Title of Invention

"PROCESS FOR THE PREPARATION OF PYRIDONE-METHIDE AZO DYESTUFFS OF FORMULA (1)"

Abstract Process for the preparation of pyridone-methide azo dyestuffs of formula (I), or its tautomeric form, wherein D is the radical of a carbo- or heterocyclic diazo component, said process comprising, diazotizing amines of the formula (IV) and the diazotization products are coupled to coupling components of the formula (V) wherein A1 to A5, D and X have the meaning as given above andrepresent H, -CO2H, -CH2OH, -SO3H, E represents H, -CO2H, -CH2OH, -SO3H, -
Full Text The present invention relates to a process for the preparation of pyridone-methide azo dyestuffs of formula (I).
Pyridone-methide azo dyestuffs
The invention relates to pyridone-methide azo dyestuffs, processes for their preparation, their use and coupling components containing pyridone-methide.
Azo dyestuffs which contain a coupling component based on methylene-triazolo-pyridines are already known from DE-A 4 020 768 and DE-A 4 C39 296. However, these azo dyestuffs still have some disadvantages in their use. Thus, for example, their build-up capacity and their stability in the dyebath when used for dyeing polyester is not satisfactory.
Pyridone-methide azo dyestuffs have now been found, which, in the form of the free acid, correspond to the formula (I) or its tautomeric forms
(Formula Removed)
wherein
D is the radical of a carbo- or heterocyclic diazo component,
A1 and A2 independently of one another denote H or a substituent typical for pyridones,
A"1 and A4 independently of one another denote an electron-withdrawing radical, or, together with the common C atom, form a cyclic methylene-active compound, ,
A5 represents H or a radical of the formula T, -OT1, -NH,, -NHT, -NT,, -NHCOH, -NHCOT, -N=CH-T, -N=CT, or NHSO,T,
wherein
T - alkyl, cycloalkyl or aralkyl, and T represents T1 or can assume the meanini of T2 to T2 where T2 = alkenvl,
T3 = alkinyl,
T4 = aryl,
T5 = hetaryl
or
A' and A1 and/or
A2 and A3 and/or
A4 and A3, together with the particular atoms in between, form an unsaturated, optionally substituted 5- or 6-membered carbo- or heterocyclic radical, with the proviso that if a ring is formed with participation of one of the two radicals A3 and A4, the radical which does not participate denotes an electron-withdrawing radical,
X represents O, NH, NT, NCOT, NCO2T or NSO2T,
K® is -NH3 -NHT2, -NH,T, -NT3 or a cycloimmonium ion,
Be is an anion,
Z is a fibre-reactive radical,
1 represents 0 to 2,
m represents 0 to 8 and
n represents 0 to 6.
According to the present invention there is provided a process for the preparation of pyridone-methide azo dyestuffs of formula (I),

(Formula Removed)
or its tautomeric form, wherein
D is the radical of a carbo- or heterocyclic diazo component,
A1 and A2 independently of one another denote H or a radical of the formula T, -COH, -CO-T, -CO2T, -CN, -CONH2, -CONHT, -CONT2, CF3, -NH2, -NHT, -NT2, -NH-COT, -NT-COT, -NHSO2T, -NTSO2T, -NO2, -NO, -SO2T, -OH, -OT, -OCOT, -OCO2T, -OSO2T, CI, Br or I
A3 and A4 independently of one another represent -CN, -CO2T,
-CONH2, -CONHT, -CONT2, CF3, -CHO, -COT, -SO2T, -SO3T4, -SO3T5, SO2NH2,
SO2NHT, SO2NT2, -SOT, -CH=NH, -CN=NT, -CT=NH, -CT=NT,

, -CO-CO2T, -NO,3 -NO, T4 or T5,
(Formula Removed)
or
A3 and A4 together with the C atom to which they are bonded, represent a cyclic

where these radicals are shown in the form of H2C
(Formula Removed)
methylene-active compound of the formula (IIa) to (IIv),
(Formula Removed)
wherein
V1 represents H or a substituent in particular Cl, Br, CH3, -CO2T1, -CN, -NO2, -CF3 or -SO2T1, and wherein A1, A2, A5, D and X have the abovementioned meanings.
A5 represents H or a radical of the formula T, -OT1, -NH2, -NHT, -NT2, -NHCOH, -NHCOT, -N=CH-T, -N=CT2 or NHSO2T,
wherein
T1 = alkyl, cycloalkyl or aralkyl, and T represents T1 or can assume the meaning of T2 to T5, where
T2 = alkenyl,
T3 = alkinyl,
T4 = aryl,
Ts = hetaryl
or
A1 and A1 and/or
A 2 and A 3 and/or
A4 and A5, together with the particular atoms in between, form an unsaturated, optionally substituted 5- or 6-membered carbo- or heterocyclic radical, with the proviso that if a ring is formed with participation of one of the two radicals A3 and A4, the radical which does not participate denotes an electron-withdrawing radical,
X represents O, NH, NT, NCOT, NCO2T or NSO2T,
K is -NH3, -NHT2, -NH2T, -NT3 or a cycloimmonium ion,
B is an anion,
Z is a fibre-reactive radical,
I represents 0 to 2,
m represents 0 to 8 and
n represents 0 to 6.
said process comprising, diazotizing amines of the formula (IV)
(Formula Removed)
and the diazotization products are coupled to coupling components of the formula (V)
(Formula Removed)
wherein A1 to A5, D and X have the meaning as given above and
E represents H, -CO2H, -CH2OH, -SO3H, -
(Formula Removed)
wherein
T can assume the meaning of T1, T2, T3, T4 or T5.
The dyestuffs of the formula (I) according to the invention can exist in various tautomeric forms. One form corresponds, for example, to the formula (I), another corresponds, for example, to the following formula
(Formula Removed)
An electron-withdrawing radical is preferably understood as meaning a radical of which the Hammett substituent constant σ (para) is > 0, one of the two substituents A1 or A preferably having a σ (para) value > 0.300. An appropriate list of Hammett substituent constants is to be found, for example, in Sykes, Reaktionsmechanismen der organischen Chemie [Reaction mechanisms of organic chemistry], 9th Edition, Weinheim, VCH Verlagsgesellschaft, 1988, or can be determined by known methods.
T1 preferably represents C1-C20-alkyl, C4-C8-cycloalkyl or C6-C10-aryl-C1-C8-
alkyl, each of which is unsubstituted or substituted by one or more substituents from the group consisting of OH, C1-C10-aikoxy,
(Formula Removed)
C1-C10-alkoxy-C2-C5-alkoxy, C1-C5-alkoxy-C2-C5alkoxy-C2-C5-alkoxy, -OCOH, COH, -OCOT. -OSO2T, -O(CH2CH2O)1-6,COT, -OCO2T, COT,

-SO2T, -CO2T, -CN, -CONH2, -CONHT, -CONT2, -CO2H, -SO2NH2, -SO2NHT, -SO2NT2, -CF3, -NO2 and halogen, such as F, Cl, Br and I.
T2 and T3 independently of one another preferably represent C2-C20-alkenyl or C2-C20-alkinyl, each of which is unsubstituted or substituted by one or more substituents from the group of substituents already mentioned under T1.
T4 preferably represents C6-C]6-aryl, which is unsubstituted or substituted by one or more substituents from the group of substituents already mentioned under T1, further possible substituents being -NH2, -NHT, -NT2, -NHCOH, -NHCOT, NHSO2T, C2-C10-alkenyl, C2-C10-alkinyl, C1-C10-alkyl, C4-C8-cycloalkyl and C6-C10-aryl-C1-C6-alkyl.
T5 preferably represents a 5- or 6-membered aromatic heterocyclic radical which contains 1 to 3 identical or different hetero atoms from the group consisting of N, O, S, NH, SO and SO2 and is unsubstituted or substituted by one or more substituents from the group of substituents already mentioned under T1 and is optionally fused with one or two aryl or hetaryl rings.
Preferred dyestuffs of the formula (I) are those wherein 1 = 1 or 2 and n = 0, and m is less than 1, and is preferably 0, which are called "cationic dyestuffs" of the formula (I) below.
Dyestuffs which are likewise preferred are those of the formula (I) wherein 1 = m = n = 0, which are called "disperse dyestuffs of the formula (I)" below.
Dyestuffs which are furthermore preferred are those of the formula (I) wherein 1 = 0 and m and/or n are not equal to 0. These dyestuffs according to the invention are called "acid dyestuffs of the formula (1)" below, if n is 0, and "reactive dyestuffs of the formula (I)" below, if n is not equal to 0.
Acid dyestuffs of the formula 1 are also understood as meaning those which carry COON groups and wherein m is 0.
Disperse dyestuffs
Preferred disperse dyestuffs of the formula (I) are those in which
A3 and A4 independently of one another represent -CN, -CO2T, -CONH2,
-CONHT, -CONT2, CF3, -CHO, -COT, -SO2T, -SO3T4 -SO3T5, SO2NH2,
SO2NHT, SO2NT2, -SOT, -CH=NH, -CH=NT, -CT=NH, -CT=NT,
(Formula Removed)
, -CO-CO2T, -NO2, -NO, T4 or T5,

wherein A3 and A4 preferably do not simultaneously represent T4 and/or T5,
or
AJ and A , together with the C atom to which they are bonded, represent a cyclic methylene-active compound of the formula (IIa) to (IIv),

