Patent GB-774682-A (GB)
Title: Improvements relating to metallisable trisazo dyestuffs and their use
IPC: C09B45/24
Filed: 1953-10-14
Abstract: Compounds of formula: <FORM:0774682/IV(b)/1> wherein "acyl" is a carbacyl radical, Q is a direct carbon linkage or a divalent bridging member of formula CO-NH, NH-CO or NH-CO-NH, of R1 and R2 one R is a p-phenylene sulphonic acid radical which contains the sulphonic acid group in m-position to Q and the other R is a phenyl radical having the acylamino or amino group in the m- or p-position to Q and x1-x4 are 0 or 1 of which only one of x2 or x4 may be different from 0, are specified and are used as components in trisazo dyestuffs (see Group IV (c)).  They may be prepared for example from polynuclear diamine compounds such as 4 : 41-diaminodiphenyl-3-sulphonic acid, 4 : 31 - or 4 : 41 - diaminodiphenylurea - 3 - sulphonic acids or 4 - (31 - or 41 - aminobenzoaminol) - 1 - aminobenzene - 2 - sulphonic acids, by reacting a cold aqueous solution of their alkali salts with diketene so that only the amino group which is not adjacent to the sulphonic acid group is acetoacetylated.  Alternatively the diamino compounds described above or 1 : 4 - diaminobenzene - 2 - sulphonic acid may be reacted with 3- or 4-nitrobenzoyl halides or 3-or 4-nitrophenyl isocyanates to give the corresponding mononitrobenzoyl or mononitrophenylcarbamyl derivatives, an aqueous solution of the alkali metal salts thereof being reacted in the warm with diketene and the nitro groups reduced to amino groups.  Propionylacetyl and benzoylacetyl groups may replace the acetoacetyl groups.  The benzene rings may be further substituted by non-salt-forming substituents. Compounds of the above formula specified are 4-amino-41-acetoacetylamino - diphenyl - 3 - sulphonic acid, 31 - or 41 -acetoacetylamino - 4 - amino - diphenylurea - 5-sulphonic acid, 31 - acetoacetylamino - 41 - methyl - 4 - amino - diphenylurea - 5 - sulphonic acid, 31 - or 41 - acetoacetylamino - 4 - amino -3 - methyl - diphenylurea - 5 - sulphonic acid, 31 - acetoacetylamino - 4 - amino - 2 - or 3-methoxy - diphenylurea - 5 - sulphonic acid, 31- or 41 - amino - 4 - acetoacetylamino - diphenylurea - 5 - sulphonic acid, 31 - amino - 4 - acetoacetylamino - 3 - methyl - or 2 - or 3 - methoxy - diphenylurea - 5 - sulphonic acid, 31-amino - 4 - benzoylacetylamino - diphenylurea-5 - sulphonic acid, 31 - amino - 4 - propionylacetylamino - 3 - methyl - or 2 - or 3 - methoxy - diphenylurea - 5 - sulphonic acid, 1 - (31- or 41 - acetoacetylaminobenzoylamino) - 4-aminobenzene - 3 - sulphonic acid, 1 - (31 -acetoacetylamino - 41 - chloro - or methyl - or methoxy - benzoylamino) - 4 - aminobenzene-3 - sulphonic acid, 1 - (41 - acetoacetylamino - 31-methyl - benzoylamino) - 4 - aminobenzene - 3-sulphonic acid, 1 - (31 - or 41 - acetoacetylaminobenzoylamino) - 5 - methyl - or 5 - or 6-methoxy - 4 - aminobenzene - 3 - sulphonic acid, 1 - (31 - or 41 - aminobenzoylamino) - 4 - acetoacetylaminobenzene - 3 - sulphonic acid, 1 - (31-or 41 - aminobenzoylamino) - 4 - acetoacetylaminobenzene - 3 - sulphonic acid, 1 - (31 - or 41 - amino - 31 - or 41 - methylbenzoylamino)-4 - acetoacetylaminobenzene - 3 - sulphonic acid, 1 - (31 - amino - 41 - chloro - or methoxybenzoylamino) - 4 - acetoacetylaminobenzene-3 - sulphonic acid, 1 - (31 - aminobenzoylamino) - 5 - methyl - or 5 - or 6 - methoxy - 4-acetoacetylaminobenzene - 3 - sulphonic acid, 1 - (31 - aminobenzoylamino) - benzoylacetylaminobenzene - 3 - sulphonic acid, 1 - (41-amino - 31 - methylbenzoylamino) - 4 - benzoylacetylaminobenzene - 3 - sulphonic acid, 1-(31 - amino - 41 - chloro - or methoxy - benzoylamino) - 4 - benzoylacetylaminobenzene - 3 - sulphonic acid, 1 - (31 - or 41 -aminobenzoylamino) - 5 - methyl - or 5 - or 6-methoxy - 4 - propionylacetylaminobenzene - 3-sulphonic acid, 41 - (411 - or 311 - aminobenzoylamino) - 4 - acetoacetylaminodiphenyl - 3 - sulphonic acid, 41 - (311-acetoacetylamino - or 311-methyl - 411 - acetoacetylamino - benzoylamino) - 4 - amino - diphenyl - 3 - sulphonic acid, 41 - (411 - or 311 - aminophenylureido) - 4 -acetoacetylaminodiphenyl - 3 - sulphonic acid, 41 - (411 - or 311 - acetoacetylaminophenylureido) - 4 - aminodiphenyl - 3 - sulphonic acid, 41 - (311 - aminobenzoylamino or aminophenylureido) - 4 - acetoacetylamino - diphenylurea-3 - sulphonic acid, 41 - (311 - or 411 - acetoacetylaminobenzoylamino) - 4 - amino - diphenylurea - 3 - sulphonic acid, 31 - (411 -aminobenzoylamino or aminophenylureido)-4 - acetoacetylaminodiphenylurea - 3 - sulphonic acid, 4 - [41 - (311 - aminobenzoylamino) -benzoylamino] - 1 - acetoacetylaminobenzene-2 - sulphonic acid, 4 - [41 - (311 - or 411 - acetoacetylamino - 311 - or 411 - methyl - benzylamino) - benzoylamino] - 1 - aminobenzene - 2-sulphonic acid, 4 - [41 - (311 - or 411 - acetoacetylaminobenzoylamino) - benzoylamino] - 1-aminobenzene - 2 - sulphonic acid, 4 - [31 - (411 -aminobenzoylamino) - benzoylamino] - 1 -aminobenzene - 2 - sulphonic acid, 4 - [31 - (311 -acetoacetylamino - 411 - methyl - benzoylamino) - benzoylamino] - 1 - aminobenzene - 2 -sulphonic acid, 4 - [41 - or 31 - (311 - aminophenylureido) - benzoylamino] - 1 - acetoacetylaminobenzene - 2 - sulphonic acid, 4 - [41 - (311-or 411 - acetoacetylaminophenylureido)-benzoylamino] - 1 - aminobenzene - 2 - sulphonic acid and 4 - [41 - (311 - or 411 - acetoacetylamino-311 - or 411 - methyl - phenylureido) - benzoylamino] - 1 - aminobenzene - 2 - sulphonic acid.  Reference has been directed by the Comptroller to Specification 723,637.ALSO:The invention comprises metallizable trisazo dyestuffs of formula:- <FORM:0774682/IV(b)/1> which are prepared by coupling, in alkaline medium, a diazonium compound of the benzene series (A) containing a metallizable substituent in the ortho-position to the diazo group with a component (B) of formula:- <FORM:0774682/IV(b)/2> wherein "acyl" is a carbacyl radical, Q is a direct carbon linkage or a divalent bridging member of formula CONH, NH-CO or NH-CO-NH, of R1 and R2 one R is a p - phenylene - sulphonic acid radical which contains the sulphonic acid group in the meta-position to Q and the other R is a phenyl radical having the acylamino or amino group in the meta- or para-position to Q, and X1-X4 are 0 or 1 of which only one of X2 or X4 may be different from 0; further diazotising the aminomonoazo dyestuff so obtained and coupling the diazo compound in acid medium with a 1 - amino - 2 - alkoxynaphthalene compound (D) coupling para to the amino group, which may be substituted in the alkoxy group, preferably by a carboxy group, and may contain a sulphonic acid group in the 6 - or 7-position, after which the resultant aminodisazo dyestuff is diazotized and coupled in alkaline medium with a 2 - acylamino - 6 - hydroxynaphthalene - 8 - sulphonic acid (E).  