WO2025119860A1

WO2025119860A1 - Liquid agrochemical formulations comprising flupyradifurone

Info

Publication number: WO2025119860A1
Application number: PCT/EP2024/084393
Authority: WO
Inventors: Gorka PERIS URQUIJO; Ralf Schulz; Christian MARIENHAGEN
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 2023-12-05
Filing date: 2024-12-03
Publication date: 2025-06-12
Anticipated expiration: 2026-06-05

Abstract

The present invention relates to novel liquid agrochemical formulations comprising flupyradifurone (4- [(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one).

Description

BCS233049 FC AF/hz 2024-10-01 LIQUID AGROCHEMICAL FORMULATIONS COMPRISING FLUPYRADIFURONE Summary of the invention The present invention relates to novel agrochemical formulations comprising 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one according to formula (1)

The compound of the formula (1) which has the common name flupyradifurone and the IUPAC-name 4- [(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one and a process for its production are known from WO-A-2007/115644. A process for its preparation is also known from WO-A-2009/036899. An amorphous and a crystalline form of the compound of formula (I) are known from WO-A- 2011/051151. It is often desirable to prepare formulations of agrochemicals containing as high an amount of active ingredient as possible. This minimizes package use, allows for a more flexible use of the formulation, reduces transport costs and transport frequency, and makes more efficient use of the inert/carrier components of the formulation. All these advantages coming from the use of a highly loaded formulation result in a lower impact on the environment from the use/transport of the formulation. At the same time, the increase of the loading of an active ingredient in a formulation must not result in a decrease in the cold stability of the formulation, a decrease in the technical properties of the formulation needed for a successful dilution in water before application on the agronomical target, or a decrease of the shelf-life stability of the formulation. Indeed, water soluble liquid (e.g. SL) agrochemical formulations must show a minimum cold stability profile in order for them to be eligible for registration (cf. CIPAC Method 39.3), as well as satisfactory dilution stability with no separate materials upon dilution in water either after direct preparation of the solution (cf. CIPAC Method 36.3) or after storage of the spray solution (cf. CIPAC Method 41.1). WO-A-2023/056540 discloses a highly loaded emulsifiable concentrate comprising 2,4-D- triethylammonium, a butyl polypropylene glycol polyethylene glycol, ethyl lactate, dimethyl sulfoxide and lactofen. BCS233049 FC -2- An emulsifiable concentrate comprising acetamiprid and indoxacarb, a butyl polypropylene glycol polyethylene glycol and a mixture of n-butylpyrrolidone and cyclohexanone as solvent is known from WO2022/189592. US2023/068010 discloses suspension concentrates comprising inter alia flupyradifurone in dissolved form, a second insecticide in suspended form, diammonium hydroxyphosphate, a butyl polypropylene glycol polyethylene glycol (Antarox B/848) and a glycol solvent. WO98/17277 discloses pour-on solutions of acetamiprid comprising acetamiprid, an alkylether of ethylene or propylene glycol and either ethyl lactate or dimethyl sulfoxide as solvent.WO2011029552 teaches that liquid formulations of water-soluble active ingredients in the presence of alkyl polypropylene glycol polyethylene glycols are possible in water soluble solvents, with exemplified concentrations of the water-soluble active ingredients up to 17% w/w in the water-soluble liquid (SL) concentrate formulations. However, the solution described in WO2011029552 is not satisfactory for preparing SL formulations containing >17% w/w of the water-soluble active ingredient flupyradifurone. The solution described in WO2011029552 leads to unsatisfactory solubilization of the formulation upon dilution with water, this leading to precipitation of the active ingredient, as well as insufficient solubilization of the active at room temperature or at cold (<=0°C) temperatures, this resulting in insolubilization of the active in the formulation or precipitation during storage at cold temperatures. The consequence of the loss of these technical properties is that the resulting formulation cannot be registered for use as a plant protection product in several countries, or cannot be reliably utilized in spray systems, due to the presence of insoluble material in the spray solution. In view of the prior art described above, it is an object of the present invention to provide a highly-loaded water-soluble liquid (SL) concentrate formulation of flupyradifurone exhibiting high insecticidal efficacy as well as sufficient cold stability and sufficient dilution spontaneity. The object described above was achieved by the provision of a water-soluble liquid (SL) concentrate formulation comprising flupyradifurone, an alkyl polypropylene glycol polyethylene glycol, a lactic acid ester and a dialkyl sulfoxide. In the present invention we show that high amounts of flupyradifurone (>17% w/w), as well as theoretically other water soluble active ingredients, can be formulated as an SL formulation by using a mixture of a dialkyl sulfoxide and an alkyl lactate as solvents, and an alkyl polypropylene glycol polyethylene glycol as solubilizer/emulsifier. In this manner, the problems observed when formulating high amounts (>17% w/w) of flupyradifurone are solved, and such formulations can then be registered, and used by customers. Hence, the present invention relates to SL-formulations with high loading of active ingredient, good biological efficacy, good cold stability and good dilution spontaneity. BCS233049 FC -3- Figures Fig. 1a: X-ray powder diffractogram of polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one Fig. 1b: FT Raman spectrum of polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one Fig. 1c: IR spectrum of polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one Fig.1d: DSC thermogram of polymorphic form A Fig. 2a: X-ray powder diffractogram of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one Fig. 2b: FT Raman spectrum of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one Fig. 2c: IR spectrum of polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one Fig.2d: DSC thermogram of polymorphic form B Detailed description & Definitions

