Patent GB-816396-A (GB)
Title: Benzothiazole mono-azo-diphenylamine compounds and materials dyed therewith
IPC: D06P1/10
Filed: 1955-09-12
Abstract: Acrylonitrile polymers are dyed with a compound of formula <FORM:0816396/IV (a)/1> where Ar is an o-arylene radicle of the benzene series and X is a diphenylamine residue joined through the carbon atom in its 4-position to the azo bond and which is substituted by at least an hydroxy group, an alkoxy group of 1-4 carbon atoms or a b -hydroxyethoxy group joined to the carbon atom in its 3-position, or with chromium, cobalt, copper, iron, manganese, nickel or vanadium complexes thereof.  Dyeing may be effected in conventional fashion in substance or on the fibre, or the dyestuffs or their metallizing agents may be incorporated in the spinning dopes.  A particular class of the dyestuffs concerned are those of formula <FORM:0816396/IV (a)/2> where Ar is as above, R is H or an alkyl group of 1-4 carbon atoms or a b -hydroxyethyl group, R1 is H, an hydroxyalkyl group of 2-4 carbon atoms, an alkyl group of 1-4 carbon atoms or a cyanoalkyl group of 3 or 4 carbon atoms and R2 is H, OH or Cl or an alkyl or alkoxy group of 1-4 carbon atoms, or their metal complexes.  The o-arylene residue may be unsubstituted or contain substituents such as alkylsulphonyl, N-alkylsulphonamide, alkoxy, alkyl, hydroxyalkyl, acetyl-, propionyl- and butyryl-amino, thiomethyl, thiocyano, cyano, trifluoromethyl and nitro groups or a chlorine atom.  For the preparation of the dyestuffs and for lists of a large number of components to be used therein (see Group IV (c)). The non-metallized dyes colour fibres of graft polymers of acrylonitrile made by graft polymerizing acrylonitrile alone or together with one or more other monoethylenic monomers with a preformed polymer which may be a homo-, inter- or ter-polymer.  The dyes are particularly useful with graft polymers containing at least 5 per cent by weight of combined acrylonitrile grafted to the preformed polymer molecule and especially for fibres made by graft polymerizing acrylonitrile and an acrylamide or methacrylamide with a preformed copolymer of acrylonitrile and the same or different acrylamide or methacrylamide.  Preformed polymers are preferably homopolymers of a vinyl pyridine, an acrylamide, a maleamide, a fumaride, an acrylate, a methacrylamide, a methacrylate, an itaconamide, a citraconamide, a fumarate, an itaconamate, a citraconamate, a maleamate, or a vinyl ester, or an interpolymer of two or more of such monomers with each other or with monomers such as styrene, acrylonitrile, substituted styrenes, vinyl or vinylidene chlorides, vinyl ethers, dialkyl maleates, alkenyl ketones, dialkyl fumarates, acrylic acid, methacrylic acid, substituted acrylonitriles, fumaronitrile and ethylene.  Examples are given illustrating the dyeing of certain of the above indicated polyacrylonitriles with the metal-free and metallized dyestuffs. Red, brown and blue shades are obtained.  Specifications 485,592 [Group IV], 764,296, 764,297, 764,298 and 781,435 are referred to.ALSO:2-Amino-6-methyl- or -trifluoromethyl-sulphonylbenzothiazoles are made by treating p-aminophenylmethyl- or -trifluoromethyl-sulphones with sodium thiocyanate and bromine in acetic acid and the products with an alkali.  2 - Acetylamino - 6 - thiocyanobenzothiazole is made by treating aniline with chlorine and ammonium thiocyanate in acetic acid and acetylating the product. 2-Amino-6-ethyl-, -n-propyl-, -isopropyl-, -n-butyl- and -isobutyl-sulphonylbenzothiazoles are made by treating 2 - acetylamino - 6 - thiocyanobenzothiazole with sodium sulphide and the requisite alkyl iodide in ethanol to give the 2-acetylamino-6-alkylthiobenzothiazoles which, on treatment with aqueous hydrogen peroxide in acetic acid and subsequently with hydrochloric acid, yield the desired compounds. 