Highly spreading ULV formulation for pesticide compound II
By employing pesticide formulations with expanders, the challenges of applying crop protection products at low spray volumes are addressed, achieving effective leaf coverage and reduced environmental impact.
Patent Information
- Application Number
- JP2021565954
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2019-05-08
- Filing Date
- 2020-05-08
- Publication Date
- 2025-03-19
- Estimated Expiration
- 2040-05-08
AI Technical Summary
Modern agriculture faces challenges in efficiently applying crop protection products with reduced environmental impact, as existing methods often require large amounts of spray fluid, leading to energy consumption and soil compaction issues.
The use of pesticide formulations containing expanders, which increase the coverage area and diameter of spray deposits even at low spray volumes, thereby maintaining efficacy on non-wetting leaf surfaces with reduced amounts of spreading agents.
This approach allows for effective leaf coverage and biological efficacy against fungicidal pathogens while minimizing the amount of additional additives applied, resulting in lower costs, improved formulation stability, and reduced environmental impact.
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Abstract
Description
[Technical field]
[0001] The present invention relates to pesticide compositions; their use for foliar application; their use in small spray volumes; their use by unmanned aerial systems (UAS), by unmanned guided vehicles (UGV) and by tractor mounted boom sprayers equipped not only with conventional nozzles but also with pulse width modulated spray nozzles or spinning disk droplet applicators; and their application for controlling agricultural pests, weeds or diseases, in particular for controlling agricultural pests, weeds or diseases on waxy leaves. [Background technology]
[0002] Modern agriculture faces many challenges in producing enough food in a safe and sustainable way. It is therefore required to utilize crop protection products to enhance safety, quality and yield while minimizing the impact on the environment and on the farmland. Many crop protection products, whether chemical or biological, are usually applied in relatively large volumes, e.g. in selected cases more than 50 L / ha, and often more than 150-400 L / ha. This results in a lot of energy having to be consumed to transport the large volumes of spray solution, which are then applied to the crop by spray application. This can be carried out by large tractors, which, due to their weight and the weight of the spray solution, generate CO2 from the mechanical work involved, and also cause harmful compaction of the soil (which affects plant root growth, health and yield), and energy is then expended to ameliorate these effects.
[0003] A solution is needed that significantly reduces the volume of spray solution and reduces the weight of the equipment required to apply the product.
[0004] In agriculture, low-volume application technologies such as unmanned aerial systems (UAS), unmanned guided vehicles (UGV) and tractor-mounted boom sprayers with pulse-width modulated spray nozzles or spinning disk droplet applicators offer farmers the solution of applying products at low volumes (typically reduced to 10-20 L / ha or less). These solutions have advantages including, for example, requiring significantly less water (which is important in areas with limited water supplies), less energy required to transport and apply the spray solution, faster due to both faster filling of spray tanks and application, reduced CO2 production due to both the reduced volume of spray solution transported and the use of smaller, lighter vehicles (which reduce soil compaction damage and allow the use of cheaper application systems).
[0005] However, Wang et al. [Field evaluation of an unmanned aerial vehicle (UAV) sprayer: effect of spray volume on deposition and the control of pests and disease in wheat. Pest Management Science 2019 doi / epdf / 10.1002 / ps.5321] showed that as spray volumes were decreased from 450 and 225 L / ha to 28.1, 16.8, and 9.0 L / ha, the area covered (% area), number of spray deposits per area, and diameter of spray deposits all decreased as measured by water test strips (see Table 3 in Wang et al., 2019). At the same time, the biological control efficacy for both aphid and powdery mildew control in wheat was reduced at low application rates, with the greatest reduction at 9.0 L / ha, followed by 16.8 L / ha (see Figures 6, 7, and 8 in Wang et al., 2019).
[0006] Therefore, even when the number of spray deposits per area is reduced (the number of spray droplets per unit area is proportionally reduced for the same spray droplet spectral size as the spray volume is reduced), it is necessary to design a formulation system that overcomes the reduction in coverage area and diameter of spray deposits at low spray volumes, particularly below 25 L / ha, more particularly below 17 L / ha, and even more particularly below 10 L / ha.
[0007] A solution is provided by formulations containing spreading agents. Such formulations provide increased coverage and increased diameter of the spray deposit at low spray rates. Moreover, the increased coverage and increased diameter of the spray deposit are comparable to the coverage achieved with higher conventional spray rates. Moreover, formulations embodying the invention are particularly effective on difficult-to-wet leaf surfaces where retention and coverage are inadequate with more conventional spray rates.
[0008] A particular advantage of the present invention is the low cost of the formulations and their ease of manufacture due to the low total amount of spreader compared to the levels required for conventional larger application rates. Further advantages include improved stability and simplified manufacture of the formulations, lower cost of goods, and less environmental impact.
[0009] The formulations known in the prior art containing spreaders (even tank-mix formulations) are primarily designed for very large application volumes and generally contain low concentrations of spreaders in the application broth. Nevertheless, due to the large application volumes used in the prior art, the total amount of spreader used is higher than in the present invention, and therefore the total amount in the environment is also higher than in the present invention.
[0010] The concentration of the spreading agent is an important element of the present invention because adequate spreading requires a certain minimum concentration of spreading agent, usually 0.05% w / w or w / v (these are spreaders with a density of about 1.0 g / cm 3 This occurs when (and therefore is equivalent to) is achieved.
[0011] For clarity, as will be understood by those skilled in the art, "spreading" means the rapid spreading of a droplet over a surface (i.e., in the context of the present invention, the surface of a plant part such as a leaf). [Prior art documents] [Non-patent literature]
[0012] [Non-Patent Document 1] Pest Management Science 2019 doi / epdf / 10.1002 / ps.5321 Summary of the Invention [Problem to be solved by the invention]
[0013] Thus, for a spray volume of 500 L / ha, as used in the prior art, about 250 g / ha of spreading agent would be required to achieve adequate spreading. Thus, faced with the task of reducing the spray volume, a person skilled in the art would apply the same concentration of spreading agent in the formulation. For example, for a spray volume of 10 L / ha, about 5 g / ha of surfactant (about 0.05% in the spray broth) would be required. However, such a small spray volume with such a low concentration of spreading agent would not be able to achieve sufficient spreading (see the examples). [Means for solving the problem]
[0014] In the present invention, the inventors have surprisingly found that the loss of coverage (due to insufficient spreading) caused by a reduction in the spray rate can be compensated for by increasing the concentration of spreading agent as the spray rate is reduced. Surprisingly, it has been found that for every 50% reduction in the spray rate, the concentration of surfactant needs to be approximately doubled.
[0015] Thus, although the absolute concentration of the extension agent is increased compared to formulations known in the art, the relative total amount per hectare can be reduced (which is advantageous both economically and ecologically), while the coverage of the formulation of the invention and the efficacy of the formulation of the invention are improved, maintained, or at least maintained at an acceptable level, taking into account the other advantages of application with low spray volumes (e.g. lower cost of formulation due to lower cost of goods, smaller vehicles with less operating costs, less soil compaction, etc.).
[0016] A further part of the present invention that allows for the use of surprisingly low total amounts of spreader is the surface texture of the target crop leaves. Bico et al. [Wetting of textured surfaces, Colloids and Surfaces A, 206 (2002) 41-46] have established that, compared to smooth surfaces, rough surfaces can enhance wetting for formulation spray dilutions with contact angles less than 90° and reduce wetting for contact angles greater than 90°.
[0017] This also applies to leaf surfaces (especially rough leaf surfaces) when sprayed according to the method of the invention, which results in a low total amount of spreader (per hectare) due to the low spray volume of the formulation of the invention with a high concentration of spreader. It was possible to demonstrate a significantly higher coverage of the leaf surface with the spray (even to a higher level than would normally be expected).
[0018] Rough leaf surfaces include leaves containing micron-scale wax crystals on the surface, such as, for example, wheat, barley, rice, rapeseed, soybean (young plants) and cabbage leaves, as well as leaves with surface texture, such as, for example, lotus plant leaves. Surface texture can be ascertained by observation with a scanning electron microscope (SEM) and by the wettability of the leaf, determined by measuring the contact angle made by a drop of water on the leaf surface.
[0019] In summary, the object of the present invention is to provide a formulation that can be applied in small amounts (i.e. less than 20 L / ha) while providing good leaf coverage, uptake and biological efficacy against fungicidal pathogens, while at the same time reducing the amount of additional additives applied per hectare, as well as to provide a method of using the formulation in small amounts (i.e. less than 20 L / ha) and the use of the formulation for applying in small amounts as defined above.
[0020] Application to rough leaves is preferred, but it has surprisingly been found that even on non-rough leaves the formulations according to the invention show better spreading and coverage and other properties compared to classical spray application formulations for 200 L / ha.
[0021] In one aspect, the present invention is directed to the use of a composition according to the present invention for foliar application.
[0022] Unless otherwise indicated, "%" in this application means percent by weight (% w / w).
[0023] It is understood that when various ingredients are combined, the percentages of all ingredients in a formulation will always add up to 100.
[0024] Additionally, unless otherwise indicated, references to "to volume" with respect to water indicate that water is added to bring the total volume of the formulation to 1000 mL (1 L). For clarity, when unknown, the density of the formulation is assumed to be 1 g / cm. 3 It is understood that it is understood to be.
[0025] In the context of the present invention, aqueous-based pesticide compositions contain at least 5% water and include suspension concentrates, aqueous suspensions, suspoemulsions or capsule suspensions, preferably suspension concentrates and aqueous suspensions.
[0026] It is further understood that the given preferred ranges of application volume or application rate, and the given preferred ranges of each component described herein, can be freely combined, and while all combinations are disclosed herein, it is understood that in more preferred embodiments, the components are preferably present within the same preferred ranges, and even more preferred components are present within the most preferred ranges. [Brief description of the drawings]
[0027] [Figure 1] FIG. 1 shows scanning electron micrographs of leaf texture, where the top photograph shows a grape leaf surface (non-textured) and the bottom photograph shows a soybean leaf surface (textured). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] In one aspect, the invention relates to a formulation comprising: (a) one or more active ingredients; (b) one or more spreaders; (c) Another formulation aid; (d) One or more carriers up to a specified volume (1 L or 1 kg); Here, (b) is present at 5 to 200 g / L.
[0029] Unless otherwise indicated in the present invention, carriers are usually used in the formulation to a certain volume.Preferably, the concentration of carriers in the formulation according to the present invention is at least 5% w / w, more preferably at least 10% w / w, such as at least 20% w / w, at least 40% w / w, at least 50% w / w, at least 60% w / w, at least 70% w / w and at least 80% w / w, or at least 50 g / L, more preferably at least 100 g / L, such as at least 200 g / L, at least 400 g / L, at least 500 g / L, at least 600 g / L, at least 700 g / L and at least 800 g / L, respectively.
[0030] The formulation is preferably a spray application used on crops.
[0031] In a preferred embodiment according to the present invention, and also for the embodiments herein below, the carrier is water.
[0032] In a preferred embodiment, the formulation of the invention comprises: (a) one or more active ingredients; (b) one or more spreaders; (c1) at least one suitable non-ionic surfactant and / or a suitable ionic surfactant; (c2) optionally, a rheology modifier; (c3) optionally, a suitable antifoaming substance; (c4) optionally, a suitable antifreeze; (c5) optionally, other suitable formulation aids; (d) Carriers up to a prescribed volume; wherein (b) is present at 5-200 g / L weight %, and wherein water is even more preferred as the carrier.
[0033] In another embodiment, at least one of e2, e3, e4 and e5 is mandatory, preferably at least two of e1, e2, e3, e4 and e5 are mandatory, and in yet another embodiment, e1, e2, e3, e4 and e5 are mandatory.
[0034] In a preferred embodiment, component (a) is present in an amount of from 5 to 300 g / L, preferably from 10 to 280 g / L, and most preferably from 10 to 250 g / L.
[0035] In an alternative embodiment, component (a) is a fungicide.
