GB1568715A - Chromium complex dyestuffs - Google Patents

Abstract

Asymmetric 1:2 chromium complexes which contain a single sulpho group in salt form and which correspond to the formula <IMAGE> wherein the variables X1, X2, Y, A, A2, B and M have the meaning given in Patent Claim 1, are prepared by addition reaction of the 1:1 chromium complex of one azo compound with the other metal-free azo compound, or vice versa. These chromium complexes are used for dyeing and printing natural and synthetic polyamides or polyurethanes, for dyeing leather or metals such as anodized aluminium, and for the bulk spin-dyeing of polyamides or of acetate rayon; chromium complexes soluble in organic solvents are moreover used in printing lacquers (varnishes) and ball point-pen inks.

Description

(54) CHROMIUM COMPLEX 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 invention relates to asymmetric 1:2-chromium complexes.

In particular, the present invention provides asymmetric 1: 2-chromium complex dyestuffs of formula I

in which either, A is a diazo compoent radical of formula

in which E is a sulpho group, a sulphonamide radical or an acyl radical of a sulphonic acid, Z is a hydrogen or nitro, and the carbon atom marked with the asterisk is bound to the azo group, or, A is a diazo component radical of the 1,2-phenylene series, B' is a diazo component radical of the 1,2-phenylene series, D is a coupling component radical of the 5-pyrazolone series which is coupled to the carbon atom next to that carrying the hydroxy group, the component being bound to the metal atom through the oxygen atom, D2 is a coupling component radical of the 5-aminopyrazole series which is coupled to the carbon atom adjacent that carrying the amino group, the component being bound to the metal atom through the amino group, and Ms is hydrogen or an equivalent of a non-chromophoric cation, with the provisos (i) that the dyestuff molecule contains a single sulpho group, which sulpho group is in salt form, and (ii) that the molecule contains at maximum a single water-solubilizing group in addition to the sulpho group, and mixtures of such 1:2 asymmetric chromium complexes.

The water solubilizing group in addition to the sulpho group present may be a carboxylic acid group or a known water solubilising derivative of sulphonic acid or carboxylic acid groups.

It will be appreciated that the phenyl diazo components as A and B and the coupling components as D, and D2 may bear substituents which are common in the chemistry of metallized azo dyestuffs, however, substituents or combinations of substituents which are known to deleteriously affect the dyeing properties of the molecule and substituents or combinations thereof which are know to present steric or stability problems should not, of course, be present.

Preferred dyestuffs of formula I are those of formula Ia,

in which A, is a group of formula (a) or (b)

in which Z is hydrogen or nitro, each of the rings A2 and B1, independently, is further unsubstituted or further substituted by a total of up to three substituents selected from halogen atoms (a total of up to three thereof), nitro groups (a total of up of two thereof), (C,~4)alkyl, (C,~4)alkoxy, -SO2R1, -SO2NR2R3, sulpho, phenylazo, chloro-, methyl-, methoxy- or sulphosubstituted phenyl-azo (only one of each of these), preferably when the ring A2 or B, is substituted by sulpho it is further unsubstituted or bears a single further substituent and when it is substituted by phenylazo or substituted phenylazo it is preferably not further substituted, preferably when the ring R is substituted it is substituted @@@@@@@@@@@@@@@@@@@@@ R is hydrogen, (C14)alkyl, phenyl, phenyl-(C1-3)alkyl, phenylsulphonyl or tosyl, each of X1 and X2, independently, is (C14)alkyl, (C14)alkoxy, -COOR, -CONH2-COO-(C1-2) alkyl, cyano or phenyl, each of Y1 and Y2, independently, is hydrogen; unsubstituted (C1-6)alkyl; (C1-8)alkyl which is substituted by a total of up to two substituents selected from halogen atoms, hydroxy, cyano and (C1-C4)alkoxy, preferably methoxy, unsubstituted (C5-6)cycloalkyl; (C5-C6) cycloalkyl which is substituted by up to three (C1~4)alkyl groups; unsubstituted phenyl; phenyl substituted by a total of up to three substituents, preferably up to two, selected from halogen, preferably chlorine, (C1~4), preferably (C,~2) alkoxy, (C1-4), preferably (C1-2)alkyl (up to two of each of these), nitro, -SO2RO41, -SO2NR2R3, cyano, sulpho (only one of each of these): unsubstituted 1- or 2-naphthyl;I-naphthyl substituted by a sulpho group in the 4-, 5-, 6-, 7- or 8- position; 2-naphthyl substituted by a sulpho group in the 1-, 5-, 6-, 7- or 8- position; or phenyl(C1-3)alkyl, R1 is unsubstituted (C1-C4)alkyl; (C1-4) alkyl monosubstituted by hydroxy, (C1-2)alkoxy, halogen or cyano, unsubstituted phenyl or phenyl substituted by a total of up to two substituents selected from halogen, nitro, (C1~2)alkyl or (C1-2)alkoxy, either R2 is hydrogen;unsubstituted (C1-4) alkyl; or (C1-4)alkyl monosubstituted by hydroxy, halogen, (C1-2)alkoxy, or cyano, and R3 is hydrogen or has one of the significances of R1, or R2 and R3, together with the nitrogen atom to which they are hound, form a 5- or 6-membered saturated heterocyclic ring which contains no further or one further hetero atom, and M0 is as defined above.

It will be appreciated that

groups should not be present owing to stability problems.

