Patent GB-775308-A (GB)
Title: New monoazo-dyestuffs and process for making them
IPC: C09B62/085
Filed: 1954-08-10
Abstract: Dyestuff intermediates are obtainable by reacting one mol proportion of a cyanuric trihalide with one mol. proportion of a diazo component of the benzene series which contains in addition to a group capable of dyestuff formation a reactive hydrogen atom bound to a nitrogen atom, and exchanging one of the two remaining halogen atoms in the cyanuric acid residue for the residue of a compound containing a reactive hydrogen atom and less than 13 carbon atoms.  Specified compounds containing less than 13 carbon atoms are methyl, ethyl and butyl alcohols, phenol, o-, m- and p-cresols, 4-sec. butyl-phenol, 4-tert. amylphenol, dialkylphenols, o- and p-chlorophenol, dodecyl and b -oxyethyl mercaptans, thiophenol, methyl-, dimethyl -, ethyl - diethyl -, isopropyl -, butyl-, hexyl -, dodecyl -, phenyl -, o - tolyl, 2 - and 4 - chlorophenyl -, N - methyl - phenyl -, cyclohexyl -, b  - chloroethyl -, methoxy -methyl-and ethanol-amines, acetamide, butyramide, urea, thiourea, p-toluene sulphonamide, glycocoll, methyl and ethyl esters of amino-carbonic acid, aminoacetic acid ethyl ester, amino acetamide and 1-aniline-3- and 4-sulphonic acids, sulphonamides and sulphones.  Specified dyestuff components are 4,41-diaminodiphenylmethane, 4,41 - dimethyl - 3,31 - diaminodiphenylmethane, 4,41 - diaminodiphenyl, 4,41-and 2,41 - diaminodiphenyl ether, 4,41 - dichloro - 2,21 - diaminodiphenyl sulphide and ether, 2,41 - and 3,31 - diaminodiphenyl sulphone and (41,411 - diamino - 31,311 - dimethyldiphenyl) - 1,11 - cyclohexane and 1,3 - and 1,4-diamino-benzene.  A preferred class of dyestuff intermediate is: <FORM:0775308/IV(b)/1> where Y and 2 are each H or a substituent incapable of imparting solubility in water and which is derived from 1,4-diaminobenzene-3-and especially 1,3-diaminobenzene-4-sulphuric acids.  The products are converted into dyestuffs (see Group IV (c)).  In examples the preparation of intermediate from certain of the above reactants is described additional specified compounds containing less than 13 carbon atoms being 2-methoxy-, 2,6-dimethyl-, 2,5- and 3,4 - dichloro - and 2 - methyl - 6 - chloroanilines and furamylmethylamine.ALSO:The invention comprises dyestuffs of formula R - N = N - Pz where R is a benzene residue and Pz is a 5 - pyrazolone residue bound in the 4 - position to the azo link, and which dyestuffs contain 1 or 2 sulphonic acid groups and a cyanuric acid residue bound to R through an N bridge and which residue contains an exchangeable halogen atom and a substituent having less than 13 carbon atoms.  They are made by coupling appropriate benzene diazo components and pyrazolones advantageously in a weakly acid to weakly alkaline medium to avoid reaction of the exchangeable halogen atom.  The benzene component may be made by condensing 1 mol proportion of a cyanuric trihalide, advantageously in the presence of an acid-binding agent, with 1 mol proportion of a dyestuff component of the benzene series which contains in addition to a group capable of dyestuff formation a reactive hydrogen atom bound to an N atom and exchanging one of the two remaining halogen atoms in the cyanuric residue for the residue of a compound containing a reactive hydrogen atom and less than 13 carbon atoms. Compounds mentioned which contain less than 13 carbon atoms are ammonium, aliphatic and aromatic hydroxy-compounds, mercaptans and especially organic nitrogen compounds such as amines, amides, amino - alcohols, amino - acids and methanes.  