WO1985000955A1 - A biocidal, particularly fungicidal and/or bactericidal composition and thiosemicarbazones and metal complexes thereof for use in the composition - Google Patents

A biocidal, particularly fungicidal and/or bactericidal composition and thiosemicarbazones and metal complexes thereof for use in the composition Download PDF

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WO1985000955A1
WO1985000955A1 PCT/DK1984/000073 DK8400073W WO8500955A1 WO 1985000955 A1 WO1985000955 A1 WO 1985000955A1 DK 8400073 W DK8400073 W DK 8400073W WO 8500955 A1 WO8500955 A1 WO 8500955A1
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compounds
composition
straight
branched chain
represents hydrogen
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PCT/DK1984/000073
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French (fr)
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Anita Wengel
Hans Kolind-Andersen
Niels Jacobsen
Axel Kristian Svendsen
Per Dausell Klemmensen
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A/S Cheminova
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/42—Radicals substituted by singly-bound nitrogen atoms having hetero atoms attached to the substituent nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C07F13/005—Compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages

Definitions

  • a biocidal, particularly fungicidal and/or bactericidal composition and thiosemicarbazones and metal complexes thereof for use in the composition are provided.
  • the present invention relates to a biocidal, particularly fungicidal and/or bactericidal, composition comprising a thiosemicarbazone or a metal complex thereof which, when using the composition, exhibits hitherto unknown biocidal properties.
  • the invention also relates to thiosemicarbazones and metal complexes thereof, and salts thereof, for use in the composition.
  • the invention relates to a method for ccmbating or preventing attacks by phytopathbgenic organisms on plants or plant material.
  • X represents hydrogen, straight or branched chain alkyl having up to 6 carbon atoms, alkoxy having up to 6 carbon atoms, phenoxy or halogen, and n is 1, 2 or 3, or (X 1 ) n when taken together form a fused benzene ring
  • R 1 represents hydrogen or straight or branched chain alkyl having up to 6 carbon atoms
  • R 2 and R 3 each independently represents hydrogen, straight or branched chain alkyl or alkenyl having up to 18 carbon atoms, cycloalkyl, arylalkyl heteroarylalkyl, aryl, substituted aryl, a heterocyclic ring containing one or more hetero atoms, acyl, hydroxy or alkoxy, alkylsulphonyl or arylsulphonyl, amino, alkylamino or dialkylamino, arylamino, hydroxy- alkyl or alkoxyalkyl, aminoalkyl, monoalkylaminoal
  • Examples of the ligands forming part of the metal complexes of the invention include neutral ligands such as H 2 O, NH 3 , amines and phosphines, anionic ligands such as the inorganic chlorides and sulphates and the organisk alcoholates, phenolates, thiolates, carboxylates (including substituted carboxylates and amino acid anions), sulphonates and anions of organic CH acids, e.g. anions of ⁇ -dicarbonyl compounds.
  • neutral ligands such as H 2 O, NH 3 , amines and phosphines
  • anionic ligands such as the inorganic chlorides and sulphates and the organisk alcoholates, phenolates, thiolates, carboxylates (including substituted carboxylates and amino acid anions), sulphonates and anions of organic CH acids, e.g. anions of ⁇ -dicarbonyl compounds.
  • Cultivated plants are here, e.g., cereals, maize, rice, vegetables, sugar beets, soya, peanuts, fruit trees, ornamental plants, but above all grape vines, hop, cucumber plants (cucumber, pumpkin, melon), solanaceae, such as potato, tobacco, and tomato, and also banana, cocoa, and natural caoutchouc plants.
  • Fungi occurring on plants or parts of plants can be inhibited or destroyed by the active compounds of the invention, whereby also plant parts growing up later on remain spared of such fungi.
  • the compounds of the invention are active against phytopatogenic fungi belonging to the following classes: Ascomycetes, Basidiomycetes such as rust fungi. Fungi imperfecti, e.g., Fusarium oxysporum and Botrytis cinerea, but particularly against the Oomycetes belonging to the class of Phycomycetes, such as Pythium sp., Phytophthora sp., Peronospora sp., Pseudoperonospora sp., and Plasmopara sp.
  • Ascomycetes Basidiomycetes such as rust fungi. Fungi imperfecti, e.g., Fusarium oxysporum and Botrytis cinerea
  • Oomycetes belonging to the class of Phycomycetes, such as Pythium sp., Phytophthora sp., Peronospora sp., Pseudoperonospora
  • the compounds of the invention can be used for treating seed material (fruits, tubers, seed corn) and cuttings to protect them against fungal infections and against phytopatogenic fungi occurring in the soil.