The water-soluble liquid agrochemical formulation according to the invention comprises flupyradifurone as component a). Preferably, the formulation contains at least 18 wt.% flupyradifurone. Preferably, the concentration of flupyradifurone in the formulation is at least 200 g/l, more preferably at least 225 g/l, even more preferably within the range of from 225 to 350 g/l, yet more preferably within the range of from 250 to 350 g/l, and most preferably within the range of from 275-325 g/l. The flupyradifurone is present in the formulation according to the invention in dissolved form. The flupyradifurone used for preparing the formulation according to the invention can be the known amorphous form or any other polymorphic or pseudopolymorphic form (namely a hydrate or solvate) of flupyradifurone or a mixture thereof. This includes the crystalline form known from WO-A-2011/051151 (polymorphic form B) and in particular the crystalline form A reported herein. Surprisingly, a new polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]- furan-2(5H)-one of formula (1) has been found which is the thermodynamic stable form compared to the BCS233049 FC -4- polymorphic form B disclosed in WO-A-2011/051151 which has been found to be only metastable although it is kinetically quite stable. The compound 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one contains hydrogen atoms at various positions which may be any hydrogen isotope, i.e.¹H or ²H (deuterium). Thus, the compound 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one may contain no, one or more than one deuterium atom. In a preferred embodiment, the compound 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one contains hydrogen in its natural abundance isotopic composition, i.e. about 0.015 % deuterium (molar ratio). The polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by X-ray powder diffractometry on the basis of the respective diffraction diagrams, which are recorded at 25°C and with Cu-K alpha 1 radiation (1.5406 Å). The polymorphic form A reported herein displays at least 3, often at least 5, in particular at least 7, more particularly at least 10, and especially all the reflections quoted in the following as values: Table 1: X-ray reflections of polymorphic form A Reflections [2Ɵ values] Reflections [2Ɵ values] Reflections [2Ɵ values] x±0,2° x±0,2° x±0,2° 12.3 22.4 30.1 13.7 22.6 30.3 14.7 23.5 31.5 15.0 24.0 32.0 16.0 24.8 32.4 16.1 25.4 33.1 17.0 26.1 33.2 18.0 26.3 33.5 18.2 27.1 34.2 20.1 27.5 35.8 20.8 27.8 36.6 21.0 28.3 37.3 21.5 29.4 15 The polymorphic form A according to the present invention is further characterized by the X-ray powder diffractogram depicted in Fig. [1a]. BCS233049 FC -5- The polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by Raman spectroscopy on the basis of the respective spectrum, which are recorded at 25°C and with a laser wavelength of 1064 nm and a resolution of 2 cm^-1.The polymorphic form A displays at least 3, often at least 5, in particular at least 7, and especially all of the bands quoted in the following as peak maxima: Table 2: Raman bands of form A Raman band Raman band Raman band [peak maxima in cm^-1] [peak maxima in cm^-1] [peak maxima in cm^-1] 3120 1352 834 3090 1343 815 3059 1318 748 3046 1293 730 3001 1278 706 2970 1245 676 2949 1210 632 2919 1180 618 2893 1164 553 2874 1136 514 1807 1111 478 1739 1098 425 1711 1071 375 1600 1046 355 1587 1026 312 1566 1005 292 1470 999 241 1457 974 228 1441 962 177 1431 917 149 1410 904 111 1396 880 84 The polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by infrared spectroscopy on the basis of the respective spectrum, which are recorded at 25°C using an universal diamond ATR device and a resolution of 4 cm^-1. The polymorphic form A displays at least 3, often at least 5, in particular at least 7, and especially all of the bands quoted in the following as peak maxima: BCS233049 FC -6- Table 3: IR bands of form A IR band IR band IR band [peak maxima in cm^-1] [peak maxima in cm^-1] [peak maxima in cm^-1] 3118 1352 916 3089 1342 904 3057 1334 879 3045 1317 873 3000 1293 823 2948 1275 809 1806 1239 762 1783 1210 729 1760 1201 706 1731 1178 674 1615 1166 630 1597 1136 622 1587 1118 609 1564 1096 602 1490 1071 588 1469 1043 583 1456 1025 575 1440 1004 568 1428 997 563 1410 975 552 1394 963 In addition to the polymorphic form A, polymorphic form B is known from WO-A-2011/051151, which is further characterized in the following. The polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by X-ray powder diffractometry on the basis of the respective diffraction diagrams, which are recorded at 25°C and with Cu-K alpha 1 radiation (1.5406 Å). The polymorphic form B displays at least 3, often at least 5, in particular at least 7, more particularly at least 10, and especially all of the reflections quoted in the following as values: BCS233049 FC -7- Table 4: X-ray reflections of polymorphic form B Reflections [2Ɵ values] Reflections [2Ɵ values] Reflections [2Ɵ values] x±0,2° x±0,2° x±0,2° 5.6 20.3 28.3 10.1 20.7 28.9 10.4 21.8 29.2 11.1 22.6 29.7 11.9 23.1 30.0 12.4 23.3 30.5 13.9 23.5 30.7 14.1 23.7 30.9 14.3 24.0 31.3 14.6 24.2 32.0 16.1 24.8 32.5 16.6 25.4 33.4 16.9 26.0 33.9 17.9 26.4 34.6 18.1 27.2 35.3 18.4 27.5 36.2 19.1 27.8 36.5 19.9 28.1 37.0 The polymorphic forms B are further characterized by the X-ray powder diffractograms depicted in Fig. [2a]. The polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by Raman spectroscopy on the basis of the respective spectrum, which are recorded at 25°C and with a laser wavelength of 1064 nm and a resolution of 2 cm^-1.The polymorphic form B displays at least 3, often at least 5, in particular at least 7, and especially all of the bands quoted in the following as peak maxima: BCS233049 FC -8- Table 5: Raman bands of form B Raman band [peak Raman band [peak Raman band [peak maxima in cm^-1] maxima in cm^-1] maxima in cm^-1] 3125 1330 738 3072 1318 725 3062 1293 709 3051 1276 682 3022 1253 636 2994 1239 626 2975 1209 597 2960 1188 558 2943 1161 543 2911 1141 471 2873 1112 422 2821 1096 390 1727 1071 375 1702 1060 351 1603 1028 342 1589 1005 333 1568 972 305 1467 951 298 1458 918 281 1441 903 237 1429 882 209 1419 869 177 1393 841 85 1372 813 1357 793 1342 785 The polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be characterized by infrared spectroscopy on the basis of the respective spectrum, which are recorded at 25°C using an universal diamond ATR device and a resolution of 4 cm^-1. The polymorphic form B displays at least 3, often at least 5, in particular at least 7, and especially all of the bands quoted in the following as peak maxima: BCS233049 FC -9- Table 6: IR bands of form B IR band IR band IR band [peak maxima in cm^-1] [peak maxima in cm^-1] [peak maxima in cm^-1] 3122 1314 942 3095 1292 915 3062 1268 903 2993 1252 881 1830 1239 868 1805 1208 836 1784 1179 823 1730 1163 813 1720 1141 794 1713 1136 778 1602 1112 736 1587 1099 727 1568 1090 711 1539 1068 685 1456 1051 680 1438 1043 634 1432 1028 626 1427 1025 585 1416 1006 578 1392 999 569 1358 972 559 1342 949 The polymorphic form A can be prepared by conducting the following steps: a) diluting and/or suspending flupyradifurone in a suitable solvent or solvent mixture; b) adjusting a temperature of between 0 and 25°C optionally by heating or cooling the same; and c) storing the solution or slurry obtained in step b) at a temperature of between 0 and 25°C until the solvent is evaporated and crystals of polymorphic form A have formed. The chemical preparation of flupyradifurone (4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]- furan-2(5H)-one according to formula (1)) is known from the prior art such WO-A-2007/115644 or WO- BCS233049 FC -10- A-2009/036899. The compound of formula (1) as used in step a) can thus be prepared according to WO- A-2007/115644 or WO-A-2009/036899 to which full reference is made hereby. Preferably, the chemical preparation of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan- 2(5H)-one is performed according to WO-A-2007/115644 with butyronitrile as a solvent. The crystallization and filtration of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one is preferably performed in butanol. After filtration the crystals obtained are preferably washed with ethanol. The compound of formula (1) in step a) can essentially be any known form of 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one. This means that 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can be used in amorphous form or in a mixture of different polymorphic forms or in a mixture containing an amorphous and one or more different polymorphic forms. Suitable solvents or solvent mixtures which can be used to dilute and/or suspend the compound of formula (1) in step a) and from which the compound of formula (1) is obtained in polymorphic form A in step c), are any suitable solvent such as aromatic solvents or alcohols or esters or water, preferably toluene, methanol, ethanol, butanol, ethyl acetate, isopropanol or water. The solution of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one can also be prepared by transferring a reaction mixture obtained by chemical reaction, containing 4-[(6-chloro-3- pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one, if necessary after removal of reagents and/or side products into a solvent or solvent mixture according to the present invention. In step b) the temperature of the solution or slurry is adjusted to a temperature of 0°C to 25°C. This can be done by cooling or heating or by waiting until the temperature has adjusted to the room temperature (if it is between 0°C and 25°C). In step c) the solution or slurry obtained in step b) is stored at a temperature of between 0 and 25°C until the solvent is evaporated and crystals of polymorphic form A have formed. Preferably, the polymorphic form A is isolated from the solvent or solvent mixture by allowing the solution or slurry to stand at the crystallization conditions of step c) until at least 90 wt.-% of the solvent or solvent mixture is evaporated. The crystallization of polymorphic form A can be promoted or accelerated by seeding with seed crystals of form A. The isolation of the polymorphic form A from the mother liquid is affected by common techniques known in the art, for example by filtration, centrifugation or by decanting. The isolated polymorphic form A can optionally be washed with any solvent, preferably with the solvent or solvent mixture used for crystallization, with water or with a mixture of the solvent or solvent mixture and water. The washing step can optionally be repeated, whereby washing with water often is the last BCS233049 FC -11- washing step. The washing is typically performed at temperatures below 30°C, often below 25°C and in particular below 20°C, optionally at 0 °C. In a further, optional step, the crystals of polymorphic form A can be dried and then supplied for further processing. By means of the crystallization described herein, form A of 4-[(6-chloro-3-pyridylmethyl)(2,2- difluoroethyl)amino]furan-2(5H)-one is obtained with at least 85 %, in particular 90 %, and most preferably at least ≥95 % yield. This means, that apart from other possible impurities, preferably the amount of remaining form B or amorphous forms is < 15 %, in particular < 10%, and most preferably < 5%. The content of form A according to the present invention is analyzed by Raman spectroscopy. Based on calculated electronically mixed Raman spectra (mixed by a software calculator in 5 % steps) a calibration curve, using a PLS regression, is generated. With this curve the proportional shares of the different forms are calculated. Due to the calibration accuracy the content of 100 % of polymorphic form A is not excluded by the above wording. Alkyl polypropylene glycol polyethylene glycol (component b) The water-soluble liquid agrochemical formulation according to the invention comprises at least one alkyl polypropylene glycol polyethylene glycol (as component b). As used herein, the term “alkyl polypropylene glycol polyethylene glycol” is exemplified by the structure in Formula 3: Formula 3 where R is a linear or branched C1-C4 alkyl fragment, preferably a linear or branched C3-C4 alkyl fragment, most preferably a linear C4 alkyl (n-butyl) fragment, A is a polypropylene glycol fragment containing between 10-40 propylene oxide (PO) units (Formula 4), preferably 15-35 PO units, most preferably 20-30 PO units, and B is a polyalkylene glycol fragment consisting of between 10-50 ethylene oxide (EO) units (Formula 5) together with 0-10 propylene glycol (PO) units, preferably 20-40 EO units together with 0-8 PO units, most preferably 30-40 EO units together with 0-5 PO units, wherein when both PO unit and EO units are present (in fragment B), said PO and EO units (in fragment B) are present in randomly copolymerized form. BCS233049 FC -12-

