Patent GB-598075-A (GB)
Title: Process for producing organometallic compounds containing 1, 3, 5-triazine rings
IPC: C07F9/90
Filed: 1945-05-18
Abstract: 1 : 3 : 5-Triazine compounds, one ring carbon atom of which is linked by a -NH- group to a phenyl group substituted by a radical of trivalent antimony are prepared by reacting a 1 : 3 : 5-triazine derivative containing at least one halogen atom or at least one -NH2 radical directly linked to a carbon atom of the triazine ring, in the case of a halogen atom with an amino-phenyl compound substituted in the benzene ring by a radical of trivalent antimony, and in the case of an -NH2 radical with a halogen-phenyl compound substituted in the benzene ring by a radical of trivalent antimony, and, if desired, reacting the product with ammonia or an amine.  In examples: (1) 2 : 4 : 6-trichloro-1 : 3 : 5-triazine is reacted with (3 - aminophenyl) - stibinous dichloride hydrochloride to yield the corresponding 2 : 4-dichloro - 1 : 3 : 5 - triazinyl - (6) - aminophenyl - antimony dichloride and is converted to the corresponding 2 : 4-dichloro - 1 : 3 : 5 - triazinyl - (6)-aminophenyl-antimony oxide by the action of ammonium hydroxide and one or both of the chlorine atoms attached to the triazine ring of either of the above triazinyl antimony compounds may be substituted with amino or substituted amino groups by reacting with ammonia, alkylamines, hydroxy-alkylamines or dialkylaminoalkylamines; (2), (3), (4) and (7) chloro-cyanuric diamide is reacted with the hydrochloride of 3-aminophenyl-stibinous oxide, 3 - amino - 4 - hydroxy - phenyldichlorostibine, 4-aminophenyl dichlorostibine, or 4-chloro-3-aminophenyl stibinous chloride to yield the hydrochloride of the corresponding 2 : 4-diamino - 1 : 3 : 5 - triazinyl - (6) - aminophenyl stibinous dichloride; (5) p - aminophenyl stibinous chloride is reacted with thioglycollic acid and the resulting hydrochloride of p-aminophenyl-dithioglycollic acid is reacted with 2 : 4-diamino-6-chloro-1 : 3 : 5-triazine to yield the corresponding 2 : 4 - diamino - 1 : 3 : 5 - tri - azinyl - (6) - aminophenyl - antimony dithioglycollic acid; (6) the condensation product obtained by reacting p-aminophenyl stibinous chloride with thiosalicylic acid is reacted with chlorocyanuric diamide to yield 2 : 4-diamino-1 : 3 : 5 - triazinyl - (6) - aminophenyl - antimony - dithiosalicylic acid.  The Specification as open to inspection under Sect. 91 refers to the preparation of compounds of the general formula <FORM:0598075/IV/1> by the methods given above.  X and Y may be equal or different and may represent halogens, residues of any inorganic or organic aliphatic, cyclic, isocyclic, heterocyclic, monocyclic or polycyclic molecule containing an active hydrogen capable of reacting with cyanuric halide with the formation of hydrogen halide, e.g. Cl, Br, I, F, -OH, -O-alkyl, -O-acyl, -O-aryl,-NH2,-NH-alkyl,-N-(alkyl)2, -NH-acyl,-NH-NH2,-NH-NH-alkyl, -N-alkyl-NH2, -N-alkyl-NH-alkyl, -NH-NH-acyl, -N-acyl-NH2, -N-acyl-NH-acyl, -NH-aryl, -NH(CH2)n CONH2, -NH-(CH2)n-NH2, -NH(CH2)n -arkyl, -NH(CH2)nN-dialkyl, -NH(CH2)n OH, -NH-CH2CHOHCH2OH, -NHOH, <FORM:0598075/IV/2> residues of cyanamide derivatives, residues of substituted guanidines, amino-derivatives of carbohydrates particularly monosaccharides such as glycose-amine, alkyl radicals or their substitution products, -SH, substituents of the type -SR, where R represents any aliphatic or cyclic group capable of carrying an -SH group such as thioglycollic acid and thiophenol.  X and Y may also represent substituted aryl radicals such as those corresponding to the formula -NH-C6H2(A, B)-E or -NH-NH-C6H2(A, B)-E, where A and B represent equal or different substituents defined below and E represents a radical in the ortho-, meta- or para-position to the -NH or -NH-NH- group and may be -SO3H, -SO2NH2 or -COOH.  X and/or Y may also represent 1 : 3 : 5-triazine groups, residues or derivatives and radicals of the formula <FORM:0598075/IV/3> where A, B and D represent radicals defined below.  The substituent radicals represented by X and/or Y may be linked directly or indirectly to the triazine ring and in the latter case the link may be formed by a cyclic or aliphatic amine radical, e.g. -NH-aryl -NH-alkyl, -NH-NH-aryl or -NH-NH-alkyl, A and B may be the same or different and represent hydrogen, halogen, nitro, hydroxyl, alkoxy, amino, substituted amino and alkyl radicals.  D represents a divalent radical selected from the group consisting of oxygen, sulphur, dihalides, radicals of the formula <FORM:0598075/IV/4> and sulphur containing groups of the type =(SR)2, wherein SR is the residue of a sulphydril compound of the type H-SR where R is selected from the group consisting of aliphatic and cyclic radicals, e.g. such sulphur containing compounds are thioglycollic acid, cysteine, glutathione, thiophenol, thioacetic acid, thiobenzoic acid, thioacetamide, thiosalicylic acid, p-sulphydril-benzene sulphonic acid, thiopropionic acid and p-sulphydril-phenylacetic acid.  Compounds of the type <FORM:0598075/IV/5> where X and Y have the above significance are prepared by subjecting a compound of the formula <FORM:0598075/IV/6> to the action of a reducing agent, e.g. stannous chloride, sodium hydrosulphite in alkaline solution or hypophosphorus acid in hydrochloric acid solution in the presence of hydriodic acid. In examples: (5) triazine derivatives of the formul <FORM:0598075/IV/7> are prepared by reacting the 2 : 4-amino-1 : 3 : 5-triazine-(6)-aminophenyl-dichlorostibine hydrochloride prepared as in example (2) above with potassium thioglycollate or sodium thiosalicylate; (8) a compound of the general formula <FORM:0598075/IV/8> is prepared by reacting p-sulphydril benzene sulphonic acid and the corresponding 2 : 4-amino - 1 : 3 : 5 - triazinyl - (6) - aminophenyl stibinous oxide.  Similar compounds containang residues of thioglycollamide, thiopropionic acid, 8-mercapto-quinoline, 2-mercapto-pyridine, cysteine or glutathione attached to the antimony atom are similarly prepared. This subject-matter does not appear in the Specification as accepted.