By halogen as used herein is meant chlorine or bromine, with chlorine being the preferred halogen.

Where any of R1, R2 and R3 is an unsubstituted or substituted (C1-4)alkyl radical it may be a linear or branched chain alkyl and preferably contains 1 to 3 carbon atoms. Methyl, ethyl and isopropyl are especially preferred as unsubstituted alkyl radicals and linear (C1~3)alkyl radicals are especially preferred as substituted alkyl radicals. Preferred substituted alkyl groups are those which are substituted by hydroxy, methoxy or ethoxy.

Where R1 or R3 is substituted phenyl, preferably the phenyl is monosubstituted by chlorine, nitro, methyl, methoxy or ethoxy or disubstituted by two methyl, methoxy or ethoxy groups. More preferably, any phenyl as R1 or R3 is unsubstituted.

Where R2 and R3, together with the nitrogen atom to which they are bound, form a heterocyclic ring they preferably form a pyrrolidine, piperidine or morpholine ring.

When Y1 and/or Y2 is an unsubstituted or substituted (C1-6)alkyl, the alkyl radical may be a linear or branched chain and preferably contains I to 4 carbon atoms. Preferred alkyl groups are methyl, ethyl, isopropyl and isobutyl. Where the alkyl radical is substituted it is preferably monosubstituted by hydroxy or cyano, which substituents are bound to the terminal carbon atom, especially preferred substituted alkyl radicals are (C23)alkyl radicals substituted by cyano or hydroxy, in particular 2-hydroxy- or 2-cyanoethyl.

Y, and/or Y2 is a (Cs~6)cycloalkyl, it is preferably cyclohexyl. Preferred substituted cycloalkyl radicals as Y1 and/or Y2 are cyclohexyl which is monosubstituted by (C1-4)alkyl, preferably in the 4-position; cyclohexyl which is disubstituted by methyl, preferably in the 3,5-positions; and cyclohexyl which is trisubstituted by methyl, preferably in the 2,4,6- or 3,5,5-positions.

Where Y, and/or Y2 is a phenyl (C,~3)alkyl group the alkyl chain is preferably linear, with benzyl being the preferred phenyl alkyl group.

Any-SO2R1 group as a substituent on the phenyl radical as Y1 and/or Y2 is preferably-SO2CH3 or-SO2CH2CH3, any-SO2NR2R3 is preferably-SO2NH2 or -SO2N(CH3)2. Where the phenyl radical as Y, and/or Y is monosubstituted it is preferably substituted by chlorine, bromine, methyl, methyl, methoxy, ethoxy, cyano, nitro, -SO2CH3, SO2CH2CH3, -SO2NH2, -SO2N(CH3)2 or sulpho. Where the phenyl group is disubstituted the substituents are preferably in the 2,4-, 2,5- or 3,4-positions. Where the phenyl group is trisubstituted the substituents are preferably in the 2,3,6-,2,4,5- or 2,4,6- positions; more preferably these substituents are identical, especially three chlorine atoms in the 2,4,6- positions.Where Y1 and/or Y2 is phenyl it is preferably unsubstituted phenyl or phenyl substituted by one or two substituents selected from chlorine, methyl, ethyl and sulpho, with unsubstituted phenyl, 3-chloro- or sulphophenyl, 4-chloro- or sulphophenyl and 2,5-dichlorophenyl being especially preferred.

Any (C1-4)alkyl as R may be linear or branched chain. Preferably any alkyl is methyl or ethyl, in particular ethyl. The preferred phenyl(C1-3)alkyl group as R is benzyl.

Where X1 and/or X2 si (C1-4)alkyl or (C1-4)alkoxy the alkyl and alkoxy groups preferably contain 1 or 2 carbon atoms.

Preferably R1 is R1', where R1' is (C1-3)alkyl or phenyl. More preferably R1, is R1", where R1" is methyl, ethyl or isopropyl, in particular methyl or ethyl.

Preferably R2 is R2', where R2' is hydrogen, (C1-3)alkyl 2-hydroxyethyl, 2- or 3hydroxy-n-propyl. More preferably R2 is R2", where R2" is hydrogen or methyl.

Preferably R3 is R3', where R3' is hydrogen; (C1-3)alkyl; 2-hydroxyethyl, 2- or 3 hydroxy-n-propyl; a R4O-(CH2)n- group in which R4 is methyl or ethyl and n is 2, 3 or 4, preferably 2 or 3; unsubstituted phenyl; phenyl monosubstituted by chlorine, nitro, methyl, methoxy or ethoxy; or phenyl disubstituted by two methyl, methoxy or ethoxy groups. More preferably R3 is R3', where R3,, is hydrogen, methyl, ethyl, isopropyl, 2-hydroxyethyl, 2-hydroxy-n-propyl, 3-methoxy-n-propyl or unsubstituted phenyl Even more preferably, R3 is R3", where R3" is hydrogen, methyl, 3-methoxy-n-propyl or unsubstituted phenyl, in particular hydrogen or methyl.

A1 is preferably a group of formula (a). Where the ring A2 and/or ring B, is further monosubstituted, the substituent is preferably in the 4- or 5-position. Where the rings are disubstituted the substituents are Preferably in the 4,5- or 4,6 positions. Where the rings are trisubstituted the substituents are preferably three identical halogens, especially three chlorine atoms in the 3,4,6-positions.

