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 R^ and R2 is independently hydrogen, C _j ^alkyl, C^alkox or COOM, each of Qi and Q2 is independently hydrogen or SO3 1, n is 0 or 1, each of M and Mi is independently hydrogen or a non-chromophoric cation; K is one of the groups (a) and (b),

in which

R3 is hydrogen, CN, N_2, OH, Cι_4alkoxy, Chalk !, C2-4alk l onosubstituted by hydroxy or C^alkoxy, C5_6cycloalk l; phenyl or phenyl-Chalk ! which phenyl group of the latter two groups is unsubstituted or substituted by one to three groups selected from Cχ_4alkyl , Cχ_4alkoxy, halogen, COOM and SO3M; a saturated or unsaturated 5- or 6-membered hetero- cyclic ring containing one to three hetero atoms which is unsubstituted or further substituted by one to three 0^.4- alky! 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; -COR5 or -(C .2)ι_3-R7,

Rg is OH,

R7 s CN, > δ is OH, NH2, halky! which is unsubstituted or monosubsti¬ tuted by OH, halogen, CN or Cι_4alkox ; C^alkoxy, phenoxy, phenyl or phenyl-Chalky! in which the phenyl groups of the latter three groups are unsubstituted or substituted by one to three groups selected from C^alkyl, Ci_4alkox , halogen, COOM and SO3M;

R4 is hydrogen, CN, halogen, SO3M, NO, N0 ₂ , -NRgR^ _Q , Chalk ! which is unsubstituted or monosubstituted by OH, halogen, CN,

Cι_4alkoxy, phenyl, SO3M or -OSO3M;

-SO NH2, -COR11, -CH2NHCOR12E, a group of the formulae

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 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 N_2, -NHCχ_4alkyl or N(Cχ_4alk l)2 or a group of the formula

in which Rχ3 is hydrogen or Chalky! which is unsubstituted or monosub¬ stituted by OH, halogen, CN, C^alkox or phenyl, Ui is S, -NH or -NC^alkyl, and

V 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 R Q is independently hydrogen, Cχ_4alkyl which is unsubstituted or monosubstituted by OH, halogen, CN, C _4~ alkoxy or phenyl; or -COR 2E,

Rχi i s OH, NH ₂ , -NHCi _ alkyl , -N(Cι_ ₄ al _yl ) ₂ , Cι_ alkyl , C1-4- alkoxy, phenyl or phenoxy which phenyl group of the latter two groups is unsubstituted or substituted by one to three groups selected from Cι_4alk l, C ^alkoxy, halogen, COOM and SO3M, ^R 12 i Cι_5alkylene,

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 5- or 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, -NHCι_4alkyl or -N(C _4 lkyl)2; Chalky!, C2-4alkenyl, C2-4alkinyl; Chal y! monosubstituted by OH, CN, Cι_4alkox , acetamido, -C0Ri6 _> SO3M or -OSO3M; Cs_6c do- alkyl, phenyl or phenyl -Chalky! which phenyl group of the latter two groups is unsubstituted or substituted by one to three groups selected from Chalky!, Cι_4alkoxy, halogen, N0 ₂ , NH ₂ , -C _5alkyl the formula

each of R14 and R15 is independently hydrogen, Cι_4alkyl, Ch¬ alky! monosubstituted by OH, halogen, CN or C _4alkox ; phenyl or phenyl substituted by one or two groups selected from halogen, Cι_4alk l and C^alkox , R 5 is OH or Cι_4alkoxy, 7 is hydrogen or C^alk l,

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

hydrazinium group or a group of the formula -

^R 18 ^{1s E} 2 _> - HC0Rι ₂ E ₂ , -S0 ₂ NHRi ₂ E ₂ or -C0NHRι ₂ E ₂ ; each Rig is independently halogen, NH or an aliphatic amine group,

E 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,

Yl is hydrogen, CN, CONH2, Cι_4alkyl, Cι_4alk l monosubstituted by OH, CN, halogen or Cι_4alkox ; phenyl or phenyl-Chalk ! which phenyl group of the latter two groups is unsubstituted or substituted by one or two groups selected from halogen,

