Classifications

• • 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

Definitions

• Liquid pesticide concentrate formulation comprising phenylsemicarbazone compounds
• the present invention relates to a liquid pesticide concentrate formulation which comprises at least one phenylsemicarbazone of the formula A as defined hereinafter and to its use for controlling organisms that are harmful to crops.
• Agriculturally active compounds can be applied in the form of aqueous emulsions, solutions, or suspensions. Usually, the active ingredients are transported in the form of liquid concentrate formulations for later dilution.
• emulsifiable concentrates are normally composed of an active ingredient, a surfactant and an organic solvent, and are used after diluting with water to form a milky oil-in-water emulsion, containing the active ingredient dissolved in the solvent droplets.
• Microemulsion concentrates have also been described and are understood as meaning a composition which forms microemulsions upon dilution with water.
• a microemulsion is understood as being an emulsion which is thermodynamically stable and has a droplet size of the emulsified phase which is generally in the submicron scale (frequently 200 nm or below).
• R 1 and R 2 are each independently hydrogen, halogen, cyano, Ci-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy and R 3 is C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy, and their agriculturally acceptable salts are known from EP 0 462 456 A1.
• the compounds of the formula A have a wide pesticidal spectrum against arthropod pests and nematodes, in particular against insect pests.
• phenylsemicarbazones of the formula A are only sparingly or even insoluble in hydrophilic media such as water. For example, they usually have a water-solubility of not more than 2 g/l, and often much less, at 25°C/1013 mbar.
• WO 2006/002984 A1 discloses liquid pesticide formulations, wherein at least one organic pesticide compound is dissolved in a mixture of a water-miscible solvent and at least one non-ionic block-copolymer.
• the pesticide compound may be a phenylsemicarbazone compound of the formula A, among many others.
• the solvent used is capable of dissolving the active ingredient and may contain water, provided that the weight ratio of water to solvent does not exceed 1 :2.
• WO 2006/133928 A2 discloses the use of the phenylsemicarbazones of formula A, or agriculturally acceptable salts thereof for seed treatment and corresponding methods of seed treatment for controlling arthropod pests. Also disclosed are seed treatment formulations comprising the phenylsemicarbazones.
• WO 2006/127399 A2 discloses high load concentrate compositions comprising metaflumizone, an optional bridging agent, a surfactant, and a suitable carrier solvent. These compositions may be topically administered to animals, and are useful for preventing or treating ectoparasitic infestations in warm-blooded animals for prolonged periods of time.
• WO 2007/017501 A2 discloses an emulsifiable concentrate formulation comprising (a) a phenylsemicarbazone compound of the formula A, (b) a solvent system, comprising ⁇ -butyrolactone, one or more aliphatic and/or aromatic ketones, and optionally one or more aromatic hydrocarbons, (c) one or more emulsifiers, and (d) optionally further formulation additives.
• JP 2006131515 A discloses a pest control agent composition containing a hydrazinecarboxamide compound, and at least one compound selected from insecticidal, acaricidal and nematocidal compounds as effective components.
• WO 2007/077246 A2 discloses a water-dilutable liquid concentrate formulation, comprising (a) at least one organic pesticide compound having a water solubility of not more than 5 g/l at 25°C/1013 mbar, (b) a solvent mixture comprising i) at least one C2-C4-alkylene glycole and ii) at least one C2-C4-alkylene carbonate and (c) at least one surfactant.
• the pesticide compound may be a phenylsemicarbazone compound of the formula A, among many others.
• WO 2007/1 10355 A discloses agrochemical formulations comprising a) 0.1-50 wt% of at least two pesticides comprising, inter alia, metaflumizone and acetamiprid; or metaflumizone and teflubenzuron; or metaflumizone and flufenoxuron, b) 30-99.8 wt% of at least two polar organic solvents, c) 0.1-50 wt% of a mixture comprising a non-ionic distyrylphenol alkoxylate and a ionic distyrylphenol alkoxylate, d) 0-50 wt% non-ionic surfactant, and e) 0-20 wt% further formulation auxiliaries.
• PCT/EP2007/060449 discloses a liquid pesticide composition, which comprises (a) a phenylsemicarbazone compound of the formula A, (b) a solvent selected from water and polyhydric C2-C4 alcohols and mixtures thereof, the pesticide compound of the formula A being soluble in the solvent in an amount of not more than 2 g/l at 25°C/1013 mbar; and (c) one or more surfactants, wherein the compound of formula A is present in the form of particles having a volume median diameter, as determined by dynamic light scattering, of not more than 1.5 ⁇ m.
• liquid concentrate formulations of the phenylsemicarbazone compound of the formula A containing relatively high concentrations of this pesticide which is particularly attractive from an economic viewpoint.
• the high pesticide loading it is further desirable to a have a liquid concentrate exhibiting good stability properties.
• the formulation Upon dilution with water, the formulation should form a stable aqueous composition of the active ingredient, and the formation of coarse constituents should be avoided.