[0036] In an alternative embodiment, component (a) is an insecticide.
[0037] In an alternative embodiment, component (a) is a herbicide.
[0038] In a preferred embodiment, component (b) is present at 5-200 g / L, preferably 10-150 g / L, and most preferably 10-130 g / L.
[0039] In a preferred embodiment, component (c) is present at 10-150 g / L, preferably 25-150 g / L, and most preferably 30-120 g / L.
[0040] In a preferred embodiment, the one or more components (c1) are present at 4 to 250 g / L, preferably at 8 to 120 g / L, and most preferably at 10 to 80 g / L.
[0041] In a preferred embodiment, the one or more components (c2) are present at 0-60 g / L, preferably at 1-20 g / L, and most preferably at 2-10 g / L.
[0042] In a preferred embodiment, the one or more components (c3) are present at 0-30 g / L, preferably at 0.5-20 g / L, and most preferably at 1-12 g / L.
[0043] In a preferred embodiment, the one or more components (c4) are present at 0-200 g / L, preferably at 5-150 g / L, and most preferably at 10-120 g / L.
[0044] In a preferred embodiment, the one or more components (c5) are present at 0-200 g / L, preferably 0.1-120 g / L, most preferably 0.5-80 g / L.
[0045] In one embodiment, the formulation comprises components (a)-(e) in the following amounts: (a) 5 to 300 g / L, preferably 10 to 280 g / L, and most preferably 10 to 250 g / L; (b) 5 to 200 g / L, preferably 10 to 150 g / L, and most preferably 10 to 130 g / L; (c) 4 to 250 g / L, preferably 8 to 120 g / L, and most preferably 10 to 80 g / L; (d) Carriers up to a specified volume.
[0046] In another embodiment, the formulation comprises components (a)-(e) in the following amounts: (a) 5 to 300 g / L, preferably 10 to 280 g / L, and most preferably 10 to 250 g / L; (b) 5 to 200 g / L, preferably 10 to 150 g / L, and most preferably 10 to 130 g / L; (c1) 4 to 250 g / L, preferably 8 to 120 g / L, and most preferably 10 to 80 g / L; (c2) 0 to 60 g / L, preferably 1 to 20 g / L, and most preferably 2 to 10 g / L; (c3) 0 to 30 g / L, preferably 0.5 to 20 g / L, and most preferably 1 to 12 g / L; (c4) 0 to 200 g / L, preferably 5 to 150 g / L, and most preferably 10 to 120 g / L; (c5) 0 to 200 g / L, preferably 0.1 to 120 g / L, and most preferably 0.5 to 80 g / L; (d) Carriers up to a specified volume.
[0047] It will be understood that where a solid support is used, the above reference amounts refer to 1 kg instead of 1 L (ie g / kg).
[0048] As indicated above, component (d) is always added to a given volume (ie, to 1 L or 1 kg).
[0049] In a further preferred embodiment of the invention, the formulation consists only of components (a)-(f) as described above in the amounts and ranges specified.
[0050] In a preferred embodiment, the herbicide is used in combination with a safener, which is preferably selected from the group comprising isoxadifen-ethyl and mefenpyr-diethyl.
[0051] The present invention is further applicable to a method of applying the above formulation, wherein the formulation is applied in a spray volume of 1 to 20 L / ha, preferably 2 to 15 L / ha, more preferably 5 to 15 L / ha.
[0052] More preferably, the present invention also applies to a method of application of said formulation, wherein the formulation is applied in a spray volume of 1-20 L / ha, preferably 2-15 L / ha, more preferably 5-15 L / ha, and (b) is present in an amount of 5-200 g / L, preferably 10-150 g / L, and most preferably 10-130 g / L, where in a further preferred embodiment (a) is present in an amount of 5-300 g / L, preferably 10-280 g / L, and most preferably 10-250 g / L.
[0053] In another aspect, the present invention relates to a method of application of the above formulation, Here, the formulation is applied in a spray volume of 1 to 20 L / ha, preferably 2 to 15 L / ha, more preferably 5 to 15 L / ha; Here, the application rate of (a) to the crop is preferably 2 to 150 g / ha, more preferably 5 to 120 g / ha, and further preferably 20 to 100 g / ha.
[0054] Furthermore, the extension agent (b) is preferably applied at 5 g / ha to 150 g / ha, more preferably at 7.5 g / ha to 100 g / ha, and most preferably at 10 g / ha to 60 g / ha.
[0055] In one embodiment, the application rate of (a) to the crop by the method set forth above is between 2 and 10 g / ha.
[0056] In another embodiment, the application rate of (a) to the crop by the method set forth above is between 40 and 110 g / ha.
[0057] In one embodiment of the above application, the active ingredient (ai) (a) is preferably applied at 2 to 150 g / ha, preferably at 5 to 120 g / ha and more preferably at 20 to 100 g / ha, while correspondingly the extension agent is preferably applied at 10 g / ha to 100 g / ha, more preferably at 20 g / ha to 80 g / ha and most preferably at 40 g / ha to 60 g / ha.
[0058] In particular, the formulations of the present invention are useful for application to plants or crops having a rough leaf surface, preferably to wheat, barley, rice, rapeseed, soybean (young plants) and cabbage, at spray volumes of 1-20 L / ha, preferably 2-15 L / ha, more preferably 5-15 L / ha.
[0059] Furthermore, the present invention relates to a method for treating crops with a rough leaf surface, preferably wheat, barley, rice, rapeseed, soybean (young plants) and cabbage, with a spray volume of 1-20 L / ha, preferably 2-15 L / ha, more preferably 5-15 L / ha.
[0060] In a preferred embodiment, said application is to crops having a rough leaf surface, preferably to wheat, barley, rice, rapeseed, soybean (young plants) and cabbage.
[0061] In one embodiment, the active ingredient is a fungicide or a mixture of two fungicides or a mixture of three fungicides.
[0062] In another embodiment, the active ingredient is an insecticide, or a mixture of two insecticides, or a mixture of three insecticides.
[0063] In yet another embodiment, the active ingredient is a herbicide or a mixture of two herbicides or a mixture of three herbicides, where preferably the mixture partner is a safener.
[0064] The corresponding dosages of spreading agent (b) in the formulation according to the invention relative to the dosages applied are as follows:
[0065] A liquid formulation at 2L / ha delivers: The 50 g / ha extension agent contains 25 g / L of surfactant (b); The 30 g / ha extension agent contains 15 g / L of surfactant (b); The 12 g / ha extension agent contained 6 g / L of surfactant (b); The 10 g / ha extension agent contains 5 g / L of surfactant (b).
[0066] 1 L / ha of the liquid formulation delivers: The 50 g / ha extension agent contains 50 g / L of surfactant (b); The 30 g / ha extension agent contains 30 g / L of surfactant (b); The 12 g / ha extension agent contains 12 g / L of surfactant (b); The 10 g / ha extension agent contains 10 g / L of surfactant (b).
[0067] A liquid formulation at 0.5 L / ha delivers: The 50 g / ha extension agent contains 100 g / L of surfactant (b); The 30 g / ha extension agent contains 60 g / L of surfactant (b); The 12 g / ha extension agent contains 24 g / L of surfactant (b); The 10 g / ha extension agent contains 20 g / L of surfactant (b).
[0068] A liquid formulation at 0.2 L / ha delivers: A 50 g / ha extension agent contains 250 g / L of surfactant (b); The 30 g / ha extension agent contains 150 g / L of surfactant (b); The 12 g / ha extension agent contains 60 g / L of surfactant (b); The 10 g / ha extension agent contains 50 g / L of surfactant (b).
[0069] A solid formulation at 2 kg / ha delivers: A 50 g / ha extension agent contains 25 g / kg of surfactant (b); 30 g / ha of extension agent contains 15 g / kg of surfactant (b); 12 g / ha extension agent contains 6 g / kg surfactant (b); 10 g / ha of extension agent contains 5 g / kg of surfactant (b).
[0070] A solid formulation at 1 kg / ha delivers: A 50 g / ha extension agent contains 50 g / kg of surfactant (b); 30 g / ha of extension agent contains 30 g / kg of surfactant (b); 12 g / ha extension agent contains 12 g / kg surfactant (b); 10 g / ha of extension agent contains 10 g / kg of surfactant (b).
[0071] A solid formulation at 0.5 kg / ha delivers: A 50 g / ha extension agent contains 100 g / kg of surfactant (b); 30 g / ha of extension agent contains 60 g / kg of surfactant (b); The 12 g / ha extension agent contains 24 g / kg of surfactant (b); A 10 g / ha spreader contains 20 g / kg of surfactant (b).
[0072] The concentrations of the extension agent (b) in formulations applied at different rates per hectare can be calculated in the same way.
[0073] In the context of the present invention, suitable formulation types are by definition suspensions, aqueous suspensions, suspoemulsions or capsule suspensions, EW formulations, water dispersible granules, oil dispersions, emulsions, dispersible concentrates, water dispersible granules, preferably suspensions, aqueous suspensions, suspoemulsions and oil dispersions, where in the case of non-aqueous or solid formulations a sprayable formulation is obtained by adding water.
[0074] Active ingredient (a): The active compounds identified herein by common names are known and are described, for example, in the Pesticides Handbook ("The Pesticide Manual" 16th Ed., British Crop Protection Council 2012) or can be found on the Internet (e.g., http: / / www.alanwood.net / pesticides). The classification is based on the "IRAC Mode of Action Classification Scheme" current at the time of filing of the patent application.
[0075] Examples of fungicides (a) according to the invention are:
[0076] (1) Inhibitors of ergosterol biosynthesis, for example: (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014). Myclobutanil, (1.015) Paclobutrazol, (1.016) Prochloraz, (1.017) Propiconazole, (1.018) Prothioconazole, (1.019) Pyrisoxazole, (1.020) Spiroxamine, (1.021) Tebuconazole, (1.022) Tetraconazole, (1.023) Triadimenol, (1.024) Tridemorph, (1.025) Triticonazole, (1.026) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H -1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.027) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol (1.029) (2R)-2-(1-chlorocyclopropyl)- 4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.030) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.031) (2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.032) (2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl) (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl )-1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.040) 1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate (1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl )-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2 ,4-dihydro-3H-1,2,4-triazole-3-thione, (1.048) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1. 050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) Mefentrifluconazole, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2, 4-Triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2- Methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(arylsulfanyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(arylsulfanyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(arylsulfanyl)- 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.063) N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methyl Imidoformamide, (1.068) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N -ethyl-N-methylimidoformamide, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide, (1.072) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.073) N'-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N'-[5 -Bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidoformamide, (1.075) N'-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide, (1.076) N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.077) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.079) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.080) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide. , (1.081) ipfentrifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.085) 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole 4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, (1.087) N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (1.087) N'-{5-bromo-2-methyl-6-[(1-propoxypropan-2-yl)oxy]pyridin-3-yl}-N-ethyl-N-methylimido-formamide, (1.088) N'-{5-bromo-2-methyl-6-[(1-propoxypropan-2-yl)oxy]pyridin-3-yl}-N-ethyl-N-methylimido-formamide, (1.089) hexaconazole, (1.090) penconazole, (1.091) fenbuconazole.
[0077] (2) Inhibitors of the respiratory chain at complex I or complex II, such as (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) isofetamide, (2.010) isopyrazam (anti-epimer enantiomer 1R,4S,9S), (2.011) isopyrazam (anti-epimer enantiomer 1S,4R,9R), (2.012) isopyrazam (anti-epimer racemate 1RS,4SR,9SR), (2.013) Isopyrazam (mixture of syn-epimeric racemate (1RS,4SR,9RS) and anti-epimeric racemate (1RS,4SR,9SR)), (2.014) Isopyrazam (syn-epimeric enantiomers 1R,4S,9R), (2.015) Isopyrazam (syn-epimeric enantiomers 1S,4R,9S), (2.016) Isopyrazam (syn-epimeric racemate 1RS,4SR,9RS), (2.017) Penflufen, (2.018) Penthiopyrad, (2.019) Pydiflumetofen, (2.020) Pyraziflumide, (2.021) Sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide boxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) Inpyrfluxam, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) Fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluindapyr Fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazoline -4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) isoflucipram, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040)040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5- Fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3-(difluoro Methyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048 ) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothioamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole -4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoine, (2.058) N-[rac-(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)-nicotinamide, (2.059) N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide.
