Patent GB-838338-A (GB)
Title: New nitro dyestuffs containing the triazine nucleus
Inventor: HOWARD HAROLD THOMPSON
IPC: C07D401/12
Filed: 1956-06-15
Abstract: Nitro-amines are made by reacting o-nitrohalogeno-benzenes or -naphthalenes with diamines.  In the absence of sulphonic acid groups the reaction may be conducted in alcoholic media such as ethanol or betaethoxyethanol in the presence of an acid-binding agent such as sodium bicarbonate or carbonate.  When sulphonic acid groups are present the reaction may be conducted in aqueous or alcoholic media in the presence of an acid-binding agent such as calcium carbonate at elevated temperatures, e.g. 100 DEG  C. Nitro-amines which may be prepared are 2 : 4 - dinitro - 31 - diphenylamine, 2 - nitro - 41 - (p - aminoanilino -) diphenylamine - 31 : 4 - disulphonic acid, 2 - nitro - 41-amino - 11 - naphthylphenylamine - 4 : 61 - disulphonic acid, and 1 : 5 - dinitro - 2 : 6 - di-(4 - amino - 3 - sulphoanilino -) naphthalene.  In examples, the appropriate o-nitro-halogeno compounds are condensed with the appropriate amines to give (1) 2 - nitro - 41 - aminodiphenylamine - 31 : 4 - disulphonic acid, 41-sulpho -, 41 - carboxy - and 51 - carboxy - 2-nitro - 31 - aminodiphenylamine - 4 - sulphonic acids; (2) 4 - sulpho - and 4 - carboxy - 2-nitro - 41 - methylaminodiphenylamine - 31 - sulphonic acid; (3) 2 : 4 - dinitro - 41 - aminodiphenylamine - 31 - sulphonic acid; (4) 4-nitro -, 4 - acetyl -, 4 - cyano -, 4 - sulphondimethylamido -, 4 - sulphon - beta - hydroxyethylamido -, 4 - methanesulphonyl - and 4-trifluoromethyl - 2 - nitro - 41 - amino - diphenylamines; (5) 4 - carbonanilido - and 4-carboncyclohexylamido - 2 - nitro - 41 - aminodiphenylamines; (14) 6 - bromo - 1 : 5 - dinitro - 2 - (41 - aminoanilino) naphthalene; and (18) 4 - trifluoromethyl -, 4 - sulphon - betahydroxyethylamido - and 4 - carboxy - 2-nitro - 41 - aminodiphenylamine - 31 - sulphonic acids, 2 - nitro - 41 - amino - 31 - sulphon-betahydroxyethylamidodiphenylamine - 4 - sulphonic p  acid, 2 - nitro - 31 - amino - 4 - sulphonbeta - hydroxyethylamidodiphenylamine - 41-sulphonic acid, 2 - nitro - 41 - amino - diphenylamine - 4 - sulphonic acid, and 2 - nitro - 4-aminodiphenylamine - 31 : 4 - bis (sulphonbeta - hydroxyethylamide).  In further examples, (12) 4 - chloro - 3 - nitroacetanilide is reacted with morpholine and the acetyl group in the product is hydrolysed; (15) 3-nitro-4-chlorobenzene sulphochloride is reacted with beta-chloroethylamine and the product condensed with aniline to give 2-nitrodiphenylamine - 4 - sulphon - beta - chloroethylamide which is reacted with phthalimide and then hydrazine to give 2-nitro-diphenylamine-4-sulphon - beta - aminoethylamide; and (19), 4-chloro - 3 - nitrobenzene - beta - hydroxyethylsulphonamide is reacted with 4-amino-41-acetylaminodiphenylamine - 3 - sulphonic acid and the acetyl group in the product is hydrolysed.  Specification 838,337 is referred to.ALSO:The invention comprises nitro dyes of the formula <FORM:0838338/IV(c)/1> where D is a naphthalene or benzene nucleus which may be further substituted and wherein the nitrogen atom N is ortho to the nitro group, X is hydrogen or a hydrocarbon radical which may be substituted, R is an organic radical attached to the nitrogen through a carbon atom, and wherein R may be joined to X, when X is a hydrocarbon radical or to D, in a position ortho to the nitrogen atom N, to form a heterocyclic ring, which dyes also contain at least once the group <FORM:0838338/IV(c)/2> where A is halogen, B is halogen, hydroxy, mercapto, amino, substituted amino, aryl, alkyl, aryloxy, arylthio, alkyloxy, or alkylthio, and Z is hydrogen or a hydrocarbon radical which may be substituted.  