WO1986001815A1 - Improvements in or relating to organic compounds - Google Patents

Abstract

Monoazo compounds which, in one of the possible tautomeric forms, correspond to formula (I), in free acid or salt form, in which K is one of the groups (II) or (III) and the symbols are as defined in the Specification, are suitable as dyestuffs. They are used as such or in form of solid or particularly liquid aqueous dyestuff preparations for dyeing or printing hydroxy group or nitrogen containing organic substrates, such as textiles consisting of or containing cellulose material, leather or especially paper.

Description

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

The invention relates to anionic heterocyclic compounds suitable for use as dyestuffs.

Aecording to the invention there is provided a compound which, in one of the possible tautomeric forms, corresponds to formula I,

in which each of R₁ and R₂ is independently hydrogen, C_1-4alkyl, C_1-4alkoxy or COOM, each of Q₁ and Q₂ is independently hydrogen or SO₃M₁, n is 0 or 1, each of M and M₁ is independently hydrogen or a non-chromophoric cation; K is one of the groups (a) and (b),

in which

R₃ is hydrogen, CN, NH₂, OH, C_1-4alkoxy, C_1-4alkyl, C_2-4alkyl monosubstituted by hydroxy or C_1-4alkoxy, C_5-6cycloalkyl; phenyl or phenyl -C_1-4alkyl which phenyl group of the latter two groups is unsubstituted or substituted by one to three groups selected from C_1-4alkyl, C_1-4alkoxy, halogen, COOM and SO₃M; a saturated or unsaturated 5- or 6-membered heterocyclic ring containing one to three hetero atoms which is unsubstituted or further substituted by one to three C_1-4alky! groups and which is bound by a carbon or nitrogen atom directly or via a bridge member provided that any is

bound via a bridge member; -COR₆ or -(CH₂)_1-3-R₇,

R₆ is OH, NH₂ or C_1-4alkoxy,

R₇ is CN, halogen, SO₃M, -OSO₃M, -COR₈ or

R₈ is OH, NH₂, C_1-4alkyl which is unsubstituted or monosubstituted by OH, halogen, CN or C_1-4alkoxy; C_1-4alkoxy, phenoxy, phenyl or phenyl -C_1-4alkyl in which the phenyl groups of the latter three groups are unsubstituted or substituted by one to three groups selected from C_1-4alkyl, C_1-4alkoxy, halogen, COOM and SO₃M;

R₄ is hydrogen, CN, halogen, SO₃M, NO, NO₂, -NR₉R₁₀, C_1-4alkyl which is unsubstituted or monosubstituted by OH, halogen, CN,

C_1-4alkoxy, phenyl, SO₃M or -OSO₃M;

-SO₂NH₂, -COR₁₁, -CH₂NHCOR₁₂E, a group of the formulae

-

₂ in which the carbonyl or sulphonyl groups are bound to two carbon atoms of an aromatic ring which are in ortho position to each other; Θ a group of the formula

in which the

ion is part of a

5- or 6-membered ring containing one to three hetero atoms which is further unsubstituted or substituted by one or two methyl groups or by NH₂, -NHC_1-4alkyl or N(C_1-4alkyl)2; or a group of the formula

in which R₁₃ is hydrogen or C_1-4alkyl which is unsubstituted or monosubstituted by OH, halogen, CN, C_1-4alkoxy or phenyl, U₁ is S, -NH or -NC_1-4alkyl, and

V₁ is a group necessary to form a 5- or 6-membered ring to which ring a further 5- or 6-membered carbocyclic or heterocyclic ring containing one or two hetero atoms may be condensated,

or

both R₃ and R₄ together form a C₃- or C₄-chain which may be part of a further 5- or 6-membered ring by two vicinal chain members,

each of R₉ and R₁₀ is independently hydrogen, C_1-4alkyl which is unsubstituted or monosubstituted by OH, halogen, CN, C_1-4- alkoxy or phenyl; or -COR₁₂E,

R₁₁ i s OH, NH₂ , -NHC_1-4alkyl , -N(C_1-4al kyl )₂ , C_{1 -4}alkyl , C_1-4- alkoxy, phenyl or phenoxy which phenyl group of the latter two groups is unsubstituted or substituted by one to three groups selected from C_1-4alkyl, C_1-4alkoxy, halogen, COOM and SO₃M, R₁₂ is C_1-6alkylene,

E is hydrogen, halogen, a protonable amine group, a quaternary ammonium group or a hydrazinium group; SO₃M or -OSO₃M;

R₅ is hydrogen, CN, NO₂, -NR₁₄R₁₅, a saturated or unsaturated 5or 6-membered heterocyclic ring containing one or two hetero atoms which is bound by a carbon or nitrogen atom and which is further unsubstituted or substituted by up to three methyl groups or by NH₂, -NHC_1-4alkyl or -N(C_1-4alkyl)₂; C_1-6alkyl, C_2-4alkenyl, C_2-4alkinyl; C_1-6alkyl monosubstituted by OH, CN, C_1-4alkoxy, acetamido, -COR₁₆, SO₃M or -OSO₃M; C_5-6cydoalkyl, phenyl or phenyl -C_1-4alkyl which phenyl group of the latter two groups is unsubstituted or substituted by one to three groups selected from C_1-4alkyl, C_1-4alkoxy, halogen, NO₂, NH₂, COOM and SO₃M; C_1-6alkylene-E₁, -C_1-6alkylene- or a group of the formula

^

each of R₁₄ and R₁₅ is independently hydrogen, C_1-4alkyl, C_1-4alky! monosubstituted by OH, halogen, CN or C_1-4alkoxy; phenyl or phenyl substituted by one or two groups selected from halogen, C_1-4alkyl and C_1-4alkoxy, R₁₆ is OH or C_1-4alkoxy, R₁₇ is hydrogen or C_1-4alkyl,

E₁ is a protonable amine group, a quaternary ammonium group or a

hydrazinium group or a group of the formula -

R₁₈ is E₂, -NHCOR₁₂E₂, -SO₂NHR₁₂E₂ or -CONHR₁₂E₂; each R₁₉ is independently halogen, NH₂ or an aliphatic amine group,

E₂ is a protonable amine group, a quaternary ammonium group or a hydrazinium group,

X is 0 or NH,

Z is OH, NH₂, methyl or ethyl, Y is 0, S or N-Y₁,

Y₁ is hydrogen, CN, CONH₂, C_1-4alkyl, C_1-4alkyl monosubstituted by OH, CN, halogen or C_1-4alkoxy; phenyl or phenyl -C_1-4alkyl which phenyl group of the latter two groups is unsubstituted or substituted by one or two groups selected from halogen, C_1-4alkyl , C_{1 -4}alkoxy, acetamido, COOM and SO₃M; 1- or 2-naphthyl ; C_1-6alkylene-SO₃M, C_1-6alkyl ene-OSO₃M or C_1-6alkyl ene-COOM, each of R₂₀ and R₂₁ i s independently hydrogen, C_1-4alkyl , phenyl or phenyl -C_{1 -4}alkyl which phenyl group of the l atter two groups is unsubstituted or substituted by one or two groups selected from halogen, C_1-4alkyl, C_1-4alkoxy, COOM and SO₃M; or, provided that Y is N-Y₁ where Y₁ is hydrogen, one of R₂₀ and R₂₁ may also have a significance additionally given for γ₁;

with the provisos that

(i) in a compound of formula I at least one sulphonic acid group is present; (ii) when in a compound of formula I (1) K is a group (b), in which Y is 0 or S,

(2) R₂ is other than COOM,

(3) one of Q₁ and Q₂ or both Q₁ and Q₂ are SO₃M₁, and (1) to (3) occur simultaneously, then at least one of M₁ is a quaternary ammonium cation; (iii) when in a compound of formula I containing as K a group (b)

(1) the diazo component radical is defined as follows: R₁ is hydrogen, R₂ is methyl, Q₁ is SO₃M₁ in the 7-position, n is 0 and Q₂ is hydrogen,

(2) X is 0 or NH, (3) each of R₂₀ and R₂₁ is hydrogen,

(4) Y is N-Y₁ in which Y₁ is hydrogen, and (1) to (4) occur simultaneously, then M₁ has a significance other than hydrogen or sodium;

which compound of formula I is in free acid or salt form with the proviso that each sulphonic acid group as well as each protonable amine group can be present in ionized form.

In the specification any halogen means fluorine, chlorine or bromine, especially chlorine. Generally, any alkyl or alkylene is linear or branched unless indicated to the contrary.