Preferably, the rings A2 and B, are A2 and B, where A2 and B;, independently, are substituted by one or two substituents selected from chlorine, nitro and sulpho.

R is preferably R', where R' is hydrogen, methyl, ethyl, unsubstituted phenyl, benzyl, phenylsulphonyl or tosyl. More preferably, R is R". where R" is hydrogen, ethyl or tosyl, in particular hydrogen.

X1 is preferably X1', where X1' is methyl, ethyl, methoxy, phenyl or-CONH2.

More preferably X1 is X1", where X1" is methyl, phenyl or -CONH2, in particular methyl.

X2 is preferably X2'where X2' is methyl, ethyl or phenyl, in particular methyl, Y1 is preferably Y1', where Y1' is unsubstituted phenyl; phenyl monosubstituted by chlorine, methyl, ethyl (the ethyl preferably in the 2-position), or sulpho, (preferably in the 3- or 4-position), phenyl substituted by two substituents selected from the group chlorine, methyl, ethyl, preferably in the 2,4-, 2,5- or 3,4-positions; or phenyl substituted by sulpho and a further substituent selected from chlorine, methyl and ethyl, preferably in the 2,4- or 2,5-positions. More preferably Y, is Y;', where Y;' is unsubstituted phenyl, 3- or 4-sulphophenyl, 3- or 4- chlorophenyl or 2.5-dichlorophenyl.

Y2 is preferably Y2', where Y2' is cyclohexyl, 4-(C1-4) alkylcyclohexyl, 3,5dimethylcyciohexyl, 2,4,6- or 3,5,5-trimethylcyclohexyl, unsubstituted phenyl, chloro- or sulphophenyl, in particular in the 3- or 4-positions dichlorophenyl, in particular 2,5-dichlorophenyl or phenyl substituted by chloro and sulpho, preferably in the 2,4- or 2,5-positions. More preferably Y2 is Y2', where Y2' has any one of the significances given for Y1".

Preferably M is other than hydrogen and signifies an alkali metal cation, an unsubstituted ammonium ion, a lower-alkyl substituted ammonium ion, a hydroxy substituted lower-alkyl ammonium ion, a higher alkyl substituted ammonium ion, a mono- or dicycloalkyl ammonium ion or a cycloimmonium ion. As exam les of alkali metal cations, may be given lithium, sodium or potassium. The unsubstituted, lower-alkyl substituted and hydroxyalkylsubstituted-ammonium may be represented by the formula N$(R6)4 where each R5 is, independently, hydrogen, (C1-3)alkyl or hydroxy(C2-4)alkyl, for example, triethyl ammonium, mono- di- and triethanol ammonium and mono-, di- and trilsopropanol ammonium.

Examples of combinations of substituents or substituents which would present steric and/or stability problems are those where each R5 is identical and is hydroxyalkyl and as previously indicated the group N(R5)4 should not contain a

group owing to stability problems.

When M is a higher, e.g. (C5-12)alkylsubstituted-, mono- or dicyclo- e.g.

(C5-7)cycloalkylsubstituted ammonium ion or a cycloimmonium ion the water solubility of the complexes is reduced such that they are scarcely water-soluble or only soluble in the presence of organic solvents. Examples of such ions include those derived from N-ethyl-N-hexylamine, cyclohexylamine, N,Ndicyclohexylamine and morpholine.

More preferably M is an alkali metal cation with sodium being most preterred.

The 1:2-complexes in which M is hydrogen, are, in general scarcely soluble in water.

The cation of the sulpho group may be any one of those given above for M and may be the same as or different from M.

Preferred compounds of formula Ia are those in which A, is a group of formula (a), R is R', preferably R", X1 is X1', X2 is X2', Y1 is Y1' and Y2 is Y2'.

More preferred compounds of formula la are those in which A, is a group of formula (a) R is hydrogen, X1 is X1", X2 is methyl, Y1 is Y1" and Y2 is Y2".

Especially preferred compounds are those of formula Ib,

in which each of Z, and Z3, independently, is hydrogen, chlorine or nitro, each of Z2 and 4, independently, is chlorine, nitro or sulpho, when Z, and/or Z3 is hydrogen, the substituent as Z2 and/or Z4 respectively, is preferably in the 4-position when chlorine or sulpho, and in the 4- or 5 position when nitro, when Z, and Z2 and/or Z3 and Z4 are the same the substituents are preferably in the 4,6-positions when Z, is nitro and Z2, is chlorine and/or Z3 is nitro and Z4 is chlorine, the substituents are preferably in the 4,5- or 4,6 positions, and when Z, and/or Z3 is chlorine or nitro and Z2, respectively Z4, is sulpho, the substituents are preferably in the 4,6 positions, with the compounds where Y1, is Y1,' being most preferred.

The invention further provides a process for the production of asymmetric 1:2chromium complexes of formula I and mixtures thereof, comprising reacting a 1:1 - chromium complex of a monoazo dye of formula II,

or a mixture thereof, or of a monoazo dye of formula III,

or a mixture thereof, with one or more metal-free monoazo dyes of formula III or II, respectively.

As will be appreciated the sulpho which is present in the dye of formula II or III may be in the free acid or salt form. Any sulpho group in free acid form is converted into the salt form during the reaction. Preferably the sulpho group is in the 1:1 complex which is reacted with the metal-free, sulpho-free monoazo dyestuff.