  • the compounds of the invention are active against rot fungi belonging to the class of basidiomycetes.
  • the compounds of the invention are bactericides which have shown activity against, e.g., Pseudomonas mors prunorum.
  • the invention relates specifically to a biocidal composition as defined above intended for combating or preventing attacks by fungi or bacteria on plants or plant material, including seed material.
  • a particularly advantageous composition of this type is intended for combating or preventing attacks by oomycetes.
  • the invention also relates to thiosemicarbazones of the general formula I or their metal complexes or salts thereof as defined above, for use in the compositions defined above.
  • the invention relates to a method for combating or preventing attacks by fungi or bacteria on plants or plant material, including seed material, which method is characterized by treating the plants or plant material with an active amount of a thiosemicarbazone or a metal complex thereof, or a salt thereof, as defined above.
  • thiosemicarbazones of the general formula I are prepared by one of the following methods known from the literature:
  • Method 1 Reaction of a carbonyl compound with a thiosemicarbazide.
  • Method 2 Reaction of a hydrazone with a isothiocyanate.
  • Method 3 Reaction of methyl 3-[1-(2-pyridyDethylidene]- hydrazinecarbodithioate with an amine.
  • Example 1 (compound No. 8, method 1) A mixture of 1.55 g of 2-acetyl-4-chloropyridine, 1.45 g of 1-pyrrolidinethiocarbohydrazide, 0.5 g of glacial acetic acid, 0.5 g of potassium acetate and 50 ml of ethanol is boiled under reflux for 7 hours. On cooling to 20°C and filtering the thiosemicarbazone is obtained as yellow needles of melting point 160-161°C.
  • Example 2 (compound No. 25, method 2) A mixture of 1.35 g of 2-acetylpyridinehydrazone, 1.49 g of 3-tolyl isothiocyanate and 25 ml of diethyl ether is stirred for 4 hours at 20°C. The precipitated crystals of the thiosemicarbazone 25 are filtered off and recrystallized from methanol and has a melting point of 148-150°C.
  • Example 3 (compound No. 17, method 3)
  • thiosemicarbazones prepared according to the Examples 1 to 3 are tabulated in Table I below together with a number of further thiosemicarbazones of the invention prepared in a similar way.
  • Complexes of the thiosemicarbazones of the invention are prepared by reacting the latter with metal salts of inorganic or organic acids, optionally in the presence of neutral ligands.
  • the preparation takes place by dissolving the two starting materials - together or separately - usually at elevated temperature in suitable solvents such as water, methanol, ethanol, methylene chloride, acetonitrile and dimethylformamide (DMF) or combinations thereof.
  • suitable solvents such as water, methanol, ethanol, methylene chloride, acetonitrile and dimethylformamide (DMF) or combinations thereof.
  • the temperature at which the starting centre have been combined is maintained for a shorter or longer time, whereupon the reaction mixture is filtered, if necessary, before cooling. On this cooling the product often crystallizes, but it may be necessary to add another solvent in order to promote this crystallization, or to evaporate the reaction mixture. Subsequently the products may be recrystallized from various solvents.
  • Example 4 (compound No. 204). 3.2 g (0.015 mole) of cupric glycolate is suspended i 200 ml of DMF at 100°C, and 3.3 g (0.015 mole) of 2-acetylpyridine-N 4 ,N 4 -dimethyl-3-thiosemicarbazone dissolved in 20 ml of hot DMF is added thereto while stirring. The stirring was continued i 2 1/4 hours at 60°C and then in 48 hours at room temperature. Filtering of the reaction mixture and drying of the matter filtered off gave 4.4 gof product which was recrystallized from methanol. The product isolated therefrom had a melting point of 212°C (dec).
  • thiosemicarbazone complexes prepared according to the Examples 4 to 5 are tabulated in Tables II to IV below together with a number of further thiosemicarbazone complexes of the invention prepared in a similar way.
  • the compounds of the invention may be formulated as compositions such as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols.
  • Wettable powders are usually formulated to contain 25, 50 or 75% of toxicant and usually contain, in addition to solid carrier, 3-10% by weight of a dispersing agent and, where necessary 0-10% by weight of stabilisers and/or additives such as penetrants or stickers.
  • Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant and are diluted in the field with further solid carrier to give a composition usually containing 1/2-10% by weight of toxicant.
  • Granules are usually prepared to have a size between 10 and 100 BS mesh, (1.676-0.152 mm) and may be manufactured by agglomeration or impregnation techniques.
  • granules will contain 1/2-25% by weight toxicant and 0-10% by weight of additives such as stabilisers, slow release modifiers and binding agents.
  • Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w/v toxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additives such as stabilisers, penetrants and corrosion inhibitors.
  • Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% by weight of toxicant, 1/2-15% by weight of dispersing agents, 0.1- 10% by weight of suspending agents such as protective colloids and thixotropic agents, 0-10% by weight of appropriate additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and as carrier, water or an organic liquid in which the toxicant is substantially insoluble. Certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as antifreeze agents for water.
  • Aqueous dispersions and emulsions for example. compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the present invention.
  • the said emulsions may be of the water-in-oil or of the olie-in-water type, and may have a thick "mayonnaise"- like consistency.
  • compositions may also contain other ingredients, for example, other compounds having pesticidal, particularly acaricidal, herbicidal or fungicidal properties.
  • Test Example 1 Agar plate test.
  • the solution of activ substance is added to steril agar liquefied by heating, in such an amount that the desired concentration of active substance therein is obtained. After thorough shaking to uniform distribution of the active substance, the agar is poured into Petri dishes under sterile conditions. After solidification of the mixture of substrate and active substance, test fungi from pure cultures are inoculated thereon in discs of a diameter of 5 mm. The Petri dishes are left in 5x 24 hours at 22°C for incubation.
  • the inhibitory effect of the active substance on the mycelial growth is determined in categories in relation to untreated control dishes. + no mycelial growth - mycelial growth, but inhibited in relation to control o mycelial growth like control.
  • Test concentrations in ppm 400, 200, 20 and 2.
  • active substance 400, 200, 20 and 2.
  • the beans are immersed in a solution of active substance for one minute and air-dried, 10 beans being immersed for each test concentration.
  • the beans are incubated in closed Petri dishes, on moist filter paper inoculated with Pythium ultimum, for 6 x 24 hours at 22°C. Thereby the germination of the beans and the mycelial growth of Pythium ultimum are initiated. After this period of time the number of healthy seedlings are determined in relation to untreated, non-inoculated control dishes. The more active the active substance is, the more seedlings are healthy.
  • Active substances, concentrations of active substances in the dressing solution and the number of healthy seedlings in % appear from the Table below.
  • the inhibitory effect of the active substance is determined, the radius of the zone of inhibition being measured and recorded in % of the maximum inhibition which is obtained by using 250 ppm of chloramphenicol.
  • Emulsif ⁇ er Triton X-155 100ppm
  • Test concentration in ppm (mg of substance per liter of solvent): 260, 130, 65, 33, 16, 8. Potato plants with 5-7 expanded leaves were sprayed until run off with the test compound.Two hours after the sporangial suspension is sprayed directly onto the treated plants, which immediately are placed in a humid chamber, 100% RH and an air temperature of 18°C. After two days under these conditions, the plants are placed in a growth chamber with 70-80% RH and an air temperature of 18°C.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

A biocidal composition, particularly a fungicidal and/or bactericidal composition, comprising a thiosemicarbazone having the general formula (I), and their complexes formed by reaction with compounds of the metals Cu, Zn, Mn, Fe, Ca, Mg, Al, Sn and Ti and having inorganic and/or organic ligands, and salts of said compounds, in which formula Y represents CH or N, X1 represents hydrogen, straight or branched chain C1-C6 alkyl, C1-C6 alkoxy, phenoxy or halogen, and n is 1, 2 or 3, or (X1)n when taken together form a fused benzene ring, R1 represents hydrogen or straight or branched chain C1-C6 alkyl, and R2 and R3 each independently represents hydrogen, straight or branched chain alkyl or alkenyl having up to 18 carbon atoms, cycloalkyl, arylalkyl, heteroarylalkyl, aryl, substituted aryl, a heterocyclic ring containing one or more hetero atoms, acyl, hydroxy or alkoxy, alkylsulphonyl or arylsulphonyl, amino, alkylamino or dialkylamino, arylamino, hydroxyalkyl or alkoxyalkyl, aminoalkyl, monoalkylaminoalkyl or diakylaminoalkyl, alkoxycarbonylalkyl or alkylideneimino, or R2 and R3 when taken together with the nitrogen atom to which they are attached form a heterocyclic ring which may optionally contain one or more additional hereto atoms selected from O, N and S. The compounds of the invention and their metal complexes may particularly be used for combating or preventing attacks by fungi or bacteria on plants or plant material including seed material.

Description

A biocidal, particularly fungicidal and/or bactericidal composition and thiosemicarbazones and metal complexes thereof for use in the composition.
