Patent GB-315451-A (GB)
Title: Process for the manufacture of dis- and poly-azo dyestuffs
IPC: C09B43/16
Filed: 1928-04-11
Abstract: 315,451. Carpmael, A., (I. G. Farbenindustrie Akt.-Ges.). April 11, 1928. Samples furnished. Azo dyes for cotton are made by condensing a heterocyclic compound having only two successively replaceable halogen atoms and containing no residue attached to the carbon atoms of the heteronucleus by means of nitrogen, sulphur, or oxygen, with an aminoazo compound (formed before or after the condensation) and with a compound coupled with a diazo compound (the said coupling being effected before or after the condensation), the two condensations being effected in either sequence. The following examples are given (1) The condensation product from 2 :4-dichloroquinazoline, H acid and the saponified dyestuff 4-aminophenyloxamic acid # 3-methoxy-2-hydroxy benzoic acid is coupled with the diazotized dyestuff H acid # 3-amino-4- cresol ethylether or with diazotized p-toluidine (2) The condensation product from 2 : 4-dichloroquinazoline, H acid and 4-aminophenyloxamic acid is coupled with the diazotized dyestuff 1-amino-8-naphthol-4 : 7-disulphonic acid #3-amino-4-cresol hydroxyethylether and the saponified product diazotized and coupled with acetoacetic acid o-chloranilide mono sulphonic acid (Specification 307,531) or 3-methyl-1-phenyl- 5-pyrazolone (on the fibre). Alternative methods for preparing the same dyestuff are also given. (3) The condensation product from 2 : 4-dichloroquinazoline, J acid and the saponified aminoazo product 4-aminoacetanilide # a pyrazolone (especially 1 - (2<1>-sulphophenyl) - 3 - methyl-5-pyrazolone) is coupled with diazodisazo compounds, e.g. that from aniline-2 : 5-disulphonic acid # 1-naphthylamine-7-sulphonic acid # 1-naphthylamine. The quinazoline may be replaced by other heterocyclic compounds, e.g. 1 : 4-dichlorophthalazine. (4) The condensation product from 4 - methyl - 2 : 6 - dichloro - pyrimidine, 4 - amino - 4<1> - hydroxyazobenzene-3'- carboxylic acid and H acid (which gives a red dyestuff with diazosulphanilic acid) is coupled in presence of pyridine with diazotized aminoazo compound H acid # 3-amino-4-cresol ethylether. The latter components may be replaced respectively by the 4: 7-(or 6-)-disulphonic acid, 5 : 7-disulphonic acid, 4- or 6 - mono - sulphonic or 4 - sulpho - 6 - carboxylic acid of 1 - amino - 8 - naphthol and the sulphuric acid ester of 3-amino-4-cresolhydroxyethyl ether (Specification 266,940), 3-amino-4- cresolmethyl ether and #-(2-amino-4-methylphenoxy)-propionic acid; other aminoazo compounds mentioned are aniline-2-sulphonic acid (or 4-aminoacetanilide-3-sulphonic acid) # anaphthylamine and 2-naphthylamine-8-sulphonic acid (or O-methyl-H-acid) # a-naphthylamine ; the above condensation products may be replaced by that from 4-methyl-2 : 6-dichloropyrimidine, 1-amino-8-naphthol-3 : 5-disulphonic acid and the reduced dyestuff 5-nitro-2-anisidine # ocresotinic acid. (5) 2 : 4-Dichloroquinazoline is condensed with the saponified dyestuff 5-sulpho- 3-aminobenzoic acid # 2-anisidine-#-methanesulphonic acid (1 mol.) and the aminotrisazo dyestuff aniline - 2 : 5 - disulphonic acid # 1- naphthylamine-7-sulphonic acid # 1-naphthylamine # J acid (1 mol.)) (6) The saponified condensation product from 2 : : 