Patent GB-1345402-A (GB)
Title: Imidazolines their preparation and compositions containing them
IPC: C07D233/50
Filed: 1971-04-19
Abstract: 1345402 2 - Phenylamino - imidazolines - (2) BOEHRINGER INGELHEIM GmbH 19 April 1971 [6 April 1970] 26373/71 Heading C2C [Also in Division A5] Novel 2 - phenylamino - imidazolines - (2) of the general formula wherein each of R 1 , R 2  and R 3  is a hydrogen, fluorine, chlorine or bromine atom or a cyano, trifluoromethyl, C 1-3  alkyl or C 1-3  alkoxy group and R 4  and R 5 , which must be different from one another, are each a hydrogen atom or a group of formula C n H 2n+1-x (OR) x , in which R is a hydrogen atom or a methyl group, n is 1-6 and x is 1-3, and acid addition salts thereof are prepared (a) by reaction of a 2-phenylamino-imidazoline-(2) of the general formula with a halide of the general formula wherein Hal is a chlorine, bromine or iodine atom; (b) when R 4  is a hydrogen atom and R 5  is a C n H 2n+1-x (OR) x  group, the carbon atom thereof attached to the imidazoline nitrogen atom being attached to one hydroxyl group, by reaction of a 2-phenylamino-imidazoline-(2) of the second general formula above with an aldehyde of the general formula (c) when one of R 4  and R 5  is a C n H 2n+1-x (OR) x  group in which n is 2-6 and the second carbon atom thereof away from the nitrogen atom to which the group is attached is attached to one hydroxyl group, by reaction of a 2-phenylaminoimidazoline-(2) of the second general formula above with an epoxide of the general formula (d) when R 5  is a hydrogen atom and R 4  is other than a hydrogen atom, by reaction of a compound of the general formula wherein A is a -C(SCH 3 )=NH, -C(NH 2 )=S or -CN group and R 4  is not a hydrogen atom, with ethylenediamine; (e) when R 4  is a hydrogen atom and R 5  is other than a hydrogen atom, by reaction of a compound of the general formula wherein each of X and Y is a chlorine or bromine atom or an alkylthio, alkoxy, amino or nitramino group, with a diamine of the general formula H 2 N(CH 2 ) 2 NHR 5 , wherein R 5  is not a hydrogen atom; (f) when at least one of R 1 , R 2  and R 3  is a chlorine or bromine atom, by reaction of the corresponding compound, wherein at least one of R 1 , R 2  and R 3  is a hydrogen atom with chlorine or bromine; (g) when one of R 4  and R 5  is a C n H 2n+1-x (OR) x  group, which group contains at least one hydroxyl group, by hydrolysis of a 2-phenylamino-imidazoline-(2) of the general formula wherein R 7 , and R 8 , which must be different from one another, are each a hydrogen atom or a C n H 2n+1-x (OR) x-y Z y  group, in which Z is a chlorine, bromine or iodine atom or an O-acyl group and y is 1-3, provided that x - y is 0, 1 or 2; (h) when one of R 4  and R 5  is a C n H 2n+1-x  (OR) x  group, which group contains at least one hydroxyl group, by cleavage of an ether of the general formula wherein R 9  and R 10 , which must be different from one another, are each a hydrogen atom or a C n H 2n+1-x (OH) x-y (OR<SP>1</SP>) y  group, in which R<SP>1</SP> is an alkyl group; (i) when one of R 4  and R 5  is a hydroxy-alkyl group of the formula C n H 2n+1-x  (OR) x  in which R is a hydrogen atom and n is 2-6, by hydration of a 2-phenylamino-imidazoline-(2) of the general formula wherein R 11  and R 12 , which must be different from one another, are each a hydrogen atom or a C 2-6  alkenyl group; (j) when at least one of R 4  and R 5 , which must be different from one another, is a C n H 2n+1-x (OR) x  group, which group contains at least one hydroxyl group, by reduction of a 2-phenylamino-imidazoline - (2) of the general formula wherein R 13  and R 14 , which must be different from one another, are each a hydrogen atom or a C n H 2n+1-x-z (OR) x-z O z,  C n-y H 2n+1-x-2y (OR) x  -y-  (COW)y, or C n H 2n+1-x (OR) x-y (O-acyl) y  group, in which z is 1 or 2, provided that x - z is 0, 1 or 2, and W is a chlorine atom or a hydroxy, alkoxy or acyloxy group, with the proviso that R 13  and R 14  must be selected to yield different R 4  and R 5  radicals upon reduction; and (k) when either R 4  or R 5  is a hydroxyalkyl group, by reaction of a 2-phenylamino-imidazoline-(2) of the general formula wherein R 15  and R 16 , which must be different from one another, are each a hydrogen atom or an alkyl group containing a carbonyl, ester, carboxyl, acid chloride or carboxyanhydride function, provided that when both R 15  and R 16  are substituted alkyl groups, they must be selected to yield different R 4  and R 5  groups upon reaction with a Grignard reagent, with a Grignard reagent and subsequent hydrolysis of the Grignard complex thus formed; followed optionally by salification of the product.