Patent GB-305487-A (GB)
Title: Process for the manufacture of azo dyestuffs
IPC: C09B43/16
Filed: 1929-02-04
Abstract: 305,487. I. G. Farbenindustrie Akt.- Ges. Feb. 3, 1928, [Convention date]. Void [Published under Sect: 91 of the Acts]. Azo dyes are made by employing as components compounds at least one of which contains a heterocyclic structure of the general formula : (A.R1)x.R2(B)y, in which A = nitro groups or reduction stages thereof, such as the azoxy or azo groups, or the amino group or acylation products thereof; R1 = a carbocyclic ring, R2 = a heterocyclic ring joined to R, by a carbon to carbon linkage, x and y = 1 or 2, and B = a halogen atom or a residue introduced in place of the halogen atom combined with R2 through a nitrogen, oxygen, or sulphur atom. Alternatively, one or more components are employed obtained by condensing a heterocyclic, compound of the above general formula, in which A = a nitro group and B = a mobile halogen atom with a compound containing a reactive hydrogen atom attached to a nitrogen, oxygen, or sulphur atom, at least one of these compounds containing the azo groups. The nitro group in these azo dyestuffs can be further reduced to azoxy-, azo-, or amino-groups, and in the latter case diazotized, acylated, or further condensed with heterocyclic compounds. According to the components selected, dyestuffs capable of application as acid wool, mordant, or direct cotton dyestuffs and cotton dyes for subsequent treatment on the fibre are obtained. The following compounds are representative types of starting materials corresponding to the first description above :-(1) Bznitro-2-chloro-benzothiazole condensed with 1 : 4- phenylene-diamine sulphonic acid or J-acid, (2) 7-nitro-4-methyl-2-chlorquinoline condensed with H-acid, (3) 7-nitro-9-chlorophenanthridine condensed with 1: 4-phenylenediamine sulphonic acid, (4) the condensation product of 6-nitro-4- chloroquinazoline and H-acid reduced to the azoxy - compound, (5) 2-(4' - aminopbenyl) - 4 - methyl-6-chloropyrimidine obtained from the corresponding nitro-compound, (6) 2-(4<1>-nitrophenyl).4: 6-dichlorpyrimidine condensed with H-acid (1 mol.) and aniline (1 mol.) or (6a) with J-acid (2 mols.), (7) 2-(3<1>-nitrophenyl)-6-chloropyrimidine-4-carboxylic acid chloride condensed with H-acid (1 mol.) and 4-methyl-thiophenol (1 mol.), (8) 2 : 6-dichloro-4-(3<1>-nitrophenyl)- pyrimidine condensed with 5-amino-2:hydroxy-, benzoic acid (1 mol.) and aniline (1 mol.), (8a) 2-(4<1>-nitrophenyl)-4-(3<1>-nitrophenyl)-6-chloropyrimidine condensed with J- or H-acid, (9) 6-nitro- 4-chloroquinazoline condensed with 1-(3<1>-aminophenyl-5-pyrazolone-3-carboxylic acid, (10) the reduced condensation product from 6-nitro-4- chloroquinazoline and J-acid, (11) 6-nitro-2 : 4- dichloroquinazoline condensed with 5-amino-2- hydroxybenzoic acid (2 mols.) or 1 : 4-phenylenediamine-sulphonic acid (2 mols.) (c.f. Specification 288,159), (12) the reduced condensation product from 6-nitro-2 : 4-dichloroquinazoline and J- acid (2 mols.), (13) the reduced condensation product from 7-nitro-2 : 3-dichloro-quinoxaline and H-acid (1 mol.) condensed with 3-nitrobenzoyl chloride and again reduced, (13a) 7-amino-2- chloro-3-methoxyquinazoline obtained from corresponding nitro compound, (13b) 7-nitro-2 : 3-dichloroquinazoline condensed with