Formula 4 Formula 5 Alkyl polypropylene glycol polyethylene glycols of formula 3 are also referred to as “alkyl alcohol EO/PO copolymers” or “EO/PO copolymer alkyl ethers”. Examples of commercially available “alkyl polypropylene polyethylene glycols” are: Commercial Name Supplier Antarox B/848 Solvay Antarox BL-470 Solvay Antarox BL-480 Solvay Emulsogen 3510 Clariant Emulsogen EP 4901 Clariant Ethylan NS 500 K Akzo Nobel Ethylan NS 500 LQ Akzo Nobel Ethylan NS 505 K Akzo Nobel Lucramul AG 411 Levaco Synergen 848 Clariant Termul 5429 Huntsman Tergitol XD Dow Toximul 8320 Stepan Toximul 8325 Stepan Ultraric 5000 Oxiteno BCS233049 FC -13- Preferred are alkyl polypropylene glycol polyethylene glycols, where R, A and B in formula 3 are defined as follows: R is a linear or branched C3-C4 alkyl fragment, A is a polypropylene glycol fragment containing between 15-35 propylene oxide (PO) units, and B is a polyalkylene glycol fragment containing between 20-40 ethylene oxide (EO) units together with 0- 8 propylene glycol (PO) units. Especially preferred are alkyl polypropylene glycol polyethylene glycols, where R, A and B in formula 3 are defined as follows: R is a linear C4 alkyl fragment (i.e. R is n-butyl), A is a polypropylene glycol fragment consisting of between 20-30 propylene oxide (PO) units, and B is a polyalkylene glycol fragment consisting of between 30-40 ethylene oxide (EO) units together with 0-5 propylene glycol (PO) units. Preferably, the water-soluble liquid agrochemical formulation according to the invention comprises at least 10% by weight of the alkyl polypropylene glycol polyethylene glycol, more preferably 15-35%, even more preferably 19-33% by weight, most preferably 21-29% by weight, in each case based on the total weight of the formulation. Dialkyl sulfoxide (component d) The water-soluble liquid agrochemical formulation according to the invention comprises at least one dialkyl sulfoxide (as component d). The formulation may contain a mixture of 2 different dialkyl sulfoxides. As used herein, the term “dialkyl sulfoxide” refers to substances exemplified in Formula 6

Formula 6 where R1 and R2 can be equal or different and R1 and R2 can be any linear C1-C4 alkyl fragment. R1 and R2 are preferably a linear C1-C2 alkyl fragment (i.e. methyl or ethyl). R1 and R2 are most preferably a C1 fragment (methyl). Even most preferably “dialkyl sulfoxide” is dimethyl sulfoxide. BCS233049 FC -14- Preferably, the water-soluble liquid agrochemical formulation according to the invention comprises at least 9% by weight, more preferably at least 15% by weight, and most preferably at least 21% by weight of the dialkyl sulfoxide, preferably dimethyl sulfoxide. In some embodiments, the content of dialkyl sulfoxide, preferably dimethyl sulfoxide, in the formulation is within the range of 9-55% by weight, more preferably 12-47% by weight, even more preferably 17-45% by weight, most preferably 20-35% by weight, and in particular 25-30% by weight. Lactic acid ester (component c) The water-soluble liquid agrochemical formulation according to the invention comprises at least one lactic acid ester (as component c). As used herein, the term “lactic acid ester” refers to substances exemplified in Formulae 7 and 8, where X can be any linear or branched C1-C12 alkyl fragment, preferably any linear or branched C2-C4 alkyl fragment, most preferably a linear C4 alkyl fragment.

Formula 7 Formula 8 Examples of “lactic acid ester” are methyl lactate, ethyl lactate, n-propyl lactate, butyl lactate, 2-ethyl hexyl lactate, octyl lactate, lauryl lactate, as either pure R or S enantiomer, as a racemate, or as an enantioenriched mixture. Butyl lactate is particularly preferred. Preferably, the water-soluble liquid agrochemical formulation according to the invention comprises at least 10% by weight, more preferably 10-25% by weight, and most preferably 15-24% by weight of the lactic acid ester. In an embodiment of the present invention, the joint concentration of lactic acid ester (component c) and alkyl polypropylene polyethylene glycol (component b) is 34-42% by weight, preferably 38-42% by weight, and most preferably 40-42% by weight, based on the total weight of the formulation according to the invention. Preferably, the liquid agrochemical formulation comprises the components a) to d) in an amount of a) 225-350 g/l BCS233049 FC -15- b) 15-35% by weight, c) 10-25% by weight, d) to 1 l. In a further preferred embodiment liquid agrochemical formulation comprises the components a) to d) in an amount of a) 250-350 g/l b) 19-33% c) 12-23% d) to 1 l. In a further preferred embodiment liquid agrochemical formulation comprises the components a) to d) in an amount of a) 275-325 g/l b) 21-29% c) 13-21% d) to 1 l. In another preferred embodiment liquid agrochemical formulation comprises the components a) to d) in an amount of a) 275-325 g/l b) 21-29% c) 10-25% d) to 1 l. As far as not otherwise indicated in this application % refers to wt% (% by weight). Antifoam (component e) Preferably, the formulation according to the invention further comprises an antifoam (component e). BCS233049 FC -16- As used herein, the term “antifoam” refers to substances known in the state of the art to be capable of preventing excess foaming in a formulation during manufacturing and/or application by the customer. Suitable defoaming performance is such that the FAO limits for foam persistence codified in the CIPAC Method 47.3 are maintained by agrochemical formulations at all times of its useful life. Suitable antifoams are all substances which are customarily used for this purpose in agrochemical compositions. Preference is given to silicone oils and magnesium stearate. Especially preferred are silicone oils, in particular poly(dimethylsiloxane). In case antifoam e) is present, it is present in a concentration range of 0.01-0.5% by weight, preferably 0.02-0.25% by weight, more preferably in the range 0.03-0.1%, by weight, and most preferably in the range 0.04-0.06% by weight, based on the total weight of the formulation. In a particularly preferred embodiment, the agrochemical formulation according to the invention comprises a) 225-350 g/l flupyradifurone b) 15-35% by weight of an alkyl polypropylene glycol polyethylene glycol” of formula Formula 3, wherein R is a linear C4 alkyl fragment, A is a polypropylene glycol fragment containing between 20-30 propylene oxide (PO) units, and B is a fragment containing between 30-40 ethylene oxide (EO) units together with 0-5 propylene glycol (PO) units. c) 10-25% by weight butyl lactate, d) 9-55% by weight dimethyl sulfoxide, and e) up to 0.5% by weight antifoam. In another preferred embodiment, the agrochemical formulation according to the invention comprises a) 250-350 g/l flupyradifurone b) 19-33% by weight of an alkyl polypropylene glycol polyethylene glycol” of formula Formula 3, wherein R is a linear C4 alkyl fragment, A is a polypropylene glycol fragment containing between 20-30 propylene oxide (PO) units, and BCS233049 FC -17- B is a fragment containing between 30-40 ethylene oxide (EO) units together with 0-5 propylene glycol (PO) units. c) 12-23% by weight butyl lactate, d) 12-47 % by weight dimethyl sulfoxide, and e) 0.01-0.5% by weight antifoam. In still another preferred embodiment, the agrochemical formulation according to the invention comprises a) 275-325 g/l flupyradifurone b) 21-29% by weight of an alkyl polypropylene glycol polyethylene glycol” of formula Formula 3, wherein R is a linear C4 alkyl fragment, A is a polypropylene glycol fragment containing between 20-30 propylene oxide (PO) units, and B is a fragment containing between 30-40 ethylene oxide (EO) units together with 0-5 propylene glycol (PO) units. c) 13-21% by weight butyl lactate, d) 21-42% by weight dimethyl sulfoxide, and e) 0.02-0.25% by weight antifoam. In yet another preferred embodiment, the agrochemical formulation according to the invention comprises a) 275-325 g/l flupyradifurone b) 21-29% by weight of an alkyl polypropylene glycol polyethylene glycol” of formula Formula 3, wherein R is a linear C4 alkyl fragment, A is a polypropylene glycol fragment containing between 20-30 propylene oxide (PO) units, and B is a fragment containing between 30-40 ethylene oxide (EO) units together with 0-5 propylene glycol (PO) units. c) 10-25% by weight butyl lactate, d) 17-45 % by weight dimethyl sulfoxide, and e) 0.02-0.25% by weight antifoam. Dialkyl carbonate (optional component f) BCS233049 FC -18- The formulation according to the invention may contain one or more dialkyl carbonates as additional solvent in a concentration of up to 20% by weight, preferably up to 15% by weight, based on the total weight of the formulation. If at least one dialkyl carbonate is present, the concentration of dialkyl carbonate is preferably within a range of 3-20% by weight, more preferably 3-15% by weight, based on the total weight of the formulation. In some embodiments of the present invention, the dialkyl carbonate is mandatorily present in the range of 3-20 % by weight. In some embodiments of the present invention, the formulation contains a mixture of two different dialkyl carbonates, wherein the total concentration of the two dialkyl carbonates is 3-20% by weight. As used herein, the term “dialkyl carbonate” refers to substances exemplified in Formula 9,