The present invention relates to a biocidal, particularly fungicidal and/or bactericidal, composition comprising a thiosemicarbazone or a metal complex thereof which, when using the composition, exhibits hitherto unknown biocidal properties. The invention also relates to thiosemicarbazones and metal complexes thereof, and salts thereof, for use in the composition. Furthermore, the invention relates to a method for ccmbating or preventing attacks by phytopathbgenic organisms on plants or plant material.
The biocidal composition of the invention is characterized in that the thiosemicarbazone contained therein belongs to the group of thiosemicarbazones having the general formula I
Figure imgf000003_0001
and their complexes formed by reaction with compounds of the metals Cu, Zn, Mn, Fe, Ca, Mg, Al, Sn and Ti and having inorganic and/or organic ligands, and salts of said compounds, in which formula Y represents CH or N,
X, represents hydrogen, straight or branched chain alkyl having up to 6 carbon atoms, alkoxy having up to 6 carbon atoms, phenoxy or halogen, and n is 1, 2 or 3, or (X1)n when taken together form a fused benzene ring, R1 represents hydrogen or straight or branched chain alkyl having up to 6 carbon atoms, and R 2 and R3 each independently represents hydrogen, straight or branched chain alkyl or alkenyl having up to 18 carbon atoms, cycloalkyl, arylalkyl heteroarylalkyl, aryl, substituted aryl, a heterocyclic ring containing one or more hetero atoms, acyl, hydroxy or alkoxy, alkylsulphonyl or arylsulphonyl, amino, alkylamino or dialkylamino, arylamino, hydroxy- alkyl or alkoxyalkyl, aminoalkyl, monoalkylaminoalkyl or dialkylaminoalkyl, alkoxycarbonylalkyl or alkylideneimino, or R2 and R3 when taken together with the nitrogen atom to which they are attached form a heterocyclic ring which may optionally contain one or more additional hetero atoms selected from O, N and S.
Examples of the ligands forming part of the metal complexes of the invention include neutral ligands such as H2O, NH3, amines and phosphines, anionic ligands such as the inorganic chlorides and sulphates and the organisk alcoholates, phenolates, thiolates, carboxylates (including substituted carboxylates and amino acid anions), sulphonates and anions of organic CH acids, e.g. anions of β-dicarbonyl compounds. It is known that certain thiosemicarbazones and their metal complexes possess antimicrobial, antitumor, antiviral and antimalarial activities, confer the references 1-13 mentioned below, but thiosemicarbazones of the general formula I and particularly their metal complexes exhibit surprising fungicidal and/or bactericidal activities which are substantially higher than those of, or hitherto unknown in, the known thiosemicarbazones and their metal complexes as well as commercial substances of reference. References:
1. B.A. Gingras, G. Colin, and CH. Bayley; Journal of Pharmaceutical Sciences, 1965, Vol. 54, 1674-1675.
2. Japan 68 00,517 (Cl 16 E 431), 09 Jan 1968, Appl.
12 May 1965 (Takeda Chemical Industries Ltd.), Chemical Abstracts, Vol. 69 (1968), abstract No. 59112r.
3. D.M. Wiles and T. Suprunchuk, Journal of Medicinal Chemistry, 1971, Vol.14, No. 3, 252-254.
4. U.S. Patent No. 3,824,276, issued July 16, 1974. (The Upjohn Company, Kalamazoo, Mich.). 5. Yun Sung Chough, Hyang Sook Yoo, and Moo Bae, Seoul University Faculty Papers, Vol. 3 (D), Oct. 1975, 45-57. 6. W. Levinson, W. Rohde, P. Mikelens, J. Jackson, A. Antony, and T. Ramakrishnan, Annals New York Academy of Sciences, 1977, 525-532.
7. L. Heinisch, W.F. Fleck and H.-E, Jacob, Zeitschrift fur Allgemeine Mikrobiologie, 20, 10, 1980, 619-626.
8. S.N. Pandeya and P. Ram, Indian Journal of Chemistry
1981, Vol. 20B, 9, 825-827.
9. A. Saxena, J. K. Koacher and J. P. Tandon, J. Antibact. Antifung. Agents, Vol. 9, 1981, 435-438. 10. J. P. Scovill, D. L. Klaymann, and C. F. Franchino, J. Med. Chem. 1982, 25, 1261-1264.
11. V. N. Biyushkin, Yu. M. Chumakov, Khim.-Farm. Zh.,
1982, 16, 9, 1090-1091.