The reaction for the production of the asymmetrical 1:2-chromium complexes may be carried out in conventional manner. In order to obtain the asymmetric 1:2 chromium complexes it is advantageous to carry out the reaction at a pH in the range of 6 to 13 preferably at pH 7 to 11. It is also advantageous to employ the reactants in approximately stoichiometric amounts avoiding an excess of the metal free monoazo dyestuff. The product obtained may be isolated in conventional manner, for example by salting out or weakly acidifying, filtering, washing with salt solution and drying.

By controlling the reaction and isolation conditions (e.g. addition of base to obtain an alkaline pH or the salt used to salt-out the product) a complex of formula I may be obtained in which M is preferably an alkali metal cation, such as lithium, sodium or potassium, or an ammonium ion and in which the salt form of the sulpho group is the same as or different from M. When a weak acid is used a complex is obtained in which M is hydrogen and the sulpho group is in salt form. The hydrogen ion may replaced by an alkali metal cation or ammonium ion by the addition of alkali metal hydroxides or organic amines. It will be appreciated that the cation of the sulpho group may also be replaced at the same time.

The preparation of the 1:1 chromium complexes of the compounds of formula II or III may be carried out in accordance with known methods and the obtained 1:1 complexes may be used to produce the 1:2 complexes without subsequent drying.

The starting materials of formula II and III, may be prepared in conventional manner.

The asymmetric 1:2-chromium complexes of formula I and mixtures thereof are useful for dyeing and printing nitrogen-containing organic substrates. Examples of suitable substrates are those which consist of or comprise natural or synthetic polyamides such as wool, silk or nylon, or polyurefhane or leather.

The complexes of formula I and mixtures thereof are suitable for dyeing from a weakly alkaline, neutral or weakly acid, for example, an acetic acid-containing dyebath.

The dyeings obtained exhibit notable light and wet fastness. They also exhibit notable rubbing fastness and resistance to carbonization, ironing, wool chlorination and the action of acids and alkalis.

The dyestuffs build-up notably on polyamide fibres and they exhaust from a neutral medium. The build-up is tone-in-tone due to their pure asymmetric character. The dyestuffs also build-up comparably on wool and nylon when dyed together. The dyestuffs are also suitable for use in combination with other 1:2 metal complexes. The complexes may be formed into stable printing pastes which buildup well on all types of polyamides.

The complexes of formula I and mixtures thereof are also useful for spindyeing synthetic polyamides and silk acetate in the mass.

The complexes of formula I which are well soluble in water, i.e. those in which M is other than hydrogen, a higher alkylammonium ion, a mono- or dicycloalkylammonium ion or cycloimmoniun ion are also useful for dyeing metals, especially anodized aluminium.

The compounds of formula I, in which M is hydrogen, a higher alkylammonium ion, a mono-, or dicycloalkylammonium ion or cycloimmonium ion may also be used in the preparation of printing laquers and ball-point pen inks.

The dyes according to the invention may be employed as such or in the form of liquid or solid preparations.

Preferably water-soluble organic solvents, optionally mixed with water, are used for the liquid preparations which are in the form of stable concentrated stock solutions; conventional additives such as dissolving agents (e.g. urea or alkali reacting organic or inorganic substances) may be added thereto. The stock solutions may be diluted with water. Such preparations may be made, for example, in accordance with the procedure described in German Patent No. 1,619,470 or in German Patent Application No. 2,033,989. Also concentrated stable aqueous preparations which contain the conventional additives may be used.

Solid preparations which are in powder or granulate form with an average particle size of at least 20u can be used, which preparations contain con ventional additives such as standardization agents. Such solid preparations may be made for example in accordance with the procedure described in British Patent 1,370,845. The solid preparations are well soluble in water.

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

Example 1.

The 1:1-chromium complex which is obtained by a known process by reacting 20.5parts of the azodestuff df'diazotised 2-amino-4-chloro-l-hydroxybenzene-6sulphonic acid and 1-phenyl-3-methyl-5-pyrazolone with 25 parts of KCr(SO4)2.l2H2O, is stirred in 400 parts of water at 8W90 together with 20 parts of the monoazo dyestuff obtained by a known process from diazotised 2-amino-4,6 dichloro- 1 -hydroxybenzene and I -(3'-chlorophenyl)-3-methyl-5-amino-pyrazole.

The suspension is set at a pH of 7.5-8.5 by adding 20% sodium carbonate solution, and is subsequently stirred at 8090 until both of the starting materials are no longer detectable. The chromium complex which is partly in solution is salted-out by the addition of sodium chloride, isolated by filtration and after washing with 5% sodium chloride solution is dried in vacuum.

The dyestuff obtained corresponds to the formula

is well soluble in water and dyes wool and synthetic polyamides in bluish-red shades. It exhausts from a neutral bath and builds-up tone-in-tone. Furthermore, it dyes wool and nylon equally when present in the same bath. The dyeings obtained have good fastness properties.

In accordance with the procedure of Example I, further 1:2-chromium complexes of formula Ia are obtained in which A1 is a group of formula (a), X1 and X2 are both methyl, R is hydrogen and the further variables are indicated in Table 1. The dyestuffs so obtained give dyeings of red shades, varying from bluish-red to bordeaux, on polyamide.

TABLE 1

Example Substituents of Substituents of No. Ring A2 Ring B1 Y1 Y2 2 4-chloro-6-sulpho 4,6-dichloro phenyl phenyl 3 do. do. 3'-chlorophenyl do.