• the precipitation of the active ingredient should be prevented upon prolonged storage or storage at elevated temperatures. It is also an object of the present invention that the liquid pesticide formulations provide good to excellent control against a broad spectrum of insect pests.
• liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate, comprising
• R 1 and R 2 are each independently hydrogen, halogen, cyano, Ci-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy and R 3 is C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy, or an agriculturally acceptable salt thereof;
• R 4 is C6-C20 alkyl, C6-C20 alkenyl or C6-C20 alkynyl, and
• R 5 and R 6 are each independently hydrogen or C1-C4 alkyl as organic solvent, and
• the liquid pesticide concentrate formulations of the present invention are effective against a broad spectrum of insect pests.
• inventive formulations contain relatively high concentrations of the pesticidal compound A, they exhibit good stability over prolonged storage times, also at elevated temperatures, without significant occurrence of phase separation phenomena or noticeable agglomeration of the active ingredients.
• the high loading of the active ingredient together with the enhanced biology provides excellent value for the end user with several advantages such as a better handling, lower costs and environmental friendliness through low application rates, as well as low exposure to workers with better safety.
• the inventive formulations show good to excellent dilution and emulsion characteristics in standard water and also in hard waters.
• the formulations of the invention also have excellent wetting and leaf absorption properties.
• Ci-C4 alkyl refers to straight or branched aliphatic alkyl groups having from 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.
• halogen as used herein as such as well as in related terms, such as haloalkyl or haloalkoxy, is selected from fluorine, chlorine, iodine and bromine, preferably from fluorine and chlorine, and more preferably is fluorine.
• Ci-C4 alkoxy refers to a C1-C4 alkyl group, as defined above, which is linked via an oxygen atom, e.g. methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.
• C1-C4 haloalkyl refers to a C1-C4 alkyl group, as defined above, which additionally contains one or more, e.g. 2, 3, 4, 5 or 6, halogen atom(s), as defined above, e.g.
• C1-C4 haloalkoxy refers to a Ci-C4 alkoxy group, as defined above, which additionally contains one or more, e.g. 2, 3, 4, 5 or 6, halogen atom(s), as defined above, e.g.
• R 1 is C1-C4 haloalkyl, in particular trifluoromethyl
• R 2 is cyano
• R 3 is C1-C4 haloalkoxy, in particular trifluoromethoxy.
• a preferred compound of the formula A is one wherein R 1 is 3-CF3 (i.e. CF3 which is disposed in the meta position), R 2 is 4-CN (i.e. CN which is disposed in the para position) and R 3 is 4-OCF3 (OCF3 which is disposed in the para position), i.e. metaflumizone.
• Metaflumizone is the common name for 2-[2-(4-cyanophenyl)-1-[3- (trifluoromethyl)phenyl]ethylidene]-N-[4-(trifluoromethoxy)phenyl]hydrazinecarboxamide (IUPAC nomenclature: (EZ)-2'-[2-(4-cyanophenyl)-1-( ⁇ , ⁇ , ⁇ -trifluoro-m-tolyl)ethylidene]- 4-(trifluoromethoxy)carbanilohydrazide), having the following formula A1 :
• the compound A1 exists in two geometric isomers with regard to the C-N double bond, i.e. 4- ⁇ (2E)-2-( ⁇ [4-(trifluoromethoxy)anilino]carbonyl ⁇ hydrazono)-2-[3-(trifluoromethyl)- phenyl]ethyl ⁇ benzonitrile and 4- ⁇ (2Z)-2-( ⁇ [4-(trifluoromethoxy)anilino]carbonyl ⁇ - hydrazono)-2-[3-(trifluoromethyl)phenyl]ethyl ⁇ benzonitrile.
• metaflumizone includes both the E- and Z-isomer of the compound as defined above, as well as any mixture thereof in any ratio.
• E- and Z-isomers of compounds A and A1 and their interconversion have been described in general in WO05/047235, incorporated herein by reference.
• metaflumizone having a E/Z-ratio higher than 1 :1 may be preferred.
• the compound A is present in the form of the pure compound A.
• the purity of compound A is usually at least 90 % by weight, preferably at least 95 % by weight.
• the compound A may be present in the neutral form or as a salt, which is obtained by treating the compound A with a suitable base.
• the salts of the compound A contain those cations which are the counterions of the base, for example sodium or potassium ions.
• the compound A will be present in the neutral form.
• the amount of the compound A may usually be in the range from 10 to 65 % by weight, in particular from 15 to 50 % by weight and more preferably from 17.5 to 48 % by weight, with particular preference from 20 to 40 % by weight, based on the total weight of the formulation.
• the following terms have the following meanings:
• C6-C2o alkyl refers to straight or branched aliphatic alkyl groups having from 6 to 20 carbon atoms, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and the like, as well as cycloalkyl groups, such as cyclohexyl and the like.
