Patent GB-1467802-A (GB)
Title: Pyrazoline derivatives and their use as optical brightening  agents
IPC: C07C45/46
Filed: 1973-07-18
Abstract: 1467802 Pyrazoline derivatives SANDOZ PRODUCTS Ltd 25 June 1974 [18 July 1973] 34111/73 Heading C2C Novel compounds have the Formula I in which either R 1 , R 2  and R 3 , which may be the same or different each signifies a hydrogen atom, a chlorine or fluorine atom, an alkyl radical of 1 to 4 carbon atoms, an alkoxy radical of 1 to 4 carbon atoms, a cyano group, a group -SO 3 M, an unsubstituted phenyl radical or a phenyl radical substituted by up to 2 substituents selected from chlorine, fluorine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and the group -SO 3 M, with the provisos (i) that only one of R 1 , R 2  and R 3  may signify an unsubstituted or substituted phenyl radical and (ii) that only one of R 1 , R 2  and R 3  may signify a group selected from -CN and -SO 3 M, or two of R 1 , R 2  and R 3 , together, form a methylenedioxy group, the other of R 1 , R 2  and R 3  having one of the above significances, R 4  signifies a hydrogen atom, a chlorine or fluorine atom, an alkyl radical of 1 to 4 carbon atoms or an alkoxy radical of 1 to 4 carbon atoms, R 5  signifies a hydrogen atom, an alkyl radical of 1 to 4 carbon atoms, an unsubstituted phenyl radical or a phenyl radical substituted by 1 or 2 substituents selected from chlorine fluorine, alkyl or 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and the group -SO 3 M, R 14  signifies an alky radical of 1 to 8 carbon atoms, A 1  signifies a C 1  to C 3  alkylene chain, unsubstituted or substituted by up to two alkyl groups of 1 to 4 carbon atoms, Y signifies -O- or -NR 6 -, in which R 6  signifies a hydrogen atom or an alkyl radical of 1 to 4 carbon atoms, Q signifies in which either R 18  and R 19 , which may be the same or different, each signifies a hydrogen atom or an alkyl radical of 1 to 4 carbon atoms, or one of R 18  or R 19 , together with R 6 , signifies an ethylene bridge, the other signifying a hydrogen atom or alkyl radical of 1 to 4 carbon atoms, or Q signifies -SO 3 M, or Q signifies -SR 21  or -S<SP>(+)</SP>R 22 R 23 An<SP>(-)</SP>, in which R 21  signifies an alkyl radical of 1 to 4 carbon atoms, unsubstituted or substituted by a hydroxy radical or an alkoxy radical of 1 to 4 carbon atoms; or a phenyl or cycloalkyl radical of 5 to 7 carbon atoms, each unsubstituted or substituted by up to 2 substituents selected from chlorine, fluorine, C 1-4  alkyl and C 1-4  alkoxy, R 22  and R 23 , which may be the same or different, each have a significance of R 21 , above, with the proviso that both do not simultaneously signify unsubstituted or substituted phenyl or cycloalkyl radicals, A 2  signifies a C 1  to C 3  alkylene chain, unsubstituted or substituted by up to two alkyl groups of 1 to 4 carbon atoms; or a phenylene group, unsubstituted or substituted by up to 2 substituents selected from chlorine, fluorine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and the group -SO 3 M, with the proviso that A 2  signifies other than substituted or unsubstituted phenylene wehn Q signifies other than -SO 3 M, An<SP>(-)</SP> signifies a colourless organic or inorganic anion, and the M's, which may be the same or different, each signifies a hydrogen atom, or a non-chromophoric cation, which compounds, where Q signifies may be in quaternary ammonium salt form or in acid addition salt form. The compounds of Formula I are obtained by (a) reacting a compound of Formula II in which Z signifies a halogen atom, a hydroxy group or an alkoxy group of 1 or 2 carbon atoms, which a compound of Formula III wherein Qx is as defined for Q but is other than S<SP>(+)</SP>R 22 R 23 An<SP>(-)</SP>, (b) reacting a compound of Formula IV in which M 2  signifies a hydrogen atom or an alkali metal cation, with a compound of Formula V: Z 1 -A 1 -CO-Y-A 2 -Qx, in which Z 1  is a halogen atom, (c) obtaining a compound of Formula Ia wherein R 13  signifies a C 3  alkylene chain optionally substituted by up to 2 alkyl groups of 1 to 4 carbon atoms, by reacting a compound of Formula IX with a sultone of Formula X or (d) obtaining a compound of Formula Ib wherein R 20  signifies a hydrogen atom or a C 1-4  alkyl group, by reacting a compound of Formula IV with a compound of Formula XI ternary sulphonium, quaternary ammonium and acid addition salt forms of said compounds being obtained from the products of (a) to (d) by ternization, quaternization or protonation. Examples prepare compounds of Formula I in which R 1  to R 3  are H, Cl, F, CH 3  or CH 3 O; R 4  is H, Cl, CH 3  or CH 3 O; R 5  is H; R 14  is CH 3  or C 2 H 5 ; A 1  is -CH 2 - or -CH 2 CH 2 -; Y is -O-, -NH-, or -N(CH 3 )-; A 2  is -(CH 2 ) 3 - or phenylene; and Q is -SO 3 Na, -N(CH 3 ) 2 , -SCH 3 , or -S<SP>(+)</SP>(CH 3 ) 2 CH 3 SO 4 <SP>(-)</SP>. The compounds and salts of Formula I are optical brighteners for polyamide (e.g. nylon and wool), polyacrylonitrile and cellulosic substrates.