Formula 9 where R1, and R2 can be equal or different. R1 and R2 can be any linear or branched C1-C4 fragment, preferably R1 and R2 are a C1-C2 fragment. As used herein, the term “dialkyl carbonate” also refers to substances exemplified in Formula 10:

Formula 10 where A is a single bond; R3, and R4 can be equal or different; R3 and R4 can be any linear or branched C1-C10 fragment. Preferably is A a single bond, R3 a C1-C3 fragment, and R4 a C1-C3 fragment; more preferably is A a single bond, R3 a C1-C2 fragment, and R4 a C1-C2 fragment; most preferably is A a single bond, R3 a C1 fragment, and R4 a C2 fragment. BCS233049 FC -19- Examples of “dialkyl carbonate” are dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, diisopropyl carbonate, methyl isopropyl carbonate, ethyl isopropyl carbonate, isopropyl propyl carbonate, dibutyl carbonate, methyl butyl carbonate, ethyl butyl carbonate, propyl butyl carbonate, isopropyl butyl carbonate, isobutyl butyl carbonate, di-tert-butyl carbonate, methyl tert-butyl carbonate, ethyl tert-butyl carbonate, propyl tert-butyl carbonate, iso-propyl tert-butyl carbonate, butyl tert-butyl carbonate, ethylene carbonate, propylene carbonate and butylene carbonate. If the dialkyl carbonate comprises a chiral center, such as propylene carbonate or 1,2-butylene carbonate, the dialkyl carbonate can be present as either pure R or S enantiomer, as a racemate, or as an enantioenriched mixture. Even most preferably “dialkyl carbonate” is propylene carbonate. The term “C₁-C₁₂-alkyl” as used herein refers to a saturated, branched or straight hydrocarbon chain having 1 to 12 carbon atoms. Examples of C₁-C₆-alkyl include methyl, ethyl, propyl (n-propyl), 1-methylethyl (iso-propyl), butyl (n-butyl), 1-methylpropyl (sec-butyl), 2-methylpropyl (iso-butyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1- dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2- trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl. Accordingly, “C₁-C₄-alkyl” refers to a saturated, branched or straight hydrocarbon chain having 1, 2, 3 or 4 carbon atoms, i.e. methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl or tert-butyl. Optional component(s) g) Further adjuvants and auxiliaries not yet listed may be present as component(s) g) like adhesives, stickers, colorants, antioxidants, light stabilizers, in particular UV stabilizers, other agents which improve chemical and/or physical stability, butylhydroxytoluene [3.5-Di-tert-butyl-4-hydroxytoluol, CAS-No. 128-37-0], fragrances, protective colloids, binders, penetrants, retention promoters, stabilizers, sequestrants, complexing agents, humectants, spreaders/wetting agents and gibberellins. In the context of the present invention suitable penetrants (penetration enhancers) are all those substances which are usually used for improving the penetration of agrochemical active compounds into plants. Penetrants are defined in this context by their ability to penetrate from the (generally aqueous) application liquor and/or from the spray coating into the cuticle of the plant and hence increase the mobility of the active compounds in the cuticle. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used for determining this property. Examples include alcohol alkoxylates such as coconut fatty ethoxylate (10) or isotridecyl ethoxylate (12), fatty acid esters, for example rapeseed oil methyl ester or soya oil methyl ester, fatty amine alkoxylates, for example tallowamine ethoxylate (15), BCS233049 FC -20- or ammonium and/or phosphonium salts, for example ammonium sulfate or diammonium hydrogenphosphate. Suitable penetration enhancers by way of example are: - ethoxylated linear and/or branched fatty alcohols (e.g. Genapol® X-type of Clariant) with 2-20 EO units; - methyl end-capped, ethoxylated linear and/or branched fatty alcohols (e.g. Genapol® XM-type of Clariant) comprising 2-20 EO units; - ethoxylated coconut alcohols (e.g. Genapol® C-types of Clariant) comprising 2-20 EO units; - ethoxylated C12/15 alcohols (e.g. Synperonic® A-types of Croda) comprising 2-20 EO units; - propoxy-ethoxylated fatty acids, Me end-capped, e.g. Leofat® OC0503M of Lion; - alkyl ether citrate surfactants (e.g. Adsee CE range, Akzo Nobel); - alkylpolysaccharides (e.g. Agnique® PG8107, PG8105 of BASF; Atplus® 438, AL-2559, AL- 2575 of Croda); - ethoxylated mono- or diesters of glycerine comprising fatty acids with 8-18 carbon atoms and an average of 10-40 EO units (e.g. Crovol® product range of Croda); - castor oil ethoxylates comprising an average of 5-40 EO units (e.g. Berol® range of Nouryon, Emulsogen® EL range of Clariant); - block-copolymer of polyethylene oxide and polypropylene oxide (e.g. Pluronic range of BASF). - Oils that function as penetration promoters are all oils of vegetable, mineral and animal origin which can customarily be employed in agrochemical agents. Examples are: o sunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, olive oil; o sunflower oil methyl ester, rapeseed oil methyl ester, corn oil methyl ester, soybean oil methyl ester, rice bran oil methyl ester, olive oil methyl ester o linear and/or branched alkyl esters of C10-C24 saturated fatty acids of vegetable or mineral origin: e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, 2-ethyl hexyl esters of capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid. BCS233049 FC -21- o linear and/or branched alkyl esters of C10-C24 usaturated fatty acids of vegetable or mineral origin: e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, 2-ethyl hexyl esters of α-Linolenic acid, linoleic acid, linolelaidic acid, palmitoleic acid, oleic acid, erucic acid. o white paraffinic mineral oils such as the Catenex®, Exxsol® ranges of Shell. o mixtures of two or more of the above Useful retention promoters include all those substances which reduce dynamic surface tension, for example dioctyl sulfosuccinate, or increase viscoelasticity, for example hydroxypropylguar polymers. Suitable wetting agents, spreading agents and/or retention agents by way of example are: - ethoxylated branched alcohols (e.g. Genapol® X-type) with 2-20 EO units; - methyl end-capped, ethoxylated branched alcohols (e.g. Genapol® XM-type) comprising 2-20 EO units; - organomodified polysiloxanes, e.g. BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwet 312, Silwett® 408, Silwet® 806; - mono-and diesters of sulfosuccinate Na salts with branched or linear alcohols comprising 1-10 carbon atoms, e.g. Geropon DOS; - ethoxylated diacetylene-diols, e.g. Surfynol® 4xx-range; The liquid agrochemical formulation according to the invention may additionally comprise one or more further active substance(s) selected from the group consisting of herbicides, insecticides, acaricides, fungicides, safeners and/or plant growth regulators. The active compounds identified here by their common names are known and are described, for example, in the pesticide 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 current IRAC Mode of Action Classification Scheme at the time of filing of this patent application. In one preferred embodiment the one or more further active substance is selected from the group of insecticides/acaricides and nematicides. Preferably those are selected from: (1) Acetylcholinesterase (AChE) inhibitors, preferably carbamates selected from 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 BCS233049 FC -22- selected from acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl) 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, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon and vamidothion. (2) GABA-gated chloride channel blockers, preferably cyclodiene-organochlorines selected from chlordane and endosulfan, or phenylpyrazoles (fiproles) selected from ethiprole and fipronil. (3) Sodium channel modulators, preferably pyrethroids selected from 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, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(1R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)- isomer)], tralomethrin and transfluthrin, or DDT or methoxychlor. (4) Nicotinic acetylcholine receptor (nAChR) competitive modulators, preferably neonicotinoids selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam, or nicotine, or sulfoximines selected from sulfoxaflor, or butenolids selected from flupyradifurone, or mesoionics selected from triflumezopyrim. (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators (Site I), preferably spinosyns selected from spinetoram and spinosad. (6) Glutamate-gated chloride channel (GluCl) allosteric modulators, preferably avermectins/milbemycins selected from abamectin, emamectin benzoate, lepimectin and milbemectin. (7) Juvenile hormone mimics, preferably juvenile hormone analogues selected from hydroprene, kinoprene and methoprene, or fenoxycarb or pyriproxyfen. (8) Miscellaneous non-specific (multi-site) inhibitors, preferably alkyl halides selected from methyl bromide and other alkyl halides, or chloropicrine or sulphuryl fluoride or borax or tartar emetic or methyl isocyanate generators selected from diazomet and metam. BCS233049 FC -23- (9) Chordotonal organ TRPV channel modulators, preferably pyridine azomethanes selected from pymetrozine and pyrifluquinazone, or pyropenes selected from afidopyropen. (10) Mite growth inhibitors affecting CHS1 selected from clofentezine, hexythiazox, diflovidazin and etoxazole. (11) Microbial disruptors of the insect gut membranes selected from Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and B.t. plant proteins selected from Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb and Cry34Ab1/35Ab1. (12) Inhibitors of mitochondrial ATP synthase, preferably ATP disruptors selected from diafenthiuron, or organotin compounds selected from azocyclotin, cyhexatin and fenbutatin oxide, or propargite or tetradifon. (13) Uncouplers of oxidative phosphorylation via disruption of the proton gradient selected from chlorfenapyr, DNOC and sulfluramid. (14) Nicotinic acetylcholine receptor channel blockers selected from bensultap, cartap hydrochloride, thiocylam and thiosultap-sodium. (15) Inhibitors of chitin biosynthesis affecting CHS1, preferably benzoylureas selected from bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron. (16) Inhibitors of chitin biosynthesis, type 1 selected from buprofezin. (17) Moulting disruptor (in particular for Diptera, i.e. dipterans) selected from cyromazine. (18) Ecdysone receptor agonists, preferably diacylhydrazines selected from chromafenozide, halofenozide, methoxyfenozide and tebufenozide. (19) Octopamine receptor agonists selected from amitraz. (20) Mitochondrial complex III electron transport inhibitors selected from hydramethylnone, acequinocyl, fluacrypyrim and bifenazate. (21) Mitochondrial complex I electron transport inhibitors, preferably METI acaricides and insecticides selected from fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad, or rotenone (Derris). BCS233049 FC -24- (22) Voltage-dependent sodium channel blockers, preferably oxadiazines selected from indoxacarb, or semicarbazones selected from metaflumizone. (23) Inhibitors of acetyl CoA carboxylase, preferably tetronic and tetramic acid derivatives selected from spirodiclofen, spiromesifen, spiropidion and spirotetramat. (24) Mitochondrial complex IV electron transport inhibitors, preferably phosphides selected from aluminium phosphide, calcium phosphide, phosphine and zinc phosphide, or cyanides selected from calcium cyanide, potassium cyanide and sodium cyanide. (25) Mitochondrial complex II electron transport inhibitors, preferably beta-ketonitrile derivatives selected from cyenopyrafen and cyflumetofen, or carboxanilides selected from pyflubumide. (28) Ryanodine receptor modulators, preferably diamides selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide and tetraniliprole. (29) Chordotonal organ Modulators (with undefined target site) selected from flonicamid. (30) GABA-gated chlorid channel allosteric modulators, preferably meta-diamides selected from broflanilide, or isoxazoles selected from fluxametamide. (31) Baculoviruses, preferably Granuloviruses (GVs) selected from Cydia pomonella GV and Thaumatotibia leucotreta (GV), or Nucleopolyhedroviruses (NPVs) selected from Anticarsia gemmatalis MNPV, Flucypyriprole and Helicoverpa armigera NPV. (32) Nicotinic acetylcholine receptor allosteric modulators (Site II) selected from GS-omega/kappa HXTX-Hv1a peptide. (33) further active compounds selected from Acynonapyr, Afoxolaner, Azadirachtin, Benclothiaz, Benzoximate, Benzpyrimoxan, Bromopropylate, Chinomethionat, Chloroprallethrin, Cryolite, Cyclobutrifluram, Cycloxaprid, Cyetpyrafen, Cyhalodiamide, Cyproflanilide (CAS 2375110-88-4), Dicloromezotiaz, Dicofol, Dimpropyridaz, epsilon-Metofluthrin, epsilon-Momfluthrin, Flometoquin, Fluazaindolizine, Flucypyriprole (CAS 1771741-86-6), Fluensulfone, Flufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon, Fluopyram, Flupyrimin, Fluralaner, Fufenozide, Flupentiofenox, Guadipyr, Heptafluthrin, Imidaclothiz, Iprodione, Isocycloseram, kappa-Bifenthrin, kappa-Tefluthrin, Lotilaner, Meperfluthrin, Nicofluprole (CAS 1771741-86-6), Oxazosulfyl, Paichongding, Pyridalyl, Pyrifluquinazon, Pyriminostrobin, Sarolaner, Spidoxamat, Spirobudiclofen, Tetramethylfluthrin, Tetrachlorantraniliprole, Tigolaner, Tioxazafen, Thiofluoximate, Tyclopyrazoflor, Iodomethane; furthermore preparations based on Bacillus firmus (I-1582, Votivo) and azadirachtin (BioNeem), and also the following compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulphinyl]phenyl}-3- (trifluoromethyl)-1H-1,2,4-triazole-5-amine (known from WO2006/043635) (CAS 885026-50-6), 2- chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4- BCS233049 FC -25- (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 WO 2010052161) (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), PF1364 (known from JP2010/018586) (CAS 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 WO 2013/050317 A1) (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 WO 2013/162715 A2, WO 2013/162716 A2, US 2014/0213448 A1) (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 CN 101337937 A) (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 CN 103109816 A) (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 WO 2012/034403 A1) (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 WO 2011/085575 A1) (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 CN 101337940 A) (CAS 1108184-52-6); (2E)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl) phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide (known from CN 101715774 A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2- yl)phenyl-cyclopropanecarboxylic acid ester (known from CN 103524422 A) (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 CN 102391261 A) (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 US 2014/0275503 A1) (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- BCS233049 FC -26- 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 WO 2007040280 A1, WO 2007040282 A1) (CAS 934001-66-8), N-[4-(aminothioxomethyl)-2-methyl-6- [(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from CN 103265527 A) (CAS 1452877-50-7), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl- 1,8-diazaspiro[4.5]decane-2,4-dione (known from WO 2014/187846 A1) (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-carbonic acid ethyl ester (known from WO 2010/066780 A1, WO 2011151146 A1) (CAS 1229023-00-0), N-[1-(2,6- difluorophenyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO 2014/053450 A1) (CAS 1594624-87-9), N-[2-(2,6-difluorophenyl)-2H-1,2,3-triazol-4-yl]-2-(trifluoromethyl)benzamide (known from WO 2014/053450 A1) (CAS 1594637-65-6), N-[1-(3,5-difluoro-2-pyridinyl)-1H-pyrazol- 3-yl]-2-(trifluoromethyl)benzamide (known from WO 2014/053450 A1) (CAS 1594626-19-3), (3R)-3-(2- chloro-5-thiazolyl)-2,3-dihydro-8-methyl-5,7-dioxo-6-phenyl-5H-thiazolo[3,2-a]pyrimidinium inner salt (known from WO 2018/177970 A1) (CAS 2246757-58-2); 3-(2-chloro-5-thiazolyl)-2,3-dihydro-8- methyl-5,7-dioxo-6-phenyl-5H-thiazolo[3,2-a]pyrimidinium inner salt (known from WO 2018/177970 A1) (CAS 2246757-56-0); N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-2-(methylsulfonyl)- propanamide (known from WO 2019/236274 A1) (CAS 2396747-83-2), N-[2-bromo-4-[1,2,2,2- tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-2-fluoro-3-[(4-fluorobenzoyl)amino]- benzamide (known from WO 2019059412 A1) (CAS 1207977-87-4), 3-Bromo-1-(3-chloro-2-pyridinyl)- N-[4,6-dichloro-3-fluoro-2-[(methylamino)carbonyl]phenyl]-1H-Pyrazole-5-carboxamide (Fluchlorodiamide; known from CN110835330 A, CN106977494 A) (CAS: 2129147-03-9). In another preferred embodiment, said further active substance is a biological pesticide. Biological pesticides comprise in particular bacteria, fungi, yeasts, plant extracts and products formed by microorganisms, including proteins and secondary metabolites. Biological pesticides comprise bacteria such as spore-forming bacteria, root-colonising bacteria and bacteria which act as biological insecticides, fungicides or nematicides. Examples of such bacteria which are employed or can be used as biological pesticides are: Bacillus amyloliquefaciens, strain FZB42 (DSM 231179), or Bacillus cereus, in particular B. cereus strain CNCM I-1562 or Bacillus firmus, strain I-1582 (Accession number CNCM I-1582) or Bacillus pumilus, in particular strain GB34 (Accession No. ATCC 700814) and strain QST2808 (Accession No. NRRL B- 30087), or Bacillus subtilis, in particular strain GB03 (Accession No. ATCC SD-1397), or Bacillus subtilis strain QST713 (Accession No. NRRL B-21661) or Bacillus subtilis strain OST 30002 (Accession No. NRRL B-50421) Bacillus thuringiensis, in particular B. thuringiensis subspecies israelensis (serotype H- 14), strain AM65-52 (Accession No. ATCC 1276), or B. thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372), or B. thuringiensis subsp. kurstaki strain HD-1, or B. thuringiensis subsp. BCS233049 FC -27- tenebrionis strain NB 176 (SD-5428), Pasteuria penetrans, Pasteuria spp. (Rotylenchulus reniformis nematode)-PR3 (Accession Number ATCC SD-5834), Streptomyces microflavus strain AQ6121 (= QRD 31.013, NRRL B-50550), Streptomyces galbus strain AQ 6047 (Acession Number NRRL 30232). Examples of fungi and yeasts which are employed or can be used as biological pesticides are: Beauveria bassiana, in particular strain ATCC 74040, Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM-9660), Lecanicillium spp., in particular strain HRO LEC 12, Lecanicillium lecanii, (formerly known as Verticillium lecanii), in particular strain KV01, Metarhizium anisopliae, in particular strain F52 (DSM3884/ ATCC 90448), Metschnikowia fructicola, in particular strain NRRL Y-30752, Paecilomyces fumosoroseus (now: Isaria fumosorosea), in particular strain IFPC 200613, or strain Apopka 97 (Accesion No. ATCC 20874), Paecilomyces lilacinus, in particular P. lilacinus strain 251 (AGAL 89/030550), Talaromyces flavus, in particular strain V117b, Trichoderma atroviride, in particular strain SC1 (Accession Number CBS 122089), Trichoderma harzianum, in particular T. harzianum rifai T39. (Accession Number CNCM I-952). Examples of viruses which are employed or can be used as biological pesticides are: Adoxophyes orana (summer fruit tortrix) granulosis virus (GV), Cydia pomonella (codling moth) granulosis virus (GV), Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, Spodoptera littoralis (African cotton leafworm) NPV. Also included are bacteria and fungi which are added as 'inoculant' to plants or plant parts or plant organs and which, by virtue of their particular properties, promote plant growth and plant health. Examples which may be mentioned are: Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp., or Gigaspora monosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp., Streptomyces spp. Examples of plant extracts and products formed by microorganisms including proteins and secondary metabolites which are employed or can be used as biological pesticides are: Allium sativum, Artemisia absinthium, azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, chitin, Armour-Zen, Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Fungastop, Heads Up (Chenopodium quinoa saponin