where these radicals are shown in the form of H C
(Formula Removed)
wherein
represents H or a substituent, in particular CI, Br, CFF,, -CO2T1, -CN, -NO2, -CF. or -SO2T', and wherein A1, A2, A5, D and X have the abovementioned meanings.
Preferred disperse dyestuffs of the formula (I) are those wherein
A1 represents H, T, -COH, -COT, -CO2T, -CN, -CONH2, -CONH2, -CONHT.
-CONT2, CF,, OH or halogen, in particular CI, Br and I,
A2 represents H, T, -COM, -COT, -CN, -CO2T, -CONH2, -CONHT, -CONT2,
-CF,, -NO,, -NO, CI, Br or I,
AJ and A4 independently of one another represent -CN, -CO2T, -CONH2,
-CONHT, -CONT2, CF3, -CHO, -COT, -SO2T, -SO3T4, -SO3T5, SO2NH2, SO2NHT, SO2NT2, -SOT, -CH=NH, -CH=NT, -CT=NH, -CT=NT, -CO-CO2T, -NO2, -NO, T4 or T5, wherein A3 and A4 preferably do not simultaneously represent T4 and/or T , or
A2 and A3, together with the C atoms in between them, form the radical of a fused indene ring which is optionally substituted by R1, or
A3 and A4, together with the C atom to which they are bonded, form a carbocyclic or heterocyclic radical of the formula (IIa) to (IIv),
A5 denotes H, T1, T2, T3, T4, -NH2, -NHT, NT2, -NHCOT, -NHCOH,
-NHSO2T or -N=CT2 or A4 and A5, together with the atoms of the pyridone ring in between, form a fused ring of the formula
(Formula Removed)
wherein the N atom labelled with corresponds to the pyridone nitrogen,
T1 denotes C1-C10-alkyl, C5-C7-cycloalkyl or Cg-C^-aryl-C^Cg-alkyl, which
are optionally substituted by one or more substituents from the group
consisting of -OH, -C1-C1()-alkoxy, -0[(CH2)2_1()-O]1-6-alkyl, in particular -
C|-Cl0-alkoxy-C2-C5-alkoxy, -C1-C5-alkoxy-C2-C5-alkoxy-C2-C1-alkoxy or
— O —(CH2—CH2O) — alkyl 1-6
-OCOT, -OSO2T, —O —(CH2—CH2O) —COT, -COT, -SO2T, -CO2T, -
CN,
-CO2H, -CONT2, -CF,, Cl, Br and I,
T2 and T3 independently of one anolher denote C2-Cl0-alkenyl or alkinyl, which are optionally substituted by one or more substituents from the group consisting of OH, -C1-C6-alkoxy, -OCOT, -OCOH, -CO2T, -CO2H, -CN, C1, Br and I,
T4 denotes phenyl, which is optionally substituted by one or more substituents such as -C1-C10-alkoxy, -(O-C2-C10-alkylene)-O-(C2-C5-alkylene)-O-(C2-C5-alkyl) ,
(Formula Removed)
in particular
C1-C10-alkoxy-C2-C5-alkoxy, C1-C5-alkoxy-C2-C5-alkoxy-C2-C5-alkoxy, -OCOH, -OCOT, -OSO2T, -COH, -COT, -SO2T, -CO2T, -CN, -CF3, -CC13, -NO2, -NO, -CO2H, -CONH2, -CONHT, -CONT2, -SO2NT2, -C1-C10-alkyl, optionally substituted by -OH, -CN, -CO2-C1-C6-alkyl, Cl, Br or I, -C2-C10-alkenyl, optionally substituted by -OH, -CN, -CO2-C1-C6-alkyl, Cl, Br or I, and -C2-C10-alkinyl, optionally substituted by C1-C10-alkoxy, -OH, -OCOH, -OCOT, Cl, Br or I,
T3 denotes thiophene, furan, pyrrole, 1,2-isothiazole, 1,3-thiazole, pyrrazole, oxazole, isooxazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, benzothiazole, benzimidazole, benzoxazole, quinoline, isoquinoline, indole, coumarone, thionaphthene or tetrazole, optionally substituted by 1 to 3 substituents such as are already described as substituents for phenyl,
X denotes O, -NCOT, -NCO2T or -NSO2T,
D denotes a radical of the formula (Ilia) to (IIIu)
(Formula Removed)
R1, R2, R3, R4, R5 and R6 independently of one another and
denotes H, T, F, CI, Br, I, -CN, -NO2, -CH=O, -COT, -CO2T1 -CONH2, -CONHT, CONT2, -CF3, -SO2NH2, -SO2NHT, -SO2NT2, -SOT, -SO.T, -, -OH, -OCOT, -OCO2T, -OSO2T, -NH2, -NHT, -NT2,
(Formula Removed)
-NHCOH, -NHCOT, -NHSO,T or -COCO2T,
wherein
R1 can additionally denote -N=-N-T4 or -N=N-T:> and
R6 can additionally denote ST.
Particularly preferred disperse dyestuffs of the formula (I) are those wherein
A1 denotes H, T1, T4 or -CF3,
A2 denotes H, -CN, -CO2T\ -CONHT1 or -CF3,
A3 and A4 independently of one another denote -CN-, -CO2T\ -CONHT1, -CF3, -CHO, -COT, -SO2T, -NO2, -T4 or -T5,
wherein AJ and A4 do not simultaneously represent T4 or T5,
A" and A4, together with the C atom to which they are bonded, form a cyclic methylene-active compound of the formula (IIa), (lid) or (Ilh), where the radicals of the cyclic methylene-active compound are shown in the form of
(Formula Removed)
A5 is H, T1, T2 or T4, or
A4 and A5, together with the atoms in between, form a fused ring of the formula
(Formula Removed)
in which the N atom marked with corresponds to the pyridone nitrogen,
D denotes a radical of the formula R
(Formula Removed)
wherein

R1 and R5 independently of one another represent H, CF3, Cl, Br, -CN, -NO-,, -CO2T1, T1, T5, -SO2T', -SO2T4, -OT1, -OT2, -OT4, -OCOT1, -OCOT4, -OSO2T' or -OSO2T4,
R2 and R4 independently of one another denote H, Cl, Br, -NO2, -CF3, T1, -OT1, -OT2, -OT4, -OCOT1, -OCOT4, OSO2T! or -OSO2T4,
R3 represents H, CI, Br, -CN, -NO2, -CF3, -CO2T1, T1, T5, -OT1, -OT2, -OT4, -OCOT1, -OCOT4, -SO.T1 or -SO;,"!4,
T1 represents C1-C8-alkyl, which is optionally substituted by -C^Cg-alkoxy, -C1-C8-alkoxy-C2-C5-alkoxy, -OCOT1, -CO2T\ Cl, Br, -CN or T4,
T2 represents C2-C8-alkenyl, which is optionally substituted by -C1-C8-alkoxy, -C1-C8-alkoxy-C2-C5-alkoxy, -CN, -CO2T1 Cl or Br,
T4 represents phenyl, which is optionally substituted by Cl, Br, T1, OT1, -CF3, -NO2, -CN or -CO2T1,
T3 denotes oxazole, phenyloxazole, benzoxazole, thiazole, benzothiazole, thia-diazole or thiophene, which is optionally substituted by Cl, Br, T1, -NO-, and/or -CO2T1 and
X denotes O.
Especially preferred disperse dyestuffs of the formula (I) are those wherein
A represents H, T or -CF,,
A: denotes H, -CN or -CO.T1, A" represents -CN or -CO,T', A4 denotes A3 or
A3 and A4, together with the C atom to which they are bonded, form a cyclic methylene-active compound of the formula (IIa) or (IId), where the radicals of the cyclic methylene-active compound are shown in the form of