2-Amino-6-trifluoromethyl- and -b -hydroxyethyl-benzothiazoles are made by treating p-amino-benzotrifluoride and -phenyl-ethyl alcohol respectively with sodium thiocyanate and bromine in acetic acid and treating the products with an alkali.  Potassium thiocyanate may be used instead of sodium thiocyanate. Specifications 485,592, [Group IV], 764,296, 764,297, 764,298 and 781,435, [all in Group IV (a)], are referred to.ALSO:The invention comprises dyestuffs of formula <FORM:0816396/IV (c)/1> where Ar is an o-arylene radicle of the benzene series and X is a diphenylamine residue bound through the C atom in the 4-position to the azo bond and contains at least an OH group, an alkoxy group of 1-4 C atoms or a b -hydroxyethoxy group bound to the C atom in its 3-position and chromium, cobalt, copper, iron, manganese, nickel or vanadium complex thereof.  They are made in conventional fashion from appropriate diazotized benzothiazoles, diphenylamines and metallizing agents.  Metallization may be effected in substance or on the fibre.  Preferred dyestuffs are of formula <FORM:0816396/IV (c)/2> where R is H, alkyl of 1-4 C atoms or -CH2CH2OH R1 is H, hydroxyalkyl of 2-4 C atoms, alkyl of 1-4 C atoms or cyanoalkyl of 3-4 C atoms and R2 is H, OH, alkoxy of 1-4 C atoms, alkyl of 1-4 C atoms or Cl and their metal complexes.  Indicated as substituents in the arylene residue are alkylsulphonyl, N-alkylsulphonamide, alkyl, alkoxy, hydroxyalkyl of 2-4 C atoms, acetylamino, propionylamino, butyrylamino, thiomethyl, thiocyano, cyano, trifluoromethyl, nitro or chlorine the alkyl residues of the first four groups having 1-4 C atoms. Specified diazo components are 2-amino-6-methyl-, methyl-, n-propyl- and n-butyl-sulphonyl-, -methoxy-, -ethoxy-, -n-propoxy-, n-butoxy-, -methyl-, -ethyl-, -n-propyl, -n-butyl-, -b -hydroxyethyl-, -g -hydroxypropyl-, -d -hydroxybutyl-, -acetyl-, -propionyl- and n-butyrylamino-, -thio-methyl- and -cyano-, -cyanotrifluoromethyl-, -chloro- and -nitro-benzothiazoles, 2-amino-benzothiazole-6-N-methyl-, -ethyl-, n-propyl and -n-butyl-sulphonamides, 2 - amino - 4,7 - and - 5,6 - dimethoxy -, - 4,7-diethoxy - and - 4,6 - dimethyl - benzothiazoles. Specified diphenylamine derivatives are 3-hydroxy-, 3,31- and 3,4-dihydroxy-, 3-hydroxy-41-methoxy-, -ethoxy-, n-propoxy-, isopropoxy-, -n-butoxy-, methyl-, -ethyl- and -n-butyl-, 3-hydroxy-21- and-31-methyl- and -chloro-, N-methyl-, -ethyl-, n-propyl- and -n-butyl-3-methoxy-, 3-methoxy-, -ethoxy-, -n-propoxy-, -isopropoxy- and -n-butoxy-, 3-b -hydroxyethoxy-N-b -hydroxyethyl-41-methoxy- and -21-chloro -, 3 - methoxy - N - b  - hydroxyethyl - g -hydroxypropyl- and d -hydroxybutyl-, 3-hydroxy - N - b  - hydroxyethyl - and - g  hydroxypropyl-, 3-hydroxy-2-methoxy-, 3-hydroxy-21-methoxy- and -chloro-N-b -hydroxyethyl-, 3-hydroxy- and -methoxy-N-b -cyanomethyl-, 3-hydroxy - 21 - methoxy - and - chloro - N - b  - hydroxyethyl-, 3-n-butoxy-N-b -hydroxyethyl- and 3-hydroxy- and -methoxy-N-g -cyanopropyl-diphenylamines.  The dyestuffs, especially the metal complexes dye cellulose alkyl carboxylic esters containing 2-4 C atoms per molecule, acrylonitrile polymers, nylon, polyesters, e.g. polyethylene terephthalates, nylon, wool and silk. Examples are provided illustrating the preparation of the dyestuffs and metal complexes thereof and the use of both in dyeing various materials in red and brown shades, the reactants being chosen from those specified above with the addition of 2-aminobenzothiazole, 3-hydroxy-41-methoxy-N-b -hydroxyethyl-, 3-methoxy - 21 - chloro- and -31- and -41 - methyl and 3-hydroxy-21-methoxy-diphenylamines as further components. Specifications 485,592, [Group IV], 764,296, 764,297, 764,298 and 781,435, [all in Group IV (a)], are referred to.