C _4alkyl , Cι_4alkoxy, acetamido, COOM and SO3M; 1- or 2-naphthyl ; Ci _6alkylene-S03M, Chalk ! ene-0S03 or Cχ.6- alkyl ene-COOM, each of R20 and 21 i s independently hydrogen, C _4alkyl , phenyl or phenyl -C _4alk l which phenyl group of the l atter two groups is unsubstituted or substituted by one or two groups selected from halogen, C^alkyl, Ci^alkoxy, COOM and SO3M; or, provided that Y is N-Yi where Yi is hydrogen, one of R 0 and 21 may also have a significance additionally given for ^γ ι>

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) R is other than COOM,

(3) one of Q and Q2 or both Qi and Q are SO3M1, and (1) to (3) occur simultaneously, then at least one of i 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: Rl is hydrogen, R2 is methyl, Qi 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- i in which Y _j is hydrogen, and (1) to (4) occur simultaneously, then Mi 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

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

Each Ri is preferably Rι _a , where each Rι _a is independently hydrogen, Chalk !, methoxy or ethoxy. More preferably it is Rib, where each R15 is independently hydrogen, methyl, ethyl, methoxy or ethoxy. Even more preferably it is Rι _c , where each Rl _c is independently hydrogen or methyl. Most preferably Ri is hydrogen. R2 is preferably R2 _a , where R2 _a is Chalk ! , Cι_4alkoxy or COOM. More preferably it is 25, where R _D is methyl, methoxy, ethoxy or COOM. Most preferably R is methyl.

Q 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 C2_3alk l group monosubstituted by hydroxy or Cι_2alkox . Any cycloalkyl is preferably cyclohexyl.

Preferably, in any substituted phenyl or phenylalkyl 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, pyrro- lidine, piperidine, piperazine or N-methylpiperazine (when satura¬ ted) 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 Rg _a , where R6 _a is OH, NH , methoxy or ethoxy. More preferably it is R , where R6 is OH or NH . 7 is preferably R7 _a , where 7 _a is CN, chlorine, SO3M, -° ^so 3 ^M _> ~0_ or -C0Ra _a , where Ra _a is OH, N_2_ ^' ethyl, ethyl, methoxy or ethoxy; more preferably it is 7 _D , where R7 _D is SO3M,

-0S03M,-(2. or -CORgb* where Rat, is OH or NH2.

R3 is preferably R3 _a , where R3 _a is hydrogen, CN, NH2, OH, methyl, ethyl, hydroxyethyl, Cι_2 ^a lkoxyethyl , methoxy, ethoxy, cyclohexyl; phenyl or phenyl-C _2alkyl in which the phenyl group is unsubstituted or substituted by one or two groups selected from

methyl, methoxy, chlorine, COOM and S0 ₃ M; -C_2-N_J> , -C0Rg _a or

-(CH2)l-2 ^R 7a- ^More preferably R3 is R35, where R^ is NH2, methyl, ethyl, hydroxyethyl, cyclohexyl, phenyl, phenyl , -CORgb or -CH2R7b- Even more preferably R3 is R3 _C , where R3 _C is NH2, methyl, hydroxyethyl, phenylethyl or -CH2SO3M. Most preferably R3 is methyl.

Any protonable amine or quaternary ammonium group as E, Ei or E 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 amine ^' group 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-Cι_4- alkyl- or a di-(Cι_4alkyl)-amine group. The alkyl group may be monosubstituted by halogen, hydroxy, cyano, C1.4al .oxy or phenyl. Any cycloaliphatic amine group is preferably Cg.gcycloalkylamino, the cycloalkyl group of which is unsubstituted or may be substi- tuted by one or two C, ₂ alkyl groups.

Any aromatic amine group is preferably phenylamino, the phenyl ring of which is unsubstituted or substituted by one or two

groups selected from halogen, Chalk !, Cι_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 Cι_4alk l groups.

More preferably B is Bi, where Bi is a protonable amine group -NR22 23 or a quaternary ammonium group - R24R25R26 » or Bi 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, Chalk !, C2_4alkyl monosubstituted by hydroxy, Cι_4alkoxy, halogen or cyano; phenyl-Cι_4alk l, the phenyl group of which is unsubstituted or substituted by one to three groups selected from chlorine, Chalk ! and Cι_4alkoxy, or Cg.gcycloalkyl, or R22 and R23, together with the N-atom to which they are attached, attached, form a heterocyclic ring of the formula