In any hydroxysubstituted alkyl group which is linked to a nitrogen atom, the hydroxy group is bound to a carbon atom other than to the C₁-atom.

Q₁ is preferably SO₃M₁ which is more preferably bound to the 7-position. n is preferably 0.

Each R₁ is preferably R_1a, where each R_1a is independently hydrogen, C_1-4alkyl, methoxy or ethoxy. More preferably it is R_1b, where each R_1b is independently hydrogen, methyl, ethyl, methoxy or ethoxy. Even more preferably it is R_1c, where each R_1c is independently hydrogen or methyl. Most preferably R₁ is hydrogen. R₂ is preferably R_2a, where R_2a is C_1-4alkyl, C_1-4alkoxy or COOM. More preferably it is R_2b, where R_2b is methyl, methoxy, ethoxy or COOM. Most preferably R₂ is methyl.

Q₂ when defined as SO₃M₁ is preferably bound to a carbon atom which is in ortho- position to the azo group.

Any alkyl or alkoxy as R₃ preferably contains 1 or 2 carbon atoms and is most preferably methyl or methoxy. Any substituted alkyl is preferably a C_2-3alkyl group monosubstituted by hydroxy or C_1-2alkoxy. Any cycloalkyl is preferably cyclohexyl.

Preferably, in any substituted phenyl or phenyl alkyl group the phenyl group contains one or two groups selected from methyl, methoxy, chlorine, COOM and SO₃M.

Any heterocyclic ring as R₃ is preferably morpholine, pyrrolidine, piperidine, piperazine or N-methylpiperazine (when saturated) which is bound by a carbon or nitrogen atom, or is pyridine, triazine, pyridazine, pyrimidine or pyrazine (when unsaturated) which is bound by a carbon or nitrogen atom where in the latter case (when bound by a nitrogen atom) a methylene bridge is present.

R₆ is preferably R_6a, where R_6a is OH, NH₂, methoxy or ethoxy. More preferably it is R_6b, where R_6b is OH or NH₂. R₇ is preferably R_7a, where R_7a is CN, chlorine, SO₃M, -OSO₃M,- or -COR_8a, where R_8a is OH, NH₂, methyl, ethyl,

methoxy or ethoxy; more preferably it is R_7D, where R_7D is SO₃M,

-OSO₃M, or -COR_8b, where R_8b, is OH or NH₂.

R₃ is preferably R_3a, where R_3a is hydrogen, CN, NH₂, OH, methyl, ethyl, hydroxyethyl, C_1-2alkoxyethyl, methoxy, ethoxy, cyclohexyl; phenyl or phenyl -C_1-2alkyl in which the phenyl group is unsubstituted or substituted by one or two groups selected from

methyl, methoxy, chlorine, COOM and SO₃M; - , -COR_6a or

-(CH₂)_1-2R_7a. More preferably R₃ is R_3b, where R_3b is NH₂, methyl, ethyl, hydroxyethyl, cyclohexyl, phenyl, phenyl -C_1-2alkyl, -COR_6b or -CH₂R_7b. Even more preferably R₃ is R_3C, where R_3C is NH₂, methyl, hydroxyethyl, phenyl ethyl or -CH₂SO₃M. Most preferably R₃ is methyl.

Any protonable amine or quaternary ammonium group as E, E₁ or E₂ is preferably a group B, where B is a primary amine group, a secondary or tertiary aliphatic, cycloaliphatic, aromatic or saturated, unsaturated or partially unsaturated heterocyclic aminegroup which latter group is attached by the N-atom or a carbon atom; or a quaternary ammonium group corresponding to the above. Any aliphatic amine group as B is preferably a mono-C_1-4alkyl- or a di-(C_1-4alkyl)-amine group. The alkyl group may be monosubstituted by halogen, hydroxy, cyano, C_1-4al koxy or phenyl. Any cycloaliphatic amine group is preferably C_5-6cycloalkylamino, the cycloalkyl group of which is unsubstituted or may be substituted by one or two C_1-2alkyl groups.

Any aromatic amine group is preferably phenyl amino, the phenyl ring of which is unsubstituted or substituted by one or two groups selected from halogen, C_1-4alkyl, C_1-4alkoxy, SO₃M and COOM.

Any heterocyclic amine group as B which is attached by the N-atom or a carbon atom is preferably a saturated, unsaturated or partially unsaturated 5- or 6-membered ring which contains one or two hetero atoms and may be further substituted by one or two C_1-4alkyl groups.

More preferably B is B₁, where B₁ is a protonable amine

group -NR₂₂R₂₃ or a quaternary ammonium group -NR₂₄R₂₅R₂₆ , or B₁ forms a protonable or quaternary 5- or 6-membered saturated heterocyclic ring of the formula

or a corresponding protonable or quaternary 5- or 6-membered unsaturated or partially unsaturated heterocyclic ring, each of R₂₂ and R₂₃, independently, is hydrogen, C_1-4alkyl, C_2-4alkyl monosubstituted by hydroxy, C_1-4alkoxy, halogen or cyano; phenyl-C_1-4alkyl, the phenyl group of which is unsubstituted or substituted by one to three groups selected from chlorine, C_1-4alkyl and C_1-4alkoxy, or C_5-6cycloalkyl, or R₂₂ and R₂₃, together with the N-atom to which they are attached, attached, form a heterocyclic ring of the formula

V

in which

U₂ is the direct bond, -CH₂-, -O-, -S-, -SO₂-, -SO-, -NH-, -N(C_1-4alkyl)- or -

(C_1-4alkyl)₂-, each of R₂₄ and R₂₅ has independently one of the cyclic or noncyclic significances of R₂₂ and R₂₃ except hydrogen, and R₂₆ is C_1-4alkyl or phenyl -C_1-4alkyl, or R₂₄, R₂₅ and R₂₆, together with the N-atom to which they are attached, form a pyridinium group unsubstituted or substituted by one or two methyl groups, or a ring of the formula

in which R₂₆ and U₂ are as defined above,

R₂₇ is hydrogen or C_1-4alkyl and each of R₂₈, independently, is C_1-4alkyl. Even more preferably B is B₂, where B₂ is a group -NR_22aR_23a or

"

NR_24aR_25aR_26a, each of R_22a and R_23a, independently, is hydrogen, C_1-2alkyl, unbranched hydroxy-C_2-3alkyl or benzyl or both R_22a and R_23a, together with the N-atom to which they are attached, form a pyrrolidine, piperidine, morpholine, piperazine or

N-methylpiperazine group, each of R_24a and R_25a has independently one of the non-cyclic or cyclic significances of R_22a and R_23a except hydrogen, and R_26a is methyl, ethyl or benzyl, or R_24a, R_25a and R_26a, together with the N-atom to which they are attached, form a pyridinium group unsubstituted or substituted by one or two methyl groups.

Most preferably B is B₃, where B₃ is a group -NR_22bR_23b or

-NR_24bR_25bR_26b, each of R_22b and R_23b is hydrogen, methyl or ethyl or both R_22b and R_23b, together with the N-atom to which they are attached, form a piperidine, morpholine, piperazine or N-methylpiperazine ring; each of R_24b and R_25b is methyl or ethyl or both R_24b and R_25b, together with the N-atom to which they are attached, has one of the cyclic significances of R_22b and R_23b,

R_26b is methyl or ethyl or

R_24b, R_25b and R_26b, together with the N-atom to which they are attached, form a pyridinium group unsubstituted or substituted by one or two methyl groups. E ist preferably E_a, where E_a is hydrogen, chlorine, a group B₂ or SO₃M; more preferably it is E_b, where E_b is hydrogen, chlorine, a group B₃ or SO₃M.

Each of R₉ and R₁₀ is preferably R_9a and R_10a, where each of R_9a and R_10a is independently hydrogen, C_1-2alkyl, C_1-2alkyl monosubstituted by OH, C_1-2alkoxy or phenyl, or -COR_12aE_a, in which R_12a is C_1-2alkylene. More preferably each of R₉ and R₁₀ is R_9b and R_10b, where each of R_9b and R_10b is independently hydrogen, methyl or -COR_12aE_b, R₁₁ is preferably R_11a, where R_11a is OH, NH₂, -NHCH₃,

-N(CH₃)₂, methyl, ethyl, methoxy or ethoxy. More preferably it is R_11b, where R_11b is NH₂, methyl, ethyl, methoxy or ethoxy.