[0078] (3) Inhibitors of the respiratory chain at complex III, such as (3.001) amethoctrazine, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.01 2) Fluoxastrobin, (3.013) Kresoxim-methyl, (3.014) Metominostrobin, (3.015) Orysastrobin, (3.016) Picoxystrobin, (3.017) Pyraclostrobin, (3.018) Pyrametstrobin, (3.019) Pyraoxystrobin, (3.020) Trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxy imino)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) fenpicoxamide, (3.0 26) Mandestrobin, (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) Methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) Methyltetraprole, (3.031) Florylpicoxamide.
[0079] (4) Mitosis and cell division inhibitors, for example, (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) pyridaclomethyl, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.011) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.012) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.013) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.014) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.015) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.016) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.017) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.018) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.019) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.020) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.021) 3-chloro-5-(6-chloropyridine-3-yl)pyridazin, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine , (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-di fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.026) fluopimomide.
[0080] (5) Compounds capable of exerting activity at multiple sites, for example, (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper chloride dibasic, (5.009) copper(2+) sulfate, (5.010) dithianone, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5. 014) Maneb, (5.015) Metiram, (5.016) Metiram zinc, (5.017) Oxine copper, (5.018) Propineb, (5.019) Sulphur and sulphur agents such as calcium polysulphide, (5.020) Thiuram, (5.021) Zineb, (5.022) Ziram, (5.023) 6-Ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.
[0081] (6) Compounds capable of inducing host defenses, such as (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) thiadinil.
[0082] (7) Inhibitors of amino acid and / or protein biosynthesis, for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline.
[0083] (8) Inhibitors of ATP production, for example, (8.001) Silthiofam.
[0084] (9) Inhibitors of cell wall synthesis, such as (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamide, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.
[0085] (10) Inhibitors of lipid and membrane synthesis, for example, (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.
[0086] (11) Inhibitors of melanin biosynthesis, for example, (11.001) tricyclazole, (11.002) tolprocarb.
[0087] (12) Inhibitors of nucleic acid synthesis, such as (12.001) benalaxyl, (12.002) benalaxyl-M (chiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).
[0088] (13) Signal transduction inhibitors, such as (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazide, (13.005) quinoxyfen, (13.006) vinclozolin.
[0089] (14) Compounds which can act as uncouplers, for example, (14.001) fluazinam, (14.002) meptyldinocap.
[0090] (15) Further fungicides selected from the group consisting of: (15.001) abscisic acid, (15.002) benthiazole, (15.003) bethoxazin, (15.004) capsimycin, (15.005) carvone, (15.006) quinomethionate, (15.007) kufuraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.011) fluthianil, (15.012) fosetyl-aluminium, (15.013) fosetyl (15.014) fosetyl sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyldithiocarbamate, (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) oxathiapiproline, (15.023) oxyfenthiin, (15.024) pentachlorophenol and salts, (15.025) phosphonic acids and their salts, (15.026) propamocarb-fosetylate, (15.027) pyriophenone (chlazafenone), (15.028) tebufloquine, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidine, lysine-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipimethitrone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5-bis(difluoro methyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl Methanesulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.041) ipflufenoquine, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) fluoxapiproline, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-Phenylphenol and salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) quinofumelin, (15.048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene 2-Sulfonohydrazide, (15.052) 5-Fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.053) 5-Fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-Fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.055) Buta-3 -yn-1-yl{6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) ethyl (2Z)-3-amino-2-cyano-3-phenylacrylate, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15 .059) Quinolin-8-ol, (15.060) Quinolin-8-ol sulfate (2:1), (15.061) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl n-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen, (15.064) (N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimido-formamide), (15.065) (N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide), (15.066) (2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), (15.067) (5-bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline), (15.068) (3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline), (15.069) (1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-di methyl-3,4-dihydroisoquinoline), (15.070) 8-fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.071) 8-fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.072) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-8-fluoroquinoline, (15.073) (N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]benzamide), (15.074) methyl {4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}carbamate, (15.075) (N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}cyclopropanecarboxamide), (15.076) N-methyl-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.077) N-[(E)-methoxyimino-methyl]-4-[5-( trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.078) N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.079) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]cyclopropanecarboxamide, (15.080) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.082) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide, (15.083) N-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-(5-(trifluoro-methyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.084) N-[(Z)-N-meth (15.085) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.086) 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.087) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, ,2,4-Oxadiazol-3-yl]benzenecarbothioamide, (15.088) 5-Methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.089) N-((2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propanamide, (15.090) 1-Methoxy-1-methyl-3-[[4-[5-(trifluoro-methyl}-1,2,4- oxadiazol-3-yl]phenyl]methyl]urea, (15.091) 1,1-diethyl-3-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092) N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.093) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, (15.094) 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)cyclopropanecarboxamide, (15.096) N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]fu. phenyl]methyl]propanamide, (15.097) N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]propanamide, (15.098) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (15.100) 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.101) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-methyl]piperidin-2-one, (15.102) 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.103) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.104) 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.105) 1-[[3-fluoro-4-(5-(trifluoromethyl)- (15.105) 4,4-dimethyl-2-[[4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-phenyl]methyl]azepan-2-one, (15.106) 4,4-dimethyl-2-[[4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-phenyl]methyl]isoxazolidin-3-one, (15.107) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.108) ethyl 1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-pyrazole-4-carboxylate, (15.109) N,N-Dimethyl-1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-1,2,4-triazol-3-amine, (15.110) N-{2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butanamide, (15.111) N-(1-methylcyclopropyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.112) N-(2,4-difluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.113) 1-(5,6-dimethylpyridine- 3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.114) 1-(6-(difluoromethyl)-5-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydro-isoquinoline, (15.115) 1-(5-(fluoromethyl)-6-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.116) 1-(6-(difluoromethyl)-5-methoxy-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.117) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl Dimethyl carbamate, (15.118) N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}propanamide, (15.119) 3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.120) 9-fluoro-3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.121) 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.122) 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-9-fluoro-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.123) 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.124) 8-fluoro-N-(4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl)quinoline-3-carboxamide, (15.125) 8-fluoro-N-[(2S) -4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl]quinoline-3-carboxamide, (15.126) N-(2,4-dimethyl-1-phenylpentan-2-yl)-8-fluoroquinoline-3-carboxamide, and (15.127) N-[(2S)-2,4-dimethyl-1-phenylpentan-2-yl]-8-fluoroquinoline-3-carboxamide.
[0091] Examples of insecticides (a) according to the invention are:
[0092] (1) Acetylcholinesterase (AChE) inhibitors, e.g. Carbamates, alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, and xylylcarb; or Organophosphates, such as acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famfur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyaphos, isofenphos, O-(methoxyaminothiophos) Sulfolyl) isopropyl salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimphos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothion.
[0093] (2) GABA-regulated chloride channel antagonists, preferably Cyclodiene-organochlorines, selected from the group of chlordane and endosulfan; or Phenylpyrazoles (fiproles), which are selected from ethiprole and fipronil.
[0094] (3) Sodium channel modulators / voltage-dependent sodium channel blockers, e.g. Pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(1R)-trans-isomer], deltamethrin, empenthrin [(EZ)-(1R)-isomer], esfenvalerate, etofenprox, fen selected from propathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, fenothrin [(1R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer], tralomethrin and transfluthrin; or DDT; or methoxychlor.
[0095] (4) Nicotinic acetylcholine receptor (nAChR) competitive activators, preferably Neonicotinoids, selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or Nicotine; or Sulfoximines, selected from sulfoxaflor; or butenolides, which are selected from flupyradifurone; or Mesoionics, which are selected from triflumezopyrim.
[0096] (5) Nicotinic acetylcholine receptor (nAChR) allosteric activators, preferably The spinosyns are selected from spinetoram and spinosad.
[0097] (6) Allosteric modulators of the glutamate-gated chloride channel (GluCl), preferably Avermectins / milbemycins, selected from abamectin, emamectin benzoate, lepimectin and milbemectin.
[0098] (7) Juvenile hormone mimetics, preferably Juvenile hormone analogs selected from hydroprene, kinoprene and methoprene; or Fenoxycarb; or pyriproxyfen.
[0099] (8) Various unspecified (multi-site) inhibitors, preferably an alkyl halide selected from methyl bromide and another alkyl halide; or Chloropicrin; or sulfuryl fluoride; or borax; or tartar emetic; or A methyl isocyanate generator, which is selected from diazomet and metham.
[0100] (9) Chordotonal organ TRPV channel modulators, selected from pymetrozine and pyrifluquinazone.
[0101] (10) Mite growth inhibitors, selected from clofentezine, hexythiazox, diflovidazine and etoxazole.
[0102] (11) Microbial disruptors of the insect gut membrane, which include Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, and Bacillus thuringiensis subspecies tenebrionis. tenebrionis) and Bt plant proteins (which are selected from Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb and Cry34Ab1 / 35Ab1).
[0103] (12) Inhibitors of mitochondrial ATP synthase, preferably ATP disruptors, selected from diafenthiuron; or an organotin compound selected from azocyclotin, cyhexatin and fenbutatin oxide; or Propargite; or tetradifon.
[0104] (13) A decoupler of oxidative phosphorylation by perturbing the proton gradient, which is selected from chlorfenapyr, DNOC, and sulfluramide.
[0105] (14) Nicotinic acetylcholine receptor channel blockers, selected from bensultap, cartap hydrochloride, thiocylam and thiosultap-sodium.
[0106] (15) Inhibitors of chitin biosynthesis (type 0), which are selected from bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.
[0107] (16) Chitin biosynthesis inhibitors (type 1), which are selected from buprofezin.
[0108] (17) Molting disruptors (especially Diptera, i.e., two-winged insects), which are selected from Cyromazine.
[0109] (18) Ecdysone receptor agonists, selected from chromafenozide, halofenozide, methoxyfenozide and tebufenozide.
[0110] (19) Octopamine receptor agonists, which are selected from amitraz.
[0111] (20) A mitochondrial complex III electron transport inhibitor selected from hydramethylnon, acequinocyl and fluacrypyrim.
[0112] (21) Mitochondrial complex I electron transport inhibitors, preferably the so-called METI acaricides, which are selected from fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad; or Rotenone (Derris).
[0113] (22) A voltage-gated sodium channel blocker selected from indoxacarb and metaflumizone.
[0114] (23) Acetyl-CoA carboxylase inhibitors, preferably Tetronic acid derivatives and tetramic acid derivatives, which are selected from spirodiclofen, spiromesifen, spirotetramat and spidoxamate (IUPAC name: 11-(4-chloro-2,6-xylyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]tetradec-11-en-10-one).
[0115] (24) Mitochondrial complex IV electron transport inhibitors, preferably phosphine-based, selected from aluminum phosphide, calcium phosphide, phosphine and zinc phosphide; or The cyanide is selected from calcium cyanide, potassium cyanide and sodium cyanide.
[0116] (25) Mitochondrial complex II electron transport inhibitors, preferably β-ketonitrile derivatives, selected from cyenopyrafen and cyflumetofen; or Carboxanilides, which are selected from piflubumid.
[0117] (28) Ryanodine receptor modulators, preferably Diamides, selected from chlorantraniliprole, cyantranilprole and flubendiamide.
[0118] (29) Chordotonal organ modulators (target structure not defined), which are selected from flonicamids.