• C6-C2o alkenyl refers to a branched or unbranched unsaturated hydrocarbon group of 6 to 20 carbon atoms containing at least one double bond in any position, such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosenyl and the like.
• C6-C2o alkynyl refers to a branched or unbranched unsaturated hydrocarbon group of 6 to 20 carbon atoms containing at least one triple bond in any position, such as hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, heptadecynyl, octadecynyl, nonadecynyl, icosynyl and the like.
• R 4 is C6-C20 alkyl, in particular C6-C12 alkyl
• R 5 is C1-C4 alkyl, in particular methyl
• R 6 is C1-C4 alkyl, in particular methyl.
• R 4 is C6-C12 alkyl, and R 5 and R 6 are both C1-C4 alkyl.
• R 4 is C6-C12 alkyl, and R 5 and R 6 are both methyl.
• R 4 is selected from hexyl, octyl, decyl and dodecyl and R 5 and R 6 are both methyl.
• the amide of formula (b1 ) is selected from N,N-dimethylhexanamide, N,N-dimethyloctanamide, N,N-dimethyldecanamide and N,N-dimethyldodecanamide. In another embodiment, the amide of formula (b1 ) is a mixture comprising N,N-dimethyloctanamide and N,N-dimethyldecanamide.
• the amide of formula (b1 ) is a mixture comprising N,N-dimethylhexanamide, N,N-dimethyloctanamide, N,N-dimethyldecanamide and N,N-dimethyldodecanamide.
• the amide of formula (b1 ) is a mixture comprising 50 to 65 % by weight of N,N-dimethyloctanamide, 37 to 50 % by weight of N,N-dimethyldecanamide, 0 to 5 % by weight of N,N-dimethylhexanamide, and 0 to 2 % by weight of N,N-dimethyldodecanamide.
• N,N-dimethyl amides of carboxylic acids have already been described as solvents or penetration promoters in agrochemical formulations, see, for example, US 3,342,673, US 5,206,225, US 5,283,229, WO 2006/029736 A1 , and WO 2005/104844 A1.
• the amount of the one or more amides (b1 ) may usually be in the range from 15 to 80 % by weight, in particular from 20 to 70 % by weight, more preferably from 30 to 65 % by weight, based on the total weight of the formulation.
• the formulation according to the invention may additionally comprise one or more further organic solvents (b2), such as, for example, nonpolar solvents, polar protic or aprotic solvents and mixtures thereof.
• further organic solvents (b2) for the purpose of this invention are b2.1) aliphatic hydrocarbons, for example pentane, hexane, octane, cyclohexane and aliphatic and isoparaffinic mineral oils; b2.2) aromatic hydrocarbons, such as derivatives of benzene, for example alkylbenzenes such as toluene, xylenes, mesitylene, and diisopropylbenzene, derivatives of naphthalene such as alkylnaphthalenes, e.g.
• Solvesso® series such as Solvesso® 100, Solvesso®150 (b.p. 187-207 0 C) and Solvesso®
• Aromatic 100, Aromatic 150, and Aromatic 200 fluid products which are both available from ExxonMobil; b2.3) halogenated aliphatic hydrocarbons such as methylene chloride; b2.4) halogenated aromatic hydrocarbons such as chlorobenzene or dichlorobenzene; b2.5) lactones such as ⁇ -butyrolactone; and b2.6) ketones, in particular aliphatic and/or aromatic ketones, such as C1-C20 aliphatic ketones, C1-C20 cycloaliphatic ketones and C1-C20 aromatic ketones, e.g. 2- heptanone, mesityl oxide, cyclohexanone, isophorone and acetophenone.
• aliphatic and/or aromatic ketones such as C1-C20 aliphatic ketones, C1-C20 cycloaliphatic ketones and C1-C20 aromatic ketones, e.g. 2- heptanone, mesityl
• the amount of the solvent b2 may usually be in the range from 0 to 25 % by weight, in particular from 5 to 20 % by weight, more preferably from 5 to 17 % by weight, based on the total weight of the formulation.
• the organic solvent b2 is selected from the groups b2.2 and b2.6.
• the organic solvent b2 is selected from the group b2.2, in particular aromatic hydrocarbons, preferably Solvesso 200 and Aromatic 200.
• the amount of the aromatic hydrocarbon is in the range from 0 to 8 % by weight, in particular from 1 to 7 % by weight, more preferably from 2 to 5 % by weight, based on the total weight of the formulation.
• the organic solvent b2 is selected from the group b2.6, in particular C1-C20 aliphatic ketones, preferably C3-C8 aliphatic ketones and more preferably 2-heptanone.
• the amount of the C1-C20 aliphatic ketone is in the range from 0 to 25 % by weight, in particular from 3 to 20 % by weight, more preferably from 4 to 15 % by weight, based on the total weight of the formulation.
• the formulation comprises (c) one or more surfactants.