R₄ is preferably R_4a, where R_4a is hydrogen, CN, chlorine, bromine, SO₃M, -NR_9aR_10a, C_1-2alkyl, C_1-2alkyl monosubstituted bv OH, phenyl, SO₃M or -OSO₃M; -COR_11a, -CH₂NHCOR_12aB₂ or a group -

forming a pyridine, pyrimidine or benzimidazole ring which is further unsubstituted or monosubstituted by methyl, NH₂, -NHCH₃ or -N(CH₃)₂. More preferably R₄ is R_4b, where R_4b is hydrogen, CN, -NHR_10b, -COR_11b, -CH₂NHCOCH₂B₃ or a group of the formulae

V 0 . Even more preferably R₄ is R_4C,

where R_4C is hydrogen, CN, -NHCOCH₂E_b, -CONH₂,

Most preferably R₄ is R_4d, where R_4d is hydrogen or CN.

It is also preferred that R₃ and R₄ together with the carbon atoms to which they are attached form part of a further ring which corresponds to the formula

V for example they form a ring of the formula

R₁₄ and R₁₅ are preferably R_14a and R_15a, where each of R_14a and R_15a is independently hydrogen, methyl, ethyl or phenyl.

R₁₆ is preferably R_16a, where R_16a is OH, methoxy or ethoxy.

R₁₇ is preferably R_17a, where R_17a is hydrogen or methyl. Any aliphatic amine group as R₁₉ is preferably a mono-C_1-4- alkyl- or di-(C_1-4alkyl)-amine group, in which the alkyl groups may be monosubstituted by halogen, OH, CN, C_1-4alkoxy or phenyl.

Each R₁₉ is preferably R_19a, where each R_19a is independently fluorine, chlorine, NH₂, -NHC_1-2alkyl or -N(C_1-2alkyl)₂, in which the alkyl groups are unsubstituted or monosubstituted by OH, CN or C_1-2alkoxy. More preferably each R₁₉ is R_19b, where each R_19b is independently chlorine, NH₂, -NHCH₃, -N(CH₃)₂, -NHCH₂CH₂OH or -N(CH₂CH₂OH)₂.

E₁ is preferably E_1a, where E_1a is a group B₂ or a group of

the formula

19a more preferably it is E_1b, where E_1b is a group B₃ or a group of

the formula

E₂ is preferably E_2a, where E_2a is a group B₂. More preferably it is E_2b, where E_2b is a group B₃. R₁₈ is preferably R_18a, where R_18a is E_2a, -NHCOR_12aE_2a,

-SO₂NHR_12aE_2a or -CONHR_12aE_2a; more preferably it is R_18b, where R_18b is E_2b, -NHCOR_12aE_2b or -CONHR_12aE_2b.

R₅ is preferably R_5a, where R_5a is hydrogen, -NR_14aR_15a, phenyl, phenyl -C_1-2 alkyl, cyclohexyl; C_1-4alkyl, C_1-4alkyl monosubstituted by OH, CN, C_1-2alkoxy, -COR_16a, SO₃M or -OSO₃M; -C_1-3alkylene-E_1a, -C_1-3alkylene-

More preferably R₅ is R_5b, where R_5b is hydrogen, -NHR_15a, phenyl, phenyl-C_1-2alkyl, methyl, ethyl, Chalkyl monosubstituted by SO₃M or -COR_{16 a}, -(CH₂ )_1-3-E_1b, -(CH₂)_1-3-NHCO-

Most preferably R₅ is hydrogen.

X is preferably 0.

Z is preferably Z_a, where Z_a is OH or NH₂.

Preferably, the phenyl group of any phenyl or phenyl alkyl as Yl (when substituted) is substituted by one or two groups selected from chlorine, methyl, methoxy, COOM and SO₃M.

Y₁ is preferably Y_1a, where Y_1a is hydrogen, CN, CONH₂, methyl, ethyl, C_2-4alkyl monosubstituted by OH, CN, chlorine or C_1-2alkoxy; phenyl or phenyl -C_{1 -2}alkyl, the phenyl group of the latter two groups is unsubstituted or substituted by one or two groups selected from chlorine, methyl, methoxy, COOM and SO₃M; C_2-4alkylene-SO₃M, C_2-4alkylene-OSO₃M or C_2-4alkylene-COOM. More preferably it is Y_1b, where Y_1b is hydrogen, CN, CONH₂, methyl, ethyl, 2-hydroxyethyl, phenyl, phenyl -C_1-2alkyl, C_2-4alkylene-SO₃M or C_2-4alkylene-COOM. Even more preferably it is Y_1c, where Y_1c is hydrogen, CN or CONH₂. Most preferably it is Y_1d where Y_1d is hydrogen or CN, of which hydrogen is most preferred.

Y is preferably Y_a, where Y_a is 0 or N-Y_1a; more preferably it is Y_b, where Y_b is O or N-Y_1b; even more preferably it is Y_c, where Y_c is 0 or N-Y_1c; most preferably it is Y_d, where Y_d is 0 or N-Y_1d.

Each of R₂₀ and R₂₁ is preferably R_20a and R_21a, where each of R_20a and R_21a is independently hydrogen, methyl, ethyl, phenyl-C_1-2alkyl or phenyl, the phenyl groups of which are unsubstituted or substituted by one or two groups selected from chlorine, methyl, methoxy, COOM and SO₃M, or in case where Y is N-Y₁ in which Y₁ is hydrogen, one of R_20a and R_21a has also a significance additionally given for Y_1a. More preferably each of R₂₀ and R₂₁ is R_20b and R_21b, where each of R_20b and R_21b is independently hydrogen, methyl, ethyl, phenyl or benzyl or in case where Y is N-Y₁ in which Y₁ is hydrogen, one of R_20b and R_21b has a significance additionally given for Y_1b. Most preferably R₂₀ and R₂₁ are hydrogen.

The group (a) is preferably (a1) of the formula

K is preferably K₁, where K₁ is one of the groups (a1) or (b1). More preferably it is K₂, where K₂ is one of the groups (a2) or (b2). Even more preferably it is K₃, where K₃ is one of the groups (a3) or (b3). Most preferably K is K₄, where K₄ is a group (a3).

A compound of formula I according to the invention is in free acid form, in alkali metal or unsubstituted or substituted ammonium salt form or in mixed salt form, or may form an internal salt. Any substituted ammonium cation present as M or M₁ may be derived from a primary, secondary or tertiary amine. For example, the following amines are suitable:- mono-, di- or trimethyl-, -ethyl-, -propyl- or -butyl-amine; mono-, di- or triethanol-, -propanol- or isopropanol-amine; N-methyl-N-hydroxyethyl amine, N-methyl-N,N-di(hydroxyethyl)amine, N-ethyl-N-hydroxyethoxyethyl amine, morpholine, piperidine, piperazine, hydroxyethylmorpholine, hydroxyethylpiperazine, aminoethylpiperazine; ethylenediamine, hexamethylenediamine; dimethylaminopropyl amine, diethylaminopropylamine, diethylene glycol amine, diglycol amine and 3-methoxypropylamine.

Also suitable as amines are polyglycol amines. They can be prepared for example by reacting ammonia, alkyl- or hydroxyalkylamine with alkylene oxides.

Any substituted ammonium ion may also be a quaternary ammonium ion (especially when M₁) derived from ammonium compounds which preferably contain one or two quaternary ammonium ions. Examples are tetramethyl-, tetraethyl-, trimethylethyl-, benzyldiethylmethyl-, trimethylphenyl-, trimethyl benzyl-, triethylcyclohexyl-, trimethylhydroxyethyl- and tetrahydroxyethyl - ammoniumhydroxide as well as N,N-dimethylpiperidinium hydroxide, or compounds corresponding to the formula

%

in which each R₃₀ is independently methyl, ethyl, hydroxyethyl or 2- or 3-hydroxypropyl and A is C_1-4alkylene or -CH₂CH₂N(CH₃)CH₂CH₂-.

Preferred compounds correspond to formula Ia

Ia

lb in which R_1b, R_2b, Q₂, M₁ and K₁ are as defined above with the provisos that (ii) when in a compound of formula I a

(1) K₁ is a group (b₁), in which Y_a is 0,

(2) R_2b is other than COOM,

(3) Q₂ is hydrogen or SO₃M₁, and (1) to (3) occur simultaneously, then at least one of M₁ is a quaternary ammonium cation as defined above;

(iii) when in a compound of formula Ia in which K₁ is a group (b₁)

(1) the diazo component radical is defined as follows: R_1b is hydrogen, R_2b is methyl and Q₂ is hydrogen,

(2) each of R_20a and R_21a is hydrogen,

(3) Y_a is N-Y_1a, in which Y_1a is hydrogen, and (1) to (3) occur simultaneously, then M₁ has a significance other than hydrogen or sodium.

