Patent GB-856348-A (GB)
Title: Improvements in or relating to water-insoluble monoazo dyestuffs containing carboxylic ester groups
IPC: C09B29/033
Filed: 1957-07-24
Abstract: Compounds of formula:  <FORM:0856348/IV(b)/1> Where R2 is Me, Et, CH2Cl, CH2OMe, CF3 or C Cl3, R3 is Me, Et, CH2 Cl or CH2OMe, R4 is an alkyl radicle of 1-4 C atoms or CH2 Cm H2m OCO R3, R5 is H or NH-y-R2, X is H or, when R5 is H, may also be Cl, Br, Me Et, OMe or OEt, y is a carbonyl, carbonyloxy, sulphur, sulphoxide or sulphonyl bridge, m is 1, 2 or 3 and n is 1 or 2 are used as coupling components for azo dyes (see Group IV(c)) and stated to be new.  They are made by reacting compounds of formula:  <FORM:0856348/IV(b)/2> Where Z is H, Me, Et, propyl, isopropyl or hydroxy-methyl, -ethyl or -propyl, or of formula:  <FORM:0856348/IV(b)/3> With a functional derivative of an appropriate aliphatic carboxylic acid, in the latter instance y-R2 in the products is COR3.  Many components are specified in list and tabular form and in Example 13 l-di-(hydroxyethyl)-amino-3-aminobenzene is triacetylated with acetic anhydride.  Reference has been directed by the Comptroller to Specifications 744,577, 764,308, 764,309 and 774,611.ALSO:The invention comprises dyestuffs of formula:  <FORM:0856348/IV (c)/1> where R1 is a residue of a benzene, naphthalene or heterocyclic diazo component free form sulphonic or a carboxylic acid groups, R2 is Me, Et, CH2Cl, CH2OMe, CF3 or CCl3, R3 is Me Et, CH2Cl or CH2OMe, R4 is an alkyl radical of 1-4 C atoms or -CH2-CmH2m-O-CO-R3, R5 is H or -NH-Y-R2, X is H or, when R5 is H, is also Cl, Br Me, Et, OMe or OEt, OMe and OEt being excluded when R1 is: <FORM:0856348/IV (c)/2> where Z is Hlg or NO2, Y is carbonyl, carbonyloxy, sulphur, sulphoxide or sulphonyl bridge, n is 1 or 2 and m is 1, 2 or 3. Of especial interest are dyestuffs of formula: <FORM:0856348/IV (c)/3> where R4, n and m are as above, S is NO2 or MeSO2-t is H, Cl, Br, MeO, CF3, CN or MeSO2 and R2 and R3 are Me or Et.  The dyestuffs are made by coupling, preferably in acid solution, an appropriate diazotised amine R, NH2 with the necessary coupling component. Dyestuffs in which R4 is CH2-Z where Z is H, Me, Et, propyl or isopropyl or CH2-CmH2m-1 H2-n-(O-COR3)n and derived from benzene or naphthalene diazo compounds, may also be made by acylating corresponding dyestuffs where -(O-COR3)n is replaced by (OH)n.  Indicated amines corresponding to R1 are 4-nitroaniline, 1-amino-4-alkylsulphonylbenzene and its 2-mono- or 2, 6-di-substituted derivatives, 1-amino-4-alkylsulphonylnaphthalene and 1- naphthylamine -4- sulphonic acid fluoride and their derivatives and 2- aminothiazole, -thiophene and thio-diazole and their derivatives.  The dyestuffs dye cellulose ester, polyamide, polyvinyl, terephthalic acid ester and polyacrylonitrile fibres in orange, red or violet shades.  A large number of illustrative examples are provided the values for R1, R2, R3, R4 R5, x, y, n, m, s, t and z in the reactants used being selected from those specified above, additional diazo components being 2- amino -6- methylsulphonyl-or -nitrobenzothiazole, 2- amino-1, 3, 5-, -5- nitro- 1, 3, 4- and 4- phenylthiodiazoles, 2- amino -5- thiocyanonitro- and -cyanothiazoles, 2-amino -5- nitro -4- methylthiazole, 2- aminothiazole -5- carboxylic acid esters, 2-amino -3- nitro -5- acetylthiophene, 1- amino-2, 4- dicyano- and -nitro-, 2- chloro -4- cyano-, 2- cyano -4- nitro -6- chloro -2, 4- dinitro -6-chloro- and -cyanobenzenes, 1- amino -2, 4-dinitrobenzene -6- sulphonethylamide, 1-amino -4- nitrobenzene -2- sulphonfluoride, 4-methylsulphonyl- and -fluorosulphonylnaphthalene.  Reference has been directed by the Comptroller to Specifications 744,877, 764,308, 764,309 and 774,611.