extract), Pyrethrum/Pyrethrins, Quassia amara, Quercus, Quillaja, Regalia, "Requiem ™ Insecticide", rotenone, ryania/ryanodine, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, BCS233049 FC -28- Veratrin, Viscum album, Brassicaceae extract, in particular oilseed rape powder or mustard powder, as well as bioinsecticidal / acaricidal active substances obtained from olive oil, in particular unsaturated fatty/carboxylic acids having carbon chain lengths C16-C20 as active ingredients, such as, for example, contained in the product with the trade name FLiPPER®. In another embodiment the compounds of the formula (I) can be combined with safeners such as, for example, benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole (- ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}sulphonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3), 2,2,5-trimethyl-3- (dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4). All named mixing partners can, if their functional groups enable this, optionally form salts with suitable bases or acids. All named mixing partners can include tautomeric forms, where applicable. Mixing partners may also be encapsulated. Preferred mixing partners are selected from the group comprising beta-cyfluthrin, Deltamethrin, Permethrin, Transfluthrin, Spiromesifen, Spidoxamat, Ethiprole, Fipronil, Thiacloprid and Tetraniliprole. Most preferred mixing partners are Deltamethrin, Transfluthrin, Spiromesifen and Spidoxamat. Moreover, in the ranges of preference stated in the present invention, the different levels of preference should be understood such that they can be combined with one another in permutations, but in any case, identical levels of preference and especially the most preferred embodiment/level of preference in each case are to be combined with one another and are indeed disclosed as such a combination. Compositions as described above that consist solely of the essential components (not optional components) should likewise be considered to be disclosed. The auxiliaries used may be substances suitable for imparting special properties, such as certain physical, technical and/or biological properties, to the formulation of the compounds of the formula (I), or to the use forms prepared from these formulations (for example ready-to-use pesticides such as spray liquors or seed dressing products). Moreover, the present invention is directed to the use of the formulation according to the invention for controlling animal pests. The term “controlling" means inhibition of animal pest development (including mortality, feeding reduction, and/or mating disruption). In a particular embodiment, the present invention is directed to controlling animal pests in crops of useful plants including cereals (wheat, rice, triticale, barley, rye, oats), maize, soya bean, potato, sugar beet, sugar cane, tomatoes, pepper, cucumber, melon, carrot, watermelon, onion, lettuce, spinach, leek, beans, Brassica oleracea (e.g. cabbage) and other vegetable species, cotton, tobacco, oilseed rape, and also fruit BCS233049 FC -29- plants (with the fruits apples, pears, citrus fruits and grapevines). In a particular preferred embodiment the useful plants are fruits and grapes, vegetables and flowers, coffee and cocoa (plantations), potatoes, cotton, cereals, sugar beet, oilseed rape, corn and soybeans. In another particular embodiment of the present invention, the useful plants are transgenic plants. The present invention is also directed to a method for controlling animal or microbial pests, wherein the formulation according to the invention is allowed to act on animal or microbial pests and/or their habitat. The formulation according to the present invention is typically diluted in water or any other agriculturally relevant carrier fluid before use. For this, the advantageous properties of the formulation according to the invention in terms of dilution spontaneity and dilution stability are of particular importance. The control of the animal pests is preferably conducted in agriculture and forestry, and in material protection. Preferably excluded therefrom are methods for the surgical or therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body. In the context of the present application, the term "pesticide" in each case also always comprises the term "plant protection agent". All plants and plant parts can be treated in accordance with the invention. Here, plants are to be understood to mean all plants and plant parts such as wanted and unwanted wild plants or crop plants (including naturally occurring crop plants), for example cereals (wheat, rice, triticale, barley, rye, oats), maize, soya bean, potato, sugar beet, sugar cane, tomatoes, pepper, cucumber, melon, carrot, watermelon, onion, lettuce, spinach, leek, beans, Brassica oleracea (e.g. cabbage) and other vegetable species, cotton, tobacco, oilseed rape, and also fruit plants (with the fruits apples, pears, citrus fruits and grapevines). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or cannot be protected by varietal property rights. Plants should be understood to mean all developmental stages, such as seeds, seedlings, young (immature) plants up to mature plants. Plant parts should be understood to mean all parts and organs of the plants above and below ground, such as shoot, leaf, flower and root, examples given being leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds, and also tubers, roots and rhizomes. Parts of plants also include harvested plants or harvested plant parts and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds. Treatment according to the invention of the plants and plant parts with the formulation according to the invention is carried out directly or by allowing the compounds to act on the surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats. If necessary, the formulation according to the invention is diluted in water or any other agriculturally relevant carrier fluid before use. BCS233049 FC -30- As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms), and parts thereof are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above. The invention is used with particular preference to treat plants of the respective commercially customary cultivars or those that are in use. Plant cultivars are to be understood as meaning plants having new properties ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, varieties, bio- or genotypes. The transgenic plants or plant cultivars (those obtained by genetic engineering) which are to be treated with preference in accordance with the invention include all plants which, through the genetic form, received genetic material which imparts particular advantageous useful properties ("traits") to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to levels of water or soil salinity, enhanced flowering performance, easier harvesting, accelerated ripening, higher yields, higher quality and/or a higher nutritional value of the harvested products, better storage life and/or processability of the harvested products. Further and particularly emphasized examples of such properties are increased resistance of the plants against animal and microbial pests, such as against insects, arachnids, nematodes, mites, slugs and snails owing, for example, to toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and also combinations thereof), furthermore increased resistance of the plants against phytopathogenic fungi, bacteria and/or viruses owing, for example, to systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and also resistance genes and correspondingly expressed proteins and toxins, and also increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin (for example the "PAT" gene). The genes which impart the desired traits in question may also be present in combinations with one another in the transgenic plants. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice, triticale, barley, rye, oats), maize, soya beans, potatoes, sugar beet, sugar cane, tomatoes, peas and other types of vegetable, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), with particular emphasis being given to maize, soya beans, wheat, rice, potatoes, cotton, sugar cane, tobacco and oilseed rape. Traits which are particularly emphasized are the increased resistance of the plants to insects, arachnids, nematodes and slugs and snails. BCS233049 FC -31- Crop protection – types of treatment The treatment of the plants and plant parts with the liquid agrochemical formulation according to the invention is carried out directly or by action on their surroundings, habitat or storage space using customary treatment methods, for example by dipping, spraying, atomizing, irrigating, injecting, watering (drenching), drip irrigating and, in the case of propagation material, in particular in the case of seed, a solution for liquid seed treatment. It is furthermore possible to apply the formulation according to the invention by the ultra-low volume method or to inject the formulation according to the invention into the soil. A preferred direct treatment of the plants is foliar application, i.e. the liquid agrochemical formulation according to the invention is applied to the foliage, where treatment frequency and the application rate should be adjusted according to the level of infestation with the pest in question. Typically, the formulation according to the invention is diluted in water or any other agrochemically relevant carrier before use. For this dilution, the advantageous properties of the formulation according to the invention in terms of dilution spontaneity and dilution stability are of particular importance. The formulation according to the invention is typically diluted to a final concentration of flupyradifurone between 0.001%-20% by weight before use. Typically it is diluted with water, but the use of organic solvents is also possible. Another preferred direct treatment of the plants is soil application, i.e. the liquid agrochemical formulation according to the invention is applied to the ground/soil where the plant grows, where treatment frequency and the application rate should be adjusted according to the level of infestation with the pest in question. Typically, the formulation according to the invention is diluted in water or any other agrochemically relevant carrier before use. For this dilution, the advantageous properties of the formulation according to the invention in terms of dilution spontaneity and dilution stability are of particular importance. The formulation according to the invention is typically diluted to a final concentration of flupyradifurone between 0.001%-20% by weight before use. Typically it is diluted with water, but the use of organic solvents is also possible. Flupyradifurone is an insecticide with systemic properties, i.e. it can access the plants via the root system. The plants are then treated by the action of flupyradifurone on the habitat of the plant. This may be done, for example, by drenching, or by mixing into the soil or the nutrient solution, i.e. the locus of the plant (e.g. soil or hydroponic systems) is impregnated with the liquid agrochemical formulation according to the invention, or by soil application, i.e. the liquid agrochemical formulation according to the invention is introduced by drip application (often also referred to as "chemigation"), i.e. the liquid formulation according to the invention from surface or sub-surface driplines over a certain period of time together with varying amounts of water at defined locations in the vicinity of the plants. BCS233049 FC -32- Materials used in the examples Lactic acid ester Trade name CAS No. Manufacturer/ supplier Chemical name P_{urasolv BL} ^{138-22-7 Corbion} _{Butyl lactate} Alkyl polypropylene polyethylene glycol Trade name CAS No. Manufacturer/ supplier Chemical name Oxirane, methyl-, polymer with oxirane, monobutyl ether Antarox B848 9038-95-3 Solvay (also known as butanol EO/PO block copolymer, MW: 2600, 48% EO) Dialkyl sulfoxide Trade name CAS No. Manufacturer/ supplier Chemical name Penpet Petrochemical n/a 67-68-5 Dimethyl sulfoxide Trading GmbH Dialkyl carbonate Trade name CAS No. Manufacturer/ supplier Chemical name n/a 108-32-7 BASF Propylene carbonate BCS233049 FC -33- Antifoam Trade name Manufacturer/ supplier Chemical name Polydimethylsiloxane SAG 1572 Momentive emulsion Tests and Methods used in the examples Polymorph Measuring Methods All data which is part of the present application has been prepared according to the methods described below unless otherwise indicated. The samples used for measurement were directly used and did not undergo any further sample preparation. XRPD X-Ray diffraction patterns were recorded at room temperature using XRD –diffractometers X`Pert PRO (PANalytical) and STOE STADI-P (radiation Cu K alpha 1, wavelength 1.5406 Å). All X-Ray reflections are quoted as °2Ɵ (theta) values (peak maxima) with a resolution of ± 0.2°. Raman Raman spectra were recorded at room temperature using FT-Raman-spectrophotometers (model RFS 100 and MultiRam) from Bruker. Resolution was 2 cm^-1. Measurements were performed in glass vials or aluminium discs. IR IR-ATR-spectra were recorded at room temperature using a FT-IR-spectrophotometer Tensor 37 with universal diamond ATR device from Bruker. Resolution was 2 cm^-1. DSC/TGA 3 DSC thermograms were recorded using thermobalances (DSC/TGA 3) from Mettler. The measurements were performed with a heating rate of 10 Kmin^-1 using perforated platinum pans. Flow gas was nitrogen. Formulation Testing Methods Spontaneity/Solubilization Testing Spontaneity/Solubilization properties are measured in order to evaluate the suitability of a formulation to be registered or to be used in a relevant agronomic context. For a water-soluble agrochemical formulation BCS233049 FC -34- (e.g. SL formulation) good spontaneity and solubilization are necessary to avoid the deposition of the formulation at the bottom of the spray tank, and the potential formation of highly viscous and difficult to solve gel-like materials. Spontaneity/Solubilization are tested on the basis of the CIPAC MT 36.3 method for the determination of emulsion properties. The formulation to be tested is mixed with a standard water (water prepared according to Method CIPAC MT 18) to form a defined aqueous emulsion/solution. Spontaneity is evaluated based on the distribution of droplets of formulation in water. The necessary amount of CIPAC water in a graduated cylinder is equilibrated at a defined temperature. 2 - 3 drops of formulation are added from a pipette to the water, holding the end of the pipette only a few millimeters above the surface of the water. The spontaneity can be evaluated based on the spontaneous distribution of the formulation in water, by viewing against light. The spontaneity is given a score between 1 and 6, 1 meaning that the formulation emulsifies/dissolves immediately, spontaneously, and completely; 6 meaning that the formulation does not emulsify/dissolve and sinks to the bottom of the cylinder. Formulations with scores between 1-4 are considered to be acceptable. Directly after evaluating spontaneity, the solubilization behavior of the formulation is tested. The rest of the required amount of test substance is added to achieve the required test concentration of 1% volume/volume. Afterwards, the number of inversions needed for complete solubilization is recorded. Low Temperature Stability Testing Low temperature stability is not only a regulatory requirement, but also an essential property of a formulation which prevents it from undergoing possible phase separation processes (e.g. precipitation) during transport or storage. The testing is made on the basis of the CIPAC MT 39.3 method for the determination of the low temperature stability of liquid formulations.100 ml of sample positioned in a sealed container are cooled to the desired temperature and stored. Optionally, a crystal of the active ingredient is seeded after 24 hours. After a certain time period, it is determined if any separation or any visible changes have taken place. If no phase separation or no visible changes have taken place, the sample is scored as “stable”. If phase separation has taken place or visible changes have taken place, the sample is scored as “not stable”. Storage Stability Storage stability testing is performed for a given number of weeks (w) at different temperatures such as -10°C, -5°C, 0°C, 20°C, 30°C, 40°C, 54°C or thaw-freeze cycling (= TW; constant temperature change from -15°C to +30°C and back within one week). BCS233049 FC -35- Biological Testing Methods Aphis gossypii test Cotton plants (Gossypium herbaceum) which are heavily infested by the cotton aphid (Aphis gossypii) are treated by being sprayed with the desired concentration of each product. The formulation according to the invention is diluted in typically 300 L/ha of water before being sprayed. Myzus persicae test Pepper plants (Capsicum sativum) which are heavily infested by the green peach aphid (Myzus persicae) are treated by being sprayed with the desired concentration of each product. The formulation according to the invention is diluted in typically 300 L/ha of water before being sprayed. After the specified period of time, the mortality in % is determined.100 % means that all the aphids have been killed; 0 % means that none of the aphids have been killed. Examples Polymorphic form A of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one Example 1 430 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011/051151, are dissolved in 60 ml of toluene and the solution is filtered. One fourth of the solution is stored at room temperature and ambient humidity until the solvent is evaporated. The residue is tested by IR spectroscopy and corresponds to the title compound in the polymorphic form A. Example 2 404 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011/051151, are dissolved in 60 ml of methanol and the solution is filtered. One fourth of the solution is stored in a refrigerator until the solvent is evaporated. The residue is tested by thermal analysis and corresponds to the title compound in the polymorphic form A. Example 3 405 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011/051151, are dissolved in 20 ml of ethyl acetate and the solution is filtered. 5 ml of n-heptane are added to a quarter of the solution and this is stored at room temperature and ambient humidity until the solvent is evaporated. The residue is tested by X-ray diffraction and corresponds to the title compound in the polymorphic form A. BCS233049 FC -36- Example 4 413 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011/051151, are dissolved in 60 ml of isopropanol and the solution is filtered. One fourth of the solution is stored at room temperature and ambient humidity until the solvent is evaporated. The residue is viscous. It is scratched and left to stand at room temperature and ambient conditions until it has crystallized. The residue is tested by X-ray diffraction and corresponds to the title compound in the polymorphic form A. Example 5 106 mg of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B, prepared as described in WO-A-2011/051151 are suspended in 1 ml of water and shaken in an Eppendorf Thermomix at 25°C (1400 rpm, 30 min shaking/30 min stop). After one week the suspension is filtered and the residue is dried at room temperature and ambient humidity. The residue is tested by IR spectroscopy and corresponds to the title compound in the polymorphic form A. Polymorphic form B of 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one 4-[(6-chloro-3-pyridylmethyl)(2,2-difluoroethyl)amino]furan-2(5H)-one in the polymorphic form B has been produced as described in Preparation Example 3 of WO-A-2011/051151. Flupyradifurone Formulation Examples Preparation of high loaded formulations of agrochemical active ingredients The herein described formulations may be prepared by mixing all components and subsequently stirring at or above room temperature (e.g. 25-100°C) until a homogeneous liquid is obtained. The dialkyl carbonate (comparative examples 1-5) or dimethyl sulfoxide (comparative example 6 and inventive examples) is added as last component in such an amount that the total volume of the mixture is 1.0 L.

