Patent GB-1378440-A (GB)
Title: Crosslinking agents for hydrophilic colloids
IPC: C07D239/46
Filed: 1972-04-05
Abstract: 1378440 Quaternary s-triazine derivatives CIBA-GEIGY AG 5 April 1972 [5 April 1971] 15610/72 Heading C2C [Also in Divisions G2 and C3] Cross-linking agents for hydrophilic colloids containing amino, imino and/or hydroxyl groups, e.g. gelatine or polyvinyl alcohol whose half-life for decomposition in aqueous solution at 40 C. is at least 8 hours have the Formula I where denotes a triazine radical substituted by halogen atoms and/or unsubstituted or substituted alkoxy groups and/or alkyl, halogenoalkyl, aryl or aryloxy group or low alkylamino or sulphonamido group; a pyrimidine radical substituted by halogen atoms and/or lower alkyl or alkoxy groups and/or nitrile groups; or a quinazoline radical substituted by one or more halogen atoms and lower alkyl groups; E<SP>(+)</SP> denotes an alkylammonium radical of which the quaternary linking nitrogen atom carries substituents selected from alkyl, alkenyl, alkynyl, carbalkoxyalkyl, cyanoalkyl or alkoxyalkyl radicals with a total of 1-5 carbon atoms, the cyclohexyl radical or the benzyl radical or E<SP>(+)</SP> denotes a cyclic ammonium radical substituted at the quaternary linking nitrogen atom by an alkyl radical which is unsubstituted or substituted by nitrile or alkoxy with a total of 1-5 carbon atoms, and of which the quaternary linking nitrogen atom belongs to a 5-membered or a 6- membered monocyclic aliphatic ring which may contain a further nitrogen, sulphur or oxygen atom or E<SP>(+)</SP> denotes a pyridine ring which is optionally substituted by an alkyl with 1-3 carbon atoms or acylamino with a total of 2-3 carbon atoms and X<SP>(-)</SP> denotes an anion, preferably halide nitrate, sulphate, perchlorate, fluoroborate, thiocyanate, sulphamate, hexafluorophosphate hexafluoroantimonate or hexafluorostannate ion and the salts of Formula I are obtained by reacting the corresponding halide of the heterocyclic unit with the appropriate amine compound, for example by combining the reactants at 0-5 C. in presence of a solvent and then converting to the desired salt. The perchlorate or perborate may be made by adding NaClO 4  or NaBF 4  to the solution of the heterocyclic halide compound and reacting the resulting salt with the basic compound, and the product may then be obtained as the mixed or double salt, e.g. as onium-sodium perchlorate chlorides. The exemplified reagents are:-(a) heterocyclic compounds-2-chloro-4,6-dimethoxy-s-triazine; 2-chloro-4,6-diethoxy-s-triazine; 2,4-dichloro-6(phenylsulphonamido)-striazine; 2,4-dichloro-6-methyl-s-triazine; 2- chloro-4-methoxy-6-phenyl-s-triazine; 2,4-dichloro-6-(beta-methoxyethoxy)-s-triazine; 2- chloro - 4 - ethoxy - 6 - (# - methoxyethoxy) - striazine; 2,4-dichloro-6-ethyl-s-triazine; 2- chloro - 4,6 - di-(# - methoxyethoxy) - s - triazine; 2,4-dichloro-6-methoxy-s-triazine; 2- chloro - 4 - methoxy - 6 - p - chlorophenyl - striazine; 2-chloro-4-methoxy-6-(piperidin-1<SP>1</SP>-yl)- s-triazine; 2-chloro-4-methoxy-6-ethoxy-s-triazine; 2-chloro-4-methoxy-6-cyanomethoxy-striazine; 2-chloro-4-methoxy-6-phenoxy-s-triazine; 2,4-dichloro-5-cyanopyrimidine; 2- chloro - 4,6 - di - (2<SP>1</SP>,2<SP>1</SP>,2<SP>1</SP> - trichloroethoxy) - striazine; and 2,4-dichloro-6-(N-methyl-N<SP>1</SP>,N<SP>1</SP>- dimethylsulphamoylamino)-s-triazine: (b) bases:-4-methyl-pyridine; N-methyl morpholine; N-methyl piperidine (bis-salt); pyridine; 3-acetylamidopyridine; N-ethylmorpholine; N- ethylpiperidine; triethylamine; N-methylpyrrolidine; N,N-dimethylcyclohexylamine; N,N<SP>1</SP>- dimethylpiperazine; 1-dimethylaminopropionitrile; 2-dimethylaminoethanol; 3-isobutoxy-methyl-tetrahydro-1,3-oxazine; N,N-dimethylbenzylamine; 4-methylthiomorpholine- 1,1-dioxide; N,N-dimethylglycine-ethyl ester; #-dimethylaminopropionic acid ethyl ester; dimethylaminopropyne; N-(delta-cyanobutyl)- pyrrolidine; 3,5-dimethylpyridine: (c) anions:- chloride; sodium perchlorate-chloride; perchlorate; tetrafluoroborate; PF 6 <SP>-</SP>.