(Formula Removed)
A5 represents H, T1 or T2,

(Formula Removed)
D represents a radical of the formula R3
wherein

R1 and R5 independently of one another denote H, CI, Br, -CN, -NO2, -CO2`T1, T1, -OT1 or -OT4,
R2 and R4 independently of one another denote H, CI, Br, -NO2, T1 or -OT1,
R3 represents H, CI, Br, -CN, -NO2, T1, -CO2T1 or -OT1,
T1 represents C1-C6-alkyl or C1-C1-T4, optionally substituted by C1-C6-alkoxy,
-C1-C4-aIkoxy-C2-C5-alkoxy or -CO2T ,
T~ denotes C2-C6-alkenyl which is optionally substituted by Cl and/or Br,
T represents phenyl, which is optionally substituted by Cl, Br, -NO2 and/or
-CO2T1 and
X denotes 0.
The disperse dyestuffs of the formula I according to the invention have a good fastness to light, high tinctorial strength and high affinity on polyester, and dye polyester in brilliant shades.
Cationic dyestuffs
Preferred cationic dyestuffs of the formula (I) are those wherein A1 to A5 and X have the meanings given for the disperse dyestuffs of the formula (I) and
D represents a radical of the formula (Ilia) to (IIIu), preferably (Ilia),
wherein K® is bonded to one or more positions, as desired, of the radicals D and/or A1 to A5,
Be denotes an anion,
1 represents 1 or 2 and m is preferably 0.
Preferred anions Be are colourless, organic and inorganic anions, for example fluoride, chloride, bromide, iodide, perchlorate, tetrafluoroborate, hydroxide, hydrogen sulphate, sulphate, dihydrogen phosphate, hydrogen phosphate, phosphate, bicarbonate, carbonate, methyl-sulphate, ethyl-sulphate, cyanate, thiocyanate, tri- and tetrachlorozincate, tetrachloroferrate, hexafluorosilicate and anions of saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic carboxylic and sulphonic acids, such as formate, acetate, hydroxyacetate, cyanoacetate, propionate, hydroxypropionate, oxalate, citrate, lactate, tartrate, the anion of cyclohexanecarboxylic acid, phenylacetate, benzoate, the anion of nicotinic acid, methanesulphonate, ethanesulphonate, benzenesulphonate, chlorobenzenesulphonate and toluenesulphonate. If the anions are polyvalent, for example sulphate or oxalate, Be in formula (I) represents one equivalent of such a polyvalent anion.
Preferred cationic diazo components D are radicals D1 of the formula
(Formula Removed)
wherein
R , K+ and Be have the abovementioned meaning and
W denotes a direct bond or a bridge member.
Possible bridge members W are, for example, the following radicals:
(Formula Removed)
wherein
R7 denotes hydrogen, methyl or ethyl and
irij and p1 independently of one another represent any number from 1 to 4.
Suitable radicals K+ are, for example:
(Formula Removed)
Acid dyestuffs
Preferred acid dyestuffs of the formula (I) are those wherein D, A1 to A5 and X have the meanings given for the disperse dyestuffs of the formula (I), at least one SO3H group and/or one COOH group being bonded to at least one of these radicals. Particularly preferred acid dyestuffs of the formula (I) are those wherein m denotes 1 to 4.
Radicals D containing sulphonic acid groups are, for example, radicals D2, wherein D2 is a phenyl, phenyl azophenyl or naphthyl radical which carries 1 or 2 SO3H, OSO3H or phenyl-SO2-NH-SO2 groups and is optionally substituted one to four times by C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, C1-C4-alkylcarbonyl-amino, benzoylamino, C1-C4-alkylsulphonylamino, benzenesulphonylamino, cyano, halogen, nitro, C1-C4-alkylsulphonyl, phenylsulphonyl, tolylsulphonyl, chloro-phenylsulphonyl, carboxyl, C1-C4-alkoxycarbonyl, aminocarbonyl, aminosulphonyl, N-mono- or di-C1-Qj-alkyl-substituted aminocarbonyl or -sulphonyl, or by one benzothiazolyl.
Suitable radicals D2 correspond, in the form of their diazo components, for example, to the following:
l-Aminobenzene-2-, -3- or -4-sulphonic acid, l-aminobenzene-2,4- or -2,5-disulphonic acid, l-amino-2-methylbenzene-4-sulphonic acid, l-amino-3-methyl-benzene-4-sulphonic acid, l-amino-4-methylbenzene-2- or -3-sulphonic acid, 2-nitroaniline-4-sulphonic acid, 4-nitroaniline-2-sulphonic acid, 2-chloroaniline-4- or -5-sulphonic acid, 3-chloroaniline-6-sulphonic acid, 4-chloroaniline-2-sulphonic acid, l-amino-3,4-dichlorobenzene-6-sulphonic acid, l-amino-2,5-dichlorobenzene-4-sulphonic acid, l-amino-4-methyl-5-chlorobenzene-2-sulphonic acid, l-amino-3-methyl-4-chlorobenzene-6-sulphonic acid, 2-amino-4-sulphobenzoic acid, 1-amino-4-acetaminobenzene-2-sulphonic acid, 1 -amino-5-acetaminobenzene-2-sulphonic acid, l-amino-2-methoxy-4-nitrobenze-ne-5-sulphonic acid, l-aminonaphfhalene-2-or 4-sulphonic acid, 2-aminonaphthalene-1 -sulphonic acid and the diazo components of the formulae
(Formula Removed)
Reactive dyestuffs
Preferred reactive dyestuffs of the formula (I) are those wherein D, A1 to A5 and X have the meanings given for the disperse dyestuffs of the formula (I), an SO3H group and/or a COOH group preferably being bonded to at least one of these radicals, and wherein one or more identical or different fibre-reactive radicals Z are bonded to at least one of the radicals mentioned.
Reactive dyestuffs of the formula (I) where n = 1 to 3 are preferred.
Preferred fibre-reactive radicals are, for example, those of the formula
-CH=CH2 or -CH2CH2-V, wherein
Y == OH or a radical which can be split off under alkaline conditions, for example OSO3H, SSO3H, OCOCH3, OP03H2, OSO2CH3, SCN, NHSO2CH3, Cl, Br, F, OCOC6H5, OSO2-C6H4, [N(CH3)3]®anione or an optionally substituted pyridinium radical (substituents on the pyridinium radical are, in particular, optionally substituted C1-C4-alkyl, COOH, SO3H, CN or carboxamide) (anion = for example, Cl, HSO4e, HCO3e and the like),
or heterocyclic fibre-reactive radicals
Suitable fibre-reactive radicals Z, i.e. those which react with the OH or NH groups of the fibre under dyeing conditions to form covalent bonds, are preferably those which contain at least one reactive substituent bonded to a 5- or 6-membered aromatic-heterocyclic ring, for example to a monoazine, diazine or triazine ring, in particular a pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetric or symmetric triazine ring, or to such a ring system which contains one or more fused-on aromatic-carboxylic rings, for example a quinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acridine, phenazine or phenanthridine ring system, and which are not bonded to a further chromophore.
Examples which may be mentioned of the reactive substituents on the heterocyclic radicals are halogen (CI, Br or F), ammonium, including hydrazinium, pyridinium, picolinium, carboxypyridinium, sulphonium, sulphonyl, azido (N3), thiocyanato, thiolether, oxy-ether, sulphinic acid and sulphonic acid.
The following radicals may be mentioned specifically as examples of Z:
2,4-Difluorotriazin-6-yl, 2,4-dichlorotriazin-6-yl and monohalogeno-sym.-triazinyl radicals, in particular monochloro- and monofluorotriazinyl radicals, which are substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, morpholino, piperidino, pyrrolidino, piperazino, alkoxy, aryloxy, alkylthio or arylthio, where alkyl preferably denotes optionally substituted C1-C4-alkyl, aralkyl preferably denotes optionally substituted phenyl-C1-C4-alkyl and aryl preferably denotes optionally substituted phenyl or naphthyl, and where preferred substituents for alkyl are halogen, hydroxyl, cyano, dialkylamino, morpholino, C1-C4-alkoxy, carboxyl, sulpho or sulphato, and preferred substituents for phenyl and naphthyl are sulpho, C1-C4-alkyl, C1-C4-alkoxy, carboxyl, halogen, acylamino, hydroxyl and amino. Further radicals to be mentioned are 2-amino-4-fluoro-triazin-6-yl, 2-methylamino-4-fluorotriazin-6-yl, 2-ethylamino-4-fluorotriazin-6-yl, 2-isopropylamino-4-fluoro-triazin-6-yl, 2-dimethyl ami no-4-fluorotriazin-6-yl, 2-diethylamino-4-fluorotriazin-6-yl, 2-B-methoxy-ethylarnino-4-fluoro-triazin-6-yl, 2-B-hydroxy ethyl ami no-4-fluoro-triazin-6-yl, 2-di-(B-hydroxy ethyl amino)-4-fl uoro-triazin-6-yl. 2-carboxy methyl ami no-4-fluoro-triazin-6-yl, 2-di -(carboxy methyl -amino)-4-fluoro-triazin-6-yl, 2-sulphomethyl-methylamino-4-fluoro-triazin-6-yI, 2-B-cvanoethylamino-4-fluoro-triazin-6-yl, 2-benzylamino-4-fluoro-triazin-6yl, 2-B-phenylethylainino-4-fluoro-triazin-6-yi, 2-benzyl-methylamino-4-fluoro-triazin-6-yl,
2-(4'-sulphobenzyl)-amino-4-fluoro-triazin-6-yl, 2-cyclohexylamino-4-fluoro-triazin-6-yl, 2-(o-, m- or p-methylphenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- or p-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2',5'-disulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- or p-chlorophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- or p-methoxyphenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-methyl-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-methyl-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-chloro-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-chloro-5'-sulpho-phenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-methoxy-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(o-, m- or p-carboxyphenyl)-amino-4-fluoro-triazin-6-yl, 2-(2',4'-disulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(3',5'-disulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-carboxy-4'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(2'-carboxy-5'-sulphophenyl)-amino-4-fluoro-triazin-6-yl, 2-(6'-sulpho-naphth-2'-yl)-amino-4-fluoro-triazin-6-yl, 2-(4',8'-disulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl, 2-(6',8'-disulphonaphth-2,-yl)-amino-4-fluoro-triazin-6-yl, 2-(N-methyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-(N-ethyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-(N-B-hydroxyethyl-N-phenyl)-amino-4-f1uoro-triazin-6-yl, 2-(N-isopropyl-N-phenyl)-amino-4-fluoro-triazin-6-yl, 2-morpho- lino-4-fluoro-triazin-6-yl, 2-piperidino-4-fluoro-triazin-6-yl,2-(4',6',8'-trisulphonaphth-2'-yl)-amino-4-fluoro-triazin-6-yl, 2-(3',6',8'-trisulphonaphth-2'-yr)-amino-4-fluoro-triazin-6-yl, 2-(3',6'-disulphonaphth-l'-yl)-amino-4-fluoro-triazin-6-yl, N-methyl-N-(2,4-dichlorotriazin-6-yl)-carbamyl, N-methyl-N-(2-methylamino-4-chlorotriazin-6-yl)-carbamyl, N-methyl-N-(2-dimethylamino-4-chlorotriazin-6-yl)-carbamyl, N-methyl- or N-ethyl-N-(2,4-dichlorotriazin-6-yl)-aminoacetyl, 2-methoxy-4-fluoro-triazin-6-yl, 2-ethoxy-4-fluoro-triazin-6-yl, 2-phenoxy-4-fluoro-triazin-6-yl, 2-(o-, m- or p-sulpho-phenoxy)-4-fluoro-triazin-6-yl, 2-(o-, m- or p-methyl- or -methoxy-phenoxy)-4-fluoro-triazin-6-yl, 2-B-hydroxyethvlmercapto-4-fluoro-triazin-6-yl, 2-phenyl-mercapto-4-fluoro-triazin-6-yl, 2-(4'-methylphenyl)-mercapto-4-fluorotriazin-6-yl, 2-(2',4'-dinitrophenyl)-mercapto-4-fluoro-triazin-6-yl, 2-methyl-4-fluoro-triazin-6-yl, 2-phenyl-4-fluoro-triazin-6-yl and the corresponding 4-chloro- and 4-bromo-triazinyl radicals and the corresponding radicals obtainable by exchange of halogen with tertiary bases, such as trim ethyl amine, triethylamine, dimethyl-B-hydroxyethylamine, triethanolamine, N,N-dimethylhydrazine, pyridine, a, B- or y-picoline, nicotinic acid or isonicotinic acid, sulphinates, in particular benzene-sulphonic acid, or hydrogen sulphite, and di- or trihalogenopyrimidinyl radicals, such as 2,4-dichloropyrimidm-6-yl, 2,4,5-trichloro-pyrimidin-6-yl, 4,5-dichloro-pyrimidin-6-yl, 2,4-difluoropyrimidin-6-yl, 4,5-difluoropyrimidin-6-yl, 4-fluoro-5-
chloropyrimidin-6-yl, 2,4-difluoro-5-chloropyrimidin-yl and 2,3-dichloro-quinoxaline-5-carbonyl and 2,3-dichloroquinoxaline-6-carbonyl.
Suitable diazo components for the reactive dyestuffs of the formula (I) are, inter alia, those wherein D has the abovementioned meaning, and represents D2 with the meaning given there, and furthermore represents reactive diazo components D3, wherein D3 denotes
(Formula Removed)
wherein
R8 can assume the meanings given for R1 and additionally can denote SO3H, OSO3H or COOH and
R9 represents H, T1 or T4.
The dyestuffs according to the invention, in particular disperse dyestuffs of the formula (I), can be prepared by coupling diazotized amines which, as the amine, correspond to the formula (IV)
(Formula Removed)
to coupling components of the formula (V)
(Formula Removed)
wherein A to A5 D and X have the abovementioned meaning and
K represents a substituent which can be replaced by electrophilic substitution,
such as, for example, H, -CO2H, -CH2OH, -SO3H, -CH=O, -COT,
(Formula Removed)
Such a coupling process with displacement of a substituent is described, for example, in GB 2 036 775 and Jp 58 157 863.
The coupling can be carried out in an aqueous and non-aqueous solvent. Nonaqueous solvents which may be mentioned are alcohols, such as methanol, ethanol, propanol, butanol, pentanol and the like, dipolar aprotic solvents, such as DMF, DMSO and NMP, and water-immiscible solvents, such as toluene and chlorobenzene.
The coupling is preferably carried out in the stoichiometric ratio, but it may be advantageous and in some cases appropriate for economic reasons to employ the cheaper components in an excess of up to 30%.
The coupling is carried out at temperatures between -30 and 100°C, temperatures from -10 to 30°C being preferred and temperatures from -5 to 10°C being particularly preferred.
The coupling can be carried out in an acid medium and also in an alkaline medium. pH values > 0.5 and 1.0 and 3.0 and An oxidative coupling of (hetero)aromatic hydrazines of the formula (VI)
(Formula Removed)
to coupling components of the formula (V) is furthermore also possible, which is characterized in that VI is coupled oxidatively in the presence of V. Methods of oxidative coupling are described, for example, in Houben-Weyl "Methoden der organischen Chemie [Methods of organic chemistry]", Volume 10/3, page 360 et seq., and also in EP 201 892 or Chem, Express 1988, 3(7), 423-6.
A process for the preparation of dyestuffs of the formula (I) wherein X denotes O is furthermore preferred, which is characterized in that compounds of the formula (VII), which can exist in the tautomeric forms of the formula (VIIa) and (VIIb)
(Formula Removed)
G1 denotes O, NH or NT, preferably O,
G2 represents -OT, -NH2 or -NHT, preferably OT1, and
D and A1 have the abovementioned meanings,
are subjected to a condensation reaction with enamines of the formula (VIII)
(Formula Removed)
wherein A" to A have the abovementioned meanings.
This condensation reaction is preferably carried out, in the case of the disperse dyestuffs of the formula (I), in organic solvents, in particular dipolar aprotic solvents. Examples which may be mentioned are alcohols, such as methanol and ethanol, and, on the other hand, DMF DMSO and NMP.
The condensation reaction is carried out at temperatures from -10 to 200°C, preferably from 0 to 150°C, in particular at 20 to 130OC.
The condensation reaction is preferably carried out in the presence of bases, such as, for example, secondary and tertiary amines and alkali metal alcoholates. The amount of base varies here between catalytic and five times the molar amounts. 1 to 3 mol of base are preferably employed. Suitable bases are, for example, triethylamine, sodium methylate, sodium ethylate, sodium butylate, sodium amylate, K2CO3, Na^Oj, DBU (diazabicycloundecene) and DBN (diazabicyclo-nonene).
The compounds of the formula (VII) are known in some cases from DE-A-2 015 172, or they can be prepared by known methods.
The enamines of the formula (VIII) are known in most cases and/or are accessible by "dimerization" or "codimerization" of cyanoacetic acid derivatives in accordance with the equation
(Formula Removed)
cf, for example, Liebigs Ann. Chem. 1987, 1131 to 11C3 and literature cited therein.