[0119] (30) Another active ingredient selected from the following: acinonapyr, afidopiropen, afoxolaner, azadirachtin, benclothiaz, benzoximate, benzpyrimoxane, bifenazate, broflanilide, bromopropylate, quinomethionate, chloroprallethrin, cryolite, cyclaniprole, cycloxapride, cyhalodiamide, dichloromezothiaz, dicofol, dimpropyridaz, epsilon-metofluthrin, epsilon-momfluthrin, flometoquin, fluazaindolizine, fluensulfone, flufenerim, flufenoxystrobin, flufpro fluhexafon, fluopyram, flupirimine, fluralaner, fluxamethamide, fufenozide, guadipyr, heptafluthrin, imidaclothiz, iprodione, isocycloceram, kappa-bifenthrin, kappa-tefluthrin, lotilaner, meperfluthrin, oxazosulfil, paichongding, pyridalyl, pyrifluquinazone, pyriminostrobin, spirobudiclofen, spiropydione, tetramethylfluthrin, tetraniliprole, tetrachlorantraniliprole, tigolaner, thioxazaphen, thiofluoximate, and iodomethane; Bacillus firmus) (I-1582, BioNeem, Votivo), as well as the following compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO 2006 / 043635) (CAS 885026-50-6), {1'-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indole-3,4'-piperidine]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO2003 / 106457) (CAS 637360-23-7), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from WO2006 / 003494) (CAS 872999-66-1), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP2647626) (CAS 1440516-42-6), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO2004 / 099160) (CAS 792914-58-0), PF1364 (known from JP2010 / 018586) (CAS-Reg.No.1204776-60-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1,1,1-trifluoro-propan-2-one (known from WO2013 / 144213) (CAS 1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO2010 / 051926) (CAS 1226889-14-0), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-Dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxido-3-thietanyl)benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamide (known from WO2013 / 050317A1) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propanamide, (+)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propanamide and (-)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propanamide (known from WO2013 / 162715A2, WO2013 / 162716A2, US2014 / 0213448A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (known from CN101337937A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thioxomethyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, (Liudaibenjiaxuanan, known from CN103109816A) (CAS 1232543-85-9; N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known from WO2012 / 034403A1) (CAS 1268277-22-0), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from WO2011 / 085575A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-dichloro-2-propen-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)pyrimidine (known from CN101337940A) (CAS 1108184-52-6;(2E)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]hydrazinecarboxamide (known from CN101715774A) (CAS 1232543-85-9);Cyclopropanecarboxylic acid-3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl ester (known from CN103524422A) (CAS 1542271-46-4;(4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN102391261A) (CAS 1370358-69-2);6-deoxy-3-O-ethyl-2,4-di-O-methyl-,1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,4-Triazol-3-yl]phenyl]carbamate]-α-L-mannopyranose (known from US2014 / 0275503A1) (CAS 1181213-14-8); 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 1253850-56-4), (8-anti)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 933798-27-7), (8-syn)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (known from WO2007040280A1, WO2007040282A1) (CAS 934001-66-8), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)thio]-propanamide (known from WO2015 / 058021A1, WO2015 / 058028A1) (CAS 1477919-27-9), and N-[4-(aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from CN103265527A) (CAS 1452877-50-7), 5-(1,3-dioxan-2-yl)-4-[[4-(trifluoromethyl)phenyl]methoxy]-pyrimidine (known from WO2013 / 115391A1) (CAS 1449021-97-9), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dione (known from WO2014 / 187846A1) (CAS 1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-Diazaspiro[4.5]dec-3-en-4-yl-carboxylic acid ethyl ester (known from WO2010 / 066780A1, WO2011151146A1) (CAS 1229023-00-0), 4-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[(4R)-2-ethyl-3-oxo-4-isoxazolidinyl]-2-methyl-benzamide (known from WO2011 / 067272, WO2013 / 050302) (CAS 1309959-62-3).
[0120] Examples of herbicides (a) according to the invention are: Acetochlor, Acifluorfen, Acifluorfen-sodium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim-sodium, Ametryn, Amicarbazone, Amidochlor, Amidosulfuron, 4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, Aminocyclopyrachlor, Aminocyclopyrachlor-potassium, Aminocyclopyrachlor-methyl, Aminopyralid, Amitrole, Ammonium sulfamate, Anilofos, Asulam, Atto azithromycin, azafenidine, azimsulfuron, beflubutamide, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazon, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanaphos, bilanaphos-sodium, bispyribac, bispyribac-sodium, bixlozone, bromacil, bromobutide, bromofenoxime, bromoxynil, bromoxynil-butyrate, potassium, heptanoate and octanoate, busoxynone (busoxinone), butachlor, butafenacil, butamiphos, butenachlor, butralin, butroxydim, butyrate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, 1-{2-chloro-3-[(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl)carbonyl]-6-(trifluoromethyl)phenyl}piperidin-2-one, 4-{2-chloro-3-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-4-( methylsulfonyl)benzoyl}-1,3-dimethyl-1H-pyrazole-5-yl-1,3-dimethyl-1H-pyrazole-4-carboxylate, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, 2-[2-chloro-4-(methylsulfonyl)-3-(morpholin-4-ylmethyl)benzoyl]-3-hydroxycyclohex-2-en-1-one, 4-{2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]benzoyl}-1-ethyl-1H-pyrazol-5-yl-1,3-dimethyl-1H-pyrazole-4-carboxylate, chlorophthalim, chlorotoluron, chlorthal-dimethyl, 3-[5-chloro-4-(trifluoromethyl)pyridin-2-yl]-4-hydroxy-1-methylimidazolidin-2-one, chlorsulfuron, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clasifos, clethodim, clodinafop, clodinafop-propanol Rugil, Clomazone, Clomeprop, Clopyralid, Cloransulam, Cloransulam-methyl, Cumiluron, Cyanamide, Cyanazine, Cycloate, Cyclopyranyl, Cyclopirimorate, Cyclosulfamuron, Cycloxydim, Cyhalofop, Cyhalofop-butyl, Cyprazine, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, -diolamine, -ethyl, 2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, -triisopropyl Propanolammonium and -trolamine, 2,4-DB, 2,4-DB-butyl, -dimethylammonium, isooctyl, -potassium and -sodium, daimuron (dymron), dalapon, dazomet, n-decanol, desmedipham, detosyl-pyrazolate (DTP), dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoco diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, 3-(2,6-dimethylphenyl)-6-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-1-methylquinazoline-2,4(1H,3H)-dione, 1,3-dimethyl-4-[2-(methylsulfonyl)-4-(trifluoromethyl)benzoyl]-1H-pyrazol-5-yl-1,3-Dimethyl-1H-pyrazole-4-carboxylate, dimetrasulfuron, dinitramine, dinoterb, diphenamide, diquat, diquat-dibromide, dithiopyr, diuron, DMPA, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyphene, ethoxyphene-ethyl, ethoxysulfuron, etobenzanide, ethyl-[(3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)phenyl]phenyl] fluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}pyridin-2-yl)oxy]acetate, F-9600, F-5231, i.e., N-{2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-5-oxo-4,5-dihydro-1H-tetrazol-1yl]-phenyl}ethanesulfonamide, F-7967, i.e., 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl, -dimethylammonium and -methyl, fluoroglucan Lycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, fluro-chloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, -sodium and -trimesium, H-9201, i.e., O-(2,4-dimethyl-6-nitrophenyl)O-ethyl isopropyl phosphoramidothioate, haloxifene, haloxifene-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e., 1-(dimethoxyphosphoryl)ethyl-(2,4-Dichlorophenoxy)acetate, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, (5-hydroxy-1-methyl-1H-pyrazol-4-yl)(3,3,4-trimethyl-1,1-dioxide-2,3-dihydro-1-benzothiophen-5-yl)methanone, 6-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-1,5-dimethyl-3-(2-methylphenyl)quinazoline-2,4(1H,3H)-dione, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-a ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil-octanoate, potassium and sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, carbutilate, KUH-043, i.e., 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-Oxazole, keto-spiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium and -sodium, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozoline, 2-({2-[(2-methoxy ethoxy)methyl]-6-(trifluoromethyl)pyridin-3-yl}carbonyl)cyclohexane-1,3-dione, methyl isothiocyanate, 1-methyl-4-[(3,3,4-trimethyl-1,1-dioxide-2,3-dihydro-1-benzothiophen-5-yl)carbonyl]-1H-pyrazol-5-ylpropane-1-sulfonate, metobromuron, metolachlor, S-metolachlor, methuracil methoxron, metribuzin, metsulfuron, metsulfuron-methyl, molinat, monolinuron, monosulfuron, monosulfuron-ester, MT-5950, i.e., N-[3-chloro-4-isopropylphenyl]-2-methylpentanamide, NGGC-011, napropamide, NC-310, i.e., [5-(benzyloxy)-1-methyl-1H-pyrazol-4-yl](2,4-Dichlorophenyl)methanone, nebulon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acid), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorophenol, pentoxazone, petroleum, phenmedi Fam, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, propoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflu, Fen, pyraflufen-ethyl, pyrasulfotole, pyrazolinate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclora , quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, QYM-201, QYR-301, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrione, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249, i.e., 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e., 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazine, terbutryn, tetflupyrolimet, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, thiaphenacyl , tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, ZJ-0862, i.e., 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline.,
[0121] The at least one active ingredient is preferably selected from the group comprising fungicides selected from the group comprising classes (1) inhibitors of the respiratory chain in complexes (especially azoles), (2) inhibitors of the respiratory chain in complexes I or II, (3) inhibitors of the respiratory chain in complexes, (4) inhibitors of mitosis and cell division, (6) compounds capable of inducing host defense, (10) inhibitors of lipid and membrane synthesis and (15) described above.
[0122] More preferably, the at least one active ingredient (a) as fungicide is selected from the group comprising fluopicolide, fluopyram, fluoxapiprolin, impirfluxam, isoflucipram.
[0123] The at least one insecticide is preferably selected from the group comprising insecticides selected from the group comprising classes (2) GABA-regulated chloride channel antagonists, (3) sodium channel modulators / voltage-gated sodium channel blockers, (4) nicotinic acetylcholine receptor (nAChR) competitive activators, (23) inhibitors of acetyl-CoA carboxylase, (28) ryanodine receptor modulators, (30) another active ingredient, as described above.
[0124] Furthermore, more preferably, the at least one active ingredient (a) as an insecticide is selected from the group comprising clothianidin, beta-cyfluthrin, deltamethrin, ethiprole, fipronil, flubendiamide, fluopyram, imidacloprid, spidoxamate, spiromesifen, spirotetramat, tetraniliprole, thiacloprid.
[0125] Finally, more preferably, the at least one active ingredient (a) as herbicide is selected from the group comprising tembotrione, triafamone and isoxadifen-ethyl.
[0126] Even more preferably, the at least one active ingredient is selected from the group comprising fluopicolide, fluopyram, fluoxapiprolin, impirfluxam, isoflucipram, clothianidin, beta-cyfluthrin, deltamethrin, ethiprole, fipronil, flubendiamide, imidacloprid, spidoxamate, spiromesifen, spirotetramat, tetraniliprole, thiacloprid, tembotrione, triafamone and isoxadifen-ethyl.
[0127] All active ingredients described above can be present in the form of free compounds and / or, if their functional groups allow, in the form of their agriculturally active salts.
[0128] Additionally, mesomeric forms and stereoisomers or enantiomers, where appropriate, are to be included, as variations of these are well known to those skilled in the art, as are polymorphs.
[0129] Unless otherwise indicated, in the context of the present invention, solid pesticidally active compounds (a) are to be understood as meaning all substances customary for the treatment of plants, the melting point of which is above 20°C.
[0130] Spreader (b): Suitable spreaders are selected from the group comprising mono- and diesters of metal sulfosuccinates with branched or linear alcohols containing 1 to 10 carbon atoms, in particular the alkali metal salts, more in particular the sodium salts, most in particular sodium dioctyl sulfosuccinate.
