Patent GB-936342-A (GB)
Title: Salts of esterified 8-hydroxyquinolines, an intermediate therefor and fungicidal compositions containing such salts
IPC: C07D215/32
Filed: 1959-09-02
Abstract: Alkyd resin and polyvinyl acetate paints comprise as a fungicide a salicylic acid salt of a quinolyl ester having one of the general formulae: <FORM:0936342/IV(a)/1> wherein R is the acyl group of a monocarboxylic acid, R1 is the diacyl group of a dicarboxylic acid and X is hydrogen, halogen or a C1-8 alkyl or alkoxy group.  In examples, the salicylic acid salt of 8-benzoyloxy quinoline is incorporated in an alkyd resin paint comprising also an aliphatic hydrocarbon vehicle, driers, Ti-Ca pigment, TiO2, CaCO3 and silica. A fungicidal ointment comprises the 8-benzoyloxy quinoline salicylate, dipropylene glycol and polyethylene glycol 1,000.ALSO:The invention comprises salicylic acid salts of mono- and di-carboxylic acid esters of an 8-hydroxy quinoline having the general formulae <FORM:0936342/IV(a)/1> wherein R and R1 are the acyl groups of a monocarboxylic acid and a dicarboxylic acid respectively, and X is hydrogen, halogen or an alkyl or alkoxy group having from 1 to 8 carbon atoms.  The invention also comprises di-8-quinolyl phthalate and its preparation by reacting 8-hydroxy quinoline with phthalic acid chloride in pyridine.  The salicylic acid salts are prepared by reacting the acid with the desired ester in an organic solvent. Examples describe the preparation of the salicyclic acid salts of the benzoic, phthalic, butyric and palmitic esters of 8-hydroxy quinoline and of the benzoic esters of 3-methyl, 4-methyl, 5-methyl, 4-chloro and 5-chloro substituted 8-hydroxy quinoline, by dissolving the salicyclic acid and ester in hot isopropanol, benzene, petroleum ether or mineral spirits and cooling to crystallise out the desired salt.  The preparation of di-8-quinolyl phthalate and the benzoates of 3-methyl and 4-methyl 8-hydroxy quinolines from the acid chlorides is described in detail.  Reference is made to the use of 8-quinolyl esters of various other carboxylic acids including acetic, butyl acetic, cyclohexyl-, cyclopentyl- and phenyl-acetic, cinnamic, furoic, malonic acid succinic acids.  The ester salts may be used as active components in antifungal compositions (see Group VI).ALSO:Fabric, leather, wood, hemp and paper are proofed against attack by fungi by applying thereto salicylic acid salts of quinolyl esters having one of the formula <FORM:0936342/IV(a)/1> wherein R is the acyl group of a monocarboxylic acid, R1 is the diacyl group of a dicarboxylic acid and X is hydrogen, halogen or a C1-8 alkyl or alkoxy group, the salts being used in solution or suspension.  The salicylic acid salts of the benzoic, phthalic, butyric, and palmitic esters of 8-hydroxy quinoline and of the benzoic acid esters of 3-methyl, 4-methyl, 5-methyl, 4-chloro and 5-chloro substituted 8-hydroxy quinolines are typical of the specified salts.  The salts may be formulated with waterproofing waxes, resins and flame-proofing chemicals; other fungicides may also be present e.g., chlorinated phenols and phenyl mercury salts.ALSO:Fungicidal and bacteriocidal compositions comprise as active ingredient, a salicylic acid salt of a quinolyl ester having one of the formul :  <FORM:0936342/VI/1> wherein R is the acyl group of a monocarboxylic acid, R1 is the diacyl group of a dicarboxylic acid and X is hydrogen, halogen or a C1-8 alkyl or alkoxy group.  The salts may be used with a pharmaceutical carrier in the treatment of fungal infections, e.g. athlete's foot.  Specified pharmaceutical compositions are (1) an ointment comprising the salicylic acid salt of 8-benzoyloxy quinoline, dipropylene glycol and polyethylene glycol 1000; (2) a solution of the same salt in dipropylene glycol containing malt agar and (3) an aerosol of the same salt and dipropylene glycol in a mixture of chlorofluoro methanes.  Also, the salts may be used in solution or suspension in a solvent, e.g. water, in proofing industrial material subject to attack by micro-organisms (see Groups IV (a) and IV (c)); such solutions and suspensions may also comprise water-proofing waxes, resins and flame-proofing chemicals.  Numerous other examples of the salts are provided and their preparation is described (see Group IV (b)).