J-acid (1 mol.) and aniline (1 mol.), (14) 2 : 4-di-(3'-nitrophenyl)- 6-chloro-1 : 3 : 5-triazine condensed with H-acid. The following are types of starting materials derived from the general formula in which A= the nitro group and B = a mobile halogen atom replaced by compounds containing a reactive hydrogen atom attached to a nitrogen, oxygen or sulphur atom, at least one of the compounds containing the azo group: (15) 2-nitro-9-chloroacridine condensed with the dye 2-amino-naphthalene-4 : 8-disulphonic acid # 3-toluidine, (16) 6-nitro-2 : 4-dichloroquinazoline condensed with the dye 4-aminotoluene-3-sulphonic acid # acetoacetyl-4-aminoanilide (1 mol.) and 5- sulpho-3-aminobenzoic acid (1 mol.), (17) 6-nitro- 2 : 4-dichloroquinazoline condensed with 4<1>- amino-4-hydroxyazobenzene-3-carboxylic acid (1 mol.) and dimethylamine (1 mol.). The following examples are specified : (1) The monoazo dyes 6-chloro-4-methyl-2-(4<1>-aminophenyl) - pyrimidine (type 5) # 1-(2<1>-sulphophenyl)-3-methyl-5- pyrazolone, Bz-amino-3-methoxy-2-ehloroquinoxaline (type 13a) # 1-(2<1>-chloro-5<1>-sulphophenyl)-3-methyl-5-pyrazolone and the reduced condensation product from 6-nitro-4-chloroquinazoline and J-acid (type 10) # acetoacetyl-2- anisidide monosulphonic acid. An orange red is. obtained when the latter is deveoped on the fibre with 4-nitro-diazobenzene. (2) The dyestuff aniline-2 : 5-disulphonic acid # 1-aminonaphthalene # 1-amino-2-ethoxynaphthalene-7-sulphonic acid is diazotized and coupled with the reduced condensation product from 2-chloro- 4 : 6<1>-di-(3<1>-nitrophenyl)-1:3:5-triazine (type 14). When tetrazotized on the fibre and de-- veloped with 3-methyl-1-phenyl-5-pyrazolone a green is obtained. The condensation product may be replaced by one of type (8a). The same dyes can be obtained by coupling the unreduced condensation products and afterwards reducing the nitro groups. Diazotized di-(2: 3<1>-methyl)- 4<1>-aminoazobenzene-4-sulphonic acid is coupled with product (type 10) and the resulting dyestuff diazotized on the fibre and developed with #- naphthol. The monoazo dyestuff 4 : 6-dinitro-2- aminophenol # condensation product (type 4) may be afterchromed. Other o-hydroxy- or ocarboxy-diazo compounds may be used. The secondary disazo dyestuffs H-acid # 3-amino- 4-cresol-ethylether # condensation product (type 14) and 4-amino-acetanilide-3-sulphonic acid # 1-amino-2-ethoxynaphthalene - 6 - sulphonic acid # condensation product (8a) give even dyeings on viscose. The condensation product. from 2 - chloro - 4 : 6-di-(3<1>-nitrophenyl)- 1: 3 : 5-triazine and 1: 4-phenylenediaminesulphonic acid (type 14) is reduced to the triamino compound, diacetylated, diazotized and coupled with 2 : 8 : 6-acid or 2-methylaminonaphthalene- 7-sulphonic acid. (3) The trisazo dye, reduced condensation product (type 11) from 6-nitro-2 : 4- dichloroquinazoline and 5-amino-2-hydroxybenzoic acid (2 mols.) # 1 amino-naphthalene-6- sulphonic acid # 1-amino-naphthalene-6-sulphonic acid # phenyl-J-acid gives a pure blue on cotton when after coppered. The first component may be replaced by condensation product (type 8). The trisazo dye, reduced condensation product from 6-nitro-4-chlorquinazoline and 3- amino-2-hydroxybenzoic acid (type 10) # 1- aminonaphthalene-7-sulphonic acid # 1-aminonaphthalene-7-sulphonic