Even more preferred are compounds of formula Ia, in which

1) K₁ is K₂;

2) K₁ is K₃; 3) R_1b is R_1c;

4) R_1b is hydrogen;

5) R_2b is methyl;

6) those of 2) to 5), in which K₁ is K₄. The compounds of formula I can be prepared in accordance with known methods reacting the diazonium salt of an amine of formula II,

II

in which R₁, R₂, Q₁, Q₂ and n are as defined above, or a mixture thereof with a compound which in one of the possible tautomeric forms corresponds to formula IlIa or IlIb,

in which R₃, R₄, R₅,-R₂₀, R₂₁, X, Y and Z are as defined above.

The starting compounds of formula II, diazo components of the 2-phenyl-benzthiazole series, are either known or may be prepared analogously to known processes, for example according to M. Schubert, Anna! en 558, 10 (1947).

Diazo components of formula II for example are as follows:- 2-(4'-aminophenyl)-6-methylbenzthiazole-7-sulphonic acid 2-(4'-aminophenyl)-6-methylbenzthiazole-5-sulphonic acid 2-(4'-aminophenyl)-6-methylbenzthiazole-3',7-disulphonic acid 2-(4'-aminophenyl)-6-carboxybenzthiazole-7-sulphonic acid 2-(4'-amino-3'-methyl-5'-sulphophenyl)-4,6-dimethyl-benzthiazole -7-sulphonic acid

2-(4'-amino-3'-methylphenyl)-4,6-dimethyl-benzthiazole-7-sulphonic acid

2-(4'-aminophenyl)-6-methylbenzthiazole primuline base. The coupling components, compounds of formula IlIa, are either known or may be prepared in accordance with known methods. Such preparation processes for example are described in: The Chemistry of Heterocyclic Compounds, Pyridine and its Derivatives, Parts I-IV; Interscience Publishers Inc. 1960-1964; furthermore in: Berichte der Oeutschen Chemischen Gesellschaft 29, (1896), page 655; and in patent references, such as DE-OS 1964690;

20 22 817; 21 18945; 21 23061; 21 41 449; 21 50 598; 21 50 772;

21 50 817; 21 62 612; 23 49 709; 2705 562; etc.

Compounds of formula Illax,

Illax

in which R_5x i s C_1-6alkyl ene-E₁ or the group

\ may be prepared for exampl e by reacti ng a compound of formul a Ill ay,

IIIay

in which W is C_1-6alkylene or a group J

wherein R₃₁ is -NHCOR₁₂, -SO₂NHR₁₂- or -CONHR₁₂, and X_O is a functional group, preferably a group which can be split off as an anion, with the amino compound E₁-H.

The coupling components, compounds of formula IIlb, are either known or may be prepared in accordance with known methods from known starting compounds. Such preparation processes for example are described in: The Chemistry of Heterocyclic Compounds. The Pyrimidines, Interscience Publishers 1962; furthermore in numerous patent references such as, US-PS 2,673,204 or DE-PS 134,984; 158,591; 165,692; 186,456, etc. Diazotisation and coupling reactions may be effected in accordance with known methods. For diazotisation, the amines or amine mixtures are advantageously dissolved in an aqueous alkali or made into a paste therein, and mixed with a 5-10% molar excess sodium nitrite. Diazotisation conveniently is carried out in a medium containing a mineral acid, preferably hydrochloric acid, at 0-20°C. Coupling conveniently is carried out at pH 3-10, preferably 4-8. Optionally, a quaternary ammonium compound is added using at least an equimolar amount which is sufficient to neutrause one sulphonic acid group.

The resultant compound of formula I may be used in form of the solution as obtained; however, this solution may also be converted into a solid by spray-drying. Furthermore, the conventional method of isolation used for dyestuffs, salting out of the solution, filtering off and drying, is also suitable.

The type of cations present in a compound of formula I may be influenced in different ways depending on the preparation process. One possibility consists in filtering off the diazonium salt which is obtained in the above process, and washing it with water. The solid diazonium compound is then added to an aqueous slurry or solution of the coupling component, which contains a basic salt, lithium-, sodium-, potassium-, ammonium-hydroxide, one or more organic amines or a quaternary ammonium compound. Another method consists in converting the compound of formula I, which is obtained by diazotisation and coupling and is isolated in the sodium salt form, into the free acid by using a mineral acid, preferably hydrochloric acid, then filtering and washing with water; the compound is subsequently neutralised and thus converted into the desired alkali salt or ammonium salt. Any type of mixed salt form may be obtained by effecting partial conversion into the free acid and/or by step-wise neutralisation. The salt-changing method, conversion of one salt form into another, can also be used. If diazotisation takes place using alkyl nitrites, dinitrogen trioxide or mixtures of nitric oxide and oxygen instead of alkali nitrite, it is possible to produce solutions of the end products which are free from metal ions. If desired, corresponding salts may be obtained by adding a base which yields cations or by adding an amine.

The compounds according to the invention in form of their water-soluble salts are useful for dyeing or printing hydroxy group or nitrogen containing organic substrates. For example, they are suitable for dyeing or printing fibres, threads or textiles produced therefrom, which consist of or contain cellulose materials, such as cotton, in accordance with known methods; cotton is preferably dyed by the exhaust method, for example from a long or short liquor, at room temperature to boiling temperatures. Printing is effected by means of impregnation with a printing paste which is prepared by known methods.

The compounds of formula I are especially suited for dyeing or printing paper in accordance with known methods, e.g. for the preparation of sized or unsized paper dyed in the stock. They may also be used for dyeing paper by the dipping process. Furthermore, the new dyestuffs can be used for dyeing or printing leather, preferably chrometanned types of leather, in accordance with known methods. The dyeings and prints obtained (especi al ly those on paper) have good fastness to usage. The compounds of formula I may be used as such or may also be used in the form of dyeing preparations, which are preferably used for dyeing paper. Suitable liquid, preferably aqueous, concentrated dyeing preparations may be made in accordance with known methods, advantageously by dissolving in suitable solvents, optionally adding an adjuvant, e.g. a hydrotropic compound or a stabiliser. The possibility of producing such stable, aqueous-concentrated preparations in the course of dyestuff synthesis without intermediate isolation of the dyestuff is particularly advantageous. In this process, coupling takes place for example in the presence of appropriate amines and in particular in the presence of quaternary ammonium hydroxides which serve to introduce corres ponding cations as defined above, and optionally in the presence of further hydrotropic adjuvants.

Suitable hydrotropic adjuvants are for example low molecular weight amides, lactones, alcohols, glycols or polyols, low molecular weight ethers or hydroxyalkyl ation products, as well as nitriles or esters; among these the following compounds are preferably used:- Methanol, ethanol, propanol; ethyl ene-, propylene-, diethylene-, thiodiethylene- and dipropylene-glycol; butanediol; β-hydroxypropionitrile, pentamethylene glycol, ethylene gycol monoethyl- and -propylether, ethylene diglycol monoethyl ether, triethyl ene glycol monobutylether, butyl polyglycol, formamide, dimethylformamide, pyrrol idone, N-methylpyrrolidone, glycol acetate, butyrolactone, urea and ε-caprolactam.

Hydrotropic compounds are described e.g. by H. Rath and S. Mϋller, in Melliand Textilberichte 40, 707 (1959) or by E.H. Daruwalla in K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. VIII, pages 86-92 (1974).

The additional content of a hydrotropic compound further improves the stability on storage of the dyestuff preparation, and the solubility of the dyestuff employed.

An example of a suitable liquid dye preparation is (all parts are by weight):-

100 parts of a compound of formula I in water-soluble salt form

1-100, preferably 1-10 parts of an inorganic salt, 100-800 parts of water,

0-500 parts of one of the hydrotropic compounds as defined above. Depending on the salt form used, the liquid dye preparation may be a suspension or is preferably a true solution. The preparations are stable and can be stored for a long period of time. Similarly, the compounds of formula I may be made into solid, preferably granulated dyeing preparations in accordance with known methods, advantageously by granulating as described in French Patent Specification No. 1.581.900. A suitable granulate preparation comprises (all parts are by weight):-

100 parts of a compound of formula I in water-soluble salt form, 1-100, preferably 1-10 parts of an inorganic salt,

0-800 parts of a standardising agent (preferably non-ionic, such as starch, dextrin, sugar, glucose and urea).

The solid preparation may contain up to 10% residual moisture.