/—\

-N U ₉ _^ ²

in which

U2 is the direct bond, -Cl -, -0-, -S-, -SO2-, -SO-, -NH-, -N(Cι_ ₄ alkyl)- or -N(Cι_ ₄ alkyl) ₂ -, each of R24 and R25 has independently one of the cyclic or non- cyclic significances of R22 and R23 except hydrogen, and ^R 26 s C _4alk l or phenyl-Ci.4a!kyl , or R24, R25 and R26, together with the N-atom to whicfi they are attached, form a pyridinium group unsubstituted or substituted by one or two methyl groups, or a ring of the formula

in which R and U2 are as defined above,

^R 27 ^1S hydrogen or Chalk ! and each of R28 _> independently, is Cι_4alkyl. Even more preferably B is B2, where B2 is a group -NR22a ^R 23a ^or

" ^NR 24a ^R 25a ^R 26a> each of R22a and R23a _> independently, is hydrogen, Cι_2 ^a l l, unbranched h drox -C2_3 alkyl or benzyl or both R22a 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 R24 _a and R25 _a has independently one of the non-cyclic or cyclic significances of R22a and R23 _a except hydrogen, and 26a ^1S 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 - R22b 23b ^or

-_ ^R 24b ^R 25b ^R 26b _> each of R22 and R 3b is hydrogen, methyl or ethyl or both R22b and R23b _» together with the N-atom to which they are attached, form a piperidine, morpholine, piperazine or N-methylpiperazine ring; each of R24 and R 5 is methyl or ethyl or both R24b and 25 _» together with the N-atom to which they are attached, has one of the cyclic significances of R2 b and R23 _»

^R 26b i methyl or ethyl or

^R 24b _> ^R 25b and R26b» 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 Eb, where Eb is hydrogen, chlor¬ ine, a group B ₃ or SO3M.

Each of R9 and RIQ is preferably Rg _a and Ri0a» where each of Rg and Rιo _a is independently hydrogen, Cι_2alkyl, Cι_ alk l mono¬ substituted by OH, C _ ₂ alkoxy or phenyl, or -COR^a^a* ⁱⁿ which ^R 12a is Cι_2alkylene. More preferably each of Rg and Rio is Rgb and Riob _> where each of Rgb and R o is independently hydro¬ gen, methyl or -C0Ri _a Eb« ii is preferably Rn _a , where Rn _a is OH, NH2, -NHCH3,

-N(CH3)2, methyl, ethyl, methoxy or ethoxy. More preferably it is ^R llb _> where Rub is NH2, methyl, ethyl, methoxy or ethoxy.

R4 is preferably R4 _a , where R _a is hydrogen, CN, chlorine, bromine, S0 ₃ M, -NRg _a Rιo _a» Ci^alk l, Cι_2alk l monosubstituted bv OH, phenyl, S0 ₃ M or -OSO3M 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 R4 _» where R4b is hydrogen, CN, -NHRiob, -CORnb, -CH2NHCOCH2B3 or a group of the formulae

-N or -N > . Even more preferably R4 is R4 _C ,

where R4 _C is hydrogen, CN, -NHC0CH ₂ E _b , -CONH2, Most preferably R4 is R4 _d , where R^ 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

for example they form a ring of the formula

Rl4 and R15 are preferably Ri4 _a and i5 _a> where each of Rχ4 _a and R 5 _a is independently hydrogen, methyl, ethyl or phenyl.

Ri is preferably Rιg _a» where Rιg _a is OH, methoxy or ethoxy.

R 7 is preferably Ri7 _a» where Rχ7 _a is hydrogen or methyl. Any aliphatic amine group as ^g is preferably a mono-Cι.4- alkyl- or di-(Cι_4alkyl)-amine group, in which the alkyl groups may be monosubstituted by halogen, OH, CN, Cι_4alkoxy or phenyl.

Each Rig is preferably Rig _a , where each Rιg _a is independent¬ ly fluorine, chlorine, H2, -NHCι_2alkyl or -N(Cι_2alkyl )2, in which the alkyl groups are unsubstituted or monosubstituted by OH, CN or Cι_2alkoxy. More preferably each Rig is Ri9b _> where each Rig is independently chlorine, NH ₂ , -NHCH3, -N(CH )2, -NHCH2CH2OH or -N(CH ₂ CH ₂ 0H) ₂ .