acid # condensation product from 2 : 4-dichloroquinazoline and J acid- (1 mol.) and 5-aminq-2-hydroxybenzoic acid (1 mol.) gives a blue when after coppered. The monoazo dye, condensation product from 6-nitro-2 : 4- dichloroquinazoline, 1 : 4-phenylene-diaminesulphonic acid (1 mol.) and 5-amino-2-hydroxybenzoic acid (1 mol.) # 2-methylaminonaphtlialene-6-carboxylic acid is reduced to the aminoazo dye and treated with phosgene. Triesazo dyes are obtained by hexazotizing the reduced condensation product from 6-nitro-2 : 4-dichloroquinazoline with 1: 4-phenylenediaminesulphonic acid (2 mols.) (type 11) and coupling with 1 : 3- phenylenediamine (3 mols.). When developed with p-nitrodiazobenzene blackish brown shades are obtained. (4) The dye H-acid # 3-amino- 4-cresolmethylether is diazotized and coupled with the reduced condensation product (type 6). O - acetyl- or O-toluenesulphonyl-H-acid may also be used as first components. Green trisazo dyes are obtained when the aminodisazo product is diazotized and coupled with 1-(2<1>-carboxyphenyl)-3-methyl-5-pyrazolone. The condensation product may be replaced by that obtained by condensing 2-(4<1>-nitrophenyl)-4 : 6-dichloropyrimidine with H acid (1 mol.) and replacing the remaining chlorine atom by hydroxyl by means of caustic soda. The H-acid may be replaced by 1 - amino-8-hydroxynaphthalene-4 : 7-disulphonic acid, the second component by 3-amino-4-cresolethyl or oxyethylether or the sulphuric acid ester thereof and the end component by acetoacetic acid anilide-4-carboxylic acid or 1-phenyl-3- methyl-5-pyrazolone (on the fibre). The nitro condensation products may also be coupled and the nitroazo compounds reduced to the aminoazo dyestuffs. The reduced condensation product (type 6) is diazotized and coupled with 1- (2<1>-sulphophenyl)-3-methyl-5-pyrazolone, acetoacetic-o-anisidide sulphonic acid or methylketol sulphonic acid and the resulting dyestuff coupled with the diazotized dye O-acetyl H acid # 3- amino-4-cresol-ethylether or a-naphthylamine. The trisazo dye 3-amino-2-hydroxybenzoic acid # alpha-naphthylamine # reduced condensation product (type 6) # 1-(5<1>-carboxy-4<1>-hydroxy- 3<1>-sulphophenyl)-3-methyl-5-pyrazolone gives a green when after coppered. The reduced condensation product (type 6a) is coupled with 3- diazo-phenyloxamic acid (2 mols.). (5) The dye H acid (or O-acetyl-H-acid)#3-amino-4-cresolmethylether # reduced condensation product (type 7) gives a blue when developed with 1- phenyl-3-methyl-5-pyrazolone. The trisazo dye 3-chloro-2-amino-1-methylbenzene - 5 - sulphonic acid # 1-amino-2-ethoxynaphthalene-6-sulphonic acid # reduced condensation product (type 7) # 1-(3<1>-carboxyphenyl)-3-methyl-5- pyrazolone is a direct green. (6) The monoazo dye, saponified condensation product from 6- nitro-2-chlorobenzothiazole and 4-oxalylamino-1- aminobenzene-3-sulphonic acid (type 1) # salicylic acid is reduced, diazotized and coupled with 1 - (4<1>-hydroxy-3<1>-carboxyphenyl)-3-methyl - 5 - pyrazolone when a yellow dye is obtained on after treatment with copper salts. The first component may be replaced by condensation product (type 3). A yellowish red is obtained with the monoazo dyestuff, reduced condensation product from 6-nitro-2-chlorobenzothiazole and J acid (1 mol.) (type 1) # 5: 5<1>-dihydroxy-2 : 2-dinaphthylurea-7