[0131] Another suitable spreading agent is an ethoxylated diacetylene-diol having 1-6 EO, such as Surfynol® 420 and 440.
[0132] Another suitable spreader is an alcohol ethoxylate, such as Break-Thru® Vibrant.
[0133] Preferably, the spreading agent is selected from the group comprising sodium dioctyl sulfosuccinate and ethoxylated diacetylene-diols having 1-6 EO.
[0134] Another formulation aid (c) is (c1) Suitable nonionic surfactants or dispersants (c1) are all substances of this type that can be conventionally used in agrochemicals. Preferably, polyethylene oxide-polypropylene oxide block copolymers (preferably with a molecular weight of more than 6000 g / mol or a polyethylene oxide content of more than 45%, more preferably with a molecular weight of more than 6000 g / mol and a polyethylene oxide content of more than 45%), polyethylene glycol ethers of branched or linear alcohols, reaction products of fatty acids or fatty acid alcohols with ethylene oxide and / or propylene oxide, furthermore polyvinyl alcohols, polyoxyalkyleneamine derivatives, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic acid esters, furthermore branched or linear alkyl ethoxylates and alkylaryl ethoxylates (here, polyethylene oxide-sorbitan fatty acid esters can be mentioned as an example). Of the above examples, selected classes may optionally be phosphorylated, sulfonated or sulfated and neutralized with bases.
[0135] Possible anionic surfactants (c1) are all substances of this type that can be conventionally used in agrochemicals. Preference is given to the alkali metal, alkaline earth metal and ammonium salts of alkylsulfonic or alkylphosphoric acids, as well as alkylarylsulfonic or alkylarylphosphoric acids. Further preferred groups of anionic surfactants or dispersants are the alkali metal, alkaline earth metal and ammonium salts of polystyrenesulfonic acid, the salts of polyvinylsulfonic acid, the salts of alkylnaphthalenesulfonic acids, the salts of naphthalene-sulfonic acid-formaldehyde condensation products, the salts of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde condensation products, and the salts of lignosulfonic acid.
[0136] (c2) Rheology modifiers are additives that provide a substantial increase in viscosity at low shear rates when added to a formulation at a concentration that reduces gravitational separation of dispersed active ingredients during storage. For purposes of this invention, low shear rates are defined as rates below 0.1 s -1 where a substantial increase is defined as greater than 2-fold, and a substantial increase is defined as greater than 2-fold. Viscosity can be measured with a rotational shear rheometer.
[0137] Suitable rheology modifiers (c4) are, by way of example, Polysaccharides including xanthan gum, guar gum and hydroxyethylcellulose, examples of which are Kelzan®, Rhodopol® G and 23, Satiaxane® CX911 and Natrosol® 250 range; Clays including montmorillonite, bentonite, sepiolite, attapulgite, laponite, hectorite, examples of which are Veegum® R, VanGel® B, Bentone® CT, HC, EW, Pangel® M100, M200, M300, S, M, W, Attagel® 50, Laponite® RD; Fumed and precipitated silicas, examples of which are Aerosil® 200, Siponat® 22.
[0138] Preferred are xanthan gum, montmorillonite clay, bentonite clay and fumed silica.
[0139] (c3) Suitable antifoaming substances (c3) are all substances customarily usable in agrochemicals for this purpose. Silicone oils and silicone oil preparations are preferred. Examples are Silcolapse® 426 and 432 from Bluestar Silicones, Silfoam® SRE and SC132 from Wacker, SAF-184® from Silchem, Foam-Clear ArraPro-S® from Basildon Chemical Company Ltd, SAG® 1572 and SAG® 30 from Momentive (dimethylsiloxanes and silicones, CAS No. 63148-62-9). Preferred is SAG® 1572.
[0140] (c4) Suitable antifreeze agents are all substances customarily usable in agricultural chemicals for this purpose. Suitable examples are propylene glycol, ethylene glycol, urea and glycerin.
[0141] (c5) Suitable further formulation auxiliaries (c5) are selected from biocides, antifreezes, colorants, pH regulators, buffers, stabilizers, antioxidants, inert filler substances, humectants, crystal growth inhibitors, micronutrients. Examples of these are:
[0142] Possible preservatives are all substances that are customarily usable in agrochemicals for this purpose.Suitable examples of preservatives are preparations that contain 5-chloro-2-methyl-4-isothiazolin-3-one [CAS-No. 26172-55-4], 2-methyl-4-isothiazolin-3-one [CAS-No. 2682-20-4] or 1,2-benzisothiazol-3(2H)-one [CAS-No. 2634-33-5].Examples that may be mentioned are Preventol® D7 (Lanxess), Kathon® CG / ICP (Dow), Acticide® SPX (Thor GmbH) and Proxel® GXL (Arch Chemicals).
[0143] Possible colorants are all substances which can be customarily used in agrochemicals for this purpose: titanium dioxide, carbon black, zinc oxide, blue pigments, Brilliant Blue FCF, red pigments and Permanent Red FGR may be mentioned by way of example.
[0144] Possible pH regulators and buffers are all substances customarily usable in pesticides for this purpose: citric acid, sulfuric acid, hydrochloric acid, sodium hydroxide, sodium hydrogen phosphate (Na2HPO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), potassium dihydrogen phosphate (K2HPO4) may be mentioned as examples.
[0145] Suitable stabilizers and antioxidants are all substances which can be customarily used in agrochemicals for this purpose. Butylhydroxytoluene [3,5-di-tert-butyl-4-hydroxytoluene, CAS No. 128-37-0] is preferred.
[0146] Carrier (d) The carriers (d) are those which can be customarily used for this purpose in agrochemical formulations.
[0147] Carrier is a solid or liquid, natural or synthetic, organic or inorganic substance that is generally inert and can be used as a solvent. Carriers generally improve the application of the compound, for example to plants, plant parts or seeds.
[0148] Examples of suitable solid carriers include, but are not limited to, ammonium salts, especially ammonium sulfate, ammonium phosphate and ammonium nitrate, natural rock powders such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, silica gel, and synthetic rock powders such as micronized silica, alumina and silicates, etc. Examples of typically useful solid carriers for preparing granules include, but are not limited to, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic and organic powders, and granules of organic materials such as paper, sawdust, coconut shells, corn cobs and tobacco stems.
[0149] Preferred solid supports are selected from clays, talcs and silicas.
[0150] Examples of suitable liquid carriers include, but are not limited to, water, organic solvents, and combinations thereof. Examples of suitable solvents include polar and non-polar organochemical liquids, such as those selected from the following classes: Aromatic and non-aromatic hydrocarbons (e.g. cyclohexane, paraffins, alkylbenzenes, xylene, toluene, tetrahydronaphthalene, alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, e.g. chlorobenzenes, chloroethylenes or methylene chloride); alcohols and polyols (which may optionally be substituted, etherified and / or esterified; for example ethanol, propanol, butanol, benzyl alcohol, cyclohexanol or glycol, 2-ethylhexanol); Ethers, such as dioctyl ether, tetrahydrofuran, dimethyl isosorbide, solketal, cyclopentyl methyl ether, solvents offered by Dow in the "Dowanol Product Range", such as Dowanol DPM, anisole, phenetole, dimethyl polyethylene glycols of various molecular weight grades, dimethyl polypropylene glycols of various molecular weight grades, dibenzyl ether; Ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, acetophenone, propiophenone); esters (which also include methylated fats and oils, such as rapeseed oil methyl ester, soybean oil methyl ester, coconut oil methyl ester, 2-ethylhexyl palmitate, 2-ethylhexyl stearate), for example butyl propionate, pentyl propionate, methyl hexanoate, methyl octanoate, methyl decanoate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, isobornyl acetate, benzyl benzoate, butyl benzoate, isopropyl benzoate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diisopropyl adipate, dibutyl adipate, benzyl-2-ethylhexyl adipate, dimethyl 2-methyl glutarate, monoacetin, diacetin, triacetin, trimethyl citrate, triethyl citrate, triethyl acetylcitrate, tributyl citrate, tributyl acetylcitrate; Lactic acid esters, for example, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethylhexyl lactate; (Poly)ethers, for example polyethylene glycols of various molecular weight grades, polypropylene glycols of various molecular weight grades; · Unsubstituted and substituted amines; Amides (for example dimethylformamide or N,N-dimethyllactamide or N-formylmorpholine or fatty acid amides, for example N,N-dimethyldecanamide or N,N-dimethyldec-9-enamide) and their esters; lactams (for example 2-pyrrolidone or N-alkylpyrrolidones, for example N-methylpyrrolidone or N-butylpyrrolidone or N-octylpyrrolidone or N-dodecylpyrrolidone or N-methylcaprolactam, N-alkylcaprolactams); Lactones (e.g., gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, or alpha-methyl gamma-butyrolactone); Sulfones and sulfoxides (e.g. dimethyl sulfoxide); oils of vegetable or animal origin, for example sunflower oil, rapeseed oil, corn oil; Nitriles (for example linear or cyclic alkyl nitriles, in particular acetonitrile, cyclohexanecarbonitrile, octanonitrile, dodecanonitrile); Linear and cyclic carbonates, such as diethyl, dipropyl, dibutyl, dioctyl or ethylene, propylene, butylene, and glyceryl carbonates; Phosphate esters, for example, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, trioctyl phosphate, tris(2-ethylhexyl) phosphate; · White mineral oil; and mixtures thereof.
[0151] Water is the most preferred liquid carrier.
[0152] These spray solutions are applied in the customary manner, ie for example by spraying, pouring or injection, in particular by spraying and most in particular by spraying by UAV.
[0153] The application rates of the formulations according to the invention can vary within relatively wide limits, depending on the particular pesticidal active substances and their amounts in the formulation.
[0154] By means of the formulations according to the invention it is possible to deliver agrochemically active substances to plants and / or their habitat in a particularly advantageous manner.
[0155] The present invention is further directed to the use of the pesticidal composition according to the invention for applying the pesticidal active compounds contained therein to plants and / or their habitat.
[0156] The formulations of the present invention can be used to treat all plants and plant parts. Here, plants refer to all plants and plant populations, such as desirable and undesirable wild plants or crop plants, including naturally occurring crop plants. Crop plants can be plants that can be obtained by conventional breeding and optimization methods, or by biotechnological and genetic engineering methods, or by a combination of these methods. Such crop plants also include transgenic plants, and also include plant varieties that can be protected by variety ownership and those that cannot. Plant parts refer to all parts and organs above and below ground of the plant, such as shoots, leaves, flowers and roots, an exemplary list of which includes leaves, needles, stems, trunks, flowers, fruiting bodies, fruits and seeds, and also roots, tubers and rhizomes. Plant parts also include harvested material, and also vegetative and generative propagation material.
[0157] In the context of the present invention, it may be emphasized that the present invention is applicable to cereal plants, such as wheat, oats, barley, spelt, triticale and rye, and also to maize, sorghum and millet, rice, sugarcane, soybean, sunflower, potato, cotton, rapeseed, canola, tobacco, sugar beet, fodder beet, asparagus, hops, and also to fruit plants, such as pome fruits, such as apple and pear, stone fruits, such as , peaches, nectarines, cherry trees, plums and apricots, citrus fruits such as oranges, grapefruits, limes, lemons, kumquats, tangerines and unshu mandarins, nuts such as pistachios, almonds, walnuts and pecans, tropical fruits such as mangoes, papayas, pineapples, dates and bananas, and grape vines), and vegetables (e.g. leafy vegetables such as endive, corn salad, Florence fennel, lettuce, cos lettuce, Swiss chard, spinach and salad chicory, cabbages such as cauliflower, broccoli, Chinese cabbage, kale (Brassica oleracea (L.) convar. acephala var. sabellica L.) (curly kale, feathered cabbage), kohlrabi, Brussels sprouts, red cabbage, white cabbage and Savoy cabbage, fruit vegetables such as eggplant, cucumber, pepper, table pumpkin, tomato, zucchini and sweet corn, root vegetables such as root celery, wild turnip, carrot (including yellow varieties), radish (Raphanus sativus var. niger and var. radicula, beetroot, scorzonera and celery, legumes such as peas and beans, and allium vegetables such as leeks and onions, for which the formulations of the invention show particularly advantageous effects.