4 do. do. 4'-chlorophenyl do.

5 do. 5-nitro phenyl do.

6 do. 4-chloro-5-nitro do. do.

7 do. 4,6-dichloro 3'-chlorophenyl 4'-chlorophenyl 8 do. do. do. 2',5'-dichlorophenyl 9 do. 4-SO2NH2 do. phenyl 10 do. 5-nitro 3',4'-dichlorophenyl do.

11 do. do. 2',5'-dichlorophenyl do.

12 do. 4,6-dichloro phenyl 4'-chlorophenyl 13 6-chloro-4-sulpho do. 3'-chlorophenyl do.

14 do. do. do. 2',5'-dichorophenyl 15 4,6-dichloro do. 4'-sulphophenyl 4'-chlorophenyl 16 do. do. do. 3'-chlorophenyl 17 do. do. do. 2',5'-dichlorophenyl 18 do. do. do. phenyl TABLE 1 (Cont'd)

Example Substituents of Substituents of No. Ring A2 Ring B1 Y1 Y2 19 4,6-dichloro 4,6-dichloro 3'-sulphophenyl 4'-chlorophenyl 20 do. 5-nitro 4'-sulphophenyl phenyl 21 do. 4-chloro-5-nitro do. do.

22 do. 4-chloro-5-SO2NH2 do. do.

23 4-nitro-6-sulpho 4,6-dichloro phenyl do.

24 6-nitro-4-sulpho 4-SO2NH2 do. do.

25 4,6-dinitro 5-nitro 3'-SO2NH2-phenyl 3'-sulphophenyl 26 5-nitro 4,6-dichloro 4'-sulphophenyl 4'-chlorophenyl 27 do. do. do. 2',5'-dichlorophenyl 28 do. do. do. phenyl 29 do. do. 3'-sulphophenyl 4'-chlorophenyl 30 do. do. do. phenyl 31 do. 5-nitro 4'-sulphophenyl 3',4'-dichlorophenyl 32 4-chloro 4,6-dichloro do. 4'-chlorophenyl 33 do. do. 3'-sulphophenyl do.

34 do. 5-SO2NH2 4'-sulphophenyl phenyl 35 do. 5-nitro do. do.

TABLE 1 (Cont'd)

Example Substituents of Substituents of No. Ring A2 Ring B1 Y1 Y2 36 4-chloro 4,6-dichloro 4'-sulphophenyl phenyl 37 4-SO2NH-phenyl 4-chloro-6-sulpho phenyl do.

38 4-chloro-6-sulpho 4,6-dichloro do. hydrogen 39 do. do. do. methyl 40 do. do. 3'-chlorophenyl ethyl 41 4,6-dichloro do. hydrogen 4'-sulphophenyl 42 do. do. benzyl 3'-sulphophenyl 43 do. do. 3'-sulphophenyl 1-naphthyl 44 do. do. do. cyclohexyl 45 5-nitro do. do. benzyl 46 4-N=N-phenyl 4-chloro-6-sulpho phenyl phenyl 47 do. do. 3'-chlorophenyl do.

48 4-methyl 4,6-dichloro do. 4'-sulphophenyl 49 4-chloro-6-sulpho 4-methyl do. 3',4'-dichlorophenyl 50 4-methyl-6-sulpho 5-nitro do. phenyl 51 4-chloro-6-sulpho 4-methoxy do. do.

TABLE 1 (Cont'd)

Example Substituents of Substituents of No. Ring A2 Ring B1 Y1 Y2 52 4-methoxy 4,6-dichloro 4'-sulphophenyl 3'-chlorophenyl 53 4-chloro-5-SO2CH3 4-methyl-6-chloro do. phenyl 54 4-chloro-5-SO2C2H5 4,6-dichloro do. do.

In the following Table 2 further dyestuffs which may be prepared in accordance with Example 1 are given. They correspond to formula la in which A, is a group of formula (b) and X2 is methyl and the other variables are given in the Table. The dyestuffs obtained give dyeings of red shades, varyin from bluish-red to bordeaux, on polyamide.

TABLE 2

Example Substituents of No. Z Ring B1 X1 Y1 Y2 R 55 H 4,6-dichloro CH3 phenyl phenyl H 56 H do. do. 4'-chlorophenyl 2',5'-dichlorophenyl H 57 H 5-nitro do. phenyl phenyl H 58 H do. CONH2 do. 4'-chlorophenyl H 59 H do. CH3 3'-chlorophenyl do. H 60 H 4,6-dichloro CH3 do. phenyl H 61 NO2 do. do. do. do. H 62 do. do. phenyl 4'-chlorophenyl do. H 63 H do. do. do. do. H 64 H do. CH3 do. do. C2H5 65 H 5-nitro CONH2 phenyl 3'-chlorophenyl do.

66 H do. phenyl 3'-cyanophenyl do. tosyl 67 NO2 4,6-dichloro do. 3'-methylphenyl phenyl do.

68 do. do. CH3 phenyl do. C2H5 69 do. do. CONH2 do. 3'-chlorophenyl H In the following Table 3 further dyestuffs made in accordance with the procedure of Example I are given. They correspond to formula la in which A1 is a group of formula (a) and the further variables are given in the Table. The dyestuffs so obtained give dyeings of red shades, varying from bluish-red to bordeaux, on polyamide.