Ei is preferably Eι _a , where Eι _a is a group B2 or a group of

the formula more preferably it is Eib _> where Eib is a group B3 or a group of

the formula

E2 is preferably E2 _a» where E2 _a is a group 82- More prefer¬ ably it is E2b» where E2 is a group B3. Rχ8 is preferably R _18a , where Rι _8a is E _2a , -NHC0Rι _2a E _2a ,

-Sθ2NHRi2 _a E2 _a or -C0NHRi2 _a E2 _a ; more preferably it is Ri8b» where ^R 18b ^{is E} 2b» - HC0Ri2 _a E ₂ b or -C0NHRι _2a E _2b .

R5 is preferably Rg _a , where Rg _a is hydrogen, -N i4 _a 5 _a , phenyl, phenyl -C1..2 lkyl , cyclohexyl; Cι_4alk l, Cι_4alkyl mono-

More preferably R5 is Rgb, where R5b is hydrogen, -NHRιs _a , phenyl, phenyl-Cι_2alkyl, methyl, ethyl, Ch lky! monosubstituted by SO3M

or -C0Rι _{6 a} , -(CH ₂ )ι. ₃ -Eib,

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 phenylalkyl as Yl (when substituted) is substituted by one or two groups selected from chlorine, methyl, methoxy, COOM and SO3M.

Yl is preferably Y _a , where Yι _a is hydrogen, CN, CONH2, methyl, ethyl, C2_4alk l monosubstituted by OH, CN, chlorine or Cι_2alkox ; phenyl or phenyl-Ci_2alkyl , 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; C2_4alk lene-Sθ3 , C2_4alk lene-0S03 or C2_4alkylene-C00M. More preferably it is Yib _» where Yib is hydrogen, CN, CONH2, methyl, ethyl, 2-hydroxyethyl, phenyl, phenyl-Cι_2alkyl, C2_4alk lene-S03M or C2_4alkylene-C00M. Even more preferably it is Yι _c , where Yι _c is hydrogen, CN or CONH2. Most preferably it is Yι<j, where Yι<j is hydrogen or CN, of which hydrogen is most preferred.

Y is preferably Y _a , where Y _a is 0 or N-Yι _a ; more preferably it is Yb _» where Y is 0 or N-Y^; even more preferably it is Y _c , where Y _c is 0 or N-Yι _c ; most preferably it is Y< _j , where Y< is 0 or N-Y _ld .

Each of R20 and R2 is preferably R2o _a and R2i _a» where each of R20a ^ar| d ^R 21a ^is independently hydrogen, methyl ,- ethyl , phenyl-Cι_2alkyl or phenyl, the phenyl groups of which are unsub¬ stituted or substituted by one or two groups selected from chlo¬ rine, methyl, methoxy, COOM and SO3M, or_ in case where Y is N-Yχ in which Yj is hydrogen, one of R20a and ^R 21a ^has also a signi¬ ficance additionally given for Y. . More preferably each

1a of R20 and R21 is R20b and R 1b» where each of R20 and R2ib s

independently hydrogen, methyl, ethyl, phenyl or benzyl or_ in case where Y is N-Yi in which Yi is hydrogen, one of 20b and R2ib has a significance additionally given for Y1 . Most preferably R20 and R21 are hydrogen.

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

more preferably (a2) of the formula

in which gb especial y is hydrogen.

The group (b) i s preferably (bi ) of the formul a

more preferably it is (b2) of the formula

l a

K is preferably _ι, where _ι is one of the groups (ai) or (bi). More preferably it is _2, where _2 is one of the groups 2) or (b2). Even more preferably it is K3, where K3 is one of the groups (33) or (b3). Most preferably K is K4, where K4 is a group (a ₃ ).

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 M 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-a ine; mono-, di- or triethanol-, -propanol- or isopropanol-amine; N-methyl-N-hydroxyethylamine, N-methyl-N,N-di(hydroxyethyl )amine, N-ethyl-N-hydroxyethoxyethyl- amine, morpholine, piperidine, piperazine, hydroxyethylmorphol ne, hydroxyethylpipe azine, aminoethylpiperazine; ethylenediamine, hexamethylenediamine; dimethylaminopropylamine, diethylamino- propylamine, diethylene glycol amine,. diglycol amine and 3-meth- oxypropylamine.