[0158] The treatment according to the invention of plants and parts of plants with the formulations of the invention is carried out directly, in accordance with customary treatment methods, for example, by dipping, spraying, vaporizing, atomizing, scattering or applying, or by acting on their surroundings, habitat or storage, and, in the case of reproductive organs, especially seeds, further by applying one or more layers of coating.
[0159] The pesticidal active substance contained therein exhibits excellent biological activity as compared to when applied in the form of the corresponding customary formulations.
[0160] Leaf surface In Table 1a and Table 1b, the contact angles of water on the leaf surface are shown for the case of being rough and the case of not being rough. [Table 1] [Table 2]
[0161] Examples of smooth crops and plants include tomato, pepper, potato, carrot, celery, sugar beet, beetroot, spinach, lettuce, legumes, pea, clover, apple, pear, peach, apricot, plum, mango, avocado, olive, citrus fruits, orange, lemon, lime, grape, fig, cucumber, melon, watermelon, strawberry, raspberry, blueberry, sunflower, pumpkin, soybean (>BBCH XX), maize (>BBCH15), cotton.
[0162] Examples of rough crops and plants include garlic, onion, leek, soybean (<BBCH-XX), rye, wheat, barley, rice, sugarcane, pineapple, banana, flax, lily, orchid, maize (<BBCH15), cabbage, Brussels sprout, broccoli, cauliflower, timothy, rapeseed, tulip and peanut.
[0163] Examples of non-rough weeds include Abutilon theophrasti, Capsella bursa-pastoris, Datura stramonium, Galium aparine, Ipomoea purpurea, Polygonum lapathifolium, Portulaca oleracea, Senecio vulgaris, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Xanthium orientale, Cyperus rotundus and Amaranthus retroflexus.
[0164] Examples of rough weeds include Cassia obtusifolia, Chenopodium album, Agropyron repens, Alopecurus myosuroides, Apera spica-venti, Avena fatua, Brachiaria plantaginea, Bromus secalinus, Cynodon dactylon, Digitaria sanguinalis, Echinochloa crus-galli, Panicum dichotomiflorum, Poa annua, Setaria faberi and Sorghum sorghum. halepense).
[0165] Since soybeans and corn change leaf characteristics throughout their life cycle, the invention makes it possible to adapt the treatment in relation to leaf characteristics, i.e. the formulation according to the invention can be applied at a growth stage when the leaves are less likely to become wet. EXAMPLES
[0166] The invention is illustrated by the following examples.
[0167] Working Example Method 1: Preparation of SCs Methods for preparing suspension formulations are known to those skilled in the art and can be prepared by known methods well known to those skilled in the art. A 2% gel of xanthan (c) and biocide (c) in water was prepared with low shear agitation. The active ingredient (a), nonionic and anionic dispersants (c), antifoaming agents (c) and other formulation aids (c) were mixed with water to form a slurry, which was first mixed using a high shear rotor-stator mixer (Ultra-Turrax®) to reduce its particle size D (v, 0.9) to about 50 microns, and then passed through one or more bead mills (Eiger® 250 Mini Motormill) to achieve a particle size D (v, 0.9) typically between 1 and 15 microns. The additives (b), (c) and (d) and the xanthan gel prepared above were then added and mixed with low shear agitation until homogeneous. Finally, the pH was adjusted with an acid or base (e) as necessary.
[0168] Method 2: Preparation of WG Methods for preparing water dispersible granule formulations are known to those skilled in the art and may be prepared by known methods well known to those skilled in the art.
[0169] For example, to produce fluidized bed granules, first, a water-based formulation concentrate must be prepared. All components (a, b and c), such as active ingredients, surfactants, dispersants, binders, defoamers, spreaders and bulking agents, are mixed in water with low shear stirring, and finally pre-milled in a high shear rotor-stator mixer (Ultra-Turrax®) to reduce their particle size D (v, 0.9) to about 50 microns, and then passed through one or more bead mills (KDL, Bachofen, Dynomill, Buhler, Drais, Lehmann) to achieve a particle size D (v, 0.9) typically between 1 and 15 microns. This water-based formulation concentrate is then spray-dried in a fluidized bed granulation process to form a water dispersible granule (WG).
[0170] Particle size was determined using the CIPAC (Collaborative International Pesticides Analytical Council; www.cipac.org ) method MT187. The particle size distribution is determined by laser diffraction. A representative amount of the sample is dispersed in degassed water at ambient temperature (self-saturation of the sample), treated with ultrasound (usually for 60 seconds) and then measured with an instrument of the Malvern Mastersizer series (Malvern Panalytical). The scattered light is measured at different angles using a multi-element detector and the relevant values are recorded. Using the Fraunhofer model, the proportion of specific size classes is calculated from the scattering data and from this the volume weighted particle size distribution is calculated. Usually the d50 or d90 value = active ingredient particle size (50% or 90% of the total volume particles) is obtained. By mean particle size is meant the d50 value.
[0171] Likewise, other spray processes (eg classical spray drying) can also be used as granulation methods.
[0172] A further technique for producing water dispersible granules is, for example, low pressure extrusion. The components of the formulation are mixed in dry form and then milled (for example using an air jet mill) to reduce the particle size. The dry powder is then stirred while water is added to the mixture (approximately 10-30 wt %, depending on the composition of the formulation). In a further step, the mixture is extruded through an extruder (for example a dome extruder, double dome extruder, basket extruder, sieve mill or similar device) with a die size usually of 0.8-1.2 mm to form an extrudate. In a final step, the extrudate is post-dried (for example in a fluid bed dryer) to reduce the moisture content of the powder, usually to a residual water level of 1-3 wt %.
[0173] Method 3: Preparation of EC Methods for preparing EC formulations are known to those skilled in the art and can be produced by known methods well known to those skilled in the art. In general, EC formulations are obtained by mixing the active ingredient (a) with the remaining formulation ingredients (which include, inter alia, surfactant (c), spreader (b), carrier (d)) in a vessel equipped with a stirring device. Optionally, the temperature is slightly elevated (not exceeding 60°C) to facilitate dissolution or mixing. Stirring is continued until a homogeneous mixture is obtained.
[0174] Method 4: Preparation of OD The formulation components (c), carrier (d), active ingredient (a), and spreader (b) are weighed out and homogenized using a high shear device (e.g., Ultraturrax or colloid mill), then milled in a bead mill (e.g., Dispermat SL50, 80% filled, 1.0-1.25 mm glass beads, 4000 rpm, circulation milling) until a particle size of less than 10 μ is achieved. Alternatively, the formulation components are mixed in a bottle, and then about 25% by volume of 1.0-1.25 mm glass beads are added. The bottle is then closed, fixed in a stirring device (e.g., Retsch MM301), and processed at 30 Hz for several minutes until a particle size of less than 10 μ is achieved.
[0175] Method 5: Coverage area Greenhouse plants at the developmental stages shown in Tables 1a and 1b were used for these experiments. Immediately prior to the spraying experiments, a single leaf was cut, placed in a Petri dish, and taped at both ends at 0° (horizontal) or 60° (allowing 50% of the leaf area to be sprayed). The leaf was transported with care to avoid damaging the wax surface. These horizontally oriented leaves were either (a) placed in a spray chamber where the spray solution was applied via a hydraulic nozzle, or (b) a 4 μL droplet of the spray solution was pipetted onto the top without touching the leaf surface.
[0176] A small amount of UV dye was added to the spray solution to visualize the spray deposit under UV light. The concentration of the dye was chosen so as not to affect the surface properties of the spray solution and not to contribute to spreading itself. Tinopal OB as a colloidal suspension was used for all flowable and solid formulations such as WG, SC, OD and SE. For formulations with dissolved active ingredient such as EC, EW and SL, Tinopal CBS-X or Blankophor SOL was used. Tinopal CBS-X was dissolved in the water phase and Blankophor SOL was dissolved in the oil phase.
[0177] After the spray solution had evaporated, the leaves were placed in a Camag, Reprostar 3UV chamber where pictures of the spray deposits were taken under visible light and 366 nm UV light. A Canon EOS700D digital camera was attached to the UV chamber and used to capture the leaf images. The pictures taken under visible light were used to subtract the leaf shape from the background. ImageJ software was used to calculate (a) the coverage area of the applied spray (%) for the sprayed leaves or (b) the spreading area of the pipette-applied droplets (mm 2 ) was calculated.
[0178] Method 6: Insecticide greenhouse testing Selected crops were grown under greenhouse conditions in plastic pots containing "peat soil T." At the appropriate crop growth stage, plants were prepared for treatment, e.g., by infesting with the target pest approximately 2 days prior to treatment (see table below).
[0179] Spray solutions were prepared directly using various doses of active ingredient by diluting the formulation with tap water and adding appropriate amounts of additives in the tank mix as required.
[0180] Applications were made to the upper leaf side using a track sprayer with spray volumes of 300 L / ha or 10 L / ha. Nozzles used: Lechler TeeJet TP8003E (for 300 L / ha) and Lechler 652.246 with Pulse Width Module (PWM) (for 10 L / ha). For each single dose applied, usually 2-5 replicates were treated simultaneously.
[0181] After treatment, the plants were artificially infested, if necessary, and kept in a greenhouse or climate chamber for the duration of the test. The efficacy of the treatment was scored after evaluation of mortality (generally given in %) and / or plant protection (e.g. calculated from feeding damage compared to the corresponding control) at different time points. Only average values are reported. [Table 3]
[0182] Selected crops were grown under greenhouse conditions in plastic pots containing "peat soil T." At the appropriate crop growth stage, plants were prepared for treatment, e.g., by infesting with the target pest approximately 2 days prior to treatment (Table M1).
[0183] Spray solutions were prepared directly using various doses of active ingredient by diluting the formulation with tap water and adding appropriate amounts of additives in the tank mix as required.
[0184] Applications were made to the upper leaf side using a track sprayer with spray volumes of 300 L / ha or 10 L / ha. Nozzles used: Lechler TeeJet TP8003E (for 300 L / ha) and Lechler 652.246 with Pulse Width Module (PWM) (for 10 L / ha). For each single dose applied, usually 2-5 replicates were treated simultaneously.
[0185] After treatment, the plants were artificially infested, if necessary, and kept in a greenhouse or climate chamber for the duration of the test. The efficacy of the treatment was scored after evaluation of mortality (generally given in %) and / or plant protection (e.g. calculated from feeding damage compared to the corresponding control) at different time points. Only average values are reported.
[0186] Method 7: Cuticle Wash Off A disk from an apple cuticle was fixed with the outer side facing up onto a glass microscope slide using a thin layer of silicone oil of medium viscosity. A 0.9 μL drop of the various formulations diluted with the spray dilution in deionized water containing 5% CIPAC C water was applied to this using a micropipette and allowed to dry for 1 hour. Each deposit was examined under a transmitted light microscope equipped with cross-polarizing filters and images were recorded. The slide containing the cuticle with the dried drop of the formulation was held under gently flowing deionized water (flow rate of approximately 300 mL / min at a height of 10 cm below the tap outlet) for 15 seconds. The glass slide was allowed to dry and the deposit was reexamined under a microscope and compared with the original image. The amount of active ingredient washed off was visually assessed and recorded in 10% increments. Three replicates were measured and the average value was recorded.
[0187] Method 8: Leaf wash-off Apple or corn leaf sections were attached to glass microscope slides. To this, 0.9 μL drops of the various formulations diluted in spray dilution in deionized water containing 5% CIPAC C water and a small amount of fluorescent tracer (Tinopal OB as a micron-sized aqueous suspension) were applied using a micropipette and allowed to dry for 1 h. The leaf deposits were imaged with a digital camera under UV illumination (365 nm). The leaf sections were then held for 15 s under gently flowing deionized water (flow rate of approximately 300 mL / min at a height of 10 cm below the tap outlet). The leaf sections were allowed to dry and the deposits were imaged again and compared to the original image. The amount of active ingredient washed off was visually assessed between 5 (most remaining) and 1 (most removed). Measurements were made for 3 or more replicates and the average value was recorded.