TABLE 3

Example Substituents of Substituents of No. Ring A2 Ring B1 X1 X2 Y1 Y2 R 70 4-chloro-6-sulpho 4,6-dichloro CONH2 CH3 phenyl phenyl H 71 do. do. CN do. do. do. H 72 do. do. COOH do. do. do. H 73 do. do. OCH3 do. do. do. H 74 do. do. phenyl do. do. do. H 75 do. do. C2H5 do. do. do. H 76 do. do. CH3 do. do. do. C2H5 77 do. do. do. do. do. do. tosyl 78 do. do. do. phenyl do. do. H 79 do. do. do. CONH2 do. do. H 80 do. do. CONH2 CH3 do. 4'-chlorophenyl H 81 do. do. CH3 do. do. do. C2H5 82 do. do. do. do. do. do. tosyl 83 4,6-dichloro do. CH3 CH3 do. 3'-sulphophenyl do.

84 do. do. do. do. do. do. C2H5 85 do. 4-chloro-5-SO2NH2 do. CONH2 4'-chloro- do. H phenyl 86 5-nitro 5-nitro do. phenyl 3'-sulpho- 4'-chlorophenyl C2H5 phenyl 87 do. do. do. do. do. do. tosyl 88 do. do. CONH2 CH3 do. phenyl H 89 do. do. do. do. phenyl 4'-sulphophenyl H 90 do. 4,6-dichloro phenyl do. do. do. H 91 do. do. do. do. do. do. C2H5 The dyestuffs of Examples 1 to 91 may also be prepared by reacting the 1:1 chromium complex of the sulpho-free monoazo dye of formula II or formula III, with the sulpho-containing metal-free monoazo dye of formula III, or II, respectively.

Application Example A.

0.05 g of the dyestuff of Example I or 12 are dissolved in 300 parts of water, and 0.2 g of ammonium sulphate are added thereto. Subsequently, the moistened material (5 g of wool gaberdine or 5 g nylon-satin) is entered into the bath which is heated over the course of 30 minutes to boiling temperature. The water which is evaporated during the next 30 minutes boiling is replaced and dyeing is completed during the next 30 minutes at the boil. The dyed material is subsequently rinsed.

After drying, a bluish-red dyeing having good light- and wet-fastness properties is obtained in both cases.

Dyeings may be made in accordance with the above procedure employing any one of the dyestuffs of Examples 2 to 11 and 13 to 91 or a mixture of any two or more of the dyestuffs of Examples I to 91.

Application Example B.

Polyamide is printed with a printing paste containing 30 parts dyestuff of Example 1 or Example 12, 50 parts urea, 50 parts dissolving agent, for example thiodiethylene glycol, 300 parts water, 500 parts suitable thickening agent, for example based on locus bean gum, 60 parts acid acceptor, for example, ammonium tartrate, and 60 parts thiourea.

The printed goods are steamed for 40 minutes at 1020C (saturated steam), then rinsed with cold water, washed for 5 minutes at 600C with a dilute solution of a conventional detergent and then rinsed again. A bluish-red print having good wetand lightfastness is obtained in both cases.

In analogous manner printing pastes may be prepared using any one of the dyestuffs of Examples 2 to 11 or 13 to 91.

WHAT WE CLAIM IS.

I. An asymmetric l:2- & romium complex dyestuff of formula I,

in which either, A is a diazo component radical of formula

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

Claims (1)

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

   The dyestuffs of Examples 1 to 91 may also be prepared by reacting the 1:1 chromium complex of the sulpho-free monoazo dye of formula II or formula III, with the sulpho-containing metal-free monoazo dye of formula III, or II, respectively.

   Application Example A.

   0.05 g of the dyestuff of Example I or 12 are dissolved in 300 parts of water, and 0.2 g of ammonium sulphate are added thereto. Subsequently, the moistened material (5 g of wool gaberdine or 5 g nylon-satin) is entered into the bath which is heated over the course of 30 minutes to boiling temperature. The water which is evaporated during the next 30 minutes boiling is replaced and dyeing is completed during the next 30 minutes at the boil. The dyed material is subsequently rinsed.

   After drying, a bluish-red dyeing having good light- and wet-fastness properties is obtained in both cases.

   Dyeings may be made in accordance with the above procedure employing any one of the dyestuffs of Examples 2 to 11 and 13 to 91 or a mixture of any two or more of the dyestuffs of Examples I to 91.

   Application Example B.

   Polyamide is printed with a printing paste containing 30 parts dyestuff of Example 1 or Example 12, 50 parts urea, 50 parts dissolving agent, for example thiodiethylene glycol, 300 parts water, 500 parts suitable thickening agent, for example based on locus bean gum, 60 parts acid acceptor, for example, ammonium tartrate, and 60 parts thiourea.

   The printed goods are steamed for 40 minutes at 1020C (saturated steam), then rinsed with cold water, washed for 5 minutes at 600C with a dilute solution of a conventional detergent and then rinsed again. A bluish-red print having good wetand lightfastness is obtained in both cases.

   In analogous manner printing pastes may be prepared using any one of the dyestuffs of Examples 2 to 11 or 13 to 91.

   WHAT WE CLAIM IS.

