Patent GB-804507-A (GB)
Title: Process for the preparation of fungicidal supermetallic associates and compositions containing them
IPC: C07C51/41
Filed: 1956-04-23
Abstract: Oil-soluble supermetallic associates are prepared by reacting an organic carboxylic or sul phonic acid or a salt thereof, which is molecularly or colloidally soluble in a hydrocarbon medium, in a hydrocarbon and alcohol reaction medium with a hydroxide of a heavy metal having an atomic number between 24 and 31, which hydroxide has been formed in situ, evaporating substantially all the alcohol present in the reaction mixture and converting the heavy metal hydroxide present in the supermetallic associate to the oxide by dehydration.  The "in situ" preparation of the metal hydroxide is defined as "formed by reaction of an alcoholic or acetone solution of a heavy metal salt and alcoholic solution of an alkali metal hydroxide in presence of, or prior to admixture with, the organic carboxylic or sulphonic acid or salt."  The preferred procedure is to dissolve the acid or a salt in a hydrocarbon and to react this with alcoholic solutions of a heavy metal salt and an alkali metal hydroxide which are either mixed before addition or preferably added separately and gradually to the solution of acid or salt.  Specified acids are carboxylic and sulphonic acids of preferably alkyl-substituted benzenes and naphthalenes, naphthenic acids and naphtha sulphonic acids.  The preferred heavy metal is copper.  Heavy metal salts specified are chlorides, bromides, nitrates, oxalates and acetates.  The hydrocarbons used may be paraffinic, naphthenic or aromatic and preferably contain not more than 10 carbon atoms in the molecule, e.g. toluene, xylene and gasoline having a boiling range of 60-80 DEG  C.  Specified alcohols are methanol, ethanol and isopropanol.  Up to 10 per cent of water may be added to the reaction mixture before the dehydration.  The final product is a solution of the supermetallic associate dissolved in the hydrocarbon and the associate may be obtained therefrom in powder form by evaporation of the hydrocarbon, or by the addition of a liquid miscible with hydrocarbon and having a dielectric constant of at least 6 (e.g. methanol, ethanol or acetone) as a precipitating agent.  The supermetallic associates and compositions thereof are used as fungicidal agents (see Group VI).  In an example alkyl salicylic acids obtained by alkylating phenol with C14-C18 olefins (1 1/2 -2 olefin chains per mol. of phenol), carboxylating the corresponding sodium phenolate and acidifying are dissolved in xylene and to the resulting solution are added with stirring methanolic copper chloride and sodium hydroxide solutions, the methanol is distilled off by heating up to a temperature of 115 DEG  C. and the copper hydroxide containing product which is insoluble is dehydrated and redissolves as the copper oxide containing product, the mixture is heated further in vacuo, centrifuged to remove insolubles and the xylene removed by distillation in vacuo to give a supermetallic copper alkylsalicylate which contains 5.74 atoms of bound copper for each mol. of salicylic acid.  Supermetallic copper, zinc or manganese naphthenate, iron alkylsalicylate and copper naphtha sulphonate are prepared similarly.ALSO:Oil-soluble fungicidal supermetallic associates, prepared by reacting an organic carboxylic or sulphonic acid or a salt thereof, which is molecularly or colloidally soluble in a hydrocarbon medium, in a hydrocarbon and alcohol reaction medium with a hydroxide of a heavy metal having an atomic number between 24 and 31, which hydroxide has been formed in situ, evaporating substantially all the alcohol present in the reaction mixture and converting the heavy metal hydroxide present in the supermetallic associate to the oxide by dehydration (see Group IV (b)) are used as fungicides or in fungicidal compositions.  The products of the reaction comprise the supermetallic associate dissolved in the hydrocarbon (e.g. toluene, xylene or gasoline) and this solution may be used as such, or emulsified with water preferably in the presence of a surface-active agent, and used for spraying.  The associate may also be obtained as a powder which may be diluted with kaolin or montmorillonite or with a surface-active agent to give a wettable powder.  It may be redissolved in white oil, benzene, light fuel oil or carbon tetrachloride.  Examples describe the use of a supermetallic copper naphthenate or alkylsalicylate prepared as above in the suppression of fungus infections on potatoes and tomatoes. The compounds are applied as oil-in-water emulsions, solutions in white oil and kerosene and as wettable powders and the results compared with known fungicides similarly prepared.