The invention further comprises a process for making the dyes by reacting a triazine of the formula <FORM:0838338/IV(c)/3> with a nitro compound of the formula <FORM:0838338/IV(c)/4> which contains at least one amino group of the formula -NH.Z. When A and B are both halogen the product obtained may be further reacted with amines or with alkali-metal salts of phenols to give compounds wherein B is substituted amino or aryloxy.  The invention further comprises dye compositions containing a dye described above and a buffering agent suitable for maintaining a pH of about 6.5 In the above formulae the group R may be alkyl, aralkyl, cycloalkyl, aryl or heterocyclic and may carry substituents.  The nucleus D may be substituted by the group aryl-Y-, where Y is a direct linkage or a divalent linking group such as -NR1-, -SO2-, -S-, -O-, -SO2NR1-NR1SO2-, -CONR1-, -NR1CO-, -CO-, -CH2-, or -CH=CH-, where R1 is hydrogen or a hydrocarbon radical which may be substituted.  The hydrocarbon radicals represented by R1, X and Z above may be alkyl, aralkyl, cycloalkyl and aryl radicals which may be substituted.  The nucleus D, the aryl nucleus in the group aryl-Y-, or any aryl nucleus present in an organic radical or hydrocarbon radical represented by X, Z, R or R1 may carry one or more substituents such as alkyl, -SO3H, -COOH, -CON(R11)2, -CN, -COOR1, -SO2N(R11)2, -COR11, -CF3. halogen, -SO2OR11, -NO2, -SO2R11, -OR11, -OH, -N(R11)2, -NR11COR11, or -NR11SO2R11, where R11 is alkyl, cycloalkyl, aralkyl or aryl, and when they occur more than once in one substituent the groups R11 may p  be the same or different or may be alkyl or substituted alkyl groups joined so that they form a heterocyclic ring with the nitrogen atom.  Substituents which may be present in alkyl radicals present in an organic radical or hydrocarbon radical represented by X, Z, R or R1 are hydroxy, cyano or halogen. Where R is connected to X or to D to form a heterocyclic ring, the ring may contain one or more nitrogen, sulphur and/or oxygen atoms in addition to the nitrogen atom N, and may be morpholine or piperazine where R is joined to X, or phenoxazine, phenothiazine or acridone when R is joined to D.  Groups which may be represented by X, Z, R and R1 are methyl, ethyl, b -hydroxy-, b -chloro-, or b -cyano-ethyl, benzyl, p - chlorobenzyl, cyclohexyl, 2 - methylcyclohexyl, phenyl, m- and p-aminophenyl, and 4 - amino - 3 - sulpho -, 3 - amino - 4 - sulpho - and 4 - methylamino - 3 - sulpho - phenyl, and heterocyclic radicals which may be represented by R are 2:4-dichloro-1:3:5-triazinyl, 2-benzthiazolyl and 2-benzoxazolyl. Groups A and B may be chlorine and bromine and B may further be methoxy, ethoxy, phenyl, p-methylphenyl, methyl thio, butyl thio, b -hydroxyethylamino, p-tolylthio, phenoxy or p-chlorophenoxy. The reaction between the triazine and the nitro compound may be effected in acetone, dioxan or water or in mixtures of acetone or dioxan with water at low temperatures and in the presence of an acid-binding agent such as sodium carbonate or bicarbonate or potassium acetate. The further reaction of a dihalo-triazinyl product with amines or with alkali-metal salts of phenols may be conducted in water or acetone at about 40 DEG  C.  