Preferred enamines of the formula (VIII) correspond to the formulae (Villa) to (VIIIc).
(Formula Removed)
Another method of preparation of enamines of the formula (VIII) is the reaction of iminoesters with methylene-active compounds in accordance with Liebigs Ann. Chem. 1986, 533 to 544

(Formula Removed)
wherein T has the abovementioned meaning.
Compounds of the formula (V) are known in some cases from AU 491 554, Aust. J. Chem. 29 (1976), 1039-50 and J. Am. Chem. Soc. M, 2452.

The invention furthermore relates to compounds of the formula (V)
(Formula Removed)
wherein
E and X have the abovementioned broadest meanings,
A and A2 independently of one another denote H or a radical of the formula T, -COH, -CO-T, -CO2T, -CN, -CONH2, -CONHT, -CONT2, CF3, -NO2, NO, -SO2T, -OH, -OT, -OCOT, -OCO2T, -OSO2T, CI, Br or I,
wherein
can assume the meanimj of T1. T2, T3 T4 or T5, where
alkyl, cycloalkyl or aralkyl
alkenyl,
alkinyl,
aryl,
hetaryl,
A3 and A4 independently of one another denote an electron-withdrawing radical, or together with the common C atom form a cyclic methylene-active compound,
A5 represents H or a radical of the formula T, -OT1, -NH2, -NHT, -NT2, -NHCOH, -NHCOT, -N=CH-T, -N=CT2 or NHSO2T, or
A1 and A2 or
A2 and A3, together with the particular atoms in between, form an unsaturated, optionally substituted 5- or 6-membered carbo- or heterocyclic radical, where, in the case of ring formation with participation of one of the radicals AJ or A4, the other particular radical denotes an electron-withdrawing radical, and where the radicals A1 to A3 optionally carry one or more SO3H, COOH or K® and Be groups, wherein K® and Be have the above meanings.
Preferred compounds of the formula (V) are those wherein
A1 denotes H, T1, T4 or CF3,
A2 denotes H, -CO2T1, -CN, -CONH2, -CONHT, -CO2T2 or -CONT^,
A3 denotes -CO2T1, -CN, -CONH2, -CONHT, -CONT12 or -CO2T2,
A4 denotes -CO2T', -CN, -CONH2 -CONHT, -CONT12 or -CO2T2,
A^ denotes H, T1 or T2 or
A1 and A4, together with the common C atom, denote a cyclic methylene-active compound of the formula (IIa) or (lid) and
\i denotes H.
Particularly preferred compounds of the formula (V) are those wherein
A1 denotes 11, CH3, C6,Hs or CF3
A2 denotes H, CO2C1-C10-alkyl, -CO2C2-C10-alkenyl,
A3 and A4 independently of one another denote -CO2C1-C10-alkyl, -CO2C2-C10-alkenyl or -CN,
A3 denotes H or C1-C10-alkyl and
E denotes H.
The invention furthermore relates to a process for the preparation of the compounds of the formula (V) in the form of the compound Va or Vb, wherein X represents O or NH, characterized in that acetic acid derivatives of the formula IXa or IXb are reacted with enamines of the formula (VIII):
(Formula Removed)
wherein
A1 to A3, E, G1 and X have the abovementioned broadest meaning,
wherein
A~ preferably represents H, and
(J has the abovementioned meaning.
Preferably,
G1 represents O,
E represents H and
G2 represents OT1.
The reaction is preferably carried out in organic solvents. Suitable solvents are alcohols, dipolar aprotic solvents, such as DMF, water-immiscible solvents and esters, above all acylacetic esters, such as, for example, methyl or ethylaceto-acetate.
Water-immiscible solvents offer the advantage that the water formed in the reaction in the case where G1 = O can be removed azeotropically with them from the reaction mixture.
A particularly preferred embodiment, especially in the case of less reactive enamines of the formula (VIII), i.e. wherein A2 represents -CO2T, comprises working with an excess of (IX) as the solvent - without using further cosolvents. This excess of (IX) over (VIII) is preferably 5 to 500% by weight.
The reaction is preferably carried out at temperatures from 0 to 200°C, preferably 20 to 150°C, particularly preferably at 70 to 120°C.
The reaction can be accelerated by catalysts. Suitable catalysts are acids, such as, for example, glacial acetic acid, and acid-base pairs, such as ß-alanine-glacial acetic acid, ammonium acetate, piperidine-glacial acetic acid and morpholine-glacial acetic acid.
Inorganic and organic bases are furthermore suitable as catalysts or reaction partners. Bases which may be mentioned are sodium hydroxide, sodium ethylate, potassium ethylate, triethylamine, piperidine, morpholine and ethanolamine, such as are also employed in condensation reactions of CH-acid compounds with acetylacetone and the like. (Compare: Monatshefte fur Chemie 95, 1201, 1473 (1964) and J. Chem. Eng. Data 29, KM).