• surfactant as used herein is used in a broad sense to include any organic substance which is capable of reducing the surface tension of a phase boundary between an organic phase and an aqueous phase, and which may be referred to as emulsifying agents, detergent, dispersing agents and wetting agents.
• the nature of the surfactants (c) is not particularly critical, e.g. they may be non-ionic, anionic, cationic or amphoteric.
• Surfactants suitable for the purpose of this invention are well known to the skilled person as are processes for the preparation thereof. Such surfactants are disclosed e.g.
• the liquid pesticide concentrate formulations of the present invention contain the at least one surfactant (c) in amounts of from 0.1 to 30 % by weight, preferably from 3 to 20 % by weight and in particular from 5 to 15 % by weight, based on the total weight of the formulation.
• the formulations of this invention comprise at least one non-ionic surfactant.
• the non-ionic surfactant is generally present in an amount of from 0.1 to 30 % by weight, in particular from 0.5 to 15 % by weight, more preferably from 1.5 to 10 % by weight and still more preferably from 2.5 to 7.5 % by weight, based on the total weight of the formulation.
• the formulations of the invention comprise at least one anionic surfactant and at least one non-ionic surfactant. If such combinations of anionic and non-ionic surfactants are used, the amount of the anionic surfactant is from 0.5 to 20 % by weight, in particular from 1 to 15 % by weight and more preferably from 2 to 7.5 % by weight, and the amount of the non-ionic surfactant is from 0.5 to 20 % by weight, in particular from 1 to 15 % by weight and more preferably from 2 to 7.5 % by weight, in each case based on the total weight of the formulation.
• non-ionic surfactants useful in this invention include: c.1 ) polyethyleneglycol-Ci-C22-alkylethers, polyethyleneglycol/polypropyleneglycol-Ci- C22-a Iky I ethers, in particular polyethoxylates and poly-ethoxylates-co- propoxylates of linear or branched C8-C2o-alkanoles, more preferably polyethoxylated Cs-C22-fatty alcohols and polyethoxylated C8-C22-oxoalcohols, such as polyethoxylated lauryl alcohol, polyethoxylated isotridecanol, polyethoxylated cetyl alcohol, polyethoxylated stearyl alcohol, poly-ethoxylates- co-propoxylates of laurylalcohol, poly-ethoxylates-co-propoxylates of cetylalcohol, poly-ethoxylates-co-propoxylate
• non-ionic block copolymers comprising at least one poly(ethylene oxide) moiety PEO and at least one polyether moiety PAO derived from C3-Cio-alkylene oxides and/or styrene oxide, in particular polyoxyethylene-polyoxypropylene- blockcopolymers; c.13) non-ionic graft copolymers containing polyethylene oxide moiety PEO grafted on a non-ionic, hydrophilic polymeric backbone; and c.14) organosilicone surfactants, such as silicone polyalkylene oxide copolymers.
• polyethyleneglycol, polyethoxylates and polyethoxylated refer to polyether radicals derived from ethyleneoxide.
• poly-ethoxylate-co-propoxylate refers to a polyether radical derived from a mixture of ethyleneoxide and propylenoxide.
• polyethoxylates have repeating units of the formula [CH2CH2O] while poly- ethoxylate-co-propoxylate have repeating units of the formulae [CH2CH2O] and [CH(CH 3 )CH 2 O].
• the non-ionic surfactant is selected from groups c.6, c.7, c.12, c.14 and mixtures thereof. Particularly preferred non-ionic surfactants are those selected from the groups c.12 and c.14.
• the non-ionic block copolymers of the surfactant class c.12 comprise at least one poly(ethylene oxide) moiety PEO and at least one hydrophobic polyether moiety PAO.
• the PAO moiety usually comprises at least 3, preferably at least 5, in particular 10 to 100 repeating units (number average) which are derived from C3-Cio alkylene oxides, such as propylene oxide, 1 ,2-butylene oxide, cis- or trans-2,3-butylene oxide or isobutylene oxide, 1 ,2-pentene oxide, 1 ,2-hexene oxide, 1 ,2-decene oxide and styrene oxide, among which C3-C4 alkylene oxides are preferred.
• the PAO moieties comprise 10 to 60% by weight of repeating units derived from propylene oxide.
• the PEO moieties usually comprise 2 to 6, preferably 3 to 5, and more preferably 3 or 4 repeating units derived from ethylene oxide (number average).
• Those surfactants c.12 are preferred which have a number average molecular weight MN ranging from more than 600 to 8000 Dalton, preferably from 1000 to 6000 Dalton and in particular from 1500 to 5000 Dalton.