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

Any substituted ammonium ion may also be a quaternary ammonium ion (especially when M^ derived from ammonium compounds which preferably contain one or two quaternary ammonium ions. Examples are tetramethyl-, tetraethyl-, trimethylethyl-, benzyl- diethylmethyl-, trimethylphenyl-, trimethylbenzyl-, triethylcyclo¬ hexyl-, trimethylhydroxyethyl- and tetrahydroxyethyl - ammonium- hydroxide as well as N,N-dimethylpiperidinium hydroxide, or compounds corresponding to the formula

H ₃ C ®H -- AA Λ -- CH ₃ 2 OH® CH ₃ CH ₃

in which each R30 is independently methyl , ethyl, hydroxyethyl or 2- or 3-hydroxypropyl and A is Cι_4alkylene or -CH ₂ CH ₂ N(CH3)CH CH -.

Preferred compounds correspond to formula Ia

^R lb in which R^, R2 > Q » ^M l ^{and κ} l ^{are as} defined above with the provisos that (ii) when in a compound of formula I a

(1) _ι is a group (b ), in which Y _a is 0,

(2) R ₂ b is other than COOM,

(3) _. 2 s hydrogen or SO3M , and (1) to (3) occur simultaneously, then at least one of M is a quaternary ammonium cation as defined above;

(iii) when in a compound of formula I a in which _ι is a group ^' (bi)

(1) the diazo component radical is defined as follows: R^ is hydrogen, R is methyl and Q is hydrogen,

(2) each of R2Q _a and R i _a is hydrogen,

(3) Y _a is -Yι _a , in which Y _a is hydrogen, and (1) to (3) occur simultaneously, then M has a significance other than hydrogen or sodium.

Even more preferred are compounds of formula I a, in which

2) Ki is K ₃ ; 3) R _lb is R _lc ;

4" R is hydrogen;

5) ^R b is methyl;

6) those of 2) to 5), in which K is 4.

The compounds of formula I can be prepared in accordance with known methods reacting the diazonium salt of an amine of formula II,

in which Ri, R2, Qi, _. 2 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, R ,-R2Q» R21. ^x _> ^γ 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'-aminop he_yl)-6-methylbenzthiazole-3' ,7-di sulphonic acid 2-(4'-aminophenyl)-6-carboxybenzthiazole-7-sulphonic acid 2-(4 ^, -amino-3'-methyl-5 ^, -sulphophenyl)-4,6-dimethyl-benzthiazo1e -7-sulp honic acid

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

2-(4 ' - ami nophenyl ) -6 -methyl benzthi azol e pri uline 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 2_ , (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 Rg _x i s Cι_galkyl ene-Eι or prepared for exampl e by reacti ng a

in which is Ci.galkylene or a group C / or ~(f ) ^ ,

wherein R ₃ ι is -NHCOR^-, -S0 ₂ NHRι ₂ - or -CONHR^-, and X _Q is a functional group, preferably a group which can be split off as an anion, with the amino compound E^-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, prefer¬ ably 4-8. Optionally, a quaternary ammonium compound is added using at least an equimolar amount which is sufficient to neutra- use 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 con¬ verted into a solid by spray-drying. Furthermore, the conventional method of isolation used for dyestuffs, salting out of the solu- tion, 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, dinitro- gen 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 mate¬ rials, such as cotton, in accordance with known methods; cotton is preferably dyed by the exhaust method, for example from a 1Ong or short liquor, at room temperature to boiling temperatures. Print- ing 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 (especially 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, con¬ centrated dyeing preparations may be made in accordance with known methods, advantageously by dissolving in suitable solvents, optio- nally adding an adjuvant, e.g. a hydrotropic compound or a stabi¬ liser. The possibility of producing such stable, aqueous-concen¬ trated preparations in the course of dyestuff synthesis without intermediate isolation of the dyestuff is particularly advanta¬ geous. 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 mole- cular weight ethers or hydroxyalkylation products, as well as nitriles or esters; among these the following compounds are preferably used:- Methanol, ethanol, propanol; ethylene-, propy- lene-, diethylene-, thiodiethylene- and dipropylene-glycol; butanediol; β-hydroxypropionitrile, pentamethylene glycol, ethylene gycol onoethyl- and -propylether, ethylene diglycol monoethylether, triethylene glycol monobutylether, butyl poly- glycol, formamide, dimethylformamide, pyrrolidone, N-methylpyrro- lidone, 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 prepara¬ tions 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 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 dissol- ving, as a dry powder or granulate, without reducing the bril¬ liance 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'-aminopheny1)-6-methylbenzthiazole-7-sul- phonic 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 20", any excess nitrous acid is decomposed by adding a small amount of sulphamic acid. Then, 3.3 parts of 4-methyl-6- hydroxypyridone-(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 hetero¬ cyclic monoazo compounds can be prepared from appropriate starting compounds. They correspond to formula (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-yeHow 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.