Particularly suitable bases, especially with less reactive enamines of the formula (VIII), wherein A2 represents -CO2T, are sterically hindered strong bases, such as, for example, potassium tert-butylate, and sterically hindered N bases, such as, for example, diazabicycloundecene (DBU) and diazabicyclononene (DBN).
The reaction can be carried out under normal pressure and also under increased or reduced pressure. It is preferable, especially in the case of less reactive enamines of the formula (VIII), to work under reduced pressure under pressures of In contrast to the acid catalysts and acid-base pairs, bases are preferably employed in the stoichiometric ratio or in an excess The excess can be 1 to 500%.
A process which is also preferred is a process for the preparation of compounds of the formula V which correspond to the formula X which is characterized in that a trifluoroacetic ester of the formula (XI), which represents a particular embodiment of the acetic acid derivative of the formula (IX), is subjected to a condensation reaction with dimeric cyanoacetic acid esters of the formula (XII), which represent a particular embodiment of the enamines of the formula (VIII)
(Formula Removed)
wherein T has the abovementioned broadest meaning. The reaction conditions are the same as those described above for less reactive enamines.
The invention also relates to a process for the preparation of compounds of the formula (V), wherein A5 represents T1, T2 or T, which is characterized in that pyridinium salts of the formula (XIII)
(Formula Removed)
An wherein
E, A1 and A2 have the abovementioned broadest meaning,
Ane is an anion, which can assume, for example, the meanings given for Be, and in particular represents Cle, Bre, Ie, T1OSO3e or TSO3e,
A5 represents T1, T2 or T3 and
Y1 and Y2 independently of one another represent a leaving group, such as F, Cl, Br, I, -OSO2T, -OT, -ST or -SO2T,
are reacted with compounds of the formula (II)
(Formula Removed)
wherein
A'"1 and A4 have the abovementioned broadest meaning,
to give compounds of the formula (XIV)
(Formula Removed)
and these are reacted with compounds of the formula (XV)
(Formula Removed)
wherein
X represents O, NH, NT1, NCOT, NCO2T or NSO2T,
to give compounds of the formula (V)
wherein A represents T , T or T .
In a preferred embodiment of this process,
E represents H,
A1 represents H or T1,
A*- represents H,
Y1 represents Cl, Br or I,
Y2 represents Cl, Br, I or -OT1 and
H2X represents H2O, NH3, H2NT1 or H2NSO2T, in particular H2O.
In a particular embodiment of the process, A5 represents T1 or T2, particularly preferably T1, and especially preferably methyl or ethyl.
The reaction of the compounds of the formulae (XIII) and (II) can be carried out in water or in aqueous or non-aqueous solvents, such as, for example, alcohols or dipolar aprotic solvents.
Suitable temperatures are -20 to 150°C, preferably 0 to 100°C, in particular 15 to
80°C.
This reaction is preferably carried out in the presence of inorganic or organic bases. Suitable bases are alkali metal hydroxides, alkali metal alcoholates, alkali metal hydrides, alkali metal oxides, alkaline earth metal oxides, alkali metal
carbonates, alkali metal bicarbonates, alkali metal hydrides or organic N bases, such as tertiary amine (triethylamine, DBU, DBN and the like). These bases are preferably employed in stoichiometric amounts, i.e. twice the molar amounts in (XIII).
Instead of the compound (II), the corresponding anion of (II)
(Formula Removed)
wherein A3 and A4 have the abovementioned broadest meaning and Cat® represents a cation, such as, for example, those of lithium, sodium and potassium, can also be employed for the reaction with pyridinium salts (XIII).
The second reaction stage - conversion of (XIV) into (V) - is also preferably carried out in the presence of bases.
In the case where the compounds of the formula (XV) correspond to the amines -NH3 or H^NT1, these reactants are also preferably employed simultaneously as the base and, where appropriate, also as the solvent.
If X represents O, alkali metal hydroxides, alkaline earth metal hydroxides and/or alkali metal carbonates are preferably employed as bases.
If X represents -NCOT, -NCO2T or -NSO2T, the corresponding anion, for example C6H5SO2NHe, is preferably employed as the base and reactant.
Further preferred bases here are also inert bases and sterically hindered bases. Suitable bases are, for example, tertiary amines, such as triethylamine, DBU and DBN. Preferably, at least 2 molar equivalents of base are employed.
Suitable solvents are preferably organic solvents which are inert under these conditions, such as, for example, dipolar aprotic solvents, aromatic hydrocarbons, such as toluene, and chlorinated hydrocarbons, such as chlorobenzene.
Depending on the nucleophilicity of the educt H2X or of the corresponding base, the reaction takes place at temperatures between -20°C and 200°C, preferably 0CC and 150°C.
The pyridinium salts of the formula (XIII) required are accessible in a simple manner by quaternization of corresponding pyridines (XVI) with alkylating agents A5-An, such as, for example, dimethyl sulphate, in accordance with the reaction
(Formula Removed)
For ecological and economic reasons, the quaternization and also the reaction with compounds (II) and, where appropriate, also the reaction with XH2 are preferably carried out without intermediate isolation.
Another process for the preparation of the coupling components of the formula (V), wherein A5 represents T, is characterized in that pyridine derivatives of the formula (XVII) are reacted with compounds of the formula (II):
(Formula Removed)
wherein X=O, A to A4 and E have the abovementioned meaning and A3 represents T.
In a preferred embodiment of this process, E represents H,
A represents H or T , especially preferably 14,
A represents H,
Y1 represents F, CI, Br, I, OSO2T, SO2T, -ST or OT, particularly preferably Cl, Br or -SO2T, and especially preferably Cl, and
A3 represents T1 or T2, particularly preferably T1, and especially preferably methyl or ethyl, and
one of the two radicals A3 and A4 preferably represent -CN, -CO2T, -CONH2, -CONHT, -CONT2, -CHO, -COT, -SO2T, -SO2NH2, -SO2NHT, -SO2NT2, -NO2, T4 or T5,
while the other preferably represents -CN, -CO2T, -CONH2, -CONHT or -CONT2,
or
AJ and A4, together with the C atom to which they are bonded, form a cyclic methylene-active compound of the formulae (Ha to IIv), preferably (Ha to Ilh), in particular (Ha and lid)
Suitable solvents for this reaction are preferably organic solvents. Both water-miscible and water-immiscible solvents are possible here.
The reaction temperatures are preferably in the range from 20 to 250°C, preferably 50 to 150°C.
Bases are preferably added, in particular more than 2 molar equivalents of base, based on the starting material of the formula (XVII).
Suitable bases are inorganic or organic in nature. For example, tertiary amines, such as triethylamine, DBU and DBN, are suitable.
Another process for the preparation of coupling components of the formula (V), which correspond to the formula (XX), wherein A3 represents T1, T2 or T\ is characterized in that 2-methylpyridones of the formula (XVIII) are reacted with phthalic acid esters of the formula (XIX) in the presence of bases
(Formula Removed)
wherein A1, A2, E, T1 and V1 have the abovementioned broadest meaning.
In a preferred embodiment of this process
E represents H,
AD represents T1, particularly preferably methyl or ethyl,
A1 represents H, T1 or T4, particularly preferably T1, and especially preferably methyl, and
V1 represents H.
In this reaction, the phthalic acid ester of the formula (XIX) simultaneously serves as the solvent.
Suitable bases are preferably alkali metal alcoholates, which are preferably employed in at least equimolar amounts, based on (XVIII).
The reaction temperature is in general 50 to 200°C, preferably 100 to 160°C, the alcohol T'OH formed preferably being distilled off from the reaction.
The removal of the alcohol can be promoted by working under reduced pressure.
The product can be isolated in crystalline form by discharging the mixture onto water and acidifying the aqueous phase.
The dyestuffs of the formula (I) according to the invention are suitable, depending on the presence of substrate-specific substituents, for dyeing and printing naturally occurring and synthetic materials, such as, for example, cellulose fibres, cotton, wool, silk, polyamide, polyacrylonitrile, polyester or polyolefins.
Thus, for example, the dyestuffs described as disperse dyestuffs of the formula (I) are particularly suitable, either as such or also as a mixture with other disperse dyestuffs, for dyeing and printing hydrophobic synthetic fibre materials and mixtures thereof with naturally occurring fibre materials.
Possible hydrophobic synthetic materials are, for example: cellulose 2!/2-acetate, cellulose triacetate, polyamides and, in particular, polyesters, such as, for example, polyethylene glycol terephthalate. Mixtures thereof with naturally occurring fibre materials are, for example, cotton, regenerated cellulose fibres or wool.
They are furthermore suitable for dyeing and, where appropriate, printing waxes, oils and plastics such as polymethacrylate, PVC, polystyrene or ABS.
They are also suitable for textile and non-textile thermotransfer printing, for example by means of a thermal head or also by means of ink-jet processes.
The compounds described as cationic dyestuffs of the formula (I) in the context of this Application are preferably used for dyeing or printing acid-modified polyester or polyamide, but preferably for dyeing and printing polyacrylonitrile.
Moreover, they can also be employed for dyeing paper.
The compounds described as reactive dyestuffs of the formula (I) in the context of this Application are preferably used for dyeing and printing materials containing hydroxyl groups, such as, for example, cellulose fibres, in particular cotton, and for dyeing and printing materials containing amide groups, such as, for example, wool, silk and polyamide.
1'he compounds described as acid dvestuffs of the formula (1) in the context o( this Application are preferably employed for dyeing and printing naturally
occurring or synthetic polyamide and base-modified polyacrylonitrile fibres. They can moreover be employed for dyeing paper.
The dyestuffs can be applied here from aqueous or non-aqueous liquors or also in printing processes.
They produce strong dyeings with good general fastnesses.
Neutral dyestuffs produce particularly brilliant dyeings of high fastness to light on polyester. The shades range here from yellow to blue, the particular strength lying in brilliant red shades.
If A3 and A4 in the formulae mentioned in the Examples have different meanings, the configuration on the carbon atom to which they are bonded is not intended to be specified by the formulae. The diamines 3-amino-2-cyano-pentene-dioic acid diesters (£ 2-amino-l-cyanoglutaconic acid diesters) used in the Examples were prepared by processes analogous to that described in Liebigs Anm. Chem. 1987, 1131, in which such enamines are described as having the Z configuration.
Examples
Example 1
Preparation of the dyestuff of the formula
(Formula Removed)
5.5 ml of 40% strength nitrosylsulphuric acid were added to 6.1 g of 4-methyl-2-nitroaniline, dissolved in 20 ml of propionic acid and 40 ml of glacial acetic acid, at 0-5°C in the course of 10 minutes. The mixture was stirred at 0-5°C for a further 2 hours. 20 ml of 10% strength aqueous amidosulphonic acid solution and then, at 5°C, the above diazotization reaction mixture were added to a solution, brought to pH 7 by means of a few ml of concentrated sodium hydroxide solution, of 5.8 g of [6-hydroxy-3-cyano-4-methyl-2(lH)-pyridinylidene]-malononitrile in 400 ml of water. The mixture was allowed to warm to room temperature in the course of 16 hours, the precipitate was filtered off with suction and the filter cake was washed neutral with water. Yield: 9.3 g
MS, m/z (%): 361 (72) [M1 ■], 315 (18) [M* -NO2] 152 (100) UV (DMF): A,max = 537 nm
lie dyestuff dyes polyester in a bluish-tinged red with good fastness properties.
The dyestuffs of the formula
(Formula Removed)
listed below, which likewise dye polyester with good properties, were obtained analogously to Example 1.
Table 1