Advantageously components are made by condensing one mol proportion of a compound of formula <FORM:0775308/IV(b)/1> where A is the substituent of less than 13 carbon atoms with one mol proportion of a diamine such as 4, 41 - diaminodiphenylmethane, 4, 41 - dimethyl - 3, 31 - diaminodiphenylmethane, 4, 41 - diaminophenyl, 4, 41 and 2, 41 - diamino - diphenyl ether, 4, 41 - dichloro - 2, 21 diaminodiphenyl sulphide and ether, 2, 41 - and 3, 31 - diaminodiphenyl sulphone and (41, 411 - diamino - 31, 311 - dimethyldiphenyl) - 1, 11 - cyclohexane and especially diamines such as 1, 3 - and 1, 4 - diaminobenzene.  A preferred class of diazo components is those of formula <FORM:0775308/IV(b)/2> where Y and Z each are H or a substituent incapable of imparting solubility in water and which is derived from 1, 4 - diaminobenzene - 3 - and particularly 1, 3 - diaminobenzene - 4 - sulphonic acids.  The diazo components may also be made from mono - amino or - oxy - benzenes which contain a group convertible into an amino group, e.g. a nitro or acyl - amino group. Specified diazo components are those made by condensing 1 mol of the above-mentioned diamines with 1 mol of cyanuric trichloride and 1 mol of methyl, ethyl or butyl alcohols, phenol, o -, m - or p - cresols, 4 - sec butyl phenol, 4 - tert amyl phenol, dialkyl phenols, o- and p - chlorophenol, dodecyl and b  - oxyethyl mercaptans, thiophenol, methyl-, dimethyl-, ethyl-, diethyl-, isopropyl-, butyl-, hexyl-, dodecyl-, phenyl-, o - tolyl-, 2- and 4 - chlorophenyl-, N - methyl - phenyl-, cyclohexyl-, b  - chloroethyl-, methoxymethyl- and ethanol - amines, acetamide, butyramide, urea, thiourea, p - toluene sulphonamide, glycerol, methyl and ethyl esters of amino-carbonic acid, aminoacetic acid ethyl ester, aminoacetamide and 1 - aniline - 3 - and - 4 - sulphonic acids - sulphonamides and - sulphones. Specified coupling components are 1 - phenyl - 3 - methyl - 5 - pyrazolone - 21 -, - 31- and - 41 - sulphonic acids, 1 - (21 - chlorophenyl - and 21, 51 - dichlorophenyl) - 3 - methyl - 5 - pyrazolone - 41 - sulphonic acids, 3 - methyl -, -phenyl - and-(21 - chlorophenyl) - 5 - pyrazolone, 5 - pyrazolone - 3 - carboxylic acid butyl - amide, 1 - (31 - chlorophenyl) - 5 - pyrazolone - 3 - carboxylic acid, 1, 3 - diphenyl-5 - pyrazolone, 1 - phenyl - 3 - methyl - 5 - pyrazolone and its - 31 - sulphonamide, 1 - n - octyl-, -(31 - and 41 - chlorophenyl) - and especially - (21, 51 - dichloro - phenyl) - - 3 - methyl - 5 - pyrazolones.  Preferred coupling components are of formula <FORM:0775308/IV(b)/3> where A is H or an alkyl or alkoxy group of up to 2 carbon atoms, or halogen and B is an alkyl group of up to 2 carbon atoms or a halogen, e.g. 1 - (21 - methyl-, - ethyl - and - chloro-, 21, 61 - dichloro- and - dimethyl - and 21 - methyl - 61 - chlorophenyl) - 3 - methyl - 5 - pyrazolone. The dyestuffs may also be made by introducing the cyanuric residue into an appropriate azo dyestuff.  Thus an appropriate dyestuff R - N = N - PZ where R is a benzene residue and PZ is the required pyrazolone may be condensed in molar proportions with a halide of formula <FORM:0775308/IV(b)/4> where A is the substituent containing less than 13 carbon atoms. The dyestuffs dye nitrogenous materials such as leather, silk, wool and superpoly-amides and -urethanes from acid or weakly alkaline dye - baths.  Examples are provided which illustrate the preparation of the dyestuffs and their use in dyeing wool and superpolyamide fibres in green and yellow shades, reactants providing substituent A, additional to those specified above, are 2 - methoxy -, 2, 6 - dimethyl-, 2, 5 - and 3, 4 - dichloro and 2 - methyl - 6 - chloro - anilines and furanylmethylamine.