12. S. Giri, Nizamuddin and U.C. Srivastava, Agric. Biol. Chem., 47, 1, 1983, 103-105.
13. C. J. Pfau, Handbook of Experimental Pharmacology, Vol 61, 147-198, 1982.
It has surprisingly been found that the compounds of formula I and their metal complexes for practical requirements have a very favourable fungicidal and bactericidal activity for protecting cultivated plants. Cultivated plants are here, e.g., cereals, maize, rice, vegetables, sugar beets, soya, peanuts, fruit trees, ornamental plants, but above all grape vines, hop, cucumber plants (cucumber, pumpkin, melon), solanaceae, such as potato, tobacco, and tomato, and also banana, cocoa, and natural caoutchouc plants.
Fungi occurring on plants or parts of plants (fruits, blossoms, flowers, foliage, stems , tubers, roots) can be inhibited or destroyed by the active compounds of the invention, whereby also plant parts growing up later on remain spared of such fungi.
The compounds of the invention are active against phytopatogenic fungi belonging to the following classes: Ascomycetes, Basidiomycetes such as rust fungi. Fungi imperfecti, e.g., Fusarium oxysporum and Botrytis cinerea, but particularly against the Oomycetes belonging to the class of Phycomycetes, such as Pythium sp., Phytophthora sp., Peronospora sp., Pseudoperonospora sp., and Plasmopara sp.
Furthermore, the compounds of the invention can be used for treating seed material (fruits, tubers, seed corn) and cuttings to protect them against fungal infections and against phytopatogenic fungi occurring in the soil.
The compounds of the invention are active against rot fungi belonging to the class of basidiomycetes.
The compounds of the invention are bactericides which have shown activity against, e.g., Pseudomonas mors prunorum.
In accordance with the above the invention relates specifically to a biocidal composition as defined above intended for combating or preventing attacks by fungi or bacteria on plants or plant material, including seed material.
A particularly advantageous composition of this type is intended for combating or preventing attacks by oomycetes.
The invention also relates to thiosemicarbazones of the general formula I or their metal complexes or salts thereof as defined above, for use in the compositions defined above.
Furthermore the invention relates to a method for combating or preventing attacks by fungi or bacteria on plants or plant material, including seed material, which method is characterized by treating the plants or plant material with an active amount of a thiosemicarbazone or a metal complex thereof, or a salt thereof, as defined above.
Among the compounds of formula I and their complexes mention should particularly be made of those described in Test Examples 1 to 4 below. Preparation of thiosemicarbazones.
The thiosemicarbazones of the general formula I are prepared by one of the following methods known from the literature:
Method 1: Reaction of a carbonyl compound with a thiosemicarbazide. Method 2: Reaction of a hydrazone with a isothiocyanate. Method 3: Reaction of methyl 3-[1-(2-pyridyDethylidene]- hydrazinecarbodithioate with an amine. These three preparation methods are described in the References A and B mentioned below.
Three detailed Examples on the use of these general preparation methods are given below.
Example 1 (compound No. 8, method 1) A mixture of 1.55 g of 2-acetyl-4-chloropyridine, 1.45 g of 1-pyrrolidinethiocarbohydrazide, 0.5 g of glacial acetic acid, 0.5 g of potassium acetate and 50 ml of ethanol is boiled under reflux for 7 hours. On cooling to 20°C and filtering the thiosemicarbazone is obtained as yellow needles of melting point 160-161°C. Example 2 (compound No. 25, method 2) A mixture of 1.35 g of 2-acetylpyridinehydrazone, 1.49 g of 3-tolyl isothiocyanate and 25 ml of diethyl ether is stirred for 4 hours at 20°C. The precipitated crystals of the thiosemicarbazone 25 are filtered off and recrystallized from methanol and has a melting point of 148-150°C. Example 3 (compound No. 17, method 3)
A mixture of 2.25 g of methyl 3-[1-(2-pyridyl)- ethylidene]hydrazinecarbodithioate, 2 g of furfuryl amine and 50 ml ethanol is boiled under reflux for 7 hours. On cooling to 20°C the thiosemicarbazone 17 is precipitated which is filtered off and washed with ethanol and has a melting point of 144-146°C. References:
A. D. L. Klayman, J. F. Bartosevich, T. S. Griffin, C.J. Mason and J. P. Scovill, J. Med. Chem. 22., 855, 1979. B. D. L. Klayman, J. P. Scovill, J. F. Bartosevich and C. J. Mason, J. Med. Chem. 22., 1367, 1979.
The thiosemicarbazones prepared according to the Examples 1 to 3 are tabulated in Table I below together with a number of further thiosemicarbazones of the invention prepared in a similar way.
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Preparation of thiosemicarbazone complexes.