All the benzene rings in the dyestuffs may be substituted by further non - salt - forming substituents.  The final coupling is preferably carried out in the presence of tertiary bases such as pyridine.  The dyestuffs dye cellulose fibres, directly or with after-coppering, in green shades. Specified components (A) are o - aminophenol, 2 - amino - 1 - hydroxy - benzene - 4 - methyl sulphone or - sulphonic acid or - sulphonic acid mono - ethyl - or diethyl - or dimethyl- or dihydroxyethyl - amide or - sulphonamide or - carboxylic acid or carboxylic acid phenyl - or diethyl - or dihydroxyethyl - amide, 2 - amino - 1 - hydroxy - 4 - methyl-or - acetylamino - benzene, 2 - amino - 1 - hydroxy - 6 - methyl - or - chloro - benzene - 4 - sulphonic acid, 2 - amino - 1 - hydroxy - 6 - chloro - or - acetylamino - benzene - 4 - methyl sulphone, anthranilic acid, 4 - or 5 - acetylamino - or 5 - succinylamino - or 4 - or 5 - methylsulphonyl - 2 - aminobenzoic acid, 2 - amino - 1 - carboxyphenyl - 4 - or 5 - carbamic acid methyl or ethyl or methoxyethyl or ethoxyethyl ester, 2 - aminobenzene - 1:4 - or - 1:5 - dicarboxylic acid, 2 - aminobenzoic acid - 4 - or 5 - sulphonic acid, 2 - aminobenzoic acid - 5 - sulphonamide or -sulphonic acid monomethylor dimethyl - or b  - hydroxyethyl - amide, and 2 - amino - 4 - or - 5 - chloro - or - 4:6 - dichloro - or - 4 - methyl - benzoic acid.  Specified components (B) (see Group IV(b)) are 4 - amino - 41 - acetoacetylamino - diphenyl - 3 - sulphonic acid, 31 - or 41 - acetoacetylamino - 4 - amino - diphenylurea - 5 - sulphonic acid, 31 - acetoacetylamino - 41 - methyl - 4 - amino - diphenylurea - 5 - sulphonic acid, 31 - or - 41 - acetoacetylamino- 4- amino- 3- methyl-diphenylurea - 5 - sulphonic acid, 31 - acetoacetylamino - 4 - amino - 2 - or - 3 - methoxy - diphenylurea - 5 - sulphonic acid (31 - or 41 - amino - 4 - acetoacetylamino-diphenylurea - 5 - sulphonic acid, 31 - amino - 4 - acetoacetylamino - 3 - methyl - or - 2 - or - 3 - methoxy - diphenylurea - 5 - sulphonic acid, 31 - amino - 4 - benzoylacetylamino - diphenylurea - 5 - sulphonic acid, 31 - amino - 4 - propionylacetylamino - 3 - methyl - or - 2 - or - 3 - methoxy - diphenylurea - 5 - sulphonic acid, 1 - (31 - or 41 - acetoacetylaminobenzoylamino) - 4 - aminobenzene - 3 - sulphonic acid, 1 - (31 - acetoacetylamino - 41 - chloro - or - methyl - or - methoxy - benzoylamino) - 4 - aminobenzene - 3 - sulphonic acid, 1 - (41 - acetoacetylamino - 31 - methyl - benzoylamino) - 4 - amino - benzene - 3 - sulphonic acid, 1 - (31 - or 41 - acetoacetylamino - benzoylamino) - 5 - methyl - or - 5 - or - 6 - methoxy - 4 - aminobenzene - 3 - sulphonic acid, 1 - (31 - or 41 - aminobenzoylamino) - 4 - acetoacetylaminobenzene - 3 - sulphonic acid, 1 - (31 - or 41 - amino - 31 - or - 41 - methyl - benzoylamino) - 4 - acetoacetylaminobenzene - 3 - sulphonic acid, 1 - (31 - amino - 41 -chloro - or - methoxy - benzoylamino) - 4 - acetoacetylaminobenzone - 3 - sulphonic acid, 1 - (31 - aminobenzoylamino) - 5 - methyl - or - 5 - or - 6 - methoxy - 4 - acetoacetylaminobenzene - 3 - sulphonic acid, 1 - (31 - aminobenzoylamino) - 4 - benzoylacetylaminobenzene - 3 - sulphonic acid, 1 - (41 - amino - 31 - methylbenzoylamin