Isolation and drying of the products is conducted at low temperature and at a pH of 6-8, preferably in the presence of a buffer such as mixtures of disodium hydrogen phosphate and sodium or potassium dihydrogen phosphate.  Triazines of the above general formula which may be used in the reaction include 2:4-dichloro-6-(b -hydroxyethylamino) - 1:3:5 - triazine and 2:4 - dichloro - 6 - methylthio - 1:3:5 - triazine, and nitro compounds specified include 2-nitro - 41 - b  - aminoethylsulphonyl - diphenylamine, 2 - nitro - 4 - amino - N - cyclohexylaniline, 5 - amino - N - 21 - nitrophenyl - benziminazole, 2 - nitro - 41 - amino - 11 - naphthylphenylamine-4:61-disulphonic acid and 1:5-dinitro - 2:6 - di - (4 - amino - 3 - sulphoanilino)-naphthalene.  The dyestuffs containing sulphonic acid groups dye cellulose textile materials such as cotton, linen or viscose rayon from aqueous solution in conjunction with a prior, simultaneous, or subsequent treatment with an acid-binding agent, and print cellulose materials from a printing paste which also contains a substance which on heating or steaming liberates an acid binding agent such as sodium bicarbonate, the material being subsequently treated with heat or steam.  They also print silk, wool and regenerated protein fibres such as casein and ardein, and dye silk, wool and polyamide textile materials such as those containing polyhexamethylene adipamide or the polymers derived from caprolactam.  The dyestuffs which are insoluble or sparingly soluble are used as a finely-divided aqueous dispersion to dye or print wool, silk, and textile materials containing fibres of polyhexamethylene adipamide, the polymer from caprolactam, cellulose acetate or triacetate, polyurethanes and polyethylene terephthalate.  Yellow, orange and red-brown shades are obtained.  In examples, cyanuric chloride is reacted with (1) 2-nitro-41-amino-diphenylamine - 31:4 - disulphonic acid, 2 - nitro - 31 - amino - diphenylamine - 41:4 - disulphonic acid, 2-nitro-31-amino-41-carboxy-diphenylamine - 4 - sulphonic acid, or 2 - nitro - 3 - amino - 51 - carboxy - diphenylamine - 4 - sulphonic acid; (2) 2 - nitro - 41 - methylamino - diphenylamine - 31:4 - disulphonic acid or 2 - nitro - 41 - methylamino - 4 - carboxy - diphenylamine - 31 - sulphonic acid; (5) 2 - nitro - 41 - amino - 4 - carbonanilido - or - 4 - carboncyclohexylamido - diphenylamine; (6) 2:4 - dinitro - 31 - amino - diphenylamine; (15) 2 - nitro - diphenylamine - 4 - sulphon - beta - aminoethylamide; and (19) 4-sulphon-betahydroxyethylamido-, 4-sulpho-, 4-sulphon-bis-(hydroxyethyl)-amido-, 4-sulphon-(N-methyl-hydroxyethyl) - amido -, 4 - sulphondimethylamido-, 4-sulphonmorpholido, 4-sulphon-(m-sulphoanilido), 4-methanesulphonyl, or 4-carboxy - 2 - nitro - 41 - (411 - aminoanilino) - diphenylamine-31-sulphonic acid; 2:4-dichloro-6-methoxy-1:3:5-triazine is reacted with (3) sodium 2:4 - dinitro - 41 - amino - diphenylamino-31-sulphonate; and (7) 2:4-dinitro - 41 - amino - diphenylamine; 2:4 - dichloro - 6 - phenoxy-1:3:5-triazine is reacted with (8) 2:4 - dinitro - 41 - amino