(Table Removed)
Example 31
Preparation of [6-hydroxy-3-cyano-4-methyl-2-(lH)-pyridinylidene]malononitrile
(Formula Removed)
15.4 g of the sodium salt of 2-amino-l,2,3-tricyano-propene ("malononitrile dimer") were heated at the boil under reflux with 13 g of ethyl acetoacetate, 1 ml of piperidine and 6 g of glacial acetic acid in 100 ml of ethanol for 16 hours. After cooling, a beige powder was filtered off with suction and washed with ethanol. Yield: 14.5 g
IRv (cm"1): 3430, 2185 (C=N), 2205(CsN), 2225(ON) 1668, 1566, 1356, 8C3
'H-NMR (d6-DMSO, 300 MHz, ppm): 5 = 2.15 (s, 3H, CH3), 5.70 (s, 1H), 7.30 (s, 2H, OH, NH)
MS, m/z (%): 198 (42 [M+], 170 (13) [M+-H20] 155 (100)
Example C3
Preparation of the dyestuff of the formula
(Formula Removed)
8.3 ml of 40% strength nitrosylsulphuric acid were added to 6.6 g of methyl 2-aminobenzoate, dissolved in IS ml of propionic acid and 30 ml of glacial acetic
acid, at 0-5°C in the course of 10 minutes. The mixture was stirred at 0°C for a further 2 hours.
70 ml of the solution, described in the following Example No. 33, of the coupling component ethyl [6-hydroxy-4-methyl-3-(ethoxycarbonyl)-2(lH)-pyridinylidene]-cyanoacetate (about 0.5 mol) in 550 ml of dimethylformamide were topped up to 200 ml with ethanol, 2 g of amidosulphonic acid were added and coupling was then carried out with the above diazotization mixture at 0°C, with the addition of 50 g of ice. The mixture was subsequently stirred for 15 hours and the product was filtered off with suction and washed with water. Yield: 15.3 g. After recrystallization from dimethylformamide, 6.3 g remained.
The dyestuff dyed polyester in a brilliant orange with good fastness properties.
MS, m/z (%): 454 (100) [M+], 422 (8) 409 (8), 350 (25), 349 (16), C32 (25) 293 (18)
^max: 483 nm (CH3CN)
Example 33
Preparation of coupling component of the formula CH,
(Formula Removed)
A solution of 113 g of diethyl 3-amino-2-cyano-pentenedioate ("dimeric ethyl cyanoacetate", 0.5 mol), 90 ml of ethyl acetoacetate and 76 g of diazabicyclo-undecene (DBU) in 500 ml of dimethylformamide was stirred at 120°C for 1 1 hours. A further 25 ml of ethyl acetoacetate were added and the mixture was stirred at 120°C for a further 9 hours the readily volatile cleavage products being distilled off. The mixture was topped up to a volume of 800 ml with 50 ml of dimethylformamide and the brown solution was employed directly for the coupling
reaction. A sample was freed from the solvent under 20 mbar/100°C. The brown oil which remained showed the following mass spectrum:
MS, m/z (%): 292 (27) [M+], 247 (14), 218 (27), 192 (42), 174 (58), 164 (35), 152 (65), 151 (51), 148 (43), 96 (33), 42 (64), 29 (100)
The dyestuffs of the formula
(Formula Removed)
listed below (Table 2), which likewise dye polyester with good fastness properties, were obtained analogously to Example C3.
Table 2

(Table Removed)
Example 46
Preparation of the dyestuff mixture of the formula
(Formula Removed)
11.7 g of ethyl 2-phenylazo-acetoacetate and 11 g of the sodium salt of dimethyl 3-amino-2-cyano-pentenedioate ("dimeric methylcyanoacetate") were stirred in 50 ml of dimethylformamide at 90°C for 10 hours. After addition of a further 2.2 g of dimeric methylcyanoacetate, the mixture was heated at 100°C for a further 6 hours. After cooling to room temperature, 100 ml of methanol, 6 g of 30% strength hydrochloric acid and 15 ml of water were added. The product was filtered off with suction and washed with methanol. Yield: 4.1 g The dyestuff dyed polyester in a brilliant scarlet with good fastness properties.
MS, m/z (%
382 (22) [M+- ethyl ester] 369 (20), 368 (89) [M+-methyl ester], 337 (9) [M+- methyl ester - OCH3], 310 (9), 276 (7), 231 (19), 199 (11), 105 (19) 93 (30), 92 (28), 77 (100)
TSnax: 486 nm (CH3CN)
The following dyestuffs of the formula
(Formula Removed)
which likewise dye polyester with good fastness properties, were obtained analogously to Example 46.

Table 3

(Table Removed)
Example 60
Preparation of the coupling component of the formula
(Formula Removed)
Diamyl 3-amino-2-cyano-pentenedioate ("dimeric amylcyanoacetate") was prepared analogously to Junek, Monatschefte fur Chemie, jjPJ. [1979] 1208.
12.2 ml of diazabicyclononene (DBN) and 34.4 g of amyl acetoacetate were added to 31 g of diamyl 3-amino-2-cyano-pentenedioate and the mixture was heated at 80°C for 4 hours. A further 8.6 g of amyl acetoacetate were added and the mixture was heated at 80°C for a further 2 hours. A brown oil was obtained which, when taken up in 200 ml of N-methylpyrrolidone, gave a weight of 276 g and was employed directly for the coupling reaction was obtained.
A sample which was concentrated under 0.5 mbar/100°C gave the following mass spectrum:
MS, m/z (%) 376 (12) [M+], 262 (8), 236 (11), 219 (18), 218 (21),
193 (11), 192 (45), 151 (30), 55 (35), 43 (100)
The dyestuffs listed below, which likewise dyed polyester with good fastness properties, were obtained by a coupling reaction analogously to Example C3.
Table 4
(Table Removed)
Example 66
Preparation of the coupler component of the formula
(Formula Removed)
1 -Amyl-5-ethyl 3-amino-2-cyano-pentenedioate
(Formula Removed)
was prepared analougously to Ivanov J.C. et al., Liebigs Ann. Chem. 1983. 753-60 and Mittelbach M. und Juneck H. Liebigs Ann. Chem. 1986. 533-544, by reaction of ethyl 3-amino-ethoxy-2-propenoate hydrochloride with amylcyanoacetate in chloroform in the presence of triethylamine. Further reaction with ethyl acetoacetate analogously to Example 33 gave the coupler component of the above formula.
Example 67
Preparation of the dyestuff of the formula
(Formula Removed)
The dyestuff of the above formula was obtained by diazotization of 2-nitro-4-methoxyaniline in hydrochloric acid with 30% strength nitrite solution at 0°C and subsequent coupling with the coupling component according to Example 66. It dyed polyester in a brilliant red with good fastness properties.
MS, m/z (%): 514 (28), [M+ + H], 513 (100) [M+] 399 (12), 370 (26), 168 (29), 43 (36)
Xmax:515nm(CH3CN)
Example 68
Preparation of the mixture of couplers of the formula
(Formula Removed)
395 g of diamyl 3-amino-2-cyano-pentenedioate (78.7% according to GC) were heated together with 258 ml of ethyl acetoacetate and 154 ml of diazobicyclo-undecane at 80°C/60 mbar for 8 hours, readily volatile components being destilled off. The excess acetoacetic ester was distilled off under 0.5 mbar/100°C. The brown oil (644 g) which remained was employed directly for the coupling reaction.
MS, m/z (%): 376 (14), [M+], 334 (5) [M+], 307 (5), 262 (12), 219 (23), 218 (22), 193 (15), 192 (67), 151 (48), 137 (20), 126 (27), 123 (27), 98 (19), 96 (17), 71 (20), 55 (33), 43 (100)
The dyestuff of the formula
(Formula Removed)
listed on the following Table 5 were obtained by coupling analogously to Example C3 with coupling components which are accessible analogously to the Examples 33, 60, and 68.
Tabe lle 5