• the non-ionic block copolymer surfactants of the group c.12 described herein are commercially available e.g. under the trade names Pluronic®, such as Pluronic® P 65, P84, P 103, P 105, P 123 and Pluronic® L 31 , L 43, L 62, L 62 LF, L 64, L 81 , L 92 and L 121 , Pluraflo® such as Pluraflo® L 860, L1030 and L 1060; Tetronic®, such as Tetronic® 704, 709, 1 104, 1304, 702, 1102, 1302, 701 , 901 , 1 101 , 1301 (BASF Aktiengesellschaft), Agrilan® AEC 167 and Agrilan® AEC 178 (Akcros Chemicals), Antarox® B/848 (Rhodia), Berol® 370 and Berol® 374 (Akzo Nobel Surface Chemistry), Dowfax® 50 C15, 63 N10, 63 N30, 64 N40
• the non-ionic surfactant of the group c.12 is an ethylene oxide- propylene oxide block copolymer comprising alkyl or alkyphenol ether bases, such as butyl ether, methyl ether, propyl ether, ethyl ether, or mixtures thereof.
• alkyl or alkyphenol ether bases such as butyl ether, methyl ether, propyl ether, ethyl ether, or mixtures thereof.
• the commercially available product Toximul® 8320 (Stepan Co.) may be mentioned, i.e. a butyl ether derivative of ethylene oxide-propylene oxide block copolymer.
• the amount of the aforementioned block copolymer is usually from 2 to 20% by weight, in particular from 5 to 17 % by weight and more preferably from 5 to 12 % by weight, based on the total weight of the formulation.
• the non-ionic surfactant of the group c.14 is a polyalkylene oxide modified dimethyl polysiloxane, such as the organosilicone surfactants marketed under the Silwet® trademark, in particular Silwet® L-77 (GE Silicones). These surfactants are disclosed in US 2,970,150.
• the amount of the organosilicone surfactant is usually from 0 to 6 % by weight, in particular from 0.5 to 5 % by weight and more preferably from 1 to 4 % by weight, based on the total weight of the formulation.
• Anionic surfactants suitable for the purpose of the present invention include the sodium, potassium, calcium or ammonium salts of
• C6-C22-alkylsulfonat.es such as lauryl sulfonate and isotridecylsulfonate
• C6-C22-alkylsulfates such as lauryl sulfate, isotridecylsulfate, cetylsulfate and stearylsulfate
• alkylarylsulfonates in particular Ci-Ci6-alkylbenzene sulfonates, such as cumylsulfonate, octylbenzene sulfonate, nonylbenzene sulfonate, and dodecylbenzene sulfonate, naphthylsulfonate, mono- and di-Ci-Ci6- alkylnaphthyl sulfonates such as dibutylnaphtylsulfonate;
• the anionic surfactant is selected from groups c.26, c.28, c.32 and mixtures thereof.
• the formulations of the present invention comprise at least one non-ionic surfactant selected from the groups c.12 and c.14 as described above and at least one anionic surfactant selected from the groups c.26, c.28 and c.32 as described above.
• the components a), b) and c) i.e. compound A, solvent and surfactant
• formulations according to the invention may also comprise (d) further customary additives, for example antifoams and preservatives.
• the amount of the additives (d) will generally not exceed 5 % by weight, in particular 4% by weight of the total weight of the formulation.
• Antifoam agents suitable for the formulations according to the invention are, for example, long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
• Typical preservatives are, for example, vitamin E acetate, benzoic acid, sorbic acid, sodium benzoate, and formaldehyde. Preference is given to vitamin E acetate.
• the amount of preservative is generally from 0 to 5 % by weight, preferably 1 to 3 % by weight of total weight of the formulation.
• the formulations of the invention may optionally comprise also pigments or dyes, in particular, if the formulation is intended for seed treatment purposes.
• Suitable pigments or dyes for seed treatment formulations are pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, and basic red 108.
• the formulation according to the present invention may comprise one or more further active ingredients used in crop protection selected from acaricides, algicides, antecedents, aricides, bactericides, bird repellents, chemosterilans, fertilizers, fungicides, herbicides, herbicide safeners, insect attractants, insect repellents, insecticides, mammal repellents, mating disrupters, moluscicides, nematicides, plant activators, plant growth regulators, rhodenticides, synergists, and virucides.
• the combinations with other active ingredients as described herein can be prepared in the form of a finished formulation or as a tank mix.
• liquid pesticide concentrate formulation denotes a pesticide concentrate formulation which is liquid at normal temperature.
• the liquid pesticide concentrate formulation is in the form of an emulsifiable concentrate (EC) or a microemulsion concentrate (MC or MEC).
• the formulation according to the invention is a liquid, water-dilutable non-aqueous concentrate formulation.
• the formulation of the present invention is an emulsifiable concentrate.
• the formulation of the present invention is a microemulsion concentrate.
• the present invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate comprising
• the present invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate comprising
• the present invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate comprising
• the present invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate comprising
• the present invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate comprising
• the present invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate comprising
• the present invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate comprising a) 15 to 50 % by weight, based on the total weight of the formulation, of the compound A (in particular the compound of formula A1 ) or an agriculturally acceptable salt thereof;
• the present invention relates to a liquid pesticide concentrate formulation in the form of an emulsifiable concentrate or a microemulsion concentrate comprising
• the formulations of the present invention can be prepared by methods which are common for the preparation of emulsifiable concentrates or microemulsion concentrates.