Table 1 / Compounds of formula (A)

Ex. 3 R ₄ 5 shade on

No. paper

2 CH ₃ CN H c

3 ^ CN H c

4 CH ₃ CN -o c

8 do. CN -CH ₂ C00C2H ₅ c

Table 1 (continued)

Ex. ^R 3 ^R 4 ^R 5 shade on

No. paper

9 CH ₃ CN -CH ₂ C00H c

10 do. CN -CH ₂ CH ₂ S0 ₃ H c

11 do. CN -CH2CH2OSO3H c

12 CH ₂ S0 ₃ H CN H c

13 do. H H b

14 CH ₃ C0NH ₂ H b

15 do. do. -C ₂ H ₅ b

16 do. COCH3

19 do Cl -C ₂ H ₅ b

20 do. H do. a

21 NH ₂ CN H a

22 do. C0NH ₂ H a

23 do. C00C2H H a

26 OH H H c

27 C00H H H b

28 CH ₃ CN ^■ CH ₂ CH ₂ 0H c

29 do. CN ^■ CH ₂ CH ₂ N -(§, c

CH3

30 . do. CN ^■ CH2CH2OCH3 c

31 do. NHCOCH3 -C ₂ H ₅ b

32 do. NH ₂ do . b

33 do. NHCOCH3 H a

Tab! e 1 (continued)

Ex. ^R 3 R ₄ R5 shade on

No. paper

34 <o>- H H a

35 CH ₃ H -(CH ₂ )3N(CH ₃ )2 a 36 do. H

37 CH ₂ CH ₂ 0H CN -CH2CH2N H C

41 do. CN -N(C ₂ H ₅ ) ₂ c

42 do ^' . SO3H -C ₂ H ₅ a

43 do. CH ₂ S0 ₃ H do. a

44 do. CN -CH2CH NH2 c

45 do. CN -C_2CH ₂ NHC0-< -N0 ₂

48 CH ₂ -fo CN

49 OCH3 H ^■ (CH2)2N(C ₂ H ₅ ) ₂

50 ^ CN

Table 1 (continued)

Ex. 3 4 R5 shade on

No. paper

51 CH ₃ CH2NHC0CH ₂ N(CH ₃ )2 -C2H5 a

53 do. CN -(CH2)3N(C ₂ H ₅ )2 c

©

54 do. H -CH ₂ CH2N(CH ₃ )3 a

5 566 ddoo.. HH --CCHH ₂ CCUH ₂ HN--cf T) a

CH.

Exa ple 57

12 Parts of 2-(4' amino-3'-sulphophenyl )-6-methylbenzthia- zole-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-methy1pyri- donyl-(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 proper¬ ties.

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

in which the symbols are defined in Table 2 below.

Table 2 / Compounds of formula (B)

Ex. No. ^R 3 R ₄ 5 shade on paper

58 CH ₃ H H a

61 do. -0- ^N(CH ₃ ⁾ ₂ H

62 do. - ^■ -(CH ₂ ) ₃ N(CH ₃ )2

63 do. CN do.

64 do. Q -CH2CH2NH

Θ

65 do. CN -CH ₂ CH2N(CH ₃ )3 c

66 NH ₂ CN H b

Table 2 (continued)

Ex. No. ^R 3 ^R 4 ^R 5 shade on paper

67 CH ₃ CN -CH ₂ CH ₂ ^

68 do. H do. a

69 do. H -CH2CH3 a

70 NH ₂ CN do. b

71 CH ₃ H CH ₂ CH ₂ NH2 a

Example 72

7 Parts of 2-(4'-aminophenyl )-6-carboxybenzthiazole-7-sul- phonic 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-hydroxy- pyridone-(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 70 ^* ; 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),

in which the symbols are defined in Table 3 below.

Table 3 / Compounds of formula (C)

Ex. No. ^R 3 R ₄ 5 shade on paper

73 CH ₃ H H b 74 do. CN H c 75 do. C0NH ₂ H b 76 do. H -CH CH ₃ b

79 do. ^• (CH ₂ ) ₃ N(CH ₃ )2

80 do. *o CN do.