(Table Removed)
Example 87
Preparation of the dyestuffs of the formula
(Formula Removed)
The coupling component was prepared by reaction of dimethylacetonedicarb-oxylate with dimethyl 3-amino-2-cyano-pentenedioate in the presence of DBU at 100°C analogously to Example 68. Coupling with diazotized 2-nitro-4-ethoxy-aniline gave the dyestuff of the above formula.
MS, m/z (%):
515 (100) [M+], 516 (27), 457 (20), 456 (19), 425 (8), 424 (36), 153 (12)
The dyestuff dyed polyester in a bluish-tinged red with good fastness properties.
Example 88
Preparation of the dyestuff of the formula
(Formula Removed)
The coupling component was prepared analogously to Example 68 by reaction of ethyl benzoyl acetate with diamyl 3-amino-2-cyano-pentenedioate. Subsequent coupling with diazotized 2-nitro-4-methoxyaniline in methanol gave the dyestuff of the above formula in crystalline form.
The dyestuff dyed polyester in a bluish-tinged red with good fastness properties.
MS, m/z (%): 514 (28) [M+ + H], 513 (100) [M+], 471 (6), 443 (6), 399 (12), 370 (26), 168 (29), 43 (36)
Xmax. 497 nm (CH3CN)
The following dyestuffs of the formula
(Formula Removed)
were obtained analogously to Hxample 88.
Table 6

(Table Removed)
Example 92
Preparation of the coupler of the formula
(Formula Removed)
49.5 g of 3-amino-2-methoxycarbonyl-2-pentenedinitrile (H. Junek et al., Synthesis 1977, 560) were heated at the boiling point under reflux with 47 g of ethyl aceto-acetate and 30.6 g of piperidine in 300 ml of ethanol for 13 hours. After cooling, the mixture was diluted to a volume of 1.8 I with ice-water and brought to pH = 2 with concentrated hydrochloric acid, and the product was filtered off with suction and washed with water. Yield 59 g.
MS, m/z (%): 2C3 (5), 23 1 (24) [MT ], 187 (42), 172 (36), 160 (14), 144 (21), (13), 92 (26), 91 (29), 84 (23), 59 (100)
1 H-NMR (d6-DMSO, 300 MHz, ppm): 5 = 2.15 (s, 3H, CH3), 3.60 (s, 3H, OCH3), 5.70 (s, IH, 5-H), 8.25 (s, (br), IH, N-H), 12.65 (s, IH, O-H)
The following dyestuffs of the formula

(Formula Removed)
were prepared analogously to Example C3 using coupling components of Example 92 or homologous coupling components.
Table 6

(Table Removed)
Example 92
Preparation of the coupler of the formula
(Formula Removed)
49.5 g of 3-amino-2-methoxycarbonyl-2-pentenedinitrile (H. Junek et al., Synthesis 1977, 560) were heated at the boiling point under reflux with 47 g of ethyl aceto-acetate and 30.6 g of piperidine in 300 ml of ethanol for 13 hours. After cooling, the mixture was diluted to a volume of 1.8 I with ice-water and brought to pH = 2 with concentrated hydrochloric acid, and the product was filtered off with suction and washed with water. Yield 59 g.
MS, m/z (%): 2C3 (5), 23 1 (24) [MT ], 187 (42), 172 (36), 160 (14), 144 (21), (13), 92 (26), 91 (29), 84 (23), 59 (100)
1 H-NMR (d6-DMSO, 300 MHz, ppm): δ = 2.15 (s, 3H, CH3), 3.60 (s, 3H, OCH3), 5.70 (s, 1H, 5-H), 8.25 (s, (br), 1H, N-H), 12.65 (s, 1H, O-H)
The following dyestuffs of the formula

(Formula Removed)
were prepared analogously to Example C3 using coupling components of Example 92 or homologous coupling components.
Table 7

(Table Removed)
Table 8
Dyestuffs of the formula
(Table Removed)
Example 107
Preparation of the coupler of the formula
(Table Removed)
The preparation proceeded analogously to Example 66 by reaction of ethyl 3-amino-4,4-dicyano-3-butenoate (Mittelbach M. and Junek H., Liebigs Ann. Chem. 1986, 533-544) with ethyl acetoacetate.
Example 108
Preparation of the mixture of the couplers of the formula
(Formula Removed)
0.25 mol of diethyl 3-amino-2-cyano-pentenediaote ("dimeric ethyl cyanoacetate"), 0.35 mol of methyl trifluoroacetoacetate and 0.25 mol of diazabicycloundecene were heated at 120°C in 250 ml of dimethylformamide for 12 hours. The solution was topped up to 400 ml with dimethylformamide and employed directly for the coupling reaction. A concentrated sample gave the following mass spectrum.
MS, m/z (%): 346 (1) [M+- X = CO2C2H5], 301 (2), 275 (3), 274 (9), [M+- X = H], 255 (7), 246 (5), 203 (11), 202 (89), 184 (14), 173 (20), 152 (44), 123 (27), 96 (27), 29 (100)
Table 9
(Table & Formula Removed)
MS, m/z (%): 409 (24), 408 (100) [M ], 275 (6), 135 (12), 120 (19), 108 (27), 93 (17), 65 (11), 58 (17)
1H-NMR (d6-DMF, 300 MHz, ppm) δ = 15 (t, 3H, OCH2-CH3), 3.94 (s, 3H, -OCH,), 4.3 (q, 2H, OCH2-CH3), 7.04 (s, 1H, hetaromatic H), 7.18 (m, 1H, aromatic H), 7.30 (m, 2H, aromatic H), 7.70 (d, 1H, aromatic H), 1 1.95 (s/br), 1H, N-H), 14 75 (s, 1H, OH or NH).
Example 113
Preparation of the dyestuff of the formula
(Formula Removed)
A solution of 18.6 g of ethyl (2'-nitro-4'-ethoxy)-2-phenylazo-formyl acetate, 13.6 g of diethyl 3-amino-2-cyanopentenedioate and 9.1 g of diazabicycloundecene (DBU) in 60 ml of dimethylformamide was heated at 80°C for 30 minutes. It was diluted with 120 ml of ethanol, 7.3 g of 30% strength hydrochloric acid and 18 ml of water. The precipitate formed was filtered off with suction and washed with ethanol. The dyestuff dyes polyester in a bluish-tinged red with good fastness properties. UV: 520 nm (CH3CN), 538 nm (DMF)
Example 114
Preparation of the coupler of the formula
(Formula Removed)
A solution of 7.8 g of 2-amino-3-cyanoindene, 6.8 g of sodium ethylate and 7.8 g of ethyl acetoacetate in 100 ml of ethanol was heated at the boiling point under reflux for 7 hours. The mixture was filtered with suction, the residue was dissolved in water, the solution was brought to pH = 1 with hydrochloric acid and the product was filtered off with suction again.
MS, m/z (%): 222 (100) [M+], 221 (5), 194 (6), 193 (10), 179 (7), 166 (7), 140 (4), 139 (4), 84 (8), 67 (5), 38 (5)
Table 10
Dyestuffs of the formula
(Table & Formula Removed)
Table 11
Dyestuffs of the formula
(Table & Formula Removed)
Table 12
Dyestuffs of the formula
(Table & Formula Removed)
Example 122
Preparation of the coupler of the formula
(Formula Removed)
4.3 g of l-methyl-6-chloro-pyrid-2-one were added to a suspension of 1.8 g of 80% strength sodium hydride in 30 ml of dimethylformamide, and 8.5 g of butyl cyanoacetate were added dropwise in the course of 15 minutes. The temperature rose to 50°C. The mixture was stirred at 50°C for a further 7 hours, cooled to 20°C and diluted slowly to a volume of 200 ml with water. The mixture was brought to pH = 7 with hydrochloric acid and extracted with methylene chloride. This extract was discarded. The aqueous phase was brought to pH = 4 and extracted again with methylene chloride. This extract was dried and concentrated. Yield: 2.0 g of oil.
MS, m/z (%): 249 (8), 248 (43) [M1], 151 (12), 148 (100), 147 (11), 121 (16), 1 19 (22), 108 (20), 57 (74), 63 (41)
Table 13
Dyestuffs of the formula
(Table & Formula Removed)
Example 126
Preparation of the coupler of the formula
(Formula Removed)
21.8 g of 2-cyanomethyl-benzothiazole and 18 g of 6-chloro-l-methyl-pyrid-2-one were added to a solution of 5 g of sodium hydroxide powder in 125 ml of di-methylformamide and the mixture was stirred at 40°C for 6 hours. A further 1.8 g of 6-chloro-l-methyl-pyrid-2-one were subsequently added and the mixture was stirred at 40°C for a further 8 hours. 300 ml of methylene chloride were added and the mixture was discharged onto 400 ml of water. 5.5 g of a crystalline crude product were filtered off with suction, the methylene chloride phase was discarded and the aqueous phase was brought to pH = 5, after which a precipitate (B) again precipitated out, this being filtered off with suction and washed with water: 7.8 g yield (B).
MS, m/z (%): 282 (27), 281 (100) [NT], 241 (20), 148 (91), 108 (50), 39 (51)
Table 14
Dyestuffs of the formula
(Table & Formula Removed)
Example 129
Preparation of the coupler of the formula
(Formula Removed)
A mixture of 37.4 g of 2,6-dichloropyridine and 47.5 ml of dimethyl sulphate was stirred at 100°C for 24 hours. After cooling, it was diluted with 75 ml of di-methylformamide, and a solution of 16.5 g of malononitrile in 25 ml of dimethyl-formamide and then 86.6 ml of triethylamine were added dropwise, while cooling with ice. The mixture was subsequently stirred for 20 hours and 14.7 g of a yellow product of the formula
(Formula Removed)
were then filtered off with suction. A further 4 g were to be obtained by dilution of the filtrate with ice-water and acidification to pH = 1.
MS (CI), m/z (%): 194 (35), 192 (100) [M+], 158 (C3)
76.6 g of [l-methyl-6-chloro-2(l)-pyridinylidene]malononitrile were stirred in 400 ml of water and 400 ml of N-methylpyrrolidone at 80°C for 10 hours and at 90°C for 5 hours, pH = 10 being maintained by dropwise addition of 30% strength sodium hydroxide solution via a titrator. The mixture was topped up to a volume of 1200 ml with water and brought to pH = 1 with concentrated hydrochloric acid, and the product was filtered off with suction and washed with water. Yield: 63.5 g.
MS, m/z (%): 173 (100) [M+], 146 (25), 145 (37), 144 (37), 130 (14), 119 (25), 118 (33), 108 (45), 39 (58).
1H NMR (d6-DMSO, 300 MHz, ppm): δ = 3.73 (s, 3H, N-CH3), 6.15 (d, I = 7.5 Hz, 1H, 5-H), 6.53 (d, I = 7.5 Hz, 1H, 3-H), 7.48 (dd, I = 7.5 Hz, 1H, 4-H), 11.80 (s(br), OH, H20).
Table 15
Dyestuffs of the formula
(Table Removed)
Table 16
Dyestuffs of the formula