Depending on the cation mixture present, the dyestuffs of formula I possess good solubility properties, particularly good solubility in cold water. Furthermore, when used in paper-making, they colour the waste water only to a slight extent or not at all. They do not mottle on paper and are substantially insensitive to filling material and pH over wide ranges. They are only slightly inclined to give two-sided dyeing on paper. The dyeings on paper have good light fastness properties, after a long-term exposure to light, the shade alters tone-in-tone. The dyed papers also have \/ery good wet fastness properties, they are fast not only to water, but also to milk, fruit juices, sweetened mineral water and tonic water, and in addition they show good alcohol fastness properties.

The dyestuffs have good substantivity, i.e. they exhaust practically quantitatively, and show good build-up; they can be added to the paper pulp directly, i.e. without previously dissolving, as a dry powder or granulate, without reducing the brilliance or the yield of colour. It is advantageous to use the genuine solutions of the dyestuffs as given above, which are stable, of low viscosity and thus capable of being accurately measured out. Fibre materials which contain mechanical wood pulp are dyed in good, even quality with the dyestuffs of the present invention. The dyed paper is both oxidatively and reductively bleachable, which is important for the recycling of waste paper. The following examples further serve to illustrate the invention. In the examples, all parts are by weight or volume, and the percentages are by weight; the temperatures are given in degrees centigrade.

Example 1

6.4 Parts of 2-(4'-aminophenyl)-6-methylbenzthiazole-7-sulphonic acid are stirred into 100 parts of water, and dissolved by adding 5.1 parts of 30% sodium hydroxide solution. 6 Parts of 4N sodium nitrite solution are added, and the solution is poured whilst stirring into a preparation of 200 parts of ice and 7 parts of 30% hydrochloric acid. A yellow diazo suspension is obtained. After stirring for three hours, whereby the temperature may increase to 20º, any excess nitrous acid is decomposed by adding a small amount of sulphamic acid. Then, 3.3 parts of 4-methyl-6hydroxypyridone-(2) are added to the diazo suspension, and 10 parts of sodium carbonate are subsequently sprinkled in. Coupling commences immediately, whereby an orange suspension is obtained. After about one hour coupling is complete. 10 parts of 30% sodium hydroxide solution are added, and the dyestuff thus formed goes totally into solution. By sprinkling in 20% by volume of sodium chloride, the dyestuff can be completely salted out. After drying, the dyestuff corresponding to the formula

is obtained in form of a powder. It dyes paper a brilliant neutral-yellow shade. The paper dyeings have very good light and wet fastness properties. By a method analogous to that of Example 1 further heterocyclic monoazo compounds can be prepared from appropriate starting compounds. They correspond to formula (A),

(A)

in which the symbols are defined in Table 1 below. In the last column of this Table 1 and also of the following Tables 2 and 3 the shade of the obtained paper dyeings is given whereby a is neutral-yeIIow b is reddish-yellow and c is orange.

The paper dyeings made with the dyestuffs in Tables 1 to 3 in conventional manner have good light and wet fastness properties.

Example 57

12 Parts of 2-(4'amino-3'-sulphophenyl)-6-methylbenzthiazole-7-sulphonic acid are dissolved in 200 parts of water. 100 Parts of ice are added, followed by 7.5 parts of 30% hydrochloric acid. Subsequently, at 0° 8 parts of 4N sodium nitrite solution are added dropwise. A yellow diazo solution is obtained which is stirred for two hours. 8 Parts of 6-hydroxy-4-methylpyridonyl-(3)-pyridinium chloride are then added. The pH is adjusted to 8 by adding 20 parts of sodium carbonate. Coupling commences immediately, and an orange suspension is formed. This suspension is stirred for four hours, afterwards the precipitated dyestuff is filtered off. After drying, a readily soluble dyestuff powder is obtained containing the dyestuff which, in the possible tautomeric forms, corresponds to one of the given formulae:

This dyestuff dyes paper a brilliant reddish-yellow shade. The paper dyeings obtained have good light and wet fastness properties.

Examples 58-71 By a method analogous to that of Example 57 further compounds may be prepared using appropriate starting compounds. They correspond to formula (B),

(B)

in which the symbols are defined in Table 2 below.

Example 72

7 Parts of 2-(4'-aminophenyl)-6-carboxybenzthiazole-7-sulphonic acid are stirred into 40 parts of water and dissolved with 4 parts of 30% sodium hydroxide solution. 5.5 Parts of 4N sodium nitrite solution are added, and this mixture is poured into a preparation consisting of 100 parts of ice and 10 parts of 30% hydrochloric acid whilst stirring. A light yellow diazo suspension is formed. After stirring for one hour, the excess nitrous acid is decomposed by adding sulphamic acid. 4 Parts of 4-amino-3-cyano-6-hydroxypyridone-(2) are added, and then 10 parts of sodium carbonate are sprinkled in. Coupling commences, and a brownish-orange suspension is obtained. After two hours coupling is complete. Subsequently, 20 parts of 30% sodium hydroxide solution are added dropwise, and the mixture is heated to 70º; the resultant dyestuff thus goes into solution. It is salted out by sprinkling in 40 parts of sodium chloride, filtered off and dried. An orange-red powder is obtained which contains the dyestuff having the formula

This dyestuff dyes paper a brilliant reddish-yellow shade. The obtained paper dyeings show notably good light and wet fastness properties.

Examples 73-89 By a method analogous to that described in Example 72 further compounds can be prepared from appropriate starting compounds. They correspond to formula (C),

(C)

in which the symbols are defined in Table 3 below.

In accordance with the reaction and isolation conditions as described the compounds of Examples 1 to 89 are obtained in the sodium salt form provided that no internal salt is formed. They may, depending on the reaction and isolation conditions, or by reacting the sodium salts in accordance with known methods also be obtained in free acid form or in other salt forms containing one or more cations indicated in the description.

Example 90 6.4 Parts 2-(4'-aminophenyl)-6-methylbenzthiazole-7-sulphonic acid are diazotised in accordance with the method described in Example 1. The mixture is stirred for three hours and then filtered. The well-pressed filter cake is made into a paste in ice water; this paste is adjusted to 40 parts with ice water. 3.3 Parts of 4-methyl-6-hydroxypyridone-(2) are added followed by 8 parts of triethanol amine. Coupling commences whereby an orange-red mixture is obtained. During coupling, a further 30 parts of ice are added portionwise. After one hour 8 parts of urea are added, then the mixture is heated to 50° whereby a solution is obtained. This solution is ready for use, it contains the dyestuff of Example 1 in the triethanol ammonium salt form.

Example 91 The dyestuff prepared according to the method given in

Example 1 is stirred into 200 parts of water prior to drying, and is mixed with 20 parts of 30% hydrochloric acid. After having stirred for a longer time, the dyestuff in the free acid form is filtered off and is added into a mixture consisting of 8 parts of diglycol amine and 5 parts ethylene glycol. The dyestuff dissolves whilst releasing heat. This solution is adjusted to 90 parts by adding water to give a dyestuff solution which is storage-stable and ready for use.

Example 92 If in Example 91 2 parts of monoethanol amine and 15 parts of urea are used instead of a mixture of diglycol amine and ethylene glycol a liquid dyestuff preparation is obtained which is stable on storage and has good dyeing properties.

Also suitable amines instead of monoethanol amine are diethanolamine, monoisopropanol amine or diisopropanol amine.

Example 93

If in Example 905 parts of tetramethyl ammonium hydroxide are used instead of triethanol amine a liquid dyestuff preparation is obtained which is ready for use. By employing tetramethylammonium hydroxide there is no need for adding a further solubilising agent.

Instead of tetramethyl ammonium hydroxide equimolar amounts of the following quaternary ammonium hydroxides may be used to produce liquid storage-stable preparations of the dyestuff of Example 1.

Example 94

If lithium hydroxide solution is used instead of the amine or amine mixture employed in one of Examples 90 to 93, a liquid aqueous dye preparation is obtained which contains the dyestuff according to Example 1 in the lithium salt form. By a method analogous to that described in one of Examples 90 to 94 the dyestuffs of Examples 2 to 89 may also be converted into liquid aqueous dyeing preparations showing high stability on storage.

Example 95

A mixture consisting of 9.5 parts of primulin base, 1.4 parts of potassium hydroxide, 40 parts of water and 4.3 parts 5N sodium nitrite solution is added to a mixture of 5 parts of hydrochloric acid and 20 parts of ice whilst stirring. Stirring is effected for a further two hours at 20°. The diazonium salt which precipitates is filtered off and washed with water. The diazonium salt together with 3 parts of 4-methyl-6-hydroxypyridone-(2) is suspended in a small quantity of water. To this suspension a 10% lithium hydroxide solution is added to adjust the pH at 8. After stirring for one hour, 20 parts of urea are added. The solution thus obtained is ready for use, it contains the dyestuff of the formula

which has notably good properties with respect to substantivity. This dyestuff solution dyes paper a brilliant golden-yellow shade.