• the formulations of the present invention can be prepared by a process comprising the steps of mixing the compound A, the solvent (b), the surfactant (c) and optionally further customary additives (d) with one another and, if appropriate, stirring and/or heating. More specifically, the formulations of the present invention can be prepared by dissolving the compound A, the surfactant (c) and optionally further customary additives (d) in the solvent (b).
• the liquid concentrate formulations according to the invention are useful for combating harmful organisms, such as arthropod pests and nematode pests.
• the formulations may be applied as such or are preferably applied after dilution with water.
• a so-called aqueous spray-liquor is prepared by diluting the liquid concentrate formulations of the present invention with water, e.g. tap water.
• the application rate of the pure compound A will be in the range of from 0.01 to 0.5 kg/ha, preferably from 0.05 to 0.4 kg/ha and in particular 0.1 to 0.3 kg/ha of active compound A.
• the diluted compositions are applied to e.g. plants or soils mainly by spraying, in particular foliar spraying.
• Application can be carried out by customary spraying techniques using, for example, water as carrier and spray liquor rates of from about 100 to 1000 I/ha (for example from 300 to 400 I/ha).
• the formulations of the present invention can be used in all areas of plant and crop protection and of the protection of materials for controlling harmful organisms or for promoting plant growth.
• the formulations of the invention can be employed both for protecting plants and for protecting materials against attack by such animal pests. It is also possible to treat plants and materials that have been attacked with the formulations according to the invention and to destroy the damaging organisms or at least to inhibit their growth, so that they cause no damage.
• the formulations of the invention are particularly suitable in the different areas of the protection of materials against attack by animal pests.
• cellulose-containing materials such as wood, and also skins, hides, leather, textiles, nonwovens and the like effectively against attack by animal pests.
• the formulations of the invention may be applied against the following pests:
• lepidopterans for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis viresc
• Sparganothis pilleriana Spodoptera eridania, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis,
• beetles Coldeoptera
• Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis,
• dipterans dipterans
• Aedes aegypti Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, May
• Thrips e.g. Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
• Hymenopterans e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Lasius niger, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
• Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis andThyanta perditor,
• homopterans e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dys
• orthopterans e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus.
• Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mex
• Arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
• Arachnids Acarina
• Argasidae e.g. of the families Argasidae, I
• Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
• Nematodes especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other
• the formulations according to the invention may also be used to combat rice phatogens such as rice water weevil (Lissorhoptrus oryzaphilus), rice stem borer (Chilo suppresalis), rice leaf roller, rice leaf beetle, rice leaf miner (Agromyca oryzae), leafhoppers (Nephotettix spp. ⁇ specially smaller brown leafhopper, green rice leafhopper), planthoppers (Delphacidae; especially white backed planthopper, brown rice planthopper), stinkbugs.
• rice phatogens such as rice water weevil (Lissorhoptrus oryzaphilus), rice stem borer (Chilo suppresalis), rice leaf roller, rice leaf beetle, rice leaf miner (Agromyca oryzae), leafhoppers (Nephotettix spp. ⁇ specially smaller brown leafhopper, green rice leafhopper), planthoppers (Delphacidae; especially white backed planthopper, brown rice planthopper
• the formulations according to the invention are particularly useful for combating pests of the orders Lepidoptera and Coleoptera.
• the liquid pesticide formulations of the invention may also be applied against non-crop pests, either as such or as an aqueous dilution or as a powder composition as described above. Therefore the invention also relates to a method for controlling non- crop pests comprising contacting the pests or their food supply, habitat, breeding grounds or their locus with the formulation according to the invention.
• the invention further relates to the use of a formulation according to the present invention for the protection of non-living organic materials against non-crop pests.
• Non-crop pests are pests of the classes Chilopoda and Diplopoda and of the orders Isoptera, Diptera, Blattaria (Blattodea), Dermaptera, Hemiptera, Hymenoptera, Orthoptera, Siphonaptera, Thysanura, Phthiraptera, Araneida, Parasitiformes and Acaridida, for example:
• centipedes e.g. Scutigera coleoptrata
• spiders e.g. Latrodectus mactans, and Loxosceles reclusa
• scabies e.g. sarcoptes sp
• ticks and parasitic mites ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae, • termites (Isoptera), e.g.
• Calotermes flavicollis Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Termes natalensis, and Coptotermes formosanus,
• cockroaches e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
• Psorophora discolor Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis,
• Earwigs e.g. forficula auricularia
• true bugs Hemiptera
• Cimex lectularius Cimex lectularius
• Cimex hemipterus Reduvius senilis
• Triatoma spp. Rhodnius prolixus
• Arilus critatus
• Vespula squamosa Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile, • crickets, grasshoppers, locusts (Orthoptera), e.g.