Complexes of the thiosemicarbazones of the invention are prepared by reacting the latter with metal salts of inorganic or organic acids, optionally in the presence of neutral ligands.
The preparation takes place by dissolving the two starting materials - together or separately - usually at elevated temperature in suitable solvents such as water, methanol, ethanol, methylene chloride, acetonitrile and dimethylformamide (DMF) or combinations thereof. The temperature at which the starting materiale have been combined is maintained for a shorter or longer time, whereupon the reaction mixture is filtered, if necessary, before cooling. On this cooling the product often crystallizes, but it may be necessary to add another solvent in order to promote this crystallization, or to evaporate the reaction mixture. Subsequently the products may be recrystallized from various solvents.
After this general preparation procedure two detailed Examples will now be given.
Example 4 (compound No. 204). 3.2 g (0.015 mole) of cupric glycolate is suspended i 200 ml of DMF at 100°C, and 3.3 g (0.015 mole) of 2-acetylpyridine-N4,N4-dimethyl-3-thiosemicarbazone dissolved in 20 ml of hot DMF is added thereto while stirring. The stirring was continued i 2 1/4 hours at 60°C and then in 48 hours at room temperature. Filtering of the reaction mixture and drying of the matter filtered off gave 4.4 gof product which was recrystallized from methanol. The product isolated therefrom had a melting point of 212°C (dec).
Example 5 (compound No. 102).
4.0 g (0.016 mole) of 2-acetylpyridine-N4,N4-tetramethylene-3-thiosemicarbazone was dissolved in 100 ml of hot methanol, and 2.15 g (0.016 mole) of cupric chloride dissolved in 50 ml of hot methanol was added thereto while stirring. The stirring was continued for
24 hours at room temperature. Filtering of the reaction mixture and drying of the matter filtered off gave a product which was directly recrystallized from DMF. After cooling a product was isolated by filtering and drying which had a melting point of 290°C. The composition of the compound was determined by microanalysis.
C12H15ClCuN4S requires: C 41.61, H 4-37, Cl 10.23, N 16.18%. Found: C 41.50, H 4.41, Cl 10.18, N 16.60%.
Related compounds are mentioned in the following references: C. J. P. Scovill, D. L. Klayman and C. F. Franchino, J. Med. Chem. 25, 1261-1264, (1982). D. Y. K. Bhoon, S. Mitra, J. P. Scovill and D. L. Klayman, Transition Met. Chem. 7 , 264-266, (1982).
The thiosemicarbazone complexes prepared according to the Examples 4 to 5 are tabulated in Tables II to IV below together with a number of further thiosemicarbazone complexes of the invention prepared in a similar way.
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
The compounds of the invention may be formulated as compositions such as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols. Wettable powders are usually formulated to contain 25, 50 or 75% of toxicant and usually contain, in addition to solid carrier, 3-10% by weight of a dispersing agent and, where necessary 0-10% by weight of stabilisers and/or additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant and are diluted in the field with further solid carrier to give a composition usually containing 1/2-10% by weight of toxicant. Granules are usually prepared to have a size between 10 and 100 BS mesh, (1.676-0.152 mm) and may be manufactured by agglomeration or impregnation techniques.
Generally, granules will contain 1/2-25% by weight toxicant and 0-10% by weight of additives such as stabilisers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w/v toxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additives such as stabilisers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% by weight of toxicant, 1/2-15% by weight of dispersing agents, 0.1- 10% by weight of suspending agents such as protective colloids and thixotropic agents, 0-10% by weight of appropriate additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and as carrier, water or an organic liquid in which the toxicant is substantially insoluble. Certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as antifreeze agents for water.
Aqueous dispersions and emulsions, for example. compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the present invention. The said emulsions may be of the water-in-oil or of the olie-in-water type, and may have a thick "mayonnaise"- like consistency.
The compositions may also contain other ingredients, for example, other compounds having pesticidal, particularly acaricidal, herbicidal or fungicidal properties.
The activities of the compounds of the invention are illustrated in detail by the following Test Examples.
Test Example 1 Agar plate test.
Testing for fungistatic activity and the breadth of the activity spectrum. Solvent: Ethanol. Test concentration in ppm (mg substance per 1 agar): 200, 20, 2, 0.2.
The solution of activ substance is added to steril agar liquefied by heating, in such an amount that the desired concentration of active substance therein is obtained. After thorough shaking to uniform distribution of the active substance, the agar is poured into Petri dishes under sterile conditions. After solidification of the mixture of substrate and active substance, test fungi from pure cultures are inoculated thereon in discs of a diameter of 5 mm. The Petri dishes are left in 5x 24 hours at 22°C for incubation.