Example 96

6.4 Parts of 2-(4'-aminophenyl)-6-methylbenzthiazole-7-sulphonic acid are stirred into 100 parts of water; and dissolved by adding 5.1 parts of 30% sodium hydroxide solution. To this solution 6 parts of 4N sodium nitrite solution are added, and the resultant mixture is poured into a preparation consisting of 200 parts of ice and 7 parts of 30% hydrochloric acid. A yellow diazo suspension is obtained. After stirring for three hours any excess nitrous acid is decomposed by the addition of a small quantitiy of sulphamic acid. The precipitation thus formed which contains the diazonium salt of the above mentional amino compound is filtered off and washed with water acid-free. This diazonium salt together with 2.7 parts of 2,4-diamino-6-hydroxypyrimidine is suspended in a small amount of water, then 20 parts of diethylene glycol amine are added. Coupling commences whereby an orange-coloured mass is produced. After coupling is complete, 10 parts of ethylene glycol and 20 parts of urea are added followed by the addition of water to adjust to a volume of 140 parts. The mixture is heated to 40º, and a clear dyestuff solution of low viscosity is formed. This dyeing preparation is ready for use and storage-stable for several months. It contains the dyestuff in the salt form corresponding to the formula

This dyestuff dyes paper a brilliant neutral-yellow shade. The paper dyeings have very good wet fastness properties. The back water of these dyeings is approximately colourless.

Example 97 6.4 Parts of 2-(4'-aminophenyl)-6-methylbenzthiazole-7-sulphonic acid are diazotised according to the method given in Example 96 and coupled with 2,4-diamino-6-hydroxypyrimidine in the presence of sodium carbonate. Then 15 parts of 30% hydrochloric acid are added. Stirring is effected for three hours at 40°. The precipitation is filtered off and washed with water until it is acid-free. The press cake thus obtained is added into a preparation consisting of 30 parts of water and 30 parts of dimethylaminopropyl amine. A clear dyestuff solution is obtained which is stable on storage for several months. It contains the dyestuff in the probable salt form corresponding to the formula

which dyes paper a brilliant neutral-yellow shade.

Example 98

6.4 Parts of 2-(4'-aminophenyl)-6-methylbenzthiazole-7-sulphonic acid are diazotised according to the method described in Example 96 and coupled with 3.3 parts of 2-cyanimino-4-amino-6hydroxypyrimidine in the presence of sodium carbonate. The thus obtained suspension is filtered, and the residue is dried. The dyestuff corresponding to the formula

is obtained in form of a powder. It dyes paper a brilliant reddish-yellow shade. The paper dyeings have notably good wet fastness properties; the back water is colourless.

Example 99

7 Parts of 2-(4'-aminophenyl)-6-carboxybenzthiazole-7-sulphonic acid are diazotised according to the method described in Example 96. To the resultant diazonium salt 2.7 parts of 2,4-diamino-6-hydroxypyrimidine are added, and coupling is effected in the presence of lithium hydroxide. After coupling is complete, the dyestuff which precipitates is filtered off and dried. The dyestuff corresponding to the formula

is obtained in the lithium salt form. It dyes paper a brilliant neutral-yellow shade. The wet fastness properties of these paper dyeings are notably good; the back water is colourless.

Example 100

If in Example 994.5 parts of 2-cyanimino-4-amino-6-hydroxypyrimidine are employed instead of 2.7 parts of 2,4-diamino-6hydroxypyrimidine the lithium salt of the dyestuff corresponding to the formula

°^{H H}

is obtained. It dyes paper a brilliant reddish-yellow shade. The wet fastness properties of these paper dyeings and their properties with respect to back water coloration are very good.

Example 101 8 Parts of 2-(4'-aminophenyl)-6-methylbenzthiazole-3',7-disulphonic acid are dissolved in 100 parts of water whilst stirring and then 7 parts of 30% hydrochloric acid are added. To this solution which is cooled to 5º 6 parts of 4N sodium nitrite solution are added. Any excess nitrous acid in the diazo solution thus obtained is decomposed by the addition of sulphamic acid. Subsequently, 2.7 parts of 2,4-diamino-6-hydroxypyrimidine are added. Coupling commences when by the addition of sodium carbonate the pH is adjusted to an alkaline range. An orange-coloured suspension is obtained. After coupling is complete, 20 parts of 30% hydrochloric acid are added, and then the strongly acidic suspension is filtered off and washed with water. The obtained press cake is added into a preparation consisting of 200 parts of water and 15 parts of lithium hydroxide. The mixture is heated to 70° whereby a solution is obtained. After cooling down, the dyestuff corresponding to the formula H

cristallizes in form of the lithium salt. It dyes paper a neutral yellow shade. The resultant back water is colourless. These paper dyeings have notably good wet fastness properties.

Example 102

32 Parts 2-(4'-aminophenyl)-6-methylbenzthiazole-7-sulphonic acid are stirred into 300 parts of water followed by the addition of 11 parts of 30% hydrochloric acid. Then 27 parts of 4N sodium nitrite solution are slowly added dropwise, and the temperature is kept at 15-20°. After stirring for two hours, any excess nitrous acid is decomposed by adding a small amount of sulphamic acid. Subsequently, the obtained diazo suspension is added dropwise a preparation consisting of 13 parts of 2,4-diamino-6-hydroxypyrimidine and 125 parts of 24.5% tetramethyl ammonium hydroxide solution. Coupling commences immediately. After coupling is complete, the solution is filtered clear. A storage-stable dyeing preparation is obtained which is ready for use containing the dyestuff which corresponds to the formula QH

This preparation dyes paper a billiant neutral-yellow shade; the back water is practically colourless. The paper dyeings thus obtained have notably good dyeing properties.

Example 103

If in Example 102 13.2 parts of barbituric acid are employed instead of 13 parts of 2,4-diamino-6-hydroxypyrimidine, a storage-stable dyeing preparation is obtained containing the dyestuff in salt form which corresponds to the formula

_{3 4}

and dyes paper a yellow shade. The paper dyeings show high general fastness properties.

If in Example 102 or 103 instead of tetramethyl ammonium hydroxide equimolar amounts of one of the quaternary ammonium hydroxides given for Examples 93a to 93j or 93I to 93x are used, storage-stable dye preparations may be obtained which have good dyeing properties.

Example 104

If in Example 102 instead of the tetramethyl ammonium hydroxide solution 33 parts of the bisquaternary ammonium hydroxide of the formula CH₂CH (OH )CH₃ CH₂CH(OH ) CH₃

H₃CNCH₂CH₂NCH₂CH₂NCH₃ 20H

®

CH₃ CH₃ CH₃ (prepared by the addition of propylene oxide to the compound of the formula

(CH₃)₂NCH₂CH₂N(CH₃)CH₂CH₂N(CH₃)₂) are used, a yellow storage-stable dye preparation is obtained containing the dyestuff of the formula

₃

The resultant solution is a liquid of low viscosity, it is therefore easily dosable. This dyeing preparation dyes paper a brilliant neutral-yellow shade.

In the following examples the application of the compounds of this invention as well as liquid aqueous dyeing preparations thereof is illustrated.

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 a Hollander in 2000 parts of water. 0.2 Parts of the dyestuff of Example 1, 98 or 101 are sprinkled into this pulp or 1.0 parts of the liquid dyestuff preparation according to Example 92, 96 or 102 are added to this pulp. After mixing for 20 minutes, paper is produced from this pulp. The absorbent paper obtained in this way is dyed a brilliant yellow shade (reddish-yellow shade, respectively). The waste water is practically colourless.

Application Example B 0.5 Parts of the dyestuff of Example 1, 98 or 101 are dissolved in 100 parts of hot water, and cooled to room temperature. This solution is added to 100 parts of chemically bleached sulphite cellulose which have been ground in a Hollander with 2000 parts of water. After thorough mixing for 15 minutes, sizing takes place in the usual way with rosin size and aluminium sulphate.

Paper which is produced from this material is of brilliant yellow shade (reddish-yellow shade, respectively) and has good waste water and wet fastness properties.

Application Example C An absorbent length of unsized paper is drawn at 40-50º through a dyestuff solution having the following composition:

0.5 parts of the dyestuff of Example 1, 98 or 101 or of the liquid dye preparation according to Example 92, 96 or 102 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 yellow (reddishyellow) shade. The dyestuffs or liquid dyestuff preparations of the remaining examples may also be used for dyeing paper according to Application Examples A to C.