BCS233049 FC -37- Flupyradifurone SL Comparative Examples Table 7- Comparative Formulations according to WO2011029552 Flupyradifu Alkyl Compara rone polypropy Dialky tive Dialkyl % (Compositi g/ lene Antifo %w/ l Formulat Carbon %w/w w/ %w/w on L glycol am w Sulfox ion ate w Mod A : polyethyle ide Example Mod B) ne glycol Flupyradifu Propyl To rone 25 ene Antarox 40. CE 1 100%/1 - - - - (100% mod 0 Carbon ¹⁾ B/848 0 L A) ate Flupyradifu Propyl To r 30 ene Antarox 40. CE 2 one 100%/1 - - - - (100% mod 0 Carbon B/848 0 L¹⁾ A) ate Flupyradifu Propyl To r 35 ene Antarox 40. CE 3 one 100%/1 - - - - (100% mod 0 Carbon B/848 0 L¹⁾ A) ate Flupyradifu Propyl To ro 40 ene Antarox 40. CE 4 ne 100%/1 - - - - (100% mod 0 Carbon L¹⁾ B/848 0 A) ate Flupyradifu Propyl To rone 30 ene SAG CE 5 100%/1 - - 0,1 - - (100% mod 0 Carbon L¹⁾ 1572 A) ate Flupyradifu Dimet To 30 SAG hyl CE 6 rone - - - - 0.1 100%/1 (100% mod 0 1572 Sulfox L¹⁾ A) ide BCS233049 FC -38- ¹⁾: “To 100%/1L” means that the dimethyl sulfoxide is added to a mixture of the other components in such an amount that the total volume of the mixture is 1.0 L.