   I. An asymmetric l:2- & romium complex dyestuff of formula I,

   in which either, A is a diazo component radical of formula

   in which E is a sulpho group, a sulphonamide radical or an acyl radical of a suiphonic acid, Z is hydrogen or nitro, and the carbon atom marked with the asterisk is bound to the azo group, or, A is a diazo component radical of the 1 ,2-phenylene series, B is a diazo component radical of the 1,2-phenylene series, D1 is a coupling component radical of the 5-pyrazolone series which is coupled to the carbon atom next to that carrying the hydroxy group, the component being bound to the metal atom through the oxygen atom, D2 is a coupling component radical of the 5-aminopyrazole series which is coupled to the carbon atom adjacent that carrying the amino group, the component being bound to the metal atom through the amino group, and Ms is hydrogen or an equivalent of a non-chromophoric cation, with the provisos (i) that the dyestuff molecule contains a single sulpho group, which sulpho group is in salt form, and (ii) that the molecule contains at maximum a single water-solubilizing group in addition to the sulpho group, and mixtures of such 1:2 asymmetric chromium complexes.

   2. An asymmetric 1:2-chromium complex dyestuff of formula

   in which A1 is a group formula (a) or (b)

   in which Z is hydrogen or nitro, each of the rings A2 and B,, independently, is further unsubstituted or further substituted by a total of up to three substituents selected from halogen atoms (a total of up to three thereof), nitro groups(a total of up of two thereof),(C1-4) alkyl, (C1-4)alkoxy, -SO2R1, -SO2NR2R3, sulpho, phenylazo, chloro-, methyl-, methoxy- or sulphosubstituted phenylazo (only one of each of these), R is hydrogen, (C1-4)alkyl, phenyl, phenyl(C1-3)alkyl, phenylsulphonyl or tosyl, each of X1 and X2, independently, is (C1-4)alkyl, (C1-4)alkoxy, -COOH, -CONH2 -COO-(C1-2)alkyl, cyano or phenyl, each of Y1 and Y2, independently, is hydrogen; unsubstituted (C1-6)alkyl; (C1-6)alkyl which is substituted by a total of up to two substituents selected from halogen atoms, hydroxy, cyano and (C1-4)alkoxy, unsubstituted (C5-6)cycloalkyl; (C5-6)cycloalkyl which is substituted by up to three (C1-4)alkyl groups; unsubstituted phenyl; phenyl substituted by a total of up to three substituents, selected from halogen, (C1-4)alkoxy, (C1-4)alkyl (up to two fo each of these), nitro, -SO2R1, -SO2NR2R3, cyano, sulpho (only one of each of these); unsubstituted 1- or 2-naphthyl; 1-naphthyl substituted by a sulpho group in the 4-, 5-, 6-, 7- or 8-position; 2-naphthyl substituted by a sulpho group in the 1-, 5-, 6-, 7- or 8-position; or phenyl (C1-3)alkyl, R1 is unsubstituted (C1-4)alkyl; (C1-4)alkyl monosubstituted by hydroxy, (C1-2)alkoxy, halogen or cyano, unsubstituted phenyl or phenyl substituted by a total of up to two substituents selected from the group consisting of halogen, nitro, (C1-2)alkyl or (C1-2)alkoxy, either R2 is hydrogen unsubstituted (C1-4)alkyl; or (C1-4)alkyl monosubstituted by hydroxy, halogen, (C1-2)alkoxy, or cyano, and R3 is hydrogen or has one of the significances of R,.

   or R2 and R3, together with the nitrogen atom to which the are bound, for a 5- or 6-membered saturated heterocyclic ring which contains no further or one further hetero atom, and MO is as defined in Claim 1, and mixtures of such 1:2 asymmetric complexes.

   3. A 1:2 complex according to Claim 2, or a mixture thereof in which R, is RI, where R1' is (C1-3)alkyl or phenyl, R2 is R2', where R2' is hydrogen, (C1-3)alkyl, 2hydroxyethyl, 2- or 3-hydroxy-n-propyl and R3 is R3', where R3' is hydrogen; (C1-3)alkyl; 2-hydroxyethyl, 2- or 3-hydroxy-n-propyl; a R4O-(CH2)n-group in which R4 is methyl or ethyl and n is 2, 3 or 4; unsubstituted phenyl; phenyl monosubstituted by chlorine, nitro, methyl, methoxy or ethoxy; or phenyl disubstituted by two methyl, methoxy or ethoxy groups.

   4. A 1:2 complex according to Claim 2 or Claim 3, or a mixture thereof, in which A1 is a group of formula (a).

   5. A 1:2 complex according to any one of Claims 2 to 4, or a mixture thereof, in which R is R', where R' is hydrogen, methyl, ethyl, unsubstituted phenyl, benzyl, phenylsulphonyl or tosyl.

   6. A 1:2 complex according to any one of Claims 2 to 5, or a mixture thereof, in which X, is X,', where X,' is methyl, ethyl, methoxy, phenyl or -CONH2 and X2 is X2, where X2 is methyl, ethyl or phenyl.

   7. A 1:2 complex according to any one of Claims 2 to 6, or a mixture thereof, in which Y, is Yt, where Y, is unsubstituted phenyl; phenyl monosubstituted by chlorine, methyl, ethyl and sulpho, phenyl substituted by two substituents selected from the group chlorine, methyl, ethyl or phenyl substituted by sulpho and a further substituent selected from chlorine, methyl and ethyl.