[0188] Method 9: Preparation of suspoemulsions Methods for preparing suspoemulsion formulations are known to those skilled in the art and can be prepared by known methods well known to those skilled in the art. A 2% gel of xanthan and biocide (e) in water was prepared with low shear mixing. The active ingredients spiroxamine (a), oil (b / c) and antioxidant (e) were mixed and added to the aqueous dispersion containing a portion of the non-ionic dispersant (c) under high shear mixing using a rotor-stator mixer until an oil-in-water emulsion was formed with a droplet size D (v, 0.9) typically between 1 and 5 microns. The active ingredient (a), the remaining nonionic and anionic dispersants (c / e) and other remaining formulation aids (c / e) were mixed with the remaining water to form a slurry, which was first mixed using a high shear rotor-stator mixer to reduce its particle size D (v, 0.9) to about 50 microns, and then passed through one or more bead mills to achieve a particle size D (v, 0.9) of typically 1 to 15 microns required for the biological performance of the active ingredient. Those skilled in the art will understand that this may vary for different active ingredients. The oil-in-water emulsion, polymer dispersion (c / d) and xanthan gel were added and mixed with low shear agitation until uniform.
[0189] Method 10: Herbicide Greenhouse Testing Instructions Seeds of crops and seeds of monocotyledonous and dicotyledonous harmful plants are placed in sandy loam in plastic pots, covered with soil and cultivated in a greenhouse under optimal growing conditions. Test plants are treated at the 1-2 leaf stage 2-3 weeks after sowing. Test herbicide formulations are prepared at different concentrations and sprayed on the green surface of plants using different spray volumes (200 L / ha for standard conventional spray volume and 10 L / ha for ultra low volume (ULV) spray volume). The nozzle type used for all applications is a TeeJet DG 95015 EVS. ULV spray volume is achieved using a pulse width modulation (PWM) system connected to the nozzle and a track sprayer. After application, test plants are left undisturbed in a greenhouse under optimal growing conditions for 3-4 weeks. The activity of the herbicide formulation is then visually assessed (eg, 100% activity = entire plant material dead, 0% activity = plants similar to untreated control plants). [Table 4]
[0190] Method 11: Fungicide Greenhouse Testing Instructions Seeds were placed in "peat soil T" in plastic pots, covered with soil and cultivated in a greenhouse under optimal growing conditions. Test plants were treated at the 1-2 leaf stage 2-3 weeks after sowing. Test fungicide formulations were prepared at different concentrations and sprayed on the plant surface using different spray volumes (200 L / ha for standard conventional spray volume and 10 L / ha for ultra low volume (ULV) spray volume). The nozzle type used for all applications was TeeJet TP 8003E, used at 0.7-1.5 bar and at a height of 500-600 mm from plant level. Grains were placed at a 45° angle, as this best reflects field application conditions for cereals. ULV spray volumes were achieved using a pulse width modulation (PWM) system connected to the nozzles and truck spray equipment at 30 Hz and 8%–100% opening (spray volumes of 10 L / ha–200 L / ha).
[0191] For protection treatments, test plants were inoculated with the respective disease one day after spray application and then kept in a greenhouse under optimal growing conditions for 1-2 weeks. The activity of the fungicide formulations was then visually evaluated.
[0192] In the treatment conditions, plants were first inoculated with the disease and then treated with the fungicide formulation 2 days later. Visual assessment of disease was performed 5 days after application of the formulation.
[0193] Methods of inoculation are well known to those skilled in the art. [Table 5]
[0194] Method 12: Cuticular penetration test The cuticle penetration test is a further developed and adapted version of the test method SOFU (Simulation of foliar uptake) originally described by Schonherr and Baur (Schonherr, J., Baur, P. (1996), Effects of temperature, surfactants and other adjuvants on rates of uptake of organic compounds. In: The plant cuticle-an integrated functional approach, 134-155. Kerstiens, G. (ed.), BIOS Scientific publisher, Oxford); it is suitable for systematic and mechanistic studies of the influence of formulations, adjuvants and solvents on the penetration of pesticides.
[0195] Apple leaf cuticles were isolated from leaves taken from trees growing in an orchard as described by Schonherr and Riederer (Schonherr, J., Riederer, M. (1986), Plant cuticles sorb lipophilic compounds during enzymatic isolation. Plant Cell Environ. 9, 459-466). Only the astomatal cuticular membrane of the upper leaf surface, lacking stomatal openings, was obtained. Disks 18 mm in diameter were punched out from the leaves and infiltrated with an enzyme solution of pectinase and cellulase. The cuticular membrane was separated from the digested leaf cell broth, cleaned by gentle washing with water and dried. After about 4 weeks of storage, the permeability of the cuticle reached a certain level and the cuticular membrane was ready for use in the permeation test.
[0196] The cuticle membrane was applied to the diffusion chamber. Correct orientation is important: the inner surface of the cuticle must face the inside of the diffusion chamber. The diffusion chamber was then sprayed onto the outer surface of the cuticle. The diffusion chamber was then turned around and carefully filled with the acceptor solution. An aqueous mixture buffered to pH 5.5 was used as the acceptor medium to simulate the apoplast as the natural desorption medium at the inner surface of the cuticle.
[0197] The diffusion chamber filled with acceptor and stirrer was transferred to a temperature-controlled stainless steel block, which ensured not only a well-defined temperature but also a constant humidity at the cuticular surface where the spray deposit was located. The temperature at the start of the experiment was 25°C or 30°C, and changed to 35°C 24 hours after application, with a constant relative humidity of 60%.
[0198] An autosampler takes aliquots of the acceptor at regular intervals and the content of active ingredient is measured by HPLC (DAD or MS). All data points are finally processed to obtain the penetration kinetics. Due to the large variability in the cuticular penetration barrier, 5-10 replicates of each penetration kinetics were performed.
[0199] material [Table 6] [Table 7]
[0200] TIFF0007649254000008.tif53166 [Table 8] [Table 9] [Table 10]
[0201] Fungicide Examples Example FN1 Impilfluxam 25SC [Table 11]
[0202] The preparation method used was similar to Method 1.
[0203] greenhouse Efficacy Data [Table 12]
[0204] The above results show that formulation FN2, which illustrates the present invention, shows higher efficacy at a spray volume of 15 L / ha than at 200 L / ha. Furthermore, formulation FN2 at 15 L / ha shows equal or higher efficacy than formulation FN2 at 200 L / ha.
[0205] Pipette spreading test on leaf surface The size of the leaf deposits was measured (2 μL droplets) according to method 5(b). [Table 13]
[0206] The results above show that formulation FN2, illustrating the present invention, exhibits significantly greater deposit size at a spray volume of 10 L / ha than at 200 L / ha, and further shows that it exhibits significantly greater deposit size compared to control formulation FN1.
[0207] Example FN2 Isoflucipram 50SC [Table 14]
[0208] The preparation method used was similar to Method 1.
[0209] Pipette spreading test on leaf surface The size of the leaf deposits was measured (2 μL droplets) according to method 5(b). [Table 15]
[0210] The results above show that formulation FN4, illustrating the present invention, exhibits significantly greater deposit size at a spray volume of 10 L / ha than at 200 L / ha, and further shows that it exhibits significantly greater deposit size compared to control formulation FN3.
[0211] Example FN3: Fluopicolide 100SC [Table 16]
[0212] Pipette spreading test on leaf surface The size of the leaf deposits was measured (2 μL droplets) according to method 5(b). [Table 17]
[0213] The results above show that formulation FN6, illustrating the present invention, exhibits significantly greater deposit size at a spray volume of 10 L / ha than at 200 L / ha, and also shows that it exhibits significantly greater deposit size compared to control formulation FN5. Efficacy is greater on rough leaf surfaces.
[0214] Example FN4: Fluopyram 200SC [Table 18]
[0215] Pipette spreading test on leaf surface The size of the leaf deposits was measured (2 μL droplets) according to method 5(b). [Table 19]
[0216] The results show that the formulation FN8, which is illustrative of the present invention, shows significantly larger deposit size at a spray volume of 10 L / ha than at 200 L / ha, and also shows significantly larger deposit size compared to the control formulation FN7. The efficacy is greater on rough leaf surfaces. The formulation FN9 containing 60 g / L Surfynol 465 shows the same wettability as the formulation FN7 without additive (b), which illustrates that high wettability occurs only with certain additives (b), and that Surfynol 420 with low ethoxylation (1 mole EO) shows wettability illustrative of the present invention, while Surfynol 465 with high ethoxylation (10 mole EO) does not.
[0217] Example FN5: Fluoxapiproline 50SC [Table 20]
[0218] Pipette spreading test on leaf surface The size of the leaf deposits was measured (2 μL droplets) according to method 5(b). [Table 21]
[0219] The results show that the formulation FN11, which illustrates the present invention, shows a significantly larger deposit size at a spray volume of 10 L / ha than at 200 L / ha, and also shows a significantly larger deposit size compared to the control formulation FN10. The efficacy is greater on rough leaf surfaces. The efficacy depends on the concentration of additive (b), with formulation FN12 containing 80 g / L Agnique PG8107 showing a smaller efficacy compared to formulation FN11 containing 120 g / L Agnique PG8107. At 0.5 L / ha, these amounts of additive (b) correspond to 0.4% w / v and 0.6% w / v, respectively, in a spray dilution of 10 L / ha.
[0220] Insecticide examples The examples were prepared and tested in accordance with the relevant procedures.
[0221] Example I1 Spirotetramat / Spiromesifen SC Formulation [Table 22]
[0222] Foliar spray coverage test Leaf encrustation size was measured according to the area coverage method 5. [Table 23]
[0223] The results above show that the formulation according to the invention shows improved spreading on non-textured leaves at 300 L / ha compared to the non-inventive formulation. [Table 24]
[0224] The results above show that the formulation according to the invention shows improved spreading at 10 L / ha in barley compared to the non-inventive formulation.
[0225] Pipette spreading test on leaf surface [Table 25]
[0226] The results show that on non-textured leaves, the size of the deposits is large at low water application rates, and that the formulation according to the invention produces larger deposits compared to the non-inventive formulation. [Table 26]
[0227] The above results show that formulation I5, illustrating the present invention, exhibits larger deposit size at application rates of 10 L / ha and 20 L / ha than at 200 L / ha, and also exhibits larger deposit size compared to control formulation I5.
[0228] Example I2 / Spidoxamate OD Formulation [Table 27]
[0229] Pipette spreading test on leaf surface Leaf encrustation size was measured according to the area coverage method 5. [Table 28]
[0230] The above results show that the formulation according to the invention promotes larger deposit size on non-textured leaves at 10 L / ha and / or 20 L / ha compared to the non-inventive formulation. Furthermore, the formulation according to the invention promotes larger deposit size at 10 L / ha and / or 20 L / ha compared to 200 L / ha. [Table 29]
[0231] The above results show that formulations I9, I8, and I7 illustrating the present invention exhibit larger deposit sizes at a spray volume of 10 L / ha than at 200 L / ha, and also show larger deposit sizes compared to the control formulation I6.
[0232] Example I3 Example X: Flubendiamide, Tetraniprole SC Formulation [Table 30]
[0233] Foliar spray coverage test Leaf encrustation size was measured according to the area coverage method 5. [Table 31]
[0234] The results above show that the formulation according to the invention shows improved spreading on non-textured leaves at 10 L / ha compared to the non-inventive formulation. [Table 32]
[0235] The above results show that formulations I12 and I11 illustrating the present invention show greater coverage at a spray volume of 10 L / ha compared to the control formulation I10.