• lice e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
• the formulations according to the invention can be used for the protection of non-living organic materials, including but are not limited to house-hold goods, such as fats, oils, mono- oligo- or polyorganosaccharides, proteins, or fresh or decaying fruits; cellulose-containing materials, e.g. wooden materials, such as houses, trees, board fences, or sleepers and also paper; and also construction materials, furniture, leathers, animal, plant and synthetic fibers, vinyl articles, electric wires and cables as well as styrene foams.
• house-hold goods such as fats, oils, mono- oligo- or polyorganosaccharides, proteins, or fresh or decaying fruits
• cellulose-containing materials e.g. wooden materials, such as houses, trees, board fences, or sleepers and also paper
• construction materials furniture, leathers, animal, plant and synthetic fibers, vinyl articles, electric wires and cables as well as styrene foams.
• a formulation according to the invention can be used for the protection of non-living organic materials against non-crop pests selected from the group consisting of the class Diplopoda and of the orders Isoptera, Diptera, Blattaria (Blattodea), Dermaptera, Hemiptera, Hymenoptera, Orthoptera, and Thysanura.
• the present invention also relates to a method for the protection of non-living organic materials against non-crop pests as mentioned above comprising contacting the pests or their food supply, habitat, breeding grounds, their locus or the non-living organic materials themselves with an pesticidally effective amount of a formulation according to the invention.
• a formulation according to the invention can be used for protecting cellulose-containing non-living organic materials, e.g. for protecting cellulose-containing non-living organic materials against non-crop pests from the Isoptera, Diptera, Blattaria (Blattodea), Hymenoptera, and Orthoptera orders, most preferably the Isoptera orders.
• the present invention also provides a method for protecting cellulose-containing nonliving organic materials against non-crop pests, preferably from the Isoptera, Diptera, Blattaria (Blattodea), Hymenoptera, and Orthoptera orders, most preferably the Isoptera orders, comprising contacting the pests or their food supply, habitat, breeding grounds, their locus or the cellulose-containing non-living organic materials themselves with a formulation according to the invention.
• a formulation according to the invention can be used for protecting mono-, oligo- or polysaccharides and proteins.
• a formulation according to the invention can be used for protection of mono-, oligo- or polysaccharides and proteins against non-crop pests selected from the Dermaptera, Diplopoda, Isoptera, Diptera, Blattaria (Blattodea), Hymenoptera, Orthoptera and Tysanura orders, most preferably the Isoptera, Diptera, Blattaria (Blattodea), and Hymenoptra orders.
• a formulation according to the invention can be used for protection of animals against non-crop pest of the class Chilopoda, and of the orders Araneida, Hemiptera, Diptera, Phthiraptera, Siphonaptera, Parasitiformes and Acaridida by treatment of the pests in water bodies and/or in and around buildings, including but not limited to walls, ground, manure piles, turf grass, pastures, sewers and materials used in the construction of buildings and also mattresses and bedding, with a formulation according to the present invention.
• Animals include warm-blooded animals, including humans and fish.
• a formulation according to the invention can be used for protection of warm-blooded animals, such as cattle, sheep, swine, camels, deer, horses, poultry, rabbits, goats, dogs and cats.
• a formulation according to the invention can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
• a formulation according to the invention can be applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc.
• the ant control formulation of the present invention is directly applied to the nest of the ants or to its surrounding or via bait contact.
• a formulation according to the invention can be applied preventively to places at which occurrence of the pests is expected.
• the invention furthermore comprises seeds treated with the formulation according to the present invention.
• Suitable seeds are for example various crop seeds, fruit species, vegetables, spices and ornamental seed, for example corn/maize (sweet and field), durum wheat, soybean, wheat, barley, oats, rye, triticale, bananas, rice, cotton, sunflower, potatoes, pasture, alfalfa, grasses, turf, sorghum, rapeseed, Brassica spp., sugar beet, eggplants, tomato, lettuce, iceberg lettuce, pepper, cucumber, squash, melon, bean, dry-beans, peas, leek, garlic, onion, cabbage, carrot, tuber such as sugar cane, tobacco, coffee, turf and forage, cruciferous, cucurbits, grapevines, pepper, fodder beet, oil seed rape, pansy, impatiens, petunia and geranium.
• corn/maize sweet and field
• durum wheat soybean, wheat, barley
• a series of liquid concentrate formulations were prepared by weighing the exact proportion of ingredients and mixing them together in a bottle until complete dissolution occurred (if needed with gentle heating). The solvents were weighed first.
• Compound A1 i.e. (EZ)-2'-[2-(4-cyanophenyl)-1-( ⁇ , ⁇ , ⁇ -trifluoro-m-tolyl)ethylidene]-4-(trifluoromethoxy) carbanilohydrazide), was dissolved completely in the solvent system followed by addition of the surfactant and further additives. All preparation examples 1 to 6 gave a clear, homogenous liquid.