(Table & Formula Removed)
Table 17
Dyestuffs of the formula
(Table & Formula Removed)
Example 149
Preparation of a coupler
(Formula Removed)
15.7 g of benzenesulphonamide were added to a solution of 5.4 g of sodium meth-ylate in 120 ml of methanol and the mixture was boiled under reflux for 2 hours, the benzenesulphonamide dissolving. The solution was concentrated to dryness, the residue was dissolved in 75 ml of N-methylpyrrolidone and a solution of 19.2 g of [l-methyl-6-chloro-2(lH)-pyridinylidene]malononitrile (see Example 129) in 75 ml of N-methylpyrrolidone was allowed to run in. After 20 hours at room temperature, a further 2.7 g of sodium methylate and 3.9 g of benzenesulphonamide were added and the mixture was heated at 50°C for 5 hours and stirred at room temperature for 60 hours. It was diluted with 600 ml of ice-water and brought to pH = 1 with hydrochloric acid, and the product was filtered with suction and washed with water. Yield 15 g.
'H-NMR (d6-DMSO, 300 MHz, ppm): δ = 3.75 (s, 3H, N-CH3), 6.38 (d, I = 7.5 Hz, 1H, heterocyclic H), 6.45 (d, I = 7.5 Hz, 1H, heterocyclic H), 7.30 (dd, I = 7.5 Hz, 1H, heterocyclic H), 7.53 (m. 3H, aromatic H), 7.78 (m, 2H, aromatic H), 9.48 (s(br), 1H, N-H).
Table 18
Dyestuffs of the formula
(Table & Formula Removed)
xample 152
10 g of polyester fabric are introduced at a temperature of 60°C into 200 ml of a dye liquor which comprises 0.3% of the finely dispersed dyestuff of Example No. 134, based on the polyester fabric, and in which the pH is adjusted to 4.5 by means of acetic acid. The fabric is treated at 60°C for 5 minutes, the temperature of the liquor is then increased to 135°C in the course of 30 minutes and kept at this temperature for 60 minutes, and the liquor is then allowed to cool to 60°C in the course of 20 minutes.
Thereafter, the dyed polyester fabric is purified reductively by being treated at 65°C for 15 minutes in 200 ml of a liquor which comprises 5 ml/1 of C3% strength by weight sodium hydroxide solution, 3 g/1 of sodium dithionite and 1 g/l of an addition product of 48 ml of ethylene oxide on 1 mol of castor oil. Finally,
the fabric is rinsed, neutralized with dilute acetic acid, rinsed again and dried. A brilliant orange dyeing with good fastness properties is obtained.





WE CLAIM :-
1. Process for the preparation of pyridone-methide azo dyestuffs of formula
or its tautomeric form, wherein
(Formula Removed)
D is the radical of a carbo- or heterocyclic diazo component,
A1 and A2 independently of one another denote H or a radical of the formula T, -COH, -CO-T, -CO2T, -CN, -CONH2, -CONHT, -CONT2, CF3, -NH2, -NHT, -NT2, -NH-COT, -NT-COT, -NHSO2T, -NTSO2T, -NO2, -NO, -SO2T, -OH, -OT, -OCOT, -OCO2T, -OSO2T, CI, Br or I
A3 and A4 independently of one another represent -CN, -CO2T,
-CONH2, -CONHT, -CONT2, CF3, -CHO, -COT, -SO2T, -SO3T4, -SO3T5, SO2NH2,
SO2NHT, SO2NT2, -SOT, -CH=NH, -CN=NT, -CT=NH, -CT=NT,
(Formula Removed)
As represents H or a radical of the formula T, -OT1, -NH2, -NHT, -NT2, -NHCOH, -NHCOT, -N=CH-T, -N=CT2 or NHSO2T,
wherein
T1 = alkyl, cycloalkyl or aralkyl, and T represents T1 or can assume the meaning of T2 to T5, where
T2 = alkenyl,
T3 = alkinyl,
T4 = aryl,
Ts = hetaryl
or
A1 and A1 and/or
A 2 and A 3 and/or
A4 and A5, together with the particular atoms in between, form an unsaturated, optionally substituted 5- or 6-membered carbo- or heterocyclic radical, with the proviso that if a ring is formed with participation of one of the two radicals A3 and A4, the radical which does not participate denotes an electron-withdrawing radical,
X represents O, NH, NT, NCOT, NCO2T or NSO2T,
K is -NH3, -NHT2, -NH2T, -NT3 or a cycloimmonium ion,
B is an anion,
Z is a fibre-reactive radical,
I represents 0 to 2,
m represents 0 to 8 and
n represents 0 to 6.
said process comprising, diazotizing amines of the formula (IV)
(Formula Removed)
and the diazotization products are coupled to coupling components of the formula (V)
(Formula Removed)
wherein A1 to A5, D and X have the meaning as given above and
E represents H, -C02H, -CH2OH, -S03H, -
(Formula Removed)
2. Process as claimed in Claim 1, wherein 1 =1 or 2, n = 0 and m is less than 1, preferably 0.
3. Process as claimed in Claim 1, wherein 1 = m = n = 0.
4. Process as claimed in Claim 1, wherein 1 = 0 and m and/or n are not equal to 0.
5. Process as claimed in Claim 1, wherein
A3 and A4 independently of one another represent -CN, -CO2T,
-CONH2, -CONHT, -CONT2, CF3, -CHO, -COT, -SO2T, -SO3T4, -SO3T5,
SO2NH2, SO2NHT, SO2NT2, -SOT, -CH=NH, -CN=NT, -CT=NH, -CT=NT,
(Formula Removed)
or
A3 and A4 together with the C atom to which they are bonded, represent a cyclic methylene-active compound of the formula (IIa) to (IIv),


where these radicals are shows in the form of H2C
(Formula Removed)
wherein
V1 represents H or a substituent in particular Cl, Br, CH3, -CO2T1, -CN, -
NO2, -CF3 or -SO2T1, and wherein A1, A2, A5, D and X have the abovementioned
meanings.
6. Process as claimed in Claim 1, wherein
A1 represents H, T1 or -CF3,
A2 denotes H, -CN or -CO2T1,
A3 represents -CN or -CO2T1,
A4 denotes A3, or
A3 and A4, together with the C atom to which they are bonded, form a cyclic methylene-active compound of the formula (IIa) or (IId), where the radicals of the cyclic methylene-active compound are
shown to the form of nil
A5 represents H, I1 or T2,

represents a mdicai of the formula

R1 and R5 independently of one another denote H, CI, Br, -CN, -NO2, -CO2T1, T1 -OT1 or-OT4,
R2 and R4 independently of one another denote H, Cl, Br, -NO2, T1 or -OT1,
R3 represents H, Cl, Br, -CN,-NO2, T1 -CO2T1 or -OT1,
T1 represents C1-C6-alkyl or C1-C4-T4, optionally substituted by C1-
C6-alkoxy, -C1-C4-alkoxy -C2-C5-alkoxy or -CO2T1,
T2 denotes C2-C6-alkenyl which is optionally substituted by C1 and/or Br,
T4 represents phenyl, which is optionally substituted by C1, Br, -NO2
and/or -CO2T1 and
X denotes 0.
7. Process for the preparation of compounds of formula (I) substantially as herein described with reference to the foregoing examples.


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1910-del-1996-abstract.pdf

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1910-del-1996-correspondence-others.pdf

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abstract.jpg


Patent Number 199802
Indian Patent Application Number 1910/DEL/1996
PG Journal Number 29/2008
Publication Date 26-Sep-2008
Grant Date 06-Apr-2007
Date of Filing 27-Aug-1996
Name of Patentee BAYER AKTIENGESELLSCHAFT
Applicant Address D-51368 LEVERKUSEN, GERMANY.
Inventors:
# Inventor's Name Inventor's Address
1 RAINER HAMPRECHT IM KERBERICH 25, 51519 ODENTHAL, GERMANY.
PCT International Classification Number C09B 29/42
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 19535501.6 1995-09-25 Germany