[0236] Pipette spreading test on leaf surface [Table 33]
[0237] The results show that on non-textured leaves the deposit size is slightly larger with less water applied and that the formulation according to the invention produces larger deposits compared to the non-textured formulation. [Table 34]
[0238] The above results show that formulation I14, illustrating the present invention, exhibits a larger deposit size at a spray volume of 10 L / ha than at 200 L / ha, and also shows that it exhibits a larger deposit size compared to the control formulation I14.
[0239] Example I4 Deltamethrin, beta-cyfluthrin SC formulation [Table 35]
[0240] Pipette spreading test on leaf surface Leaf encrustation size was measured according to the area coverage method 5. [Table 36]
[0241] The results show that on non-textured leaves the deposit size is slightly larger with less water applied and that the formulation according to the invention produces larger deposits compared to the non-textured formulation. [Table 37]
[0242] The results above show that formulation I17, illustrating the present invention, exhibits larger deposit size at application rates of 10 L / ha and 20 L / ha than at 200 L / ha and 300 L / ha, and also exhibits larger deposit size compared to control formulation I16. [Table 38]
[0243] The results show that on non-textured leaves the deposit size is slightly larger with less water applied and that the formulation according to the invention produces larger deposits compared to the non-inventive formulation. [Table 39]
[0244] The results above show that formulation I19, illustrating the present invention, exhibits larger deposit size at application rates of 10 L / ha and 20 L / ha than at 200 L / ha and 300 L / ha, and also exhibits larger deposit size compared to control formulation I18.
[0245] Example I5 Clothianidin, Imidacloprid, Thiacloprid SC Formulation [Table 40]
[0246] Pipette spreading test on leaf surface Leaf encrustation size was measured according to the area coverage method 5. [Table 41]
[0247] The results show that on non-textured leaves the deposit size is slightly larger with less water applied and that the formulation according to the invention produces larger deposits compared to the non-textured formulation. [Table 42]
[0248] The above results show that formulation I21, illustrating the present invention, exhibits greater coverage and larger deposit size at application rates of 10 L / ha and 20 L / ha than at 200 L / ha, and also exhibits greater coverage and larger deposit size compared to control formulation I20. [Table 43]
[0249] The results show that on non-textured leaves the deposit size is slightly larger with less water applied and that the formulation according to the invention produces larger deposits compared to the non-textured formulation. [Table 44]
[0250] The results above show that formulation I23, illustrating the present invention, exhibits larger deposit size at application rates of 10 L / ha and 20 L / ha than at 200 L / ha, and also exhibits larger deposit size compared to control formulation I22. [Table 45]
[0251] The results show that on non-textured leaves the deposit size is slightly larger with less water applied and that the formulation according to the invention produces larger deposits compared to the non-inventive formulation. [Table 46]
[0252] The results above show that formulation I25, illustrating the present invention, exhibits larger deposit size at application rates of 10 L / ha and 20 L / ha than at 200 L / ha, and also exhibits larger deposit size compared to control formulation I24.
[0253] Example I6 Ethiprole, Fipronil, Imidacloprid SC Formulation [Table 47]
[0254] Pipette spreading test on leaf surface Leaf encrustation size was measured according to the area coverage method 5. [Table 48]
[0255] The results show that on non-textured leaves the deposit size is slightly larger with less water applied and that the formulation according to the invention produces larger deposits compared to the non-inventive formulation. [Table 49]
[0256] The results above show that formulation I27, illustrating the present invention, exhibits larger deposit size at application rates of 10 L / ha and 20 L / ha than at 200 L / ha and 300 L / ha, and also exhibits larger deposit size compared to control formulation I26. [Table 50]
[0257] The results show that on non-textured leaves the deposit size is slightly larger with less water applied and that the formulation according to the invention produces larger deposits compared to the non-inventive formulation. [Table 51]
[0258] The results above show that formulation I29, illustrating the present invention, exhibits larger deposit size at application rates of 10 L / ha and 20 L / ha than at 200 L / ha and 300 L / ha, and also exhibits larger deposit size compared to control formulation I28. [Table 52]
[0259] The results show that on non-textured leaves the deposit size is slightly larger with less water applied and that the formulation according to the invention produces larger deposits compared to the non-inventive formulation. [Table 53]
[0260] The results above show that formulations I29 and I32 illustrating the present invention exhibit larger deposit sizes at application rates of 10 L / ha and 20 L / ha than at 200 L / ha and 300 L / ha, and also show that they exhibit larger deposit sizes compared to the control formulation I30. [Table 54]
[0261] The results show that on non-textured leaves, the size of the deposits is slightly larger at lower water application rates, and that at lower water application rates, the formulation according to the invention produces larger deposits compared to the non-inventive formulation. [Table 55]
[0262] The results above show that formulation I33, illustrating the present invention, exhibits a larger deposit size at a spray volume of 10 L / ha than at 200 L / ha, and also exhibits a larger deposit size compared to the control formulation I30.
[0263] Example I7 Fluopyram SC Formulation [Table 56]
[0264] Pipette spreading test on leaf surface The size of the leaf deposits was measured according to the area coverage method. [Table 57]
[0265] The results show that on non-textured leaves, the deposit size is slightly larger at lower application rates and that at lower application rates, the formulation according to the invention produces larger deposits compared to the non-inventive formulation. [Table 58]
[0266] The results above show that formulation I35, illustrating the present invention, exhibits larger deposit size at application rates of 10 L / ha and 20 L / ha than at 200 L / ha, and also exhibits larger deposit size compared to control formulation I34.
[0267] Example I8 Flupyradifurone SC Formulation [Table 59]
[0268] Pipette spreading test on leaf surface The size of the leaf deposits was measured according to the area coverage method. [Table 60]
[0269] The results show that on non-textured leaves, the deposit size is slightly larger at lower application rates and that at lower application rates, the formulation according to the invention produces larger deposits compared to the non-inventive formulation. [Table 61]
[0270] The results above show that formulation I37, illustrating the present invention, exhibits a larger deposit size at a spray volume of 10 L / ha than at 200 L / ha, and also exhibits a larger deposit size compared to the control formulation I36.
[0271] Example I9 Greenhouse Test Tetraniliprole SC040 Formulation [Table 62]
[0272] The above results show that the formulation according to the invention has higher efficacy at a spray volume of 10 L / ha than at 300 L / ha. Furthermore, the formulation according to the invention is slightly more effective than the non-inventive formulation.
[0273] Herbicide Examples Example HB1: [Table 63]
[0274] Pipette spreading test on leaf surface Leaf area coverage was measured according to the area coverage method 5. [Table 64]
[0275] The results above show that the coverage area on non-textured leaves is higher at higher application rates. [Table 65]
[0276] The above results show that formulations HB2 and HB3 illustrating the present invention show greater or equal coverage on rough leaves at a spray volume of 10 L / ha than 200 L / ha, and also show greater or equal coverage compared to the control formulation HB1.
[0277] Example HB2: [Table 66]
[0278] The preparation method used was similar to Method 1.
[0279] Pipette spreading test on leaf surface Leaf encrustation size was measured according to the area coverage method 5. [Table 67]
[0280] The results above show that on non-textured leaves the size of the deposits is larger with less water application. [Table 68]
[0281] The results above show that formulation HB5, illustrating the present invention, exhibits a larger deposit size at a spray volume of 10 L / ha than at 200 L / ha, and also exhibits a larger deposit size compared to the control formulation HB4.
Claims
1. 1. A method of applying a pesticide formulation to a plant, weed or crop, comprising: The formulation comprises: (a) one or more active ingredients; (b) one or more spreading agents; (c) other formulation aids; and (d) one or more carriers up to a predetermined volume; where (a) is present in an amount of 5 to 300 g / L; (b) is present at 10-150 g / L; and (c) is present at 4 to 250 g / L; wherein (b) is selected from the group consisting of mono- and diesters of metal sulfosuccinates with branched or linear alcohols containing 1 to 10 carbon atoms, ethoxylated diacetylenic diols and alcohol ethoxylates having 1 to 6 EO; wherein the active ingredient (a) is selected from the group consisting of fluopicolide, fluopyram, fluoxapiprolin, impirfluxam, isoflucipram, clothianidin, beta-cyfluthrin, deltamethrin, ethiprole, fipronil, flubendiamide, imidacloprid, spidoxamate, spiromesifen, spirotetramat, tetraniliprole, thiacloprid, tembotrione, triafamone and isoxadifen-ethyl; Here, component (c) is (c1) at least one nonionic surfactant and / or ionic surfactant; (c2) optionally, one rheology modifier; (c3) optionally, one antifoaming material; (c4) optionally, at least one antifreeze agent; and (c5) optionally, other suitable formulation auxiliaries, and wherein the formulation is applied by spraying with a spray volume of 1 to 20 L / ha, and The spreading agent (b) is applied at 5 g / ha to 150 g / ha; method.
2. 2. The method of claim 1, wherein (b) is selected from the group of sodium dioctyl sulfosuccinate and ethoxylated diacetylene-diols having 1-6 EO.
3. The method of claim 1 or 2, wherein (a) is present in an amount of 10 to 280 g / L.
4. The method of any one of claims 1 to 3, wherein (b) is present at 10 to 130 g / L.
5. The method of any one of claims 1 to 4, wherein (c) is present at 8 to 120 g / L.
6. The process according to any one of claims 1 to 5, wherein (c) comprises the following amounts of components (c1) to (c5): (c1) 4-250g / L, (c2) 0-60g / L, (c3) 0-30g / L, (c4) 0 to 200 g / L, and (c5) 0-200g / L.
7. 6. The method according to claim 1, wherein component (c) comprises at least one non-ionic and / or ionic surfactant (c1), one rheology modifier (c2), one antifoam substance (c3), at least one antifreeze agent (c4) and suitable further formulation auxiliaries (c5).
8. 8. The method according to claim 7, comprising the following amounts of components (c1) to (c5): (c1) 8-120g / L, (c2) 1-20g / L, (c3) 0.5-20g / L, (c4) 5-150g / L, (c5) 0.1-120g / L.
9. The method according to any one of claims 1 to 8, wherein the formulation is applied at a spray volume of 5 to 15 L / ha.
10. The method according to any one of claims 1 to 9, wherein the application rate of (a) to the plant, weed or crop is from 2 to 150 g / ha.
11. 11. The method according to any one of claims 1 to 10, wherein the spreading agent (b) is applied at from 10 g / ha to 60 g / ha.
12. 12. The method according to any one of claims 1 to 11, wherein the formulation is applied to plants, weeds or crops having a rough leaf surface, Here, the rough leaf surface is Garlic, onion, leek, soybean, oats, wheat, barley, rice, sugarcane, pineapple, banana, flaxseed, lilies, orchids, corn with a BBCH of less than 15, cabbage, Brussels sprouts, broccoli, cauliflower, rye, rapeseed, tulips, peanuts, Cassia obtusifolia, Chenopodium album, Agropyron repens, Alopecurus myosuroides, Apera spica-venti, Avena fatua, Alexander grass, plantaginea, Bromus secalinus, Cynodon dactylon, Digitalia sanguinalis, Echinochloa crus-galli, Panicum dichotomiflorum, Poa annua, Setaria fabaeri, and Sorghum halepense.
13. 13. The method according to any one of claims 1 to 12 in the application of a pesticidal compound to control pests, wherein the formulation is applied by unmanned aerial vehicle (UAV), unmanned guided vehicle (UGV) or pulse width modulation (PWM).
14. 13. A method for controlling pests, comprising contacting pests, their habitats, their hosts, including plants and seeds, as well as the soil, areas and environments in which they grow or may grow, and also materials, plants, seeds, soils, surfaces or spaces to be protected from attack or infestation by pests harmful to plants, with an effective amount of the formulation, according to any one of claims 1 to 12, characterized in that the formulation is applied by unmanned aerial vehicle (UAV), unmanned guided vehicle (UGV) or pulse width modulation (PWM).
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