Patent GB-954992-A (GB)
Title: New dyestuffs containing substituted pyrimidine or triazine radicals
Inventor: ARBUCKLE ALEXANDER WEIR
IPC: C09B62/02
Filed: 1960-11-24
Abstract: Diethyl a -(4-6-dichloro-1:3:5-triazin -2- yl)-malonate is obtained by reacting sodio diethylmalonate with cyanuric chloride. 2-Chloro-4:6-di[bis(carboethoxy)methyl]-1:3:5-triazine is similarly prepared.  3-(4:6-dichloro-11:31:51-triazinyl -61- yl pentane dione is obtained by reacting sodio acetylacetone with cyanuric chloride. 2-Chloro-4:6-di [bis (acetyl) methyl]-1:3:5-methyl]-1:3:5-triazine is similarly prepared.  Ethyl -a - (4:6-dichloro-1:3:5-triazin-2 yl) cyanacetate is obtained by reacting sodio ethyl cyanacetate with cyanuric chloride.  Ethyl 3-(41:61-dichloro-11:31:51 -triazin-21-yl) pentane-2:4-dione -3- carboxylate is obtained by reacting sodio ethyl diacetylacetate with cyanuric chloride.  1-carboethoxy -1-(41:61-dichloro-11:31:51 -triazin -2- yl)-propan -2- one is obtained by reacting sodio ethyl acetoacetate with cyanuric chloride. Diethyl 1-(41:61-di chloro-11:31:51-triazin -21-yl)-propane-1:1-dicarboxylate is obtained by reacting sodio diethyl ethylmalonate with cyanuric chloride.  1-Phenyl carbamyl -1-(41:61-dichloro-11:31:51 -triazin -21- yl)-propan -2- one is obtained by reacting acetoacetanilide with cyanuric chloride. 3-(21(41) 61-dichloropyrimidin-41(21) yl) heptane -2:4-dione is obtained by reacting sodio acetylacetone with 2:4:6-trichloro pyrimidine.ALSO:Dyestuffs are made by a process which comprises reacting a 1:3:5-triazine or pyrimidine carrying at least two reactive halogen atoms and/or labile groups (i.e. a group capable of being split off in the form of an anion), with (a) a dyestuff compound which contains at least one group of the formula -AH wherein A represents-O,-S-or <FORM:0954992/C3/1> and R represents a hydrogen atom or a cycloalkyl radical or a substituted or unsubstituted alkyl radical and (b) a compound of the formula <FORM:0954992/C3/2> wherein X represents a hydrogen atom or a substituted or unsubstituted hydrocarbon radical or a COR1 or COOR1 group and Y and Z independently represent a -CN, -NO2, CF3, -CHO, -COR1, -COOR1, -COCOOR1, -CONH2, -CSR1, -CONR1R2, -SO2R1, -SO2NH2, -SO2NR1R2, -CH = CH2 or -CH = C(COOR1)2 group, wherein R1 represents a substituted or unsubstituted hydrocarbon radical or an alkali metal derivative of the compound of the formula given above. Alternatively the dyes are made by diazotising a primary aromatic amine, which may be an aminoazo compound, and coupling the diazo compound with a coupling component, either the primary aromatic amine and/or the coupling component containing a group of the formula AH, where A represents -O-, -S-, or -NR- and R has the meaning given above, which group has previously been reacted with (a) a 1 : 3 : 5-triazine or pyrimidine as defined above and a compound as defined in (b) above. Representative of the values specified for R1, R2 and X are methyl, butyl, ethoxyethyl, benzyl, phenyl, naphthyl and aryl radicals substituted with halogens, nitro, alkoxy or carboxylic ester groups. Many compounds of the above formula are listed, those preferred being lower alkyl esters of acetylacetic, cyanacetic and malonic acids, acetoacetarylides and acetylacetone.  Halogens specified as present in the triazines or pyrimidines are bromine and chlorine.  Labile groups specified include sulphonic acid, thiocyano, sulphonated aryloxy and sulphonated arylthio groups of the formulae <FORM:0954992/C3/3> where T1 and T2 represent substituted or unsubstitute alkyl, cycloalkyl, aryl, aralkyl or heterocyclic radicals or T1 and T2 form with the nitrogen atom N a 5- or 6-membered heterocyclic ring and T3 represents atoms required to form a 5- or 6-membered heterocyclic ring.  