Patent GB-735897-A (GB)
Title: Azo compounds prepared from a 2-amino-5-nitrothiazole and an n-monosubstituted aniline compound
IPC: C09B29/08
Filed: 1952-12-22
Abstract: The invention comprises azo compounds of formula <FORM:0735897/IV (c)/1> where R is an alkyl group of 1-10 C atoms, an alkoxyalkyl, dialkoxyalkyl or alkoxy-hydroxyalkyl group of 3-6 C atoms, a hydroxyalkyl or dihydroxyalkyl group of 2-5 C atoms, a cyanoalkyl group with 2-5 C atoms in the alkyl residue, a sulphoalkyl group with 2-4 C atoms, a sulphato, phosphato- or phosphonoalkyl group of 2-5 C atoms, a b -nitroethyl group, an alkenyl group of 2-4 C atoms, cyclohexyl, cyclopentyl, benzyl, phenethyl, chlorallyl, tetrahydrofurfuryl, pyridyl or -(CH2)m COOR1 groups, where m is 1-3 and R1 is an alkyl group of 1-4 C atoms, X is H, an alkyl group of 1-6 C atoms or cyano, trifluoromethyl or <FORM:0735897/IV (c)/2> groups, where Q is H, a nitro group, F, Cl, Br or an alkyl group of 1-4 C atoms, Z and Z1 are alkyl or alkoxy groups of 1-4 C atoms, Cl, Br, F or a -NH.CO.Y group, where Y is an alkyl group of 1-3 C atoms and n and n1 are 0 or 1.  They are made by diazotizing the appropriate 2-amino-5-nitrothiazole and coupling with the necessary secondary amine.  Specified thiazoles are 2-amino-5-nitrothiazole and its 4-methyl, ethyl, n-butyl, n-hexyl, cyano, trifluoromethyl, phenyl, o-, m- and p-nitrophenyl, o- and p-chloro-, o-bromo- and o- and p-fluoro-phenyl, and o- and p-methyl and p-n-butyl-phenyl derivatives.  2 - Amino - 5 - nitrothiazole is preferred.  Further specified values of R are methyl, ethyl, n-propyl, isopropyl, n-butyl, n-amyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, b -methoxy-, ethoxy-, propoxy- and n-butoxy-ethyl, g -n-propoxypropyl, g -ethoxypropyl, 2,3-dimethoxypropyl, 3-methoxy-2-hydroxypropyl, b  - hydroxy - b  - ethoxyethyl, 3 - methoxy - 2 - methyl - 2 - hydroxypropyl, b -hydroxy-ethyl and -propyl, g -hydroxy-propyl, b ,g -dihydroxypropyl, b -methyl-b ,g -dihydroxypropyl, d  - hydroxy - butyl, e  - hydroxyamyl, d ,e  - dihydroxyamyl, b  - cyano - ethyl, g - cyanopropyl, d -cyanobutyl, e -cyanopentyl, b -sulphocetyl, g -sulphopropyl, d -sulphobutyl, b -sulphatoethyl, g -sulphatopropyl, sulphated b ,g -dihydroxypropyl, d -sulphatobutyl, e -sulphatoamyl, phosphato- and phosphono-ethyl, g -phosphato- and phosphono-propyl, g -phosphato- and phosphono-butyl, e -phosphato- and phosphano-amyl, vinyl, allyl, methallyl, crotyl, -CH2COOCH5, -CH2COOC2H5, -CH2COOCH2CH2CH2CH3, -CH2CH2COOCH3, -CH2CH2COOC2H5, -CH2CH2COOCH2CH2CH2CH3, -CH2CH2CH2COOCH3, -CH2CH2CH2COOC2H5 and <FORM:0735897/IV (c)/3> Specified groups for Z, Z1 and Q are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl and tert.-butyl, Z and Z1 may also be methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy.  Methyl, ethyl, n-propyl and isopropyl groups are specified for Y.  Sulphato-, sulpho-, phosphato- and phosphono-alkyl groups may be present as salts, e.g. sodium, platinum, ammonium, magnesium, calcium or lithium salts.  Textile materials consisting of or containing a cellulose alkyl carboxylic acid ester of 2-4 C atoms in the acid groups thereof, wool, silk, superpolyamide, polyethylene terephthalate or a modified polyacrylonitrile are dyed red and blue shades.  The dyestuffs are usually applied as an aqueous dispersion. Sodium lignum sulphonate, soap, turkey red oil and oleyl glyceryl sulphate are specified dispersing agents.  Examples and tables are given illustrating the preparation of dyestuffs from certain of the above-specified components, diazotization being effected with nitrosyl sulphuric acid in acetic and propionic acid mixture which solvent is also used for coupling.ALSO:The Specification discloses the preparation of certain 2-amino-4- and -5-substituted thiazoles as described in the parent Specification.  Additionally 2-amino-4-methylthiazole is made by reacting thiourea with chloroacetone and other -4-alkyl-thiazoles may be made in a similar way.  4-Alkyl-thiazoles may be nitrated to the 5-nitro-derivative with fuming nitric in sulphuric acid at about 5 DEG  C.  References are given to alternative methods of preparing 2-amino-4-phenyl- and -(m-nitrophenyl)-5-nitrothiazole.