Patent GB-510453-A (GB)
Title: Manufacture of new dyestuffs of the azo-series and of the amino-anthraquinone series
IPC: C09B1/26
Filed: 1938-02-02
Abstract: 510,453. Dyes. SOC. OF CHEMICAL INDUSTRY IN BASLE. Feb. 2, 1938,' Nos. 3254. 3255, and 3256. Convention dates, Feb. 3, 1937, Feb. 20, 1937, and April 8. 1937. [Classes 2 (iii) and 15 (ii)] Azo dyes; aminoanthraquinones.-New dyestuffs of the azo and aminoanthraquinone series are obtained by reaction of a thiosuiphate with dyestuffs of these series containing an exchangeable halogen atom attached to an aliphatic residue of at least 2 carbon atoms. Alternatively, in the case of the azo dyes, the thiosulphate may first react with a suitable component containing the group N <<R1># wherein R1 represents hydrogen, alkyl or a hydroxyalkyl or polyhydroxyalkyl radicle, which may be etherified or esterified and R2 represents a halogenated aliphatic radicle containing at least 2 carbon atoms and the product be then converted into an azo dyestuff by diazotizing and coupling with a component or by coupling with a diazo component. The alkyl radicles R1 include such as contain oxygen bridges or substituents such as CN, halogen or SO 3H and the aliphatic radicles R 2 may be substituted, e.g., by OH, O-alkyl or halogen. Numerous N-#-thiosulphuric acid derivatives of ethylaniline and its substitution products are specified as intermediates. There may also be used intermediates containing the groups O-alkylene-S.SO 3H, wherein the alkylene group contains at least 2 carbon atoms, -NH.CO.CH2S.SO3H, -CO. NH.CR2.CH2.S.SO3H or -NH.CO.NH.CH2. CH2.S.SO3H. In examples, (1) diazotized 4 - nitraniline, (2) 2 - chloro - 4 - nitraniline and (3) 2 4-dinitraniline are coupled with N-ethyl - # - thiosulphuric acid - ethylaniline or N ethyl - y - thiosulphuric acid - # - hydroxypropylaniline to obtain dyestuffs which dye acetate artificial silk from an aqueous Glauber salt bath ; (4) diazotized 2-cyano- 4 - nitraniline, 4 - nitraniline - 2 - methylsulphone, 2 : 4 - dinitraniline substituted in 6-position by halogen, cyano, methoxy, alkyl, hydroxy or methylsulphone, 2 - cyano - 4 - nitraniline substituted in 6-position by halogen and 2 : 6 - dichloro - 4 - nitraniline are each coupled with N - ethyl - # - thiosulphuric acidethylaniline to obtain dyestuffs suitable for dyeing or printing acetate artificial silk; (5) diazotized 4 - methoxyaniline is coupled (acid) with 3 - aminophenol and the product is treated successively with chloracetyl chloride in boiling glacial acetic acid in presence of anhydrous sodium acetate and with sodium thiosulphate in boiling aqueous acetone to obtain a dyestuff for acetate artificial silk ; (6) the 4 - (y - chloro - # - hyclroxypropyl) amino derivative of 1 - methylamino - or 1 - anilino - anthraquinone - the 4 - (# - chlorethyl)amino derivative of 1 - amino - or - # - hydroxyethylamino - anthraquinone, 1 - # - chlorethylamino - anthraquinone and 1 : 4 - di - (# - chlorethylamino) - 5 : 8 - dihydroxyanthraquinone are each heated for 5 hours in a closed vessel at 100-120C. with sodium thiosulphate in aqueous acetone to obtain dyestuffs for acetate artificial silk; (7) 1-amino-4- methylamino - anthraquinone, (8) 1 - amino - 4.- phenylamino - anthraquinone, and (9) 1 : 4- diaminoanthraquinone or 1 - amino - 4 - (4<1> - aminophenyl)amino-anthraquinone are treated successively with epichlorhydrin in glacial acetic acid and with sodium thiosulphate in aqueous acetone under pressure to obtain dyestuffs for dyeing and printing animal fibres and acetate artificial silk ; (10) acetate artificial silk is dyed a pure scarlet by treatment for 1 hour in an aqueous bath at 80C. containing sodium sulphate and the first dyestuff of (1) above ; (11) wool is dyed a pure deep blue by treatment for 1 hour in an aqueous bath at 95-100C. containing sodium sulphate, formic acid and the first dyestuff of (9) above ; (12) acetate artificial silk is printed with an aqueous paste containing the dyestuff of (7) above and gum thickening, with, or without urea, dried, steamed and rinsed to obtain a brilliant blue pattern; (13) chlorinated wool is printed with an aqueous paste containing the dyestuff of (7) above, glycerol, gum thickening and tartaric acid, dried, steamed and rinsed to obtain a brilliant blue pattern. Specification 447,661 is referred to. The Specification as open to inspection under Sect. 91 comprises also the similar production of other dyestuffs, e.g., of the indigoid, oxazine and thiazine series, containing the group -S.SO3H. This subjectmatter does not appear in the Specification as accepted. N - Ethyl - # thiosulphuric acid - ethylaniline is obtained by reaction of N - (ethyl- # - bromethyl) - aniline with sodium thiosulphate in boiling aqueous acetone. 2 - Cyano - 4 - nitranilines substituted in 6-position by chlorine or bromine are obtained by the action of chlorine or bromine on the product obtained by the action of ammonia under pressure on 1 - chloro - 2 - cyano - 4 nitrobenzene which is obtained by treating diazotized 1 - chloro - 2 - amino - 4 - nitrobenzene with cuprous cyanide. 4 - Nitraniline - 2 - methylsulphone is obtained by the action of ammonia under pressure on 1 - chloro - 4 - nitrobenzene - 2 - methylsulphone obtained by reaction of methyl bromide with the sodium salt of the sulphinic acid resulting from the reduction of 1 - chloro - 4 - nitrobenzene - 2 - sulphonic acid chloride, e.g., with sodium sulphite. 2: 4 - Dinitraniline - 6 - methylsulphone is obtained by the action of ammonia on 1- methoxy 2 : 4 - dinitrophenyl - 6 - methylsulphone obtained by nitration of the corresponding 4 - nitro compound resulting from the treatment of 1 - chloro - 4 - nitrophenyl - 2 - methylsulphone with methyl alcohol and potassium hydroxide.