4-dichloroquinazoline, the trisazo dyestuff aniline-2 : 5-disulphonic acid # 1-naphthylamine-7-sulphonic acid # 1- naphthylamine-7-sulphonic acid # J acid and 4-aminophenyloxamic acid is diazotized and coupled with 1 - (2<1>-carboxy-5<1>-chlorophenyl)-3- metbyl-5-pyrazolone. (7) The condensation product from 4-methyl-2 :6-dichloropyrimidine, H acid and 4-amino-4<1>-hydroxyazobenzene-3<1>-carboxylic acid is coupled with the diazotized aminoazo compound 3-amino-2-hydroxybenzoic acid # a-naphthylamine or 4-amino-1 : 3-xylene-5-sulphonic acid # 1-amino-2-naphtholethylether- 6-sulphonic acid. (8) The condensation product from dichloroacetoguanamide, H acid and 4- amino - 4<1> - hydroxyazobenzene-3<1>-carboxylic acid (which gives a red dyestuff with diazotized aniline) is coupled in pyridine with the diazotized aminoazo compound H acid # 3-amino-4- cresolmethylether ; other aminoazo compounds specified are 4-toluidine-3-sulphonic acid # 1- amino-2-ethoxynaphthalene-6-sulphonic acid, 3- amino-2-hydroxybenzoic acid # alpha-naphthylamine, and 2 - amino-4<1>-hydroxy-3<1>-carboxydiphenylsulphone-4-sulplonic acid # a-naphthylamine. (9) The reduced condensation product from 2 - chlorohyridine - 5 - carboxylic acid, J and 3-nitro-1-monomethylaniline is coupled with the diazotized aminodiazo compound aniline- 2-sulplionic acid # 1 - naphthylamine-7-sulphonic acid # 1-amino-2-ethoxynaphthalene-6- sulphonic acid: the product may be diazotized and developed with 3-methyl-1-phenyl-5-pyrazolone. (10) The reduced condensation product from dichloroacetoguanamide, H acid and 3- nitraniiine is coupled with the diazotized aminoazo compound 4 : 5 - dichloraniline-2-sulphonic acid # 1-amino-2-ethoxynaphthalene - 6 - sulphonic acid and the product diazotized on the fibre and developed with 3-methyl-1-phenyl-5- pyrazolone. (11) The condensation product from dichloroacetoguanamide, J acid and 4-amino-51- methyl-4<1>-hydroxyazobenzene-3<1> carboxylic acid is coupled with diazotized picramic acid. (12) The condensation product from dichloroacetoguanamide, 4 - amino - 2 sulpho-4<1>-hydroxyazobenzene-3<1>-carboxylic acid and 1 - (31-aminophenyl)-3-methyl-5-pyrazolone is coupled with diazotized 3-amino-2-hydroxybenzoic acid. Some of the above dyestuffs may be after coppered. Specification 309,102 also is referred to. Heterocyclic compounds also mentioned as suitable for the above condensations are,: alpha : # dichloroquinoline, 2-chloroisatin-5-carboxylic acid chloride (made from 2-chlorisatin-5-carboxylic acid and phosphorus pentachloride), 9-chloroacridine sulphochloride (from 9-hydroxyacridine, chlorsulphonic acid and phosphorus pentachloride), trichloropurine, trichloropyrimidine, 4- phenyl-2 : 6-dichloropyrimidine (obtained from benzoylacetic ester and urea, the 4-phenyl-2 : 6- dihydroxypyrimidine being chlorinated with phosphorus pentachloride), 2 - chloropyrimidine - 4<1>- sulphochloride (obtained from 1 : 8-diaminonaphthalene-4-sulphonic acid and phosgene, and then phosphorus pentachloride), dichlorobenzopyridazine (prepared from the dioxy compound and phosphorus pentachloride), 4-phenyl-2-chloroquinazolinesulphochloride (obtained from 4- phenyl-2-oxyquinazoline and phosphorus pentachloride and treating the product obtained with chlorsulphonic acid), 2-phenyl-(3<1>-carboxylic acid chloride)-4-chloroquinazoline (prepared by oxidizing 2 - (3<1> - methylphenyl)-4-hydroxyquinazoline, made from anthranilic acid and m-tolunitrile, with potassium permanganate to form 2-(3'-carboxyphenyl)-4-hydroxyquinazoline and treating this with phosphorus pentachloride), 4 : 4<1>-dichloro-6 : 6<1>-diphenylÀ1 : 1<1> : 3 : 3<1>-bisdiazine (prepared by heating 4 : 4<1>-diaminodiphenyl-3 : 3<1>-dicarboxylic acid with formamide and treating the 4 : 4<1>-dihydroxy - 6 : 6<1> - diphenyl-1 : 1<1> : 3 : 3<1>-bisdiazine formed with phosphorus pentachloride), 2 : 4 : 7 - trichloroquinazoline (by heating the quinazoline obtained from 4-chloro-2-aminobenzoic acid and urea with phosphorus pentachloride), 2 : 4- dichlora-5 : 7-dibromoquinazoline (obtained similarly from 4 : 6-dibromo-2-aminobenzoic acid, urea and phosphorus pentachloride), 1-phenyl-(4<1>- carboxylic acid chloride)-4-chlorophthalazine (prepared by oxidizing 4-methyl-1 : 11-benzophenone- 2<1>-carboxylic acid to form benzophenone-2<1> : 4- dicarboxylic acid, acting on the latter with hydrazine to form the hydrazine salt of 1-phenyl- (4' - carboxylic acid) - hydroxyphthalazine, and treating this with phosphorus oxychloride to form 1-phenyl-(4<1>-carboxylic acid)-4-chlorophthalazine, which is converted into the acid chloride with thionyl chloride), 2-chloroquinoxaline-3-carboxylic acid chloride (obtained by treating with phosphorus pentachloride the 2-oxyquinoxaline-3-carboxylic acid obtained from 1 : 2-diaminobenzene and mesoxalic acid), 2 : 3-dichloroquinoxaline-6- carboxylic acid chloride (obtained similarly from 2 : 3-dioxyquinoxaline-6-carboxylic acid made from 3 4-diaminobenzoic acid and oxalic acid ethyl ester), 2 : 4-dichlorocopazoline (from the corresponding oxy compound and phosphorus pentachloride), 2 : 4-dichlorobenzo - 10 - monazine-1 : 3- diazine (obtained from the corresponding 2 : 4- dioxycompound or 2 : 4-diketo-1 : 2 : 3 : 4-tetrahydro-1 : 3-quinolinediazine and phosphorus pentachloride) and 2 : 4 - dichloro-1 : 3-diazine-5 : 8- diazine (obtained from alloxazine and phosphorus pentachloride). The heterocyclic compounds referred to in the examples are made as follows : 1 : 4-dichlorophthalazine (from the corresponding dioxycompound and phosphorus pentachloride), 4- methyl-2 : 6-dichloropyrimidine (from acetoacetic ester and urea, chlorination being effected with phosphorus oxychloride), dichloracetoguanamide (by action of the chlorides of phosphorus on acetoguanamide) and 2-chloropyridine-5-carboxylic acid chloride (from 2 - hydroxypyridine-5-carboxylic acid and phosphorus pentachloride). 4 : 6-Dibromo-2-aminobenzoic acid is made by oxidizing 4 : 6-dibromisatin with hydrogen peroxide. 4 : : 6-Dibromisatin is made by transforming 3 : 5-dibromaniline into dibromoisonitrosoacetanilide, converting this into the corresponding #-imine of isatin and splitting off the imino group. 1 - Amino-8-naphthol-4-sulpho-6-carboxylic acid is obtained from 2-naphthylamine-4 : 8-disulphonic acid by diazotization, conversion into the nitrile, saponification, nitration, reduction and fusion with caustic potash. #-(2-Amino-4-methylphenox)-propionic acid is made from 4-methyl-2-nitrophenol and #-chloropropionic acid and reducing. 1- (2<1>- Carboxy-5<1>-chlorophenyl)-3-methyl-5-pyrazolone is made from 2-hydrazine-4-chlorobenzoic acid (obtained by reducing diazoti