Patent GB-453437-A (GB)
Title: Improvements in the manufacture and production of azo dyestuffs
IPC: C09B62/447
Filed: 1935-03-07
Abstract: Azo dyestuffs are manufactured by choosing such coupling components and diazo compounds that the molecule of the dyestuff contains at least one sulphonic acid group and at least one basic group of the general formula <FORM:0453437/IV/1> where R1 and R2 may be identical or different and may be hydrogen or alkyl, cycloalkyl, hydroxyalkyl or aralkyl radicles, or <FORM:0453437/IV/2> may be a saturated ring system, and X is an aliphatic radicle combined with an aromatic nucleus of the dyestuff molecule either directly or by means of a non-basic bridge, e.g. --O--, --S--, --CO--, --SO2--, --O--CO--, --NH--CO--, --SO2--NH or --CO--NH.  Alternatively, at least one such basic group may be introduced into a dyestuff containing a sulphonic group but preferably not yet containing a basic group of the kind described, e.g. by reacting the amino group of an aminoazo dyestuff with chloracetyl chloride and treating the product with a dialkylamine or piperidine, or by reacting a hydroxyazo dyestuff in the form of its alkali salt with a 1 : 2-dihalogenethane and treating the resulting ether with an amine containing at least one reactive hydrogen atom.  If the coupling component employed contains an amino group, the monoazo dyestuff may be diazotized and coupled to produce a disazo dyestuff.  When the dyestuffs contain metal complex forming groups, they may be converted in substance or on the fibre into their complex metal compounds.  In examples: (1) 4 - methyl - 3 - aminophenyl - 1 - o  - (diethylamino) - ethyl sulphone (obtainable by saponifying the acetyl group of the product of Example 5 of Specification 453,443) is diazotized and coupled with 1 - (4<1> - sulphophenyl) - 3 - methyl - 5 - pyrazolone, 1 - (3<1> - chloro - 5<1> - sulphophenyl) - 3 - methyl - 5 - pyrazolone, 2 - hydroxynaphthalene - 6 - or 8 - sulphonic acid or 3 : 6- or 6 : 8-disulphonic acid, 1-benzoylamino - 8 - hydroxynaphthalene - 4 : 6 - disulphonic acid or 2-amino-8-hydroxynaphthalene-3 : 6-disulphonic acid; the products dye wool, silk and leather; the diazo component may be replaced by p-aminophenyl-o -ethyl-aminoethyl sulphone, m- or p-amino-o -(dimethylamino) or (diethylamino)-phenetol, p-aminobenzyldimethylamine or -diethylamine, or the corresponding dibutyl-, dihexyl-, dicyclohexyl- or dodecylamino or piperidino compounds; (2) 4-methyl-3-aminophenyl-1-o -(diethylamino)-ethyl sulphone is diazotized and coupled with 1 - (2<1> - hydroxy - 3<1> - carboxy - 5<1> - sulphophenyl) - 3 - methyl - 5 - pyrazolone; the product dyes wool yellow shades and may be chromed in substance or on the fibre yielding redder shades; (3) p-toluidine, sulphanilic acid, 4<1> - aminoazobenzene - 4 - sulphonic acid, 1 - methyl - 3 - amino - 6 - chlorobenzene - 4 - sulphonic acid or 1 - aminonaphthalene - 2 - sulphonic acid is diazotized and coupled with 2 - (dimethylaminoacetyl) - amino - 8 - hydroxynaphthalene - 6 - sulphonic acid or 1 - or 2 - (dimethylaminoacetyl) - amino - 8 - hydroxynaphthalene - 3 : 6 - disulphonic acid; (4) the dyestuff p-toluidine --> 1-amino-2-methoxynaphthalene-6-sulphonic acid is treated with chloracetyl chloride followed by dimethylamine; the product dyes wool red shades; (5) p-nitraniline is diazotized and coupled with 1 - amino - 8 - naphthol - 3 : 6 - disulphonic acid and the product is coupled with diazotized m - amino - o  - diethylaminophenetol; the first diazo - component may be replaced by o - nitraniline, p - nitro - o - anisidine, p - chloraniline or 2 : 5 - dichloro - 4 - nitraniline, and the second by p-amino-o -diethylaminophenetol, p - aminobenzyldiethylamine, 4 - methyl - 3 - aminophenyl - 1 - o  - (diethylamino) - ethyl sulphone or 4 - methoxy - 3 - aminophenyl - 1 1 o  - (dimethylamino) - ethyl sulphone; (6) diazotized aniline is coupled with the urea of 2 - amino - 5 - naphthol - 7 - sulphonic acid and the product is coupled with diazotized 4 - methyl - 3 - aminophenyl - 1 - (o  - diethylamino) - ethyl sulphone or one of the other amines described in (1); the products dye cotton and viscose artificial silk; (7) diazotized 4 - methyl - 3 - aminophenyl - 1 - o  - (diethylamino) - ethyl sulphone is coupled with 1-amino-2 - methoxynaphthalene - 6 - sulphonic acid; the product may be acetylated, or a dimethylaminoacetyl group may be introduced by the process of (4); (8) 4-hydroxy-3-amino-1-o -(diethylamino)-ethyl sulphone (prepared by demethylating the corresponding methoxy compound) is diazotized and coupled with 2 - hydroxynaphthalene - 6 - sulphonic acid; the product dyes wool orange-red shades, and may be chromed on the fibre or in substance, yielding bordeaux-red shades; (9) the potassium salt of 2-methyl-3-aminophenyl-1-o -(diethylamino) - ethyl sulphone - 5 - sulphonic acid (prepared by sulphonating 2-methyl-3-aminophenyl - 1 - o  - (diethylamino) - ethyl sulphone) is diazotized and coupled with 1-phenyl-3-methyl-5-pyrazolone, b -naphthol or 2-acetylamino - 8 - naphthol - 6 - sulphonic acid; (10) diazotized sodium sulphanilate is coupled with 3 - (2<1> : 3<1> - hydroxynaphthoyl) - amino - 4 - methoxyphenyl - 1 - o  - (diethylamino) - ethylsulphone or 4 - (2<1> : 3<1> - hydroxynaphthoyl) - amino - 6 - benzyldiethylamine; (11) 4 - amino phenyl - 1 - o  - (diethylamino) - ethyl sulphone is diazotized and coupled with the sodium salt of 2-hydroxynaphthalene-6 : 8-disulphonic acid; (12) 3-amino-4-methoxyphenyl-1-o -(diethylamino)-ethyl sulphone is diazotized and coupled with 1-hydroxynaphthalene-4-sulphonic acid sodium salt, 1-(2<1>-chloro-5<1>-sulphophenyl)-or 1 - (4<1> - sulphophenyl) - 3 - methyl - 5 - pyrazolone or 1 - benzoylamino - 8 - naphthol - 4 : 6 - disulphonic acid; (13) 3 - amino - 4 - methyl - 5 - nitrophenyl - 1 - o  - (dibutylamino) - ethyl sulphone (obtainable by reducing the corresponding 3 : 5-dinitro compound) is diazotized and coupled with 2 - amino - 8 - naphthol - 6 - sulphonic acid; (14) p - amino - o  - diethylaminophenetol is diazotized and coupled with 1 - aminonaphthalene - 7 - sulphonic acid, and the product is diazotized and coupled with 1 - phenylaminonaphthalene - 8 - sulphonic acid; the diazo component may be replaced by other amines containing external basic groups, e.g. 4-aminobenzyldimethylamine, 3 - amino - 4 - methyl - or methoxyphenyl - 1 - o  - (dimethylamino) - ethyl sulphone, or the corresponding diethyl compounds, the first coupling component by 1-aminonaphthalene-6-sulphonic acid or a mixture thereof with the 7-acid, or, when the diazo component contains a sulphonic acid group, by a -naphthylamine, and the second coupling component by 1-(4<1>-methylphenyl) - aminonaphthalene - 8 - sulphonic acid; (15) diazotized sulphanilic acid is coupled in an alkaline or acetic acid medium with 2 - amino - 8 - naphthol - 6 - o  - (diethylamino) - ethyl sulphone.  Intermediates containing a basic group of the kind defined above may be prepared by the following methods: (a) p-(dimethylamino ethyl)-aniline is obtainable by converting p-nitrophenylethyl alcohol by means of thionyl chloride into p-nitro-o -chlorethylbenzene, reacting this with dimethylamine and reducing the nitro group; (b) mono-o -(dimethylamino)-acetyl-m-phenylene diamine is obtainable by reacting m-nitraniline with chloracetyl chloride, condensing the product with dimethylamine and reducing the nitro group; (c) m-amino-o -ethylaminoacetophenone is obtainable by reacting m - nitro - o  - chloracetophenone with ethylamine and reducing the nitro-group; (d) 1 - bromo - 2 - (diethylamino) - ethane may be reacted with p-acetaminothiophenol to form the corresponding sulphide, which may be saponified to form the amine or may be first oxidized to the corresponding sulphone and then saponified; (e) 2-amino-8-hydroxy naphthalene-6-sulphonic acid may be reacted with chloracetyl chloride or a chloropropionic acid chloride and the product condensed with piperidine, dimethylamine or other nitrogen bases having at least one reactive hydrogen atom; 1 - (dimethylaminoacetyl) - amino - 8 - hydroxynaphthalene - 3 : 6 - disulphonic acid may be similarly prepared; (f) 2 : 3 - hydroxynaphthoic acid o  - (diethylamino) - ethylamide is obtainable by reacting 2 - acetoxy - 3 - naphthoic acid chloride with N-diethylethylenediamine and splitting off the acetyl group; (g) pyrazolones and acetoacetyl, benzoylacetyl or 2 : 3-hydroxynaphthoyl derivatives may be prepared by known methods from the amines described above; (h) m- and p-amino-o -(dimethylamino)- and (diethylamino)-phenetol are obtainable by reacting m- or p-nitrophenol respectively with 1 : 2-dibromethane, condensing the ethers with dimethylamine or diethylamine respectively, and reducing the nitro group; (i) 2 - amino - 8 - naphthol - 6 - o  - (diethylamino)-ethyl sulphone is obtainable by converting 2 - acetylamino - 8 - naphthol - 6 - sulphonic acid by means of phosphorus pentachloride into its sulphochloride, reducing this with zinc dust in aqueous solution to the corresponding sulphonic acid, treating the sodium salt of this with b -chlorethyldiethylamine in the presence of sodium alcoholate, and saponifying the acetylamino group.