After this period the inhibitory effect of the active substance on the mycelial growth is determined in categories in relation to untreated control dishes. + no mycelial growth - mycelial growth, but inhibited in relation to control o mycelial growth like control.
Active substances, concentrations of active substance, test fungi and inhibitory effect obtained appear from the Table below.
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Test Example 2 Seed dressing test.
Testing for protective activity against decay of bean seedlings caused by Pythium ultimum. Solvent: 10% acetone in water. Emulsifier: Triton X-155 100 ppm.
Test concentrations in ppm (mg of substance per liter of solvent) : 400, 200, 20 and 2. In dressing beans, they are immersed in a solution of active substance for one minute and air-dried, 10 beans being immersed for each test concentration. The beans are incubated in closed Petri dishes, on moist filter paper inoculated with Pythium ultimum, for 6 x 24 hours at 22°C. Thereby the germination of the beans and the mycelial growth of Pythium ultimum are initiated. After this period of time the number of healthy seedlings are determined in relation to untreated, non-inoculated control dishes. The more active the active substance is, the more seedlings are healthy.
Active substances, concentrations of active substances in the dressing solution and the number of healthy seedlings in % appear from the Table below.
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Comparative Tests To compare the activity of the compounds of the invention to the activity of known commercial fungicides of the formulae A, B, C, D, E, and F and to the activity of a thiosemicarbazone and its metal complex of similar, structures having the formulae G and I, tests were carried out according to the methods stated in the Examples 1 and 2.
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Test Example 3 Bacterial growth inhibition test.
Testing of bactericidal activity against Pseudomonas mors prunorum. Solvent: Ethanol. Test concentrations in ppm (mg of substance per liter og solvent): 500, 250, 125. Active substance is dissolved in ethanol in an amount such as to obtain the concentration required. Filter paper discs of 13 mm in diameter are immersed therein, air-dried and placed in Petri dishes (90 mm) with cooled solidified meat peptone agar inoculated on the surface with the test organism. The Petri dishes are incubated in 48 hours at 22°C.
After this period of time the inhibitory effect of the active substance is determined, the radius of the zone of inhibition being measured and recorded in % of the maximum inhibition which is obtained by using 250 ppm of chloramphenicol.
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
TEST EXAMPLE 4
Potato Late Blight Test
Testing for protectant activity of foliar applied against potato late blight caused by Phytophthora infestans.
Solvent; 10% acetone in water
Emulsif±er: Triton X-155 100ppm
Test concentration in ppm (mg of substance per liter of solvent): 260, 130, 65, 33, 16, 8. Potato plants with 5-7 expanded leaves were sprayed until run off with the test compound.Two hours after the sporangial suspension is sprayed directly onto the treated plants, which immediately are placed in a humid chamber, 100% RH and an air temperature of 18°C. After two days under these conditions, the plants are placed in a growth chamber with 70-80% RH and an air temperature of 18°C.
7-10 days after inoculation the plants are rated on a scale of 0 -10 where 0 = no disease control to 10 = 100% disease control.
Figure imgf000054_0001
Figure imgf000055_0001

Claims

STATEMENT UNDERARTICLE 19
Claim 1 has been restricted particularly in view of the prior art disclosed in GB, A, 1,084,700 and Chemical Abstracts, Vol. 69 (1968), abstract no. 59112r, as cited in the International Search Report, by directing claim 1 to a fungicidal rather than a biocidal composition, by deleting hydrogen from the definition of R2 and R3, and by adding a disclaimer at the end of claim 1. Furthermore, formula I has been restricted to 2-pyridyl compounds and several groups have been deleted from the definition of R2 and R3, and the ligands forming part of the complexes of the invention, have been defined based on the first full paragraph on page 2 of the description.
Claim 2 has been added as a new claim on a composition containing particularly active compounds of the invention, as substantiated by the test data stated in the description.
The new claims 3, 4 and 5 correspond to the original claims 2, 3 and 5, except that the words "and bacteria" have been deleted from line 2 of the new claim 3 and the words "o r bacteria" have been deleted from line 2 of claim 5.
The original claim 4 has been deleted.