• the liquid concentrate formulations of preparation examples 1 to 6 were diluted with water at formulation/water weight ratios of 1 :100 and 2:100. Different water hardness conditions were employed (342 ppm, 500 ppm and 1000 ppm WHO hard water). All formulations according to the invention showed good water dilution and emulsion characteristics across the different hardnesses of water. No crystals were observed upon dilution with water.
• the preparation examples 1 to 5 were tested for freeze-thaw stability between temperatures of -15°C to 40 0 C.
• One cycle constituted a total of 24 hours, wherein the samples were exposed to 10 hours at -15 0 C and 10 hours at 40 0 C with 2 hours of transition from one temperature to the other.
• a stock composition of the formulation of preparation example 4 was diluted into a container of water.
• Preparation example 4 was tested at 0.3, 1 , 3, 5, 10 and 30 and 100 ppm.
• Cabbage leaves were dipped into the thus prepared dilution and allowed to air-dry.
• a single treated leaf disc was each placed topside-up onto water-moistened filter paper in multiple plastic petri dishes.
• Ten larvae (3 rd instar) were placed onto each leaf, and then each arena was sealed with petri dish covers.
• Larval complete mortality was assessed at 72 hours after infestation.
• Table 4 lists the LC50 and LC90 data which have been obtained for various concentrations of a.i. (active ingredient) applied after 72 hours of exposure. The LC50 and LC90 was calculated using probit analyses of the mortality observed for the different concentrations of preparation example 4.
• Preparation example 4 provided excellent potency against larvae of imported cabbage worm based on LC50/LC90 values (2.413 and 4.7 ppm).
• Preparation example 4 also provided good leaf protection based on feeding damage at
• Table 4 Potency (LC50/LC90) of preparation example 4 against imported cabbage worm (Pieris rapae) 3 rd instar in a leaf dip study
• a stock composition of each of the formulations of preparation examples 1 to 5 was diluted into water (100 ml). Lima bean leaves were sprayed with the thus prepared dilution in a sprayer chamber and allowed to air-dry. The sprayer was calibrated to apply 200 I/ha and all the dilutions were based on g a.i./ha.
• Trials were arranged in randomized complete blocks with three replications. Plots were 10m long and one row wide. Applications were conducted with a tractor-mounted sprayer with a three-nozzle row crop boom delivering side and overhead coverage, at 3-bar pressure and 300 I/ha. Numbers of larvae (L1/2) (L3/4) were recorded per plot at 3, 7, 14 and 21 days after application (DAT) and feeding damage was assessed at 21 days after application (see Tables 6, 7 and 8). No crop injury was observed 3-14 days after the application with any of the formulations tested.
• preparation examples 1 to 5 provided excellent control of Colorado potato beetle larvae.
• Table 6 Efficacy of preparation examples 1 to 5 for control of Colorado potato beetle (Leptinotarsa decemlineata) in potatoes, Larval Stage: 1 st and 2 nd instar
• Table 7 Efficacy of preparation examples 1 to 5 for control of Colorado potato beetle (Leptinotarsa decemlineata) in potatoes, Larval Stage: 3 rd and 4 th instar.
• Table 8 Efficacy of preparation examples 1 to 5 for control of Colorado potato beetle (Leptinotarsa decemlineata) in potatoes. Larval stage: 1 st , 2 nd , 3 rd and 4 th instar.
• Preparation example 4 was tested at the rates of 160, 200 and 250 ppm on cabbage against 2 species being Diamond backmoth and Common cutworm.
• the product at different rates was diluted in water and sprayed in the field at a spray volume of 2000 I/ha.
• the youngest unfolded leaves of field planted cabbage plants were marked just before spray application. Older leaves than the marked leaves or the marked leaves were collected at 1 , 3, 7, 14 days after application (DAT) respectively for laboratory bio- assay.
• Five leaf discs (diameter 2.5cm) were punched out from the collected eaves and put into a petri dish. About 10 3rd instar larvae/petri dish were released onto them and were kept in an insectary under 24°C, 16 hours light / 8 hours dark conditions.
• Table 10 Effect of preparation example 4 against Common cutworm (Spodoptera litura) on cabbage in a field bioassay trial
• the formulation of preparation example 6 was spiked with C-14 labeled Compound A-1.
• the treatment solution was prepared at a concentration of 240 g/ha and diluted with water to 200 I/ha.
• the treatment solution was applied on the surface of cotton leaves using a microliter syringe in microliter droplets.
• the treated leaves were allowed to dry in the hood and plants were then placed in the greenhouse. After pre-determined periods of time, the treated leaves were washed in sequence with water, methanol, and dichloromethane. At the end leaf was combusted.
• the amount of carbon-14 in washes and combustions was determined by LSC (liquid scintillation counter). The percent distributions of residues derived from C-14 Compound A-1 of the applied dose in cotton leaves were then determined.

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