Patent GB-917780-A (GB)
Title: New pyrimidine dyestuffs
Inventor: ANDREW HERBERT FRANCIS
IPC: C09B62/20
Filed: 1959-10-23
Abstract: The invention comprises dyes which have at least one group AX where A is O, S or NR, R is H or an alkyl radical, which may be substituted, and X is a pyrimidine ring attached to A via the 2- or 4-C atom of the ring and which carries a cyano, carboxy or carboalkoxy group attached to the 5-position of the ring and which has two Cl or Br atoms attached to the remaining C atoms.  The dyes may be made by treating a dye containing at least one group AH with an appropriate halopyrimidine.  Azo pyrimidine dyes may also be obtained by usual diazotisation and coupling processes. The AX groups are attached to carbon atoms in the dye residue which may be part of an aryl residue or an alkyl chain which is directly attached to an aryl residue in the dye or is so attached via a bridging atom or group such as O, S, CO, SO2 NH, N alkyl, CONH, SO2NH and SO2 N alkyl.  Preferably A is NR.  Preferred dyes are the mono- or polyazo, nitro, phthalocyanine or anthraquinone series and may contain solubilising groups such as sulphonic, carboxylic or sulphamyl groups.  Metal complexes, e.g. of Cu, Cr or Co, are also described.  Specified 5-carboalkoxy groups are carbo-meth-, eth- and prop-oxy groups.  Representative of values specified for R are methyl and butyl, and for its substituents are ethoxy and hydroxy.  Representative of specified diazo components from which azo dyes may be made are aniline, p-anisidine, 2,5-dichloroaniline, 4-aminodiphenyl, aniline-2-carboxylic acid, 2-aminodiphenylether, 3-aminobenzenesulphondiethylamide, dehydrothio-p-toluidine disulphonic acid, 3-aminobenzotrifluoride-4-sulphonic acid, a -naphthylamine and 2-naphthylamine-3,6,8-trisulphonic acid.  Representative of specified coupling components for these dyes are aniline, o-toluidine, 1-ethylamino-8-naphthol-6-sulphonic acid, 1(31- or 41-aminobenzoylamino)- 8-naphthol- 3,6-disulphonic acids and 1-(41-amino- 31-carboxyphenyl)-3-methyl-5-pyrazolone. Representative of specified diamines from which disazo dyes may be made are benzidine-2,21-disulphonic acid, 3,31-dimethoxybenzidine and 4,41-diaminostibene2,21-disulphonic acid.  Disazo dyes may also be made from diazo components containing azo groups such as 4-aminoazobenzene-41-sulphonic acid and 41-amino-21-methylphenylazo-2-naphthalene-4, 8-disulphonic acid.  Azo dyes may also be made from diazo components which contain an NHR group and coupling components which optionally contain an NHR group. Representative of such diazo components are 1,4-phenylenediamine-2-carboxylic and 1,4-diamino-naphthalene-2-sulphonic acids, and of such coupling components (additional to those listed above) are phenol, b -naphthol, 1-naphthol-4-sulphonic acid, 2-benzoylamino- 5-naphthol-7-sulphonic acid, 1-phenyl- 3-methyl- 5-pyrazolone, and acetoacetanilide.  Amino-azo dyes may also be used, as starting materials, which are obtained by the hydrolysis of the corresponding acylaminoazo dye. Illustrative of specified anthraquinones used are 1-amino-4-(41-aminoanilino)-anthraquinone- 2, 31-disulphonic acid, 1-amino- 4-[41-(411-aminophenylazo-) anilino-] anthraquinone-2,211,5-trisulphonic acid and 1-amino-4-(31- b -hydroxyethylamino) - anilino-anthraquinone-2,5-disulphuric acid. Phthalocyanines used preferably contain metal, e.g. copper, and at least one water-solubilising group as well as the NHR group.  The NHR group may be attached directly to the benzrings of the phthalocyanine nucleus or via a divalent bridging radical, e.g. phenylene, CO-phenylene, SO2-phenylene, NH-phenylene, S-phenylene, O- phenylene, CH2S- phenylene, CH2O- phenylene, CH2- phenylene, SCH2phenylene, SO2CH2-phenylene, SO2NR1-phenylene-CH2, SO2NR1-arylene, NR1CO-phenylene, NR1SO2- phenylene, SO2O- phenylene, CH2, CH2NR1- phenylene, CH2NH CO phenylene, SO2NR1-alkylene, CH2NR1-alkylene, SO2, CO, CONR1-phenylene CH2 and CONR1-arylene, where R1 is H, alkyl or cycloalkyl, alkylene may include hetero atoms, e.g. CH2CH2NCH2 CH2 and phenylene may be substituted, e.g. by halogen, alkyl or alkoxy. Illustrative of indicated arylene residues are benzene, naphthalene, acridine and carbazole residues and radicals of formula <FORM:0917780/IV (b)/1> where D is a bridging group such as -CH=CH-, NH, S, SO, SO2, NO=N, N=N, NHCONH, CONH, OCH2CH2O and <FORM:0917780/IV (b)/2> Indicative of specified phthalocyanines are copper phthalocyanine-4-N- (4-amino- 3-sulphophenyl) - sulphonamide- 41-411,4111- trisulphonic acid, cobalt phthalocyanine-4, 41-di-N(31-amino-41- sulphophenyl-) carbonamide-411, 4111-dicarboxylic acid and copper-4-(41-amino31-sulphobenzoyl)- phthalocyanine. Mixtures of aminophthalocyanines may be used. Preferred nitro dyes used are those of formula NO2-DN-N(Z)Q where D is a benzene or naphthalene residue which may be substituted, N is o to NO2, Z is H or a hydrocarbon radical which may be substituted, Q is H or a residue attached to N via a carbon atom, provided that both Q and Z are not H and Q may be connected to Z when Z is hydrocarbon or to D, in the o-position to the N atom, and which also have the group NHR.  Types of dyes used may be monoazo dyes of formula <FORM:0917780/IV (b)/3> where D1 is an at most dicyclic aryl radical which is free from azo and NHR groups, NHR is preferably in the 6, 7 or 8 position and another SO3H group may be in the 5 or 6 position, the NHR group may be attached to a benzoylamino or anilino group which is attached to the 6, 7 or 8 position and D1 is indicated as a benzene, naphthalene, stilbene, diphenyl, diphenylamine or benzthiazolylphenyl residue and is preferably a sulphonated phenyl or naphthyl residue with the SO2H group o to the azo link; disazo dyes of the above formula where D1 is a residue of the azobenzene, azonaphthalene or phenylazonaphthalene series; monoazo dyes of formula <FORM:0917780/IV (b)/4> where D1 is as above and is preferably a disulphonaphthyl or stilbene residue and the benzene nucleus may be substituted; monoor dis-azo dyes of formula H-N(R)-D1-N=N-K where D1 is an arylene residue such as azobenzene, azonaphthalene or preferably an at most dicyclic residue of the benzene or naphthalene series, especially a sulphophenyl group, and K is the residue of a naphthol sulphonic acid or an enolised or enolisable keto-methylene compound with OH o to the azo group; mono- or dis-azo dyes of formula D1-N=N-K2-NHR where D1 is as above and K2 is the residue of an enolisable ketomethylene compound with OH o to the azo group; metal complexes, e.g. Cu, Cr and Co complexes, of the above dyes which have a metallisable group o to the azo group; anthraquinones of formula <FORM:0917780/IV (b)/5> which may contain another SO3H group in the 5, 6, 7 or 8 position and Z1 is a bridging group, preferably a divalent benzene residue, e.g. phenylene, diphenylene, 4,41-stilbene or azobenzene and preferably Z1 should contain one SO3H group for each benzene ring present; phthalocyanines of formula <FORM:0917780/IV (b)/6> Pc being preferably a copper phthalocyanine, o  is OH and/or NH2, Z1 is a bridging group, n and m are 1, 2 or 3 but their sum is not more than 4 and nitro dyes of formula NO2-V-NH-B-NHR where V and B are monocyclic aryl nuclei and V is o to NH.  Preferred are dyes which have at least one COOH or SO3H group and one or two groups of formula <FORM:0917780/IV (b)/7> where the halogen are Br or preferably Cl.  The dyes, which have water-solubilising groups, are especially valuable for colouring cellulosic textile materials and are preferably applied in conjunction with an acid-binding agent.  Dyes, which do not contain watersolubilising groups, may be applied as an aqueous dispersion. The dyes may be applied to nitrogenous textile materials, e.g. wool and polyamides, from a mildly alkaline, neutral or acid dyebath.  The dyes may also be applied to textiles, especially cellulosic textiles, in conjunction with a resin-forming composition and an acid catalyst. Numerous examples are provided of the preparation of the dyes and their use in various colouring processes.  A variety of colour shades are obtained.  In the Provisional Specification the pyrimidine ring in the product dyes may contain one or two Cl or Br atoms attached to carbon atoms of the pyrimidine ring.  When only one halogen atom is present the remaining pyrimidine carbon atom may optionally be attached to an alkyl group.  Specifications 529,847 569,200, 589,118, 717,137, 724,212 and 875,862 are referred to.