PCT/DK1984/000073 1983-08-22 1984-07-27 A biocidal, particularly fungicidal and/or bactericidal composition and thiosemicarbazones and metal complexes thereof for use in the composition WO1985000955A1 (en)

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MD4127C1 (en) * 2010-10-06 2012-04-30 Государственный Университет Молд0 Use of di(m-S)-bis{chloro-[1-(pyridine-2-yl)ethanone-4-methylthiosemicarbazonato(1-)]copper} as substance with antimicrobial activity against Staphylococcus aureus
MD4179C1 (en) * 2011-05-23 2013-02-28 Государственный Университет Молд0 Coordinative compounds of copper(II), containing 4-phenylthiosemicarbazone 2-formylpyridine and sulfonylamides, exhibiting antimicrobial activity against bacteria of Bacillus cereus species
US20150307519A1 (en) * 2014-04-29 2015-10-29 The Regents Of The University Of California Small molecules for restoring function to p53 cancer mutants
MD4383C1 (en) * 2015-03-06 2016-06-30 Государственный Университет Молд0 Acetato-(8-formylquinolinethiosemicarbazono)copper(II) compound, exhibiting antibacterial activity
MD4393C1 (en) * 2015-09-04 2016-08-31 Государственный Университет Молд0 Inhibitor of human myeloid leukemia HL-60 cells based on nitrato-[N′-(1-pyridine-2-ylmethylidene)-morpholine-4-carbothiohydrazido(1-)]copper
MD4407C1 (en) * 2015-04-29 2016-10-31 Государственный Университет Молд0 Inhibitor of human myeloid leukemia HL-60 cells based on bis[N-(prop-2-en-1-yl)-2-(pyridine-2-ylmethylidene)hydrazinecarbothioamide]nickel(II) chloride hydrate
MD4434C1 (en) * 2015-10-09 2017-04-30 Государственный Университет Молд0 Use of N'-[1-(2-pyridyl)ethylidene]morpholin-4-carbothiohydrazide as a human myeloid leukemia HL-60 cell proliferation inhibitor
CN107311945A (en) * 2017-07-19 2017-11-03 河南理工大学 Thiosemicarbazones part and preparation method thereof, thiosemicarbazones metal complex and preparation method thereof
WO2020107221A1 (en) * 2018-11-27 2020-06-04 Tsinghua University Chemical activators of nicotinamide mononucleotide adenlyly transferase 2 (nmnat2) and uses thereof
CN111362868A (en) * 2018-12-25 2020-07-03 国科维思（北京）药物研究有限公司 Substituted thiosemicarbazone compound and application thereof in resisting mycobacterium tuberculosis

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MD4127C1 (en) * 2010-10-06 2012-04-30 Государственный Университет Молд0 Use of di(m-S)-bis{chloro-[1-(pyridine-2-yl)ethanone-4-methylthiosemicarbazonato(1-)]copper} as substance with antimicrobial activity against Staphylococcus aureus
MD4179C1 (en) * 2011-05-23 2013-02-28 Государственный Университет Молд0 Coordinative compounds of copper(II), containing 4-phenylthiosemicarbazone 2-formylpyridine and sulfonylamides, exhibiting antimicrobial activity against bacteria of Bacillus cereus species
US20150307519A1 (en) * 2014-04-29 2015-10-29 The Regents Of The University Of California Small molecules for restoring function to p53 cancer mutants
MD4383C1 (en) * 2015-03-06 2016-06-30 Государственный Университет Молд0 Acetato-(8-formylquinolinethiosemicarbazono)copper(II) compound, exhibiting antibacterial activity
MD4407C1 (en) * 2015-04-29 2016-10-31 Государственный Университет Молд0 Inhibitor of human myeloid leukemia HL-60 cells based on bis[N-(prop-2-en-1-yl)-2-(pyridine-2-ylmethylidene)hydrazinecarbothioamide]nickel(II) chloride hydrate
MD4393C1 (en) * 2015-09-04 2016-08-31 Государственный Университет Молд0 Inhibitor of human myeloid leukemia HL-60 cells based on nitrato-[N′-(1-pyridine-2-ylmethylidene)-morpholine-4-carbothiohydrazido(1-)]copper
MD4434C1 (en) * 2015-10-09 2017-04-30 Государственный Университет Молд0 Use of N'-[1-(2-pyridyl)ethylidene]morpholin-4-carbothiohydrazide as a human myeloid leukemia HL-60 cell proliferation inhibitor
CN107311945A (en) * 2017-07-19 2017-11-03 河南理工大学 Thiosemicarbazones part and preparation method thereof, thiosemicarbazones metal complex and preparation method thereof
WO2020107221A1 (en) * 2018-11-27 2020-06-04 Tsinghua University Chemical activators of nicotinamide mononucleotide adenlyly transferase 2 (nmnat2) and uses thereof
CN111362868A (en) * 2018-12-25 2020-07-03 国科维思（北京）药物研究有限公司 Substituted thiosemicarbazone compound and application thereof in resisting mycobacterium tuberculosis

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