Patent GB-938890-A (GB)
Title: New fungicidal compositions and compounds
Inventor: STEVENSON HERBERT AUBREY
IPC: A01N41/10
Filed: 1961-02-03
Abstract: As agents capable of controlling the growth of fungi, use is made of compounds of the formula <FORM:0938890/IV(a)/1> where n is 1 or 2 and (a) when n is 1, R represents an alkyl radical of 5-7 carbon atoms, a cycloalkyl radical, a phenylalkyl radical which may be substituted with halogen atoms and (or) nitro groups, or a phenyl radical which may be substituted with halogen atoms and (or) nitro, alkyl, alkoxy or alkoxycarbonyl groups and (b) when n is 2, R represents an alkyl radical of 1-7 carbon atoms, a halogen-methyl or halogen-propyl group, a cycloalkyl group or a phenylalkyl group which may be substituted with halogen atoms and (or) nitro groups.  The compounds of the formula above which fall within the scope of the formula <FORM:0938890/IV(a)/2> where R1 is an alkyl radical of 5-7 carbon atoms, a cycloalkyl radical, a halogenated and (or) nitrated benzyl radical, or a substituted phenyl radical in which the substituents are halogen atoms or nitro, alkyl, alkoxy or alkoxycarbonyl radicals (excepting 2,4-dinitrophenyl or o-methoxycarbonylphenol), or the formula <FORM:0938890/IV(a)/3> in which R11 represents a dichloromethyl, dibromomethyl, 3-chloropropyl or a halogenated and (or) nitrated benzyl radical, are stated to be novel compounds.  They may be prepared by oxidising the corresponding sulphides or sulphides in which the radical R1 or R11 is replaced by a radical readily convertible into a radical R1 or R11.  In the examples, (1) 4-chlorophenyl 2,4-dinitrophenyl sulphide is 2,4-dinitrophenyl sulphide is oxidised with hydrogen peroxide in glacial acetic acid to yield 4-chlorophenyl or 2,4-dinitrophenyl sulphoxide; 4-bromophenyl-2,4-dinitrophenyl sulphoxide, 4-fluorophenyl 2,4-dinitrophenyl sulphoxide, p-tolyl 2,4-dinitrophenyl sulphoxide, 2,5-dichlorophenyl 2,4-dinitrophenyl sulphoxide, 4-chlorobenzyl 2,4-dinitrophenyl sulphoxide, 4-nitrobenzyl 2,4-dinitrophenyl sulphoxide, 2-chloro-4-(or 5-)-methylphenyl 2,4-dinitrophenyl sulphoxide, and n-hexyl (or n-heptyl) 2,4-dinitrophenyl sulphoxide are similarly obtainable; (2) 4-nitrophenyl 2,4-dinitrophenyl sulfide is treated with fuming nitric acid at below 40 DEG C. to yield 4-nitrophenyl 2,4-dinitrophenyl sulphoxide; n-pentyl 2,4-dinitrophenyl sulphoxide, 3-methylbutyl 2,4-dinitrophenyl sulphoxide, and cyclopentyl (or cyclohexyl) 2,4-dinitrophenyl sulphoxide are similarly obtainable; (3) 4-bromophenyl 2,4-dinitrophenyl sulphoxide is nitrated in sulphuric acid at below 20 DEG C. to yield 4-bromo-3-nitrophenyl 2,4-dinitrophenyl sulphoxide; 4-chloro-3-nitrophenyl 2,4-dinitrophenyl sulphoxide and 3-nitrophenyl 2,4-dinitrophenyl sulphoxide are similarly obtainable; (4) 4-methoxyphenyl 2,4-dinitrophenyl sulphide is treated for several days at atmospheric temperature with monoperphthalic acid to yield 4-methoxyphenyl 2,4-dinitrophenyl sulphoxide; (5) 2,5-dichlorophenyl 2,4-dinitrophenyl sulphoxide is nitrated to yield 2,5-dichloro-X-nitrophenyl 2,4-dinitrophenyl sulphoxide; (6) 4-carboxyphenyl 2,4-dinitrophenyl sulphide is oxidised to yield, after separation with methanol, 4-methoxycarbonyl 2,4-dinitrophenyl sulphoxide and 4-methoxycarbonyl-X-nitrophenyl 2,4-dinitrophenyl sulphoxide; (7) 4-chlorobenzyl 