Application Example D (leather)

100 Parts of intermediately dried chrome velours leather are agitated for one hour at 50° in a vessel with a liquor consisting of 400 parts of water, 2 parts of 25% ammonium hydroxide solution and 0.2 parts of a conventional wetting agent. Then the liquor is run off. To the agitated still wet chrome velours leather 400 parts of water of 60° and 1 part 25% ammonium hydroxide solution are added. After the addition of 5 parts of the dyestuff of Example 1 dissolved in 200 parts of water, dyeing is effected during 90 minutes at 60". Subsequently, 50 parts of 8% formic acid are slowly added to adjust to an acidic pH, and agitating is continued for a further 30 minutes. The leather is then rinsed, dried and prepared in the normal way giving a leather evenly dyed in a yellow tone with good light fastness properties.

Application Example E ( cotton)

To a dyebath consisting of 3000 parts of demineralized water, 2 parts of sodium carbonate and 1 part of the dyestuff of Example 1, 100 parts of pre-wetted cotton fabric are added at 30°. After the addition of 10 parts of sodium sulphate, the dyebath is heated to the boil within 30 minutes whereby, at a temperature of 50º and 70°, at each of these stages a further 10 parts of sodium sulphate are added. Dyeing is continued for a further 15 minutes at the boil followed by the addition of a further 10 parts of sodium sulphate. The dyebath is then cooled down. At 50° the dyed fabric is removed from the dye liquor, rinsed with water and dried at 60". A golden-yellow cotton dyeing is obtained having good light and wet fastness properties.

Application Example F (polyamide)

0.1 Parts of the dyestuff of Example 1 are dissolved in 300 parts of water, and 0.2 parts of ammonium sulphate are added to this solution. Then the pre-wetted textile fabric (5 parts wool gaberdine or 5 parts nylon satin) is entered into the bath which is heated to the boil during the course of 30 minutes. The water that evaporates during the dyeing process for 30 minutes is replaced, and dyeing at the boil is continued for a further 30 minutes. Finally, the dyed fabric is removed from the liquor and rinsed with water. After drying a clear yellow polyamide dyeing is obtained having good light and wet fastness properties.

In analogous manner as described in Application Examples D to F the dyestuffs of the remaining examples may be used for dyeing. The thus obtained substrates are dyed in a yellow tone and have good fastness properties.

List of maximum absorption wavelenghts (in nanometer) for the exemplified compounds. These values were measured in 1% acetic acid solution with the exception that for the compounds of Examples 96, 97 and 102 demineralised water, and for the compounds of Examples 99-101 0.1% sodium carbonate solution was used.

Claims

CLAIMS: -

1. A compound which, in one of the possible tautomeric forms, corresponds to formula I,

in which each of R₁ and R₂ i s independently hydrogen, C_1-4alkyl , C_1-4alkoxy or COOM, each of Q₁ and Q₂ is independently hydrogen or SO₃M₁, n is 0 or 1, each of M and M₁ is independently hydrogen or a non-chromophoric cation; K is one of the groups (a) and (b), R₃

in which

R₃ is hydrogen, CN, NH₂, OH, C_1-4alkoxy, C_1-4alkyl, C_2-4alkyl monosubstituted by hydroxy or C_1-4alkoxy, C_5-6cycioalkyl; phenyl or phenyl-C_1-4alkyl which phenyl group of the latter two groups is unsubstituted or substituted by one to three groups selected from Chalkyl, C_1-4alkoxy, halogen, COOM and SO₃M; a saturated or unsaturated 5- or 6-membered heterocyclic ring containing one to three hetero atoms which is unsubstituted or further substituted by one to three C_1-4- alkyl groups and which is bound by a carbon or nitrogen atom directly or via a bridge member provided that any is

bound via a bridge member; -COR₆ or -(CH₂)_{1- 3}-R₇, R₆ is OH, N_H2 or C_1-4alkoxy,

R₇ is CN, halogen, SO₃M, -OSO₃M, -COR₈ or

R₈ is OH, NH₂, C_1-4alkyl which is unsubstituted or monosubstituted by OH, halogen, CN or C_1-4alkoxy; C_1-4alkoxy, phenoxy, phenyl or phenyl -C_1-4alkyl in which the phenyl groups of the latter three groups are unsubstituted or substituted by one to three groups selected from C_1-4alkyl, C_1-4alkoxy, halogen, COOM and SO₃M; R₄ is hydrogen, CN, halogen, SO₃M, NO, NO₂, -NR₉R₁₀. C_1-4alky! which is unsubstituted or monosubstituted by OH, halogen, CN, C_1-4alkoxy, phenyl, SO₃M or -OSO₃M; -SO₂NH₂, -COR₁₁, -CH₂NHCOR₁₂E, a group of the formulae

₂ in which the carbonyl or sulphonyl groups are bound to two carbon atoms of an aromatic ring which are in ortho position to each other; a group of the formula

^ in which the

ion is part of a 5- or 6-membered ring containing one to three hetero atoms which is further unsubstituted or substituted by one or two methyl groups or by NH₂, -NHC_1-4alkyl or N(C_1-4alkyl)₂; or a group of the formula R

in which

R₁₃ i s hydrogen or C_1-4alkyl which is unsubstituted or monosubstituted by OH, halogen, CN, C_1-4al koxy or phenyl ,

U₁ is S, -NH or -NC_1-4alkyl , and

V₁ is a group necessary to form a 5- or 6-membered ring to which ring a further 5- or 6-membered carbocyclic or heterocyclic ring containing one or two hetero atoms may be condensated, or

both R₃ and R₄ together form a C₃- or C₄-chain which may be part of a further 5- or 6-membered ring by two vicinal chain members,

each of R₉ and R₁₀ is independently hydrogen, Chalkyl which is unsubstituted or monosubstituted by OH, halogen, CN, C_1-4- alkoxy or phenyl; or -COR₁₂E_,

R₁₁ is OH, NH₂, -NHC_1-4alkyl, -N(C_1-4alkyl)₂, C_1-4alkyl, C_1-4- alkoxy, phenyl or phenoxy which phenyl group of the latter two groups is unsubstituted or substituted by one to three groups selected from Chalky!, C_1-4alkoxy, halogen, COOM and SO₃M, R₁₂ is C_1-6alkylene,

E is hydrogen, halogen, a protonable amine group, a quaternary ammonium group or a hydrazinium group; SO₃M or -OSO₃M;

R₅ is hydrogen, CN, NO₂, -NR₁₄R₁₅, a saturated or unsaturated 5or 6-membered heterocyclic ring containing one or two hetero atoms which is bound by a carbon or nitrogen atom and which is further unsubstituted .or substituted by up to three methyl groups or by NH₂, -NHC_1-4alkyl or -N(C_1-4alkyl)2; C_1-6alkyl, C_2-4alkenyl, C_2-4alkinyl; Chalkyl monosubstituted by OH, CN, C_1-4alkoxy, acetamido, -COR₁₅, SO₃M or -OSO₃M; C_{5 -6}cycloalkyl, phenyl or phenyl -C_1-4alkyl which phenyl group of the latter two groups is unsubstituted or substituted by one to three groups selected from C_1-4lkyl, C_1-4alkoxy, halogen, NO₂, NH₂, COOM and SO₃M; C_1-6alkylene-E₁, -C_1-6alkylene- or a group of the formula

each of R₁₄ and R₁₅ is independently hydrogen, C_1-4alkyl, C_1-4- alkyl monosubstituted by OH, halogen, CN or C_1-4alkoxy; phenyl or phenyl substituted by one or two groups selected from halogen, C^alkyl and C_1-4alkoxy, R₁₆ is OH or C_1-4alkoxy,

R₁₇ is hydrogen or C_1-4alkyl,

E₁ is a protonable amine group, a quaternary ammonium group or a

hydrazinium group or a group of the formula —

R₁₈ is E_2, -NHCOR₁₂E₂, -SO₂NHR₁₂E₂ or -CONHR₁₂E₂; each Rig is independently halogen, NH₂ or an aliphatic amine group,

E₂ is a protonable amine group, a quaternary ammonium group or a hydrazinium group,

