(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2015/189080 Al 17 December 2015 (17.12.2015) P O P C T
(51) International Patent Classification: (DE). SALINGER, Daniel; i den Weihergarten 20, A01P 7/04 (2006.01) A01N 43/58 (2006.01) 67071 Ludwigshafen (DE). GOCKEL, Birgit; Eschen- A01N 43/56 (2006.01) bachstrafie 42, 67063 Ludwigshafen (DE). WACH, Jean- Yves; N2, 4, 68161 Mannheim (DE). LANGEWALD, (21) International Application Number: Jurgen; Joseph-Haydn-Strasse 3-5, 68165 Mannheim PCT/EP2015/062359 (DE). REINHARD, Robert; Berwartsteinstr. 6, 671 17 (22) International Filing Date: Limburgerhof (DE). 3 June 2015 (03.06.2015) (81) Designated States (unless otherwise indicated, for every (25) Filing Language: English kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (26) Publication Language: English BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, (30) Priority Data: DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, 141721 16.7 12 June 2014 (12.06.2014) EP HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 62/089,870 10 December 2014 (10. 12.2014) US KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, 14197173.9 10 December 2014 (10. 12.2014) EP MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (71) Applicant: BASF SE [DE/DE]; 67056 Ludwigshafen SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, (DE). TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (72) Inventors: POHLMAN, Matthias; 26 Davis Drive, Re (84) Designated States (unless otherwise indicated, for every search Triancle Park, 27709 (US). KOERBER, Karsten; kind of regional protection available): ARIPO (BW, GH, Hintere Lisgewann 26, 69214 Eppelheim (DE). SO- GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, ERGEL, Sebastian; Marienstr. 19, 67063 Ludwigshafen TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU,
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(54) Title: PESTICIDALLY ACTIVE MIXTURES (57) Abstract: The present invention relates to pesticidal mixtures compris ing as active compounds 1) at least one pesticidally active anthranilamide compound of formula (I) wherein R 1, R2, R3, R4, R5, R6, R7 and k are as defined in the description; and 2) at least one pesticidally active compound of formula (II) wherein R2 1, R22, R23, R24 and R25 are as defined in the descrip tion. The invention relates further to methods and use of these mixtures for combating and controlling insects, acarids or nematodes in and on plants, and for protecting such plants being infested with pests, especially also for pro - tecting plant propagation material, such as seeds. wo 2015/189080 Ai III III II II III III 1 1 I II II I III I II III II III
TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, Published: DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, — with international search report (Art. 21(3)) LU, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG). Pesticidally active mixtures
The present invention relates to mixtures of active ingredients having synergistically enhanced action and to methods comprising applying said mixtures.
One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control. Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests. There also exists the need for pest control agents that combine knock-down activity with prolonged control, that is, fast action with long lasting action. Another difficulty in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selection of pests which have developed natural or adapted resistance against the active compound in question. Therefore there is a need for pest control agents that help prevent or overcome resistance induced by pesticides.
Furthermore, there is a desire for pesticide compounds or combination of compounds, which when applied improve plants, which may result in "plant health", "vitality of plant propagation material" or "increased plant yield".
It is therefore an object of the present invention to provide agricultural combinations which solves one or more than one of the discussed problems as - reducing the dosage rate, - enhancing the spectrum of activity, - combining knock-down activity with prolonged control, - improving resistance management, - Improved plant health; - Improved vitality of plant propagation material, also termed seed vitality; - Increased plant yield..
It was therefore an object of the present invention to provide pesticidal mixtures which solve at least one of the discussed problems as reducing the dosage rate, enhancing the spectrum of activity or combining knock-down activity with prolonged control or as to resistance management. It has been found that this object is in part or in whole achieved by the combination of active compounds defined below.
The present invention relates to pesticidal mixtures comprising as active compounds 1) at least one pesticidally active anthranilamide compound of formula (I): wherein R is selected from the group consisting of H, F, C I, Br and C N; R2 is selected from the group consisting of F, CI, Br, I, CH3; R3 is selected from the group consisting of Br, CI, C HF2, CF3 and OCH2F; 4 R is C I or C F3; R5, R6 are selected independently of one another from the group consisting of hydrogen, Ci-C4-alkyl, Cs-Cs-cycloalkyl, or R and R6 together represent a C2-C7-alkylene, C2-C7-alkenylene or
C 6-Cg-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, k is Oor l ; or a stereoisomer, salt, tautomer or N-oxide, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof; and
2) at least one pesticidally active compound of formula ( II)
wherein
2 R is H, Ci-C 2-alkyl, or Ci-C 2-alkoxy-Ci-C 2-alkyl; R22 is CH3, or halomethyl; 23 R is C N, C2-C6-alkyl, -C6-haloalkyl, Ci-C 2-alkoxy-Ci-C 2-alkyl, C2-C6-alkenyl and C2- C 6-alkynyl, C3-C6 -cycloalkyl, Cs-Ce-cycloalkenyl, Ci-C6-alkoxy, wherein the C-atoms may be unsubstituted, or partially or fully substituted by Ra; R24 is Ci-C4-alkyl, or a group mentioned for R23; or R23 and R24 may together form a five- to six-membered carbocycle, which may be substituted by Ra; R25 is H, or a group mentioned for R24 ; a R is halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C4 -alkoxy, Ci-C2-haloalkoxy, and the stereoisomers, salts, tautomers and N-oxides thereof;
in synergistically effective amounts.
