Patent GB-416778-A (GB)
Title: New azo dyes and application thereof
IPC: C09B29/20
Filed: 1933-02-14
Abstract: Azo dyes; acid wool dyes and substantive dyes, dyeing with.--Azo dyes are manufactured by coupling a diazo component free from solubilizing groups with a 2 : 3-hydroxynaphthoic arylamide of the formula <FORM:0416778/IV/1> where Ar represents an aromatic residue of the benzene series which may carry non-solubilizing substituents, e.g. halogen, alkyl or alkoxy, X represents --S-- or --O--, Y represents --CH2--, --CH Alkyl-- or --C(Alkyl)2--, R represents hydrogen or alkyl and Z represents NH2 or a group readily converted into NH2, Z being in the o-position to the --X--Y--COOR grouping, and the groups Z and COOR being subsequently converted if necessary into NH2 and COOH respectively.  When R is alkyl and Z is a nitro group, the hydrolysis of the COOR group may be carried out during the process of reducing the nitro group by aqueous sodium sulphide solution, excess of which serves as a hydrolysing agent.  Textile fibres are dyed with the products which are, if desired, lactamized on the fibre by treatment with dilute mineral acid.  In examples: (1) 5-chloro-o-toluidine (or 2 : 5-dichloroaniline, 5-nitro-o-anisidine, 4 - benzoylamino - 2 : 5 - dimethoxyaniline or dianisidine) is diazotized and coupled with the sodium salt of 2-amino-4-(2<1>-3<1>-hydroxynaphthoylamino) - phenylthioglycollic acid; (2) wool or silk is dyed scarlet with the product of (1) from 2 : 5-dichloroaniline, in the presence of acetic acid, the dyeing being treated with dilute mineral acid, e.g. \baN/10\be hydrochloric acid; (3) 4-benzoylamino-2 : 5-dimethoxyaniline is diazotized and coupled with the p-thioglycollic acid of the m-aminobenzoyl-m-aminoanilide of 2 : 3-hydroxynaphthoic acid; (4) wool or silk is dyed blue with the product of (3) by a process similar to that of (2); (5) 2 : 5-dichloroaniline is diazotized and coupled with 2 - nitro - 5 - (2<1> : 3<1> - hydroxynaphthoylamino) - phenylthioglycollic acid and the product is reduced by means of sodium sulphide; (6) the product of (5) is obtained by reducing the coupling component before coupling; (7) wool is dyed yellowish scarlet with the product of (5) and (6) in the presence of ammonium acetate and the dyeing is lactamized; (8) 6 - chloro - 2 - toluidine is diazotized and coupled with the methyl ester of 2 - nitro - 4 - (2<1> : 3<1> - hydroxynaphthoylamino) - phenylglycollic acid and the product is reduced and hydrolysed by means of sodium sulphide; (9) wool is dyed bright scarlet with the product of (8) and the dyeing is lactamized; (10) the methyl ester of 2 - nitro - 4 - (2<1> : 3<1> - hydroxynaphthoylamino) - phenylglycollic acid is reduced and hydrolysed by means of sodium sulphide and coupled with diazotized 3-nitro-4-toluidine; (11) p-chloroaniline is diazotized and coupled with the sodium salt of 5-(2<1> : 3<1> - hydroxynaphthoylamino) - 4 - chloro - 2 - aminophenylthioglycollic acid; (12) 2 : 5-dichloroaniline is diazotized and coupled with 3-(2<1> : 3<1>-hydroxynaphthoylamino) - 6 - nitro - 4 - methoxyphenylthioglycollic acid and the product is reduced; (13) the product of (12) is applied as in (2); (14) 5 - nitro - 2 - anisidine is diazotized and coupled with the sodium salt of 2-amino - 4 - (2<1> : 3<1> - hydroxynaphthoylamino - phenylthiolactic acid. Specifications 6379/12, [Class 2 (iii)], 377,739, and 406,281 are referred to.  2 - Amino - 4 - (2<1> - 3<1> - hydroxynaphthoylamino) - phenylthioglycollic acid sodium salt is obtained by condensing the methyl ester of 2 - nitro - 4 - aminophenylthioglycollic acid with 2 : 3 - hydroxynaphthoic acid and reducing and hydrolysing the product by means of sodium sulphide.  The p-thioglycollic acid of the m-aminobenzoyl-m-aminoanilide of 2 - 3-hydroxynaphthoic acid is obtained (as the sodium salt) by condensing 2 : 3 - hydroxynaphthoic - m - aminoanilide (prepared by reduction of the corresponding nitro-compound) with 3-nitro-4-chlorobenzoyl chloride, treating the product with sodium sulphide and sulphur to produce a disulphide of the probable formula [OH.C10H6.CO.NH. C6H4.NH.CO.C6H3(NO2).S]2, reducing this with more sodium sulphide to the corresponding o-aminothiophenol (sodium salt), and reacting this with sodium chloracetate.  Alternatively the 1 - (2<1> : 3<1> - hydroxynaphthoylamino) - 3 - (4<11> - chloro - 3<11> - nitrobenzoylamino) - benzene is reacted with thioglycollic acid and caustic soda and the product is reduced with sodium sulphide.  2 - Nitro - 5 - (2<1> : 3<1> - hydroxynaphthoylamino) - phenylthioglycollic acid is obtained by reacting 2 : 3 - hydroxynaphthoic - 3<1> - chloro - 4<1> - nitroanilide (from 2 : 3 - hydroxynaphthoic acid and 3 - chloro - 4 - nitraniline) with thioglycollic acid and caustic soda and precipitating the acid with hydrochloric acid.  The methyl ester of 2-nitro-4-(2<1> : 3<1>-hydroxynaphthoylamino) - phenylglycollic acid is obtained by esterifying 2-nitro-4-aminophenylglycollic acid with methyl alcohol and condensing the product with 2 : 3-hydroxynaphthoic acid.  The sodium salt of 5-(2<1> : 3<1>-hydroxynaphthoylamino) - 4 - chloro - 2 - aminophenylthioglycollic acid is obtained by reacting the 2 : 5-dichloro-4-nitranilide of 2 : 3-hydroxynaphthoic acid (from the acid and 2 : 5-dichloro - 4 - nitraniline) with thioglycollic acid and caustic soda, precipitating the product with acid and reducing it with sodium sulphide.  3 - (2<1> : 3<1> - Hydroxynaphthoylamino) - 6 - nitro - 4 - methoxyphenylthioglycollic acid is prepared from 2 : 3 - hydroxynaphthoic - 5<1> - chloro - 4<1> - nitro - 2<1> - methoxyanilide and thioglycollic acid.  The arylide is obtained from the acid and 5-chloro-4-nitro-2-anisidine.  The sodium salt of 2-amino-4-(2<1> : 3<1>-hydroxynaphthoylamino)-phenylthiolactic acid is obtained by condensing 2 : 3-hydroxynaphthoic acid with methyl 2-nitro-4-aminophenylthiolactate (prepared by esterifying with methyl alcohol the acid obtained by condensing 2 : 4 - dinitrothiophenol with a -bromopropionic acid and reducing the 4-nitro group with sodium sulphide), and reducing and saponifying the product with sodium sulphide.