X is 0 or NH, Z is OH, NH₂, methyl or ethyl, Y is 0, S or N-Yχ,

Y₁ is hydrogen, CN, CONH₂, C_1-4alkyl, Chalkyl monosubstituted by OH,-CN, halogen or C_1-4alkoxy; phenyl or phenyl-C_1-4alkyl which phenyl group of the latter two groups is unsubstituted or substituted by one or two groups selected from halogen, C_1-4alkyl, C_1-4alkoxy, acetamido, COOM and SO₃M; 1- or 2-naphthyl; Cι_galkylene-SO₃M, Chalky!ene-OSO₃M or C_1-6- alkylene-COOM, each of R₂₀ and R₂₁ is independently hydrogen, Chalkyl, phenyl or phenyl-C_1-4alkyl which phenyl group of the latter two groups is unsubstituted or substituted by one or two groups selected from halogen, C_1-4alkyl, C_1-4alkoxy, COOM and SO₃M; or, provided that Y is N-Y₁ where Y₁ is hydrogen, one of R₂₀ and R₂₁ may also have a significance additionally given for Y₁; with the provisos that

(i) in a compound of formula I at least one sulphonic acid group is present; (ii) when in a compound of formula I (1) K is a group (b), in which Y is O or S,

(2) R₂ is other than COOM,

(3) one of Q₁ and Q₂ or both Q₁ and Q₂ are SO₃M₁, and (1) to (3) occur simultaneously, then at least one of M₁ is a quaternary ammonium cation; (iii) when in a compound of formula I containing as K a group (b)

(1) the diazo component radical is defined as follows: R₁ is hydrogen, R₂ is methyl, Q₁ is SO₃M₁ in the 7-position, n is 0 and Q₂ is hydrogen,

(2) X is 0 or NH, (3) each of R₂₀ and R₂₁ is hydrogen,

(4) Y is N-Y₁ in which Y₁ is hydrogen, and (1) to (4) occur simultaneously, then M₁ has a significance other than hydrogen or sodium;

which compound of formula I is in free acid or salt form with the proviso that each sulphonic acid group as well as each protonable amine group can be present in ionized form.

2. A compound according to Claim 1, in which each R₁ is R_1b, where each R_1b is independently hydrogen, methyl, ethyl, methoxy or ethoxy; R₂ is R_2b, where R_2b is methyl, methoxy, ethoxy or COOM; n is 0, and Q₁ is SO₃M₁ in the 7-position.

3. A compound according to Claim 1, in which K is K₁, where K₁ is a group (a₁) or (b₁)

i n which

^R3a is hydrogen, CN, NH₂, OH, methyl, ethyl, hydroxyethyl, C_1-2alkoxyethyl, methoxy, ethoxy, cyclohexyl; phenyl or phenyl-C_1-2alkyl in which the phenyl group is unsubstituted or substituted by one or two groups selected from methyl, methoxy,

chlorine, COOM and SO₃M; -CH₂- , -COR_6a or -(CH₂)_1-2R_7a,

R_{6 a} is OH, NH₂, methoxy or ethoxy, R_7a is CN, chlorine, SO₃M, -OSO₃M, or -COR_8a,

R_8a is OH, NH₂, methyl, ethyl, methoxy or ethoxy; R_4a is hydrogen, CN, chlorine, bromine, SO₃M, -NR_9aR_10a, C_1-2alkyl, C_1-2alkyl monosubstituted by OH, phenyl, SO₃M or -OSO₃M; -COR_11a, -CH₂NHCOR_12aB₂ or a group -

forming a pyridine, pyrimidine or benzimidazole ring which is further unsubstituted or monosubstituted by methyl, NH₂, -NHCH₃ or -N(CH₃)₂, each of R_9a and R_10a is independently hydrogen, C_1-2- alkyl, C_1-2alkyl monosubstituted by OH, C_1-2alkoxy or phenyl, or

-COR_12aE_a,

R_12a is C_1-2alkylene,

E_a is hydrogen, chlorine, a group B₂ or SO₃M, B₂ is a group R_22aR_23a or -NR_24aR_25aR_26a, each of R_22a and R_23a, independently, is hydrogen, C_1-2- alkyl, unbranched hydroxy-C_2-3alkyl or benzyl or both R_22a and R_23a, together with the N-atom to which they are attached, form a pyrrol idine, piperidine, morpholine, piperazine or N-methylpiperazine group, each of R_24a and R_25a has independently one of the noncyclic or cyclic significances of R_22a and R_23a except hydrogen, and

R_26a is methyl, ethyl or benzyl, or R_24a, R_25a and R_26a, together with the N-atom to which they are attached, form a pyridinium group unsubstituted or substituted by one or two methyl groups

R_11a is OH, NH_2, -NHCH₃, -N(CH₃)2, methyl, ethyl, methoxy or ethoxy; R_5a is hydrogen, -NR_14aR_15a, phenyl, phenyl -C_1-2alkyl, cyclohexyl; C₁_₄alkyl, C_1-4alkyl monosubstituted by OH, CN,

C_1-2alkoxy, -COR_16a, SO₃M or -OSO₃M;

-C_1-3alkylene-E_1a, -C_1-3alkylene-N f^

_{2 18a} each of R_14a and R_15a is independently hydrogen, methyl, ethyl or phenyl,

^R16a is OH, methoxy or ethoxy,

E_1a is B₂ or a group of the formula

19a R_17a is hydrogen or methyl, each R_19a is independently fluorine, chlorine, N H₂,

-NHC_1-2alkyl or -N(C_1-2alkyl)2, in which the alkyl groups are unsubstituted or monosubstituted by OH, CN or C_1-2alkoxy,

R_18a is E_2a, -NHCOR_12aE_2a, -SO₂NHR_12aE2_a or -CON R_12aE_2a, E_2a is a group B₂; Z_a is OH or NH₂,

Y_a is 0 or N-Y_1a,

Y_1a is hydrogen, CN, CONH₂, methyl, ethyl, C_2-4 alkyl monosubstituted by OH, CN, chlorine or C_1-2alkoxy; phenyl or phenyl -C_1-2 alkyl, the phenyl group of the latter two groups is unsubstituted or substituted by one or two groups selected from chlorine, methyl, methoxy, COOM and SO₃M; C_2-4alkylene-SO₃M, C_2-4alkylene-OSO₃M or C_2-4alkylene-COOM, each of R_20a and 21_a is independently hydrogen, methyl, ethyl, phenyl-C_1-2alkyl or phenyl, the phenyl groups of which are unsubstituted or substituted by one or two groups selected from chlorine, methyl, methoxy, COOM and SO₃M, or in case where Y_a is N-Y_1a in which Y_1a is hydrogen, one of R_20a and R_21a also has a significance additionally given for Y_1a.

4. A compound according to any one of Claims 1 to 3 which compound corresponds to formula I a,

Ia

in which M₁ and Q₂ are as defined in Claim 1, R_1b and R_2b are as defined in Claim 2, and K₁ is as defined in Claim 3, with the provisos that (ii) when in a compound of formula I a

(1) K₁ is a group (b₁), in which Y_a is 0, (2) R_2b is other than COOM,

(3) Q₂ is hydrogen or SO₃M₁, and (1) to (3) occur simultaneously, then at least one of M₁ is a quaternary ammonium cation asdefined above;

(iii) when in a compound of formula Ia in which K₁ is a group (b₁)

(1) the diazo component radical is defined as follows: R_1b is hydrogen, R_2b is methyl and Q₂ is hydrogen,

(2) each of R_20a and R_21a is hydrogen, (3) Y_a is N-Y_1a, in which Y_1a is hydrogen, and (1) to (3) occur simultaneously, then M₁ has a significance other than hydrogen or sodium.

5. A compound according to Claim 4, in which K₁ is a group of the formul

wherein R_4d is hydrogen or cyano.

6. A process for the preparation of a compound of formula I as defined in Claim 1 comprising reacting the diazonium salt of an amine of formula II

in which R₁, R₂, Q₁, Q₂ and n are as defined in Claim 1, or a mixture thereof with a compound which in one of the possible tautomeric forms corresponds to formula IlIa or IIlb

in which R₃, R₄, R₅, R₂₀, R₂₁, X, Y and Z are as defined in Claim 1.

7. A process according to Claim 6 comprising reacting the diazonium salt of an amine of formula II with a compound of formula Ilia or Illb in the presence of a basic salt, lithium-, sodium-, potasium-, ammonium-hydroxide, one or more organic amines or a quaternary ammonium compound.

8. A storage-stable, liquid aqueous dyeing preparation containing a compound of formula I defined in Claim 1 in watersoluble salt form.

9. A process for dyeing or printing comprising applying to a hydroxy group or nitrogen containing organic substrate a compound of formula I defined in Claim 1 in water-soluble salt form.

10. A process according to Claim 9 wherein said substrate is a textile consisting of or containing cellulose material, leather or paper.