2,4-dinitrophenyl sulphide is oxidised with hydrogen peroxide in glacial acetic acid to yield 4-chlorobenzyl 2,4-dinitrophenyl sulphone; 4-nitrobenzyl (and 3-chloropropyl) 2,4-dinitrophenyl sulphones are similarly obtainable; (8) dibromo (or dichloro) 2,4-dinitrophenyl sulphone is prepared by brominating (or chlorinating) 2,4-dinitrophenylsulphonyl acetic acid, which is obtainable by oxidising methyl 2,4-dinitrophenylthioacetate with hydrogen peroxide and hydrolysing the resulting ester.ALSO:As agents capable of controlling the growth of fungi, use is made of compounds of the formula <FORM:0938890/VI/1> where n is 1 or 2 and (a) when n is 1, R represents an alkyl radical of 5-7 carbon atoms, a cycloalkyl radical, a phenylalkyl radical which may be substituted with halogen atoms and (or) nitro groups, or a phenyl radical which may be substituted with halogen atoms and (or) nitro, alkyl, alkoxy or alkoxycarbonyl groups, and (2) when n is 2, R represents an alkyl radical of 1-7 carbon atoms, a halogen-methyl or halogen-propyl group, a cycloalkyl group or a phenylalkyl group which may be substituted with halogen atoms and (or) nitro groups (see Group IV (b)).  The compounds are used in association with an inert diluent and may be marketed as dusting powders, dilute or concentrated dispersions or emulsions, smokes and aerosols.  The smoke compositions may comprise, besides the active ingredient, a fuel, e.g. sucrose, a source of oxygen, e.g. potassium chlorate, and a dampener, e.g. kaolin.  The aerosol compositions may comprise, besides the active ingredient, a volatile or a high-boiling solvent, with or without a non-volatile oil, e.g. vegetable oil, and (or) a propellant, e.g. "Freon" (Registered Trade Mark).  The compositions may contain conventional additives, e.g. magnesium stearate, polyvinyl alcohol, silicic acid, bentonite or casein, and other fungicides or insecticides, e.g. D.D.T., benzene hexachloride, dinocap, dinoseb methacrylate or sulphur.  The compositions may be applied to the crops or to the soil.  A number of compounds from which the compositions may be prepared are listed, and examples and experimental results are given.  Specified compounds include 4-chlorophenyl 2,4-dinitrophenyl sulphoxide; 4-bromophenyl-2,4-dinitrophenyl sulphoxide, 4-fluorophenyl 2,4-dinitrophenyl sulphoxide, p-tolyl 2,4-dinitrophenyl sulphoxide, 2,5-dichlorophenyl 2,4-dinitrophenyl sulphoxide, 4-chlorobenzyl 2,4-dinitrophenyl sulphoxide, 4-nitrobenzyl 2,4-dinitrophenyl sulphoxide, 2-chloro4-(or 5-)methylphenyl 2,4-dinitrophenyl sulphoxide, n-hexyl (or n-heptyl) 2,4-dinitrophenyl sulphoxide, 4 - nitrophenyl 2,4 - dinitrophenyl sulphoxide; n-pentyl 2,4-dinitrophenyl sulphoxide, 3-methylbutyl 2,4-dinitrophenyl sulphoxide, cyclopentyl (or cyclohexyl) 2,4-dinitrophenyl sulphoxide, 4-bromo-3-nitrophenyl 2,4-dinitrophenyl sulphoxide; 4 - chloro - 3 - nitrophenyl 2,4 - dinitrophenyl sulphoxide, 3 - nitrophenyl 2,4-dinitrophenyl sulphoxide, 4-methoxyphenyl 2,4-dinitrophenyl sulphoxide, 2,5-dichloro-#c-nitrophenyl 2,4-dinitrophenyl sulphoxide, 4-methoxycarbonylphenyl 2,4-dinitrophenyl sulphoxide, 4-methoxycarbonyl-x-nitrophenyl 2,4-dinitrophenyl sulphoxide, 4-chlorobenzyl 2,4-dinitrophenyl sulphone, 4-nitrobenzyl (and 3-chloropropyl) 2,4-dinitrophenyl sulphones, and dibromo (or dichloro) 2,4-dinitrophenyl sulphone.