Patent GB-650850-A (GB)
Title: New dyestuffs containing isothiouronium salt groups
IPC: C09B69/00
Filed: 1948-07-19
Abstract: p - (o  - Hydroxyethoxyethoxy) - aniline is obtained by condensing sodium p-nitrophenate with b -chloro-b 1-hydroxydiethyl ether and reducing the nitro group with sodium sulphide.ALSO:Water-soluble dyes containing isothiouronium salt groups are made by heating with thiourea or a substituted thiourea a coloured compound in which at least one chlormethyl or brommethyl group is connected through a linking atom or group of atoms to an aromatic nucleus.  The linking atom or group may be -NR.SO2-, -CONR-, -CO-O-CH2-, -CH2.NR-, -CH2.O.CH2.CH2-O- where R is hydrogen or a hydrocarbon or substituted hydrocarbon radical and where the CM2-halogen radical is attached to the left-hand side of the linkage and the aromatic residue to the right-hand side of the linkage.  The halogen-methyl body may be made in situ.  Solvents or diluents specified are water, phenol, and b -ethoxyethanol. In examples, tetramethylthiourea is heated with (1) an azo dye obtained by coupling diazotized p - amino - N - cyclohexyl - o -chloracetanilide with 2-hydroxy-3-naphthoic-(21 - methyl - 41 - chloro) - anilide, or with 1-phenyl - 3 - methyl - 5 - pyrazolone, or with acetate - m - xylidide; (2) copper tri - (o -chloracetoxymethyl) - phthalocyanine; (3) di - (o  - chloracetoxy - methyl) - 4.41 - di - (6-methylbenzthiazyl - 2) - azobenzene; (4) 1-methylamino - 4 - b  - chlorethylamino - anthraquinone (thiourea itself is also condensed with this substance); (5) 1-methylamino-4-p-(o -chloroethoxyethoxy) - anilinoanthraquinone,; (6) copper tetra-4-(chloracetylamino)-phthalocyanine; (7) copper phthalocyanine-tetra-4-(N-methylsulphonamide) and sym-dichlorodimethyl ether; (8) the azo dye obtained by coupling diazotized m-aminobenzenesulphonamide with 2 - hydroxy - 3 - naphthoic - (31-N - methylsulphonamido) - anilide.  Dyes of the dioxazine series are also referred to.  Other thioureas listed as suitable are N-methyl-thiourea, the N-phenyl-, N,N1-dimethyl-, N,N-dimethyl-, and N,N,N1-trimethyl-thioureas and ethylenethiourea. The products may be applied to textiles by dyeing, padding, or printing according to Specifications 630,463, 633,160, 633,602, and 638,124.  Copper tri - (o  - chloracetoxymethyl) - phthalocyanine is prepared by heating copper tri-(chlormethyl) phthalocyanine (Specification 586,340) with sodium acetate and di - (b -hydroxyethyl) ether followed by heating with b -ethoxyethanol and sodium hydroxide to give copper tri-(hydroxymethyl) phthalocyanine which is reacted with chloracetyl chloride.  Di - (o  - chloracetoxy - methyl) - 4,41 - di - (6-methylbenzthiazyl-2)-azobenzene is obtained from chloracetyl chloride and di(hydroxymethyl)-4,41 - di - (61 - methylbenzthiazyl - 2) - azobenzene which is made from the dichlormethyl body (see Specification 576,270) by the action successively of sodium acetate and di-(b -hydroxyethyl) ether, b  - ethoxyethanol and sodium hydroxide, and hydrogen peroxide.  1 - Methylamino - 4 - p - (o  - hydroxyethoxytyhoxy) - anilinoanthraquinone is prepared by condensing 4 - bromo - 1 - methylaminoanthraquinone with p - (o  - hydroxyethoxyethoxy) aniline, (see Group IV (b)), and is converted to the o -chlor body with thionyl chloride.  Copper tetra - 4 - (chloracetylamino) - phthalocyanine is made by heating copper tetra-4-aminophthalocyanine with chloracetyl chloride.  Copper phthalocyanine tetra - 4 - (N - methylsulphonamide) is made by reacting the tetra-4-sulphonyl chloride with methylamine. Specifications 587,636 and 613,980 also are referred to.