Table 3 (continued)

Ex . No . ^R 3 R ₄ ^R 5 shade on paper

81 •CH ₂ C_2- ~ CN -CH ₂ CH ₂ - - CH.

82 CH ₃ CN do. c

83 do. C0CH ₃ H b

84 do. Br -CH2CH3 b

85 NH ₂ CN do. b

86 CH ₃ H -CH2CH2OH a

87 do. H -CH ₂ CH ₂ N- a CH ₃

88 do. H -(CH ₂ )3N(CH ₃ )2 a

89 do. H -(CH ₂ ) ₃ t(CH3)3 a

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-sul- phonic 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 triethanolamine. 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 triethanolammonium 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 monoethanolamine 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 monoethanolamine are dietha- nolamine, monoisopropanolamine or diisopropanolamine.

Example 93

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

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

Examples 93a to 93x

93m:

93BJ_

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 hydro¬ chloric 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 brill ant golden-yellow shade.

Example 96

6.4 Parts of 2-(4'-aminophenyl)-6-methylbenzthiazole-7-sul- phonic acid are stirred into 100 parts of water; and dissolved by adding 5.1 parts of 30% sodium hydroxide"solution. To this solu- tion 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 a ino 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 40", 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-sul- phonic 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 prepara¬ tion consisting of 30 parts of water and 30 parts of dimethyl- aminopropylamine. 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-sul- phonic acid are diazotised according to the method described in Example 96 and coupled with 3.3 parts of 2-cyanimino-4-amino-6- hydroxypy i idine 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-sul- phonic acid are diazotised according to the method described in Example 96. To the resultant diazonium salt 2.7 parts of 2,4-di- amino-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-hydroxy- pyrimidine are employed instead of 2.7 parts of 2,4-diamino-6- hydroxypyrimidine the lithium salt of the dyestuff corresponding to the formula

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

Example 101 8 Parts of 2-(4'-aminophenyl)-6-methylbenzthiazole-3' ,7-di- sulphonic acid are dissolved in 100 parts of water whilst stirring and then 7 parts of 30% hydrochloric acid are added. To this solu¬ tion which is cooled to 5 ^β 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. Subse¬ quently, 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 correspon¬ ding to the formula

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-hydroxy- pyrimidine and 125 parts of 24.5% tetramethylammonium 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 dye¬ stuff which corresponds to the formula

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 dye¬ stuff in salt form which corresponds to the formula

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

If in Example 102 or 103 instead of tetramethylammonium hydroxide equimolar amounts of one of the quaternary ammonium hydroxides given for Examples 93a to 93j or 931 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 tetramethylammonium hydroxide solution 33 parts of the bisquaternary ammonium hydroxide of the formula

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

(CH3)2NC_2C_ N(C_3)C_2CH N(C.3)2) are used, a yellow storage-stable dye preparation is obtained containing the dyes

The resultant solution is a liquid of low viscosity, it is there¬ fore easily dosable. This dyeing preparation dyes paper a bril¬ liant 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 cellu¬ lose 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 dis¬ solved 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 40-50" 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 (reddish- yellow) 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 dye¬ bath is heated to the boil within 30 minutes whereby, at a tempe¬ rature of 50" 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 demineral sed water, and for the compounds of Examples 99-101 0.1% sodium carbonate solution was used.

Ex. No. -^ max. ( ^nm ) ^Ex - ^{No «} -^max. ( ⁿ ) ^Ex - ^{No «} nax. ( ⁿ )

1 429 29 448 65 448

2 449 30 448 66 432

3 459 31 454 69 431

4 496 32 431 72 438

5 446 33 429 73 432

6 458 34 427 74 440

7 452 35 432 75 429

8 456 36 432 76 431

9 456 37 449 77 438

10 457 38 449 78 438

11 458 39 451 79 440

12 466 40 452 80 448

13 443 41 454 81 447

14 444 42 432 83 431

15 448 43 430 - 84 435

16 446 44 447 90 429

17 442 45 448 91 429

18 435 46 480 92 429

19 442 47 452 93 429

20 430 48 454 94 429

21 403 57 438 96 413

22 422 58 430 97 413

23 426 59 445 98 400

24 437 60 436 99 432

25 438 61 448 100 422

26 443 62 439 101 436

27 430 63 442 102 412

28 448 64 438