Patent GB-769771-A (GB)
Title: Improvements in and relating to hydrazones
IPC: A01N51/00
Filed: 1955-05-24
Abstract: The invention comprises acylated hydrazones of the formula <FORM:0769771/IV(b)/1> wherein R represents an alkyl or haloalkyl radical containing 1 to 4 carbon atoms, R1 represents a phenyl, styryl or furyl radical which may contain halogen, methyl and/or nitro groups and R2 represents hydrogen or an alkyl radical containing 1 to 3 carbon atoms.  Such compounds are obtained by reacting in the presence of an acid-binding agent, trichloromethane sulphenyl chloride with a sulphonyl hydrazone of the general formula <FORM:0769771/IV(b)/2> or with an alkali metal salt of such a sulphonyl hydrazone.  The sulphonyl hydrazones are obtained by reacting together appropriate sulphonic acid hydrazides and aldehydes or ketones to produce, for example, N1-methane, N1-ethane, N1-propane, N1-chloromethane and N1-a -chlorethane sulphonyl hydrazones of benzaldehyde, 4-chlorobenzaldehyde, 3,4-dichlorobenzaldehyde, 3- or 4-nitro-benzaldehyde, 4-methylbenzaldehyde, cinnamaldehyde, 4-chlorocinnamaldehyde, furfural, 5-nitro-furfural, acetophenone, 4-chloro-acetophenone, butyrophenone, 3,4-dichlorobutyrophenone, benzal-acetone and 4-chloro-benzalacetone.  In examples: (1) benzaldehyde methane sulphonyl hydrazone is reacted with perchloromethyl mercaptan in the presence of caustic soda for N1-methane sulphonyl - N - trichloromethane sulphenyl-N-benzylidene hydrazine; (2) N1-methane sulphonyl-N-trichloromethane sulphenyl-N-furfurylidene hydrazine is prepared similarly. Analagously prepared are N1-methane sulphonyl - N1 - trichloromethane sulphenyl derivatives of hydrazine of the above formula in which = CR1R2 represents a 4-chlorobenzylidene, 4-nitrobenzylidene, 4-methylbenzylidene, a  - methylbenzylidene, 2 - chloro - 5 - nitrobenzylidene, cinnamylidene, a -methyl-3,4-di-chlorobenzylidene, a  - n - propyl - 3,4 - dichloro-benzylidene and a -methyl-4-chlorocinnamylidene groups, N1-ethane sulphonyl-N1-trichloromethane sulphonyl-N-benzylidene hydrazine, N1 - (a  - chlorethane sulphonyl) - N1 - trichloromethane sulphenyl-N-benzylidene (and N-4-nitrobenzylidene) hydrazines, and N1-chloromethane sulphonyl-N1-trichloromethane sulphenyl N-benzylidene (and N-furfurylidene) hydrazines.  The products are useful as fungicides (see Groups I and VI).ALSO:Compositions suitable as fungicidal seed dressings comprise as active ingredient an acylated hydrozone of the formula <FORM:0769771/I/1> wherein R represents an alkyl or haloalkyl radical containing 1 to 4 carbon atoms, R1 represents a phenyl, styryl or furyl radical which may contain halogen, methyl and/or nitro groups and R2 represents hydrogen or an alkyl radical containing 1 to 3 carbon atoms.  The preparation of such compounds is described (see Group IV(b)).  In specific compounds described R is selected from methyl, chloromethyl and a -chlorethyl and =CR1R2 is selected from benzylidene, furfurylidene, 4-chloro-nitro or methyl benzylidene, a -methyl-benzylidene, 2-chloro-5-nitro-benzylidene, cinnamylidene, a -methyl- or n-propyl-3,4-dichloro-benzylidene, and a -methyl-4-chloro-cinnamylidene.  The products can be applied to bulbs, seeds and tubers.  Carriers specified are talc, kaolin, bole, bentonite, chalk, ground limestone, water (with wetting and dispersing agents), chlorinated hydrocarbons, petroleum fractions, acetone or other ketones.  The compounds can also be applied as aerosols, smoke or mist.ALSO:Fungicidal compositions contain as active ingredient an acylated hydrazone of the formula <FORM:0769771/VI/1> wherein R represents an alkyl or haloalkyl radical containing 1 to 4 carbon atoms, R1 represents a phenyl, styryl or furyl radical which may contain halogen, methyl and/or nitro groups and R2 represents hydrogen or an alkyl radical containing 1 to 3 carbon atoms.  The preparation of such compounds is described (see Group IV(b)).  Specific compounds described correspond to the above formula where R is selected from methyl, chloromethyl and a -chlorethyl and =CR1R2 is selected from benzylidene, furfurylidene, 4 - chloro-, nitro- or methyl-benzylidene, a -methylbenzylidene, 2-chloro-5-nitrobenzylidene, cinnamylidene a -methyl- or n-propyl-3.4-dichlorobenzylidene and a  - methyl - 4 - chlorocinnamylidene.  Carriers specified are talc, kaolin, bole, bentonite, chalk, ground limestone, water (with wetting agents), chlorinated hydrocarbons, petroleum fractions, acetone or other ketones.  The compounds can also be applied as aerosols, smoke or mist.  Examples describe compositions of (3) N1-methane sulphonyl-N1-trichloro-methane sulphenyl-N-benzylidene hydrazine and talc, to which an adhesive substance may be added, (4) N1 - methane - sulphonyl - N1 - trichloromethane sulphenyl-N-furfurylidene hydrazine with kaolin or chalk, sulphite waste liquor and an ethylene oxide condensation product of alkylphenols, which may be dispersed in water, (5) N1-chloromethane sulphonyl-N1-trichloromethane sulphenyl-N-benzylidene-hydrazine, xylene and an ethylene oxide condensation product of alkyl-phenols.