Patent GB-418295-A (GB)
Title: Improvements in and relating to the manufacture of substantive dyestuffs
IPC: C09B43/128
Filed: 1933-01-23
Abstract: Substantive water soluble azo dyes are produced by acylating water soluble azo dyes containing one or more primary amino groups with the halogenides or anhydrides of carboxylic acids of the general formula R--(CH=CH)x--COOH, wherein R stands for a substituted or unsubstituted aromatic hydrocarbon residue and x for 1 or 2. Suitable carboxylic acids are cinnamic and p  cinnamal-acetic acids (the latter being the condensation product of cinnamaldehyde with acetic acid).  In examples: (1) the azo dye b -aminoacetanilide --> 2-naphthol-3,6-disulphonic acid is saponified to split off the acetyl group and condensed with cinnamic acid chloride; cotton and viscose artificial silk are dyed in fast violet shades; (2) the azo dye 2-naphthylamine-6,8-disulphonic acid --> m-toluidine is cinnamoylated by condensation in aqueous pyridine with cinnamic acid chloride (dyes yellow); (3) the dye benzoyl-p-phenylenediamine --> H acid is condensed with o-chlorcinnamoyl chloride in aqueous pyridine (dyes red-violet); (4) the azo dye m-aminophenyltrimethylammonium --> m-phenylenediamine is condensed with o-nitrocinnamoyl chloride in aqueous pyridine (dyes yellow-brown); (5) the disazo dye aniline --> H acid \sM p-phenylenediamine is condensed in aqueous pyridine with cinnamoyl chloride (dyes blue-green); (6) the disazo dye o-anisidine --> Cleve's acid 1,6 --> Cleve's acid 1,6 is condensed in aqueous pyridine with cinnamic acid chloride (dyes violet).  Specifications 343,006 and 393,873 are referred to.  The Specification as open to inspection under Sect. 91 relates to the manufacture of dyestuffs by condensing dyes containing primary amino groups or substitutable carbon-linked hydrogen atoms with compounds containing the group R--CO--C=C-- or R--CO--C=N-- (R stands for hydrogen, hydroxy, alkoxy, halogen or any desired carbon-linked radical); or dye intermediates are condensed with the foregoing compounds having the specified grouping and dye formation subsequently brought about by any suitable means.  The dyes or dye-components for condensation with the foregoing carbonyl compounds may be of the azo-, nitro-, azine-, oxazine-, thiazine-, acridine-, triphenylmethane-, or anthraquinone dye series; specified components are 2,4-dinitrotoluol, 2,4,6-trinitrotoluol, 1-methyl-2,4-dinitro-3-oxybenzene-6-sulphonic acid, a -picoline, quinaldine, and acetoacetic arylides.  Specified carbonyl compounds are mesityl oxide, phoron, crotonaldehyde, crotonic acid, sorbic acid, trichlorphenomallic acid fumaric acid, muconic acid cinnamaldehyde, benzalacetone, dibenzalacetone, aldehyde-ketone condensation products, pyruvic acid, furfurol, furan a -carboxylic and a a -dicarboxylic acids and pyridine 2,5-dicarboxylic acid.  The following additional examples are given: (a) p-phenylenediamine is condensed with cinnamic acid and the product diazotized and coupled with R salt or 1-naphthol-3,6,8-trisulphonic acid, 2-naphthol3,6,8-trisulphonic acid or 1,8-aminonaphthol-3,6-disulphonic acid; (b) H acid is condensed with cinnamoyl chloride and coupled with diazotized aniline (dyes red); coupling with diazotized aminoazobenzene gives a violet dye, and with the diazotized dye aniline --> 1-naphthylamine-7-sulphonic acid gives a green-blue dye; (c) Gamma acid is condensed with cinnamoyl chloride and coupled with diazotized metanilic acid (dyes scarlet - red); using cinnamalacetyl chloride instead of cinnamic acid a similar dye is obtained; (d) 2-amino-5-naphthol-7-sulphonic acid is condensed with cinnamoyl chloride and coupled with diazotized metanilic acid (dyes orange), with diazotized naphthionic acid (dyes red), with the diazotized azo dye H acid --> a -naphthylamine (dyes black-blue); cinnamoyl chloride may be replaced by furan a -carboxylic acid or pyridine monocarboxylic acids; (e) 1-hydrazino - 8 - naphthol-3,6-disulphonic acid is condensed with cinnamaldehyde and coupled with diazotized aniline (dyes blue-grey); cinnamaldehyde may be replaced by benzalacetone; (f) 2-methyl-3-amino-6-dimethylaminophenazine is condensed with fumaric acid chloride (dyes red).  This subject-matter does not appear in the Specification as accepted.