BCS233049 FC -39- Comments to Table 7 Comparative examples CE1 to CE6 were prepared as described above, using mod A of Flupyradifurone. Examples CE1 to CE5 are based on the teachings of WO2011029552, whereas CE6 serves as an example of using only a dialkyl sulfoxide without the necessary ingredients for a functioning formulation to support concentrations of Flupyradifurone > 225 g/L. Flupyradifurone Formulation Examples According to the Invention Table 8: Composition of Flupyradifurone SL Formulations with improved spontaneity and cold stability, according to the invention Formul ation Examp Flupyrad Alkyl Dia % ifurone lk % % Dialk le polypropyle lactic % Anti g/ yl w yl % i (Compo w/ accord s w ne glycol acid foa L Carb w/ / Sulfo w¹⁾ ng to ition / polyethylen w/w w ester m he Mod onate w xide t A : w e glycol inventi Mod B) on Flupyrad Prop Dime 3 To ifurone ylene 3. Antarox 29 Puraso SAG 0. thyl 7 0 13.0 100% (100% Carb 8 B/848 .0 lv BL 1572 1 Sulfo 0 /1L mod A) onate xide Flupyrad Prop Dime 3 To ifu ylene 3. Antarox 21 Puraso SAG 0. thyl 8 rone 0 21.0 100% (100% Carb 6 B/848 .0 lv BL 1572 1 Sulfo 0 /1L mod A) onate xide Flupyrad Dime 3 0. To if Antarox 29 Puraso SAG thyl 9 urone 0 - - 13.0 0 100% (100% B/848 .0 lv BL 1572 Sulfo 0 5 /1L mod A) xide BCS233049 FC -40- Formul ation Examp Flupyrad % Alkyl ifur Dialk % % Dialk le one polypropyle lactic % Anti ( g/ yl w yl %w/ accordi Compos w ne glycol acid foa L Car w/ ¹⁾ ition b / Sulfo w ng to / polyethylen ester w/w m onate w M w xide the od A : w e glycol inventi Mod B) on Flupyrad Dime 3 0. To ifurone Antarox 21 Puraso SAG thyl 10 0 - - 21.0 0 100% (100% B/848 .0 lv BL 1572 Sulfo 0 5 /1L mod A) xide Flupyrad ifurone Dime 3 To ( Antarox 29 Puraso SAG 0. thyl 11 90% 2 - - 13.0 100% mod B/848 .0 lv BL 1572 1 Sulfo 5 /1L A:10% xide mod B) Flupyrad Dime 3 To ifu Antarox 21 Puraso SAG 0. thyl 12 rone 2 - - 21.0 100% (100% B/848 .0 lv BL 1572 1 Sulfo 5 /1L mod A) xide Flupyrad Dime 3 To ifuro Antarox 21 Puraso SAG 0. thyl 13 ne 5 - - 21.0 100% (100% B/848 .0 lv BL 1572 1 Sulfo 0 /1L mod A) xide Flupyrad Dime 2 To ifurone Antarox 25 Puraso SAG 0. thyl 14 7 - - 13.0 100% (100% B/848 .0 lv BL 1572 1 Sulfo 5 /1L mod A) xide Flupyrad 2 To ifuro Antarox 25 Puraso SAG 0. 15 ne 5 - - 13.0 Dime 100% (90% B/848 .0 lv BL 1572 1 0 thyl /1L mod BCS233049 FC -41- Formul ation Examp Flupyrad % Alkyl if Dialk % % Dialk le urone polypropyle lactic % Anti (Compos g/ yl w w yl %w/ accordi ne glycol acid foa L Carb w/ / Sulf ¹⁾ g to itio o w n n / polyethylen w/w w ester m Mod A : onate w xide the w e glycol inventi Mod B) on A:10% Sulfo mod B) xide Flupyrad Dime 2 To Antarox 23 Puraso SAG 0. thyl 16 ifurone 5 - - 12.0 100% (100% B/848 .0 lv BL 1572 1 Sulfo 0 /1L mod A) xide Flupyrad Dime 2 To ifu Antarox 24 Puraso SAG 0. thyl 17 rone 2 - - 10.0 100% (100% B/848 .0 lv BL 1572 1 Sulfo 5 /1L mod A) xide Flupyrad ifurone Dime 2 To (90% Antarox 26 Puraso SAG 0. thyl 18 2 - - 10.0 100% mod B/848 .0 lv BL 1572 1 Sulfo 5 /1L A:10% xide mod B) Flupyrad Dime 2 To ifurone Antarox 21 Puraso SAG 0. thyl 19 2 - - 15.0 100% (100% B/848 .0 lv BL 1572 1 Sulfo 5 /1L mod A) xide “To 100%/1L” means that the dimethyl sulfoxide is added to a mixture of the other components in such an amount that the total volume of the mixture is 1.0 L. BCS233049 FC -42- Comments to Table 8 Examples according to the invention 7 to 19 were prepared as described above, using mod A of Flupyradifurone, or mixtures of mod A and mod B. All examples contain the necessary components to support the formulation of concentrations of Flupyradifurone > 225 g/L, so that the resulting formulations meet the necessary requirements of cold stability and dilution spontaneity.