The compounds of formula (I) are also referred to as compounds of formula I or compounds I. The compounds of formula (II) are also referred to as compounds of formula II or compounds II. Both compounds of formula (I) and compounds of formula (II) are referred to as "compound(s) of the present invention".
Moreover, it has been found that simultaneous, that is joint or separate, application of one or more active compound(s) I and one or more compound(s) II or successive application (that is immediately one after another and thereby creating the mixture "in-situ" on the desired location, as e.g. the plant) of one or more active compound(s) I and one or more active compound(s) II allows enhanced control of pests compared to the control rates that are possible with the individual compounds. Therefore, the term "mixture" as used herein is intended to include also combinations.
The present invention also provides methods for the control of insects, acarids or nematodes comprising contacting the insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a pesticidally effective amount of mixtures of at least one active compound I with at least one active compound II.
Moreover, the present invention also relates to a method of protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a pesticidally effective amount of a mixture of at least one active compound I with at least one active compound II.
The invention also provides a method for the protection of plant propagation material, preferably seeds, from soil insects and of the seedlings' roots and shoots from soil and foliar insects which comprises contacting the plant progagation material as e.g. the seeds before sowing and/or after pregermination with a pesticidally effective amount of a mixture of at least one active compound I with at least one active compound II.
The invention also provides seeds comprising a mixture of at least one active compound I with at least one active compound II.
The invention also provides pesticidal compositions, comprising a liquid or solid carrier and a mixture of at least one active compound I with at least one active compound II. The invention also relates to the use of a mixture of at least one active compound I with at least one active compound II for combating insects, arachnids or nematodes.
The mixture(s) of at least one active compound of formula (I) with at least one active compound II are herein referred to as "mixture(s) according to the invention". In a specific embodiment, the mixture according to the invention is a mixture of one active compound of formula (I) with one active compound II (binary mixture). In another embodiment, the mixture according to the invention is a mixture of one active compound of formula (I) with at least one active compound II. The term "composition(s) according to the invention" or "composition(s) of the present invention" encompasses composition(s) comprising at least one compound of the present invention, i.e. at least one compound of formula I or II or mixtures of the compounds of formula I and formula II for being used and/or applied in methods according to the invention as defined herein, wherein the compounds of formula I or II are understood to include their stereoisomers, salts, tautomers or N-oxides, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof.
The compounds I of formula (I) and their examples include their tautomers, racemic mixtures, individual pure enantiomers and diasteroemers and their optically active mixtures.
Depending on the substitution pattern, the compounds of the present invention may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the pure enantiomers or pure diastereomers of the compounds of the present invention, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds of the present invention or their mixtures. Suitable compounds of the formula of the present invention also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond, nitrogen-sulfur double bond or amide group. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
Salts of the compounds of the present invention are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality. In general, suitable "agriculturally useful salts" or "agriculturally acceptable salts" are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NhV) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4 -alkyl, Ci-C4 -hydroxyalkyl, Ci-C4 -alkoxy, Ci-C4 -alkoxy -Ci -C4 -alkyl, hydroxy-Ci-
C 4-alkoxy -Ci -C4 -alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2- hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri (Ci -C4 -alkyl)sulfonium, and sulfoxonium ions, preferably tri (Ci -C4- alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4 -alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae (I) or (II) with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid. Preferred compounds of the present invention are compounds of formula (I) or (II) or a stereoisomer, N-oxide or salt thereof, wherein the salt is an agriculturally or veterinarily acceptable salt.
The compounds of the present invention may be present in the form of their N-oxides. The term "N-oxide" includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. N-oxides of compounds of the present invention can in particular be prepared by oxidizing the ring nitrogen atom(s) of the pyridine ring and/or the pyrazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides. The person skilled in the art knows if and in which positions compounds of the present invention, i.e. of the formula (I) or (II), may form N-oxides.
The compounds I of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of formula (I), their enantiomers or diastereomers, mixtures of different crystalline states of the respective compound of formula (I), its enantiomers or diastereomers, as well as amorphous or crystalline salts thereof. Polymorphic forms of compounds of formula (I) are e.g. described in WO201 3/024008 or the unpublished application EP14167567.8.
The term "co-crystal" denotes a complex of the compounds of the present invention or a stereoisomer, salt, tautomer or N-oxide thereof, with one or more other molecules (preferably one molecule type), wherein usually the ratio of the compound according to the invention and the other molecule is a stoichiometric ratio. The term "solvate" denotes a co-complex of the compounds of the present invention, or a stereoisomer, salt, tautomer or N-oxide thereof, with solvent molecules. The solvent is usually liquid. Examples of solv