   8. A 1:2 complex according to any one of Claims 2 to 7, or a mixture thereof, in which Y2 is Y2 where Y2 is cyclohexyl, 4-(Ct~4)alkylcyclohexyl, 3,5dimethylcyclohexyl, 2,4,6- or 3,5,5-trimethylcyclohexyl, unsubstituted phenyl, chloro- or sulphophenyl, dichlorophenyl or phenyl substituted by chloro and sulpho.

   9. A 1:2 complex according to any one of Claims 2 to 8, or a mixture thereof, in which A, is a group of formula (a) and the rings A2 and B, are A2 and B;, where A2, and B" independently, are substituted by one or two substituents selected from chlorine, nitro and sulpho.

   10. A 1:2 complex according to any one of Claims 2 to 9, or a mixture thereof, in which R is R", where R" is hydrogen, ethyl or tosyl.

   I 1. A 1:2 complex according to any one of Claims 2 to 10, or a mixture thereof, in which X1 is X1", where X1" is methyl, phenyl or - CONH2, X2 is methyl, Y1 is Y1", where Y1" is unsubstituted phenyl, 3- or 4-sulphophenyl, 3- or 4-chlorophenyl or 2,5-dichlorophenyl and Y2 is Y2", where Y2" has one of the significances of Y1",

   12. A 1:2 complex according to Claim 2, of formula Ib,

   in which each of Z1 and Z3, independently, is hydrogen, chlorine or nitro, each of Z2 and Z4, independently, is chlorine, nitro or sulpho, and Y,' and Y2' are as defined in Claims 7 and 11, respectively, and mixtures of such 1:2 asymmetric complexes.

   13. A 1:2 complex according to Claim 12, or a mixture thereof, in which Y1' is Y,', where Y'' is as defined in Claim 11.

   14. A 1:2 complex according to Claim 12 or Claim 13, or a mixture thereof, in which when Z, and/or Z3 is hydrogen, the substituent as Z2 and/or Z3 respectively, is in the 4-position when chlorine or sulpho, and in the 4- or 5- position when nitro, when Z, and/or Z3 and Z4 are the same the substituents are in the 4,6-positions, when Z1 is nitro and Z2 is chlorine and/or Z3 is nitro and Z4 is chlorine, the substituents are in the 4,5- or 4,6-positions, and when Z, and/or Z3 is chlorine or nitro and Z2, respectively Z4, is sulpho, the substituents are in the 4,6-positions.

   15. An asymmetric 1:2 chromium complex of formula

   in which M# is as defined in Claim 1, and M' has one of the significances of M#.

   16. An asymmetric 1:2 chromium complex of formula

   in which M is as defined in Claim 1, and M' has one of the significances ot MW.

   17. An asymmetric 1:2 chromium complex of formula

   in which M is as defined in Claim 1, and M' has one of the significances of Me.

   18. An asymmetric 1:2 chromium complex of formula

   in which MO is as defined in Claim 1, and M' has one of the significances of Me.

   20. An asymmetric 1:2 chromium complex of formula

   in which M@ is as defined in Claim 1, and M' has one of the significances of M#.

   21. An asymmetric 1:2 chromium complex of formula

   in which Me is as defined in Claim 1, and M' has one of the significances of M#.

   22. An asymmetric 1:2 chromium complex of formula

   in which Me is as defined in Claim 1, and M' has one of the significances of M.

   23. An asymmetric 1:2 chromium complex of formula

   in which M# is as defined in Claim 1, and M' has one of the significances of M#.

   24. An asymmetric 1:2 chromium complex of formula

   in which M is as defined in Claim 1, and M' has one of the significances of M.

   25. An asymmetric 1:2 chromium complex of formula

   in which M is as defined in Claim 1, and M' has one of the significances of Mm.

   26. An asymmetric 1:2 chromium complex of formula

   in which M is as defined in Claim 1, and M' has one of the significances of M&commat;.

   27. A complex or mixture according to Claim 2, in which R is hydrogen and Y, is unsubstituted or substituted phenyl.

   28. A complex or mixture according to any one of the preceding claims in which the cation of the sulpho group and M, independently, signify an alkali metal cation.

   29. An asymmetric 1:2 chromium complex according to any one of Examples 3,4,9 to 11, 13, 14, 16, 18, 19 to 25 and 29 to 91.

   30. A process for the production of an asymmetric 1:2 chromium complex of formula I, as defined in Claim 1, or a mixture thereof, comprising reacting a 1:1 chromium complex of a monoazo dye of formula II,

   or a mixture thereof, or of a monoazo dye of formula III,

   or a mixture thereof, with one or more metal-free monoazo dyes of formula III or II, respectively.

   31. A process for the production of a 1:2 complex of formula I, or a mixture of such complexes, substantially as hereinbefore described with reference to any one of Examples 1 to 91.

   32. A 1:2 chromium complex or a mixture thereof, whenever obtained by a process according to Claim 30 or Claim 31.

   33. A process for dyeing or printing nitrogen-containing organic substrates, comprising employing a complex or mixture according to any one of Claims 1 to 29 or 32 as dyeing or printing agent.

   34. A process according to Claim 33, in which the substrate consists of or comprises natural or synthetic polyamides, polyurethane or leather.

   35. A process for dyeing or printing nitrogen-containing organic substrates substantially as hereinbefore described with reference to Example A or B.

   36. Dyed or printed substrates whenever obtained by a process according to any one of Claims 33 to 35.