Each of the -AH groups is attached to a carbon atom in the dyestuff used and may form part of an aryl residue or of an alkyl chain or is attached to the aryl residue through a bridging atom or group e.g. -O-, -S-, -NH-, <FORM:0954992/C3/4> alkyl.  Preferably the dyestuff is of the mono- or polyazo, nitro, anthraquinone or phthalocyanine series. Preferably a water-solubilising group e.g. carboxylic acid, alkyl sulphone, sulphonamide or sulphonic acid group is present. Types of dyes used may be <FORM:0954992/C3/5> where D1 represents a mono- or dicyclic aryl radical which is free from azo groups and -NHR groups, the -NHR group is preferably attached to the 6-, 7- or 8-position of the naphthalene nucleus and another SO3H group may be present in the 5 or 6 position, the NHR group may be attached to a benzoyl amino or anilino group attached to the 6, 7 or 8-position and D1 may be a stilbene, diphenyl, benzthiazolyl or diphenyl radical, preferably a sulphonated phenyl or naphthyl radical with a -SO3H group in ortho position to the azo link; disazo dyes wherein D1 stands for a radical of the azobenzene, azonaphthalene or phenylazonaphthalene; monoazo dyes of the formula <FORM:0954992/C3/6> where D1 is as above and is preferably a disulphonaphthyl or stilbene radical and the benzene nucleus may be substituted; monoor disazo of the formula <FORM:0954992/C3/7> where D1 is an arylene radical such as azobenzene, azonaphthalene or phenylazonaphthalene or preferably an at most dicyclic arylene radical of the benzene or naphthalene series and K is the residue of a naphthol sulphonic acid or of an enolised or enolisable ketomethylene compound with OH in a -position to the azo group; the metal complexes e.g. Cu, Cr and Co complexes of the above dyes which contain a metallisable group o to the azo group; anthraquinones of the formula <FORM:0954992/C3/8> which may contain an additional sulphonic acid group in the 5, 6, 7 or 8 position and V represents a bridging group, preferably a divalent benzene residue e.g. phenylene, diphenylene or 4,41-stilbene or azobenzene and preferably V contains one SO3H group for each benzene ring present; phthalocyanines of the formula <FORM:0954992/C3/9> Pc being preferably a copper phthalocyanine, o  is OH and/or a amino group, optionally substituted, V is a bridging group, preferably an aliphatic, cycloaliphatic or aromatic group n and m are 1, 2 or S but their sum is not greater than 4 and nitro dyes of the formula <FORM:0954992/C3/100> where B and B1 are monocyclic aryl nuclei and the NO2 group in B is o to the NH group.  Dyestuffs obtained by the process which contain halogen attached to the triazine or pyrimidine ring may be reacted with such compounds as ethanol, phenol, sodium phenol-4-sulphonate, ammonia various aliphatic and aromatic amines, mercaptans sodium sulphite, potassium thiocyanate, sodium diethyl dithiocarbamate, sodium N - methyl - N - phenyldithiocarbamate, 2 - mercapto-oxazole, - benzthiazole, - benzselenazole,-benziminazole and 2- or 4-mercaptopyridine. The dyes which have water solubilizing groups are particularly valuable for colouring cellulosic textile materials and are preferably employed in conjunction with an acidbinding agent. The dyes may be applied to nitrogen-containing textile materials e.g. wool and polyamides from a mildly alkaline, neutral or acid dyebath.  The dyes may be applied to textile materials in conjunction with resin-forming compositions and acid catalysts. Numerous examples are provided.