Patent GB-929425-A (GB)
Title: New heterocyclic-nitrogen containing dyestuffs
Inventor: RATTEE IAN DURHAM
IPC: C09B69/00
Filed: 1959-07-02
Abstract: The invention comprises dyes which contain at least one sulphonic acid group and at least one group of formula <FORM:0929425/IV(a)/1> where R is H or an alkyl group which may be substituted and Z is a 1,3,5-triazine or pyrimidine ring attached to N via a C atom of the ring and carrying at least one group of formula <FORM:0929425/IV(a)/2> attached to a C atom of the ring where R1 is H or an alkyl group which may be substituted and X is an alkyl or cycloalkyl group with at least two OH groups and optionally having a keto or aldehydic group.  The dyes may be made by conventional diazotization and coupling processes or by treating an appropriate dye containing at least one sulphonic acid group and at least one group of formula <FORM:0929425/IV(a)/3> where Z1 is a 1,3,5-triazine or pyrimidine ring which carries at least one halogen atom attached to a C atom thereof, with an amine of formula R1N(H)X Products containing a halogen atom attached to a C atom of the heterocylic ring may be treated with various reagents to convert the halogen atom into other groups.  The <FORM:0929425/IV(a)/4> group is attached to a C atom of the dye which may be part of an aryl residue or an alkyl chain which is directly attached to an aryl residue or via a bridging member, e.g. -O-, -S-, -NH-, -N-alkyl, -CONH-, -NHCO-, -SO2NH- and <FORM:0929425/IV(a)/5> Preferably the dyes are of the azo, nitro, anthraquinone and phthalocyanine series.  The dyes may contain co-ordinately bound metal, e.g. copper, chromium and cobalt. Illustrative of specified values for R and R1 are methyl, butyl, b ,g -dihydroxypropyl, b -ethoxyethyl and b -phenylethyl. Cyclohexyl is an additional value specified for R. Representative of specified values for X are dihydroxypropyl, pentahydroxyhexyl, tri(hydroxymethyl) methyl and dihydroxycyclohexyl.  When X contains a keto or aldehydic group and is derived from a carbohydrate of 5 to 6 carbon atoms it may ring-close to a tetrahydropyranyl or tetrahydrofuryl residue. Indicative of substituents for the heterocyclic ring, other than the <FORM:0929425/IV(a)/6> group are chlorine, methylmercapto, ethyl, tolyl, hydroxy, propoxy, sulphophenoxy, cyano, thiocyano, amino, b -hydroxyethylamino, dimethylamino, disulphoanilino, carboxyanilino, nitro, sulphonaphthylamino and sulphonic acid. Indicated starting materials are compounds of formula <FORM:0929425/IV(a)/7> where D1 is an at most dicyclic aryl radical which is free from azo and NHR groups, the NHR group is preferably in the 6-, 7- or 8-position and an SO3H group may be in the 5-or 6-position; D1 may be, e.g. a stilbene, diphenyl, benzthiazolyl phenyl, or diphenylamine residue and the NHR group may be attached to the 6-, 7- or 8-position via a benzoylamino or anilino group, preferably D1 is a sulphonated phenyl or naphthyl residue with SO3H oto the azo link; compounds where D1 is an azo-benzene or -naphthalene or phenylazo-naphthalene series and the naphthalene nucleus substituted by NHR; monoazo compounds, containing at least one SO3H group, of formula <FORM:0929425/IV(a)/8> where D1 is an at most dicyclic aryl residue, preferably disulphonaphthyl or stilbene and the phenyl residue may contain substituents such as halogen atoms or alkyl, alkoxy, carboxylic acid and acylamino groups; mono- or dis-azo compounds containing at least one sulphonic acid group of formula H-N(R)D1-N=N-K where D1 is an arylene residue, e.g. an azobenzene, azonaphthalene or phenylazonaphthalene residue or, preferably, an at most dicyclic arylene residue of the benzene or naphthalene series and K is a naphthol sulphonic acid or an enolized or enolizable keto-methylene residue with the OH group o to the azo group, D1 preferably being a benzenic residue containing a sulphonic acid group, or of formula D1-N=N-K2-NHR where D1 is as above and K2 is an enolizable ketomethylene with OH o to the azo group; metal complexes of the above dyes which are metallizable; compounds of formula <FORM:0929425/IV(a)/9> where an additional SO3H group may be in the 5-, 6-, 7- or 8-position and Y is a bridging group which is preferably of the benzene series, e.g. phenylene, diphenylene, or 4,41-stilbene or azobenzene radicals, Y preferably having one SO3H group for each benzene ring present; compounds of formula <FORM:0929425/IV(a)/10> where Pc is a phthalocyanine nucleus, preferably of copper phthalocyanine, o  is OH and/or NH2, Y is a bridging group, preferably an aliphatic, cycloaliphatic or aromatic group, n and m are 1, 2 or 3 with n + m not greater than 4 and dyes of formula NO2-A-NH-B-NHR where A and B are monocyclic nuclei which contain at least one sulphonic acid group with the NO2 group o to NH. Preferred classes of dyes are those which contain one or two groups of formula <FORM:0929425/IV(a)/110> or <FORM:0929425/IV(a)/121> or <FORM:0929425/IV(a)/132> where Z, is a pyrimidine ring with one group of formula <FORM:0929425/IV(a)/143> and a Cl or Br atom, where Hal is Cl or Br and X is preferably pentahydroxy-n-hexyl.  The dyes are used to colour cellulosic textile materials, especially when applied in conjunction with a treatment with HCHO and/or a resin-forming composition and an acid catalyst.  Examples are provided of the preparation of the dyes and their use in colouring processes a variety of colours being obtained.  Specifications 209,723, 298,494, 467,815, 503,609, 772,030, 774,925, 781,930, 785,120, 785,222, 803,473, 805,562, 822,047, 826,405, 828,353, 829,042, 832,400, 834,304, 836,248, 836,647, 837,035, 837,124, 838,311, 838,335, 838,340, 846,405, 847,635, 849,772, 851,537, 852,120, 852,911 863,155 and 929,426 are referred to.  The first Provisional Specification also refers to Specifications 802,935, 837,990, 838,338, 855,792, 863,754 and 864,227.