 offormula Ill

in which each R6 independently is hydrogen, methyl or-CH2CH2OH; each ring B can be further substituted by one substituent selected from halogen, C1-4alkyl and C1-4alkoxy; Me A#, p are as defined in Claim 1; and Xa is as defined in Claim 3.

9. Acompoundasclaimed in Claim 6 or Claim 7 or formula IV

in which Xa is defined in Claim 3, m, Z and Me are defined in Claim 1 and each ring B can be further substituted as defined in Claim 8.

10. A compound as claimed in Claim 6 or Claim 7 of formula V

in which each Y' independently has the significance of Y as defined in Claim 1 other than C24 alkylene, each R9 independently is hydrogen or C14 alkoxy, each ring B and E can be further substituted by up to q substituents selected from halogen, C14 alkyl and C1-4alkoxy, whereby for rings marked Bq = 1 and for rings marked E q = 1 when R9 is alkoxy and q = 2 when R9 is hydrogen; Me and Z are defined in Claim 1; and Xa is defined in Claim 3.

11. A compound as claimed in Claim 6 or Claim 7 of formula VI

in which Xa is defined in Claim 3, Me and Z are defined in Claim 1 and Y' is defined in Claim 10, and ring B and ring D are substituted by up to q substituents selected from halogen, C14 alkyl and C14 alkoxy, whereby for ring B q = 1 and for ring D q = 2.

12. A compound as claimed in Claim 10 in which R9 is R9' where R9' is hydrogen or methoxy.

13. A compound as claimed in Claim 10 of formula Va

in which Xb is defined in Claim 4; * Y"' is -CH2-, -NH-CO-CH2- OR CO-NH- (CH2)3; and # Z' is -N(CH3)2, -N(CH3)3 A# or where p is as defined in Claim 1.

14. A compound of formula II as defined in Claim 6 substantially as herein described with reference to any one of Examples 1 to 61.

15. A process for the production of a compound i of formula II defined in Claim 6 comprising metallis ing a compound of formula Vll

in which R1, R3, Y, Z, A and n are defined in Claim 1 and each R10 independently is hydrogen or C1-4 alkyl.

16. A compound as claimed in Claim 1 of formula VIII

in which X and Z are defined in Claim 1 Y' and R9 are as defined in Claim 10, R10 is defined in Claim 15; risOor1; and rings E and rings G may be further substituted by up to q substituents whereby for ring G q = 1 when r = 1 and q = 2 when r = 0, and for ring E q = 1 when R9 is alkoxy and q = 2 when R9 is hydrogen.

17. A compound as claimed in Claim 16 of for mula IX

in which Z is as defined in Claim 1; Xa is as defined in Claim 3; R'3 is defined in Claim 12; R10 is defined in Claim 15; ris as defined in Claim 16; p' is 0 or 1; V" is is-CH2-,-CO-NH-(CH2)m'*-, and -NH-CO(CH2)m,*-, or SO2-NH-(CH2)m,*-, where m' is 2 or 3 and m is defined in Claim 1 R is chlorine, -CH3-, -C2H5-, -OCH3- OR -OC2H5-.

18. A compound as claimed in Claim l6offor- mula XI

in which Xb is defined in Claim 4 and Z' and Y"' are defined in Claim 13.

19. A compound of formula VIII as defined in Claim 16 substantially as herein described with reference to any one of Examples 62 to 91.

20. A process for the production of a compound of formula VIII@ defined in Claim 16 comprising coupl- ing 1 mole of a tetra azo compound formed from a diamine of formula XII

with 2 moles of a coupling component of formula XIII

in which Z is defined in Claim 1 R6, Y' and ring E are deffined in Claim 10 R10 is defined in Claim 15 and rand ring G are defined in Claim 16.

21. A process for dyeing or printing on a substrate comprising applying to the substrate a compound offormula I as defined in Claim 1.

22. A dyeing composition comprising a compound of formula I as defined in Claim 1.

23. A substrate when dyed by a process as claimed in Claim 21.