BCS233049 FC -43- Technical properties of comparative Flupyradifurone SL formulations The cold stability and emulsion/dilution stability of the comparative formulations were tested as described in the methods section. Table 9: Technical properties of flupyradifurone comparative formulations Cold Formulation Dilution Spontaneity Stability Example (7d, 0°C) (evaluation after dilution in water 10°C/20°C/30°) CE 1 Not stable - CE 2 Flupyradifurone does not dissolve in the formulation CE 3 Flupyradifurone does not dissolve in the formulation CE 4 Flupyradifurone does not dissolve in the formulation CE 5 Stable 5/5/5 Not stable CE 6 - @ -10°C Comments to Table 9 The comparative formulations with loadings above 225 g/L are characterized by not being cold stable (examples 1 and 6), or not dissolving flupyradifurone (examples 2 to 4), or not showing sufficient dilution spontaneity (example 5) Technical properties of Flupyradifurone SL formulations according to the invention The cold stability and emulsion/dilution stability of the formulations according to the invention were tested as described in the methods section BCS233049 FC -44- Table 10: Technical properties of flupyradifurone formulations according to the invention Formulation Cold Stability Dilution Spontaneity Dilution Stability Dilution Stability Example (7d, 0°C) (evaluation after (mL separated @ (mL separated @ dilution in water 10°C/20°C/30° 10°C/20°C/30° 10°C/20°C/30°) after 1h) after 24 h) 7 Trace sediment 4/4/4 0/0/0 0/0/0 8 Stable 4/4/4 0/<0.1/<0.1 0/0/0 9 Stable @-10°C 4/4/4 0/0/<0.05 0/0/0 10 Stable @-10°C 4/4/4 0/0/0 0/0/0 11 Stable 4/4/4 <0.1/<0.1/<0.1 0/0/0 12 Trace sediment 4/4/4 <0.1/<0.1/<0.1 0/0/0 13 Stable 4/4/4 <0.1/<0.1/<0.1 <0.1/<0.1/<0.1 14 Stable 4/4/4 0/<0.1/<0.1 0/0/0 15 Stable 4/4/4 0/0/0 0/0/0 16 Stable 4/4/4 0/0/0 0/0/0 17 Stable 4/4/4 0/0/0 0/0/0 18 Stable 4/4/4 0/0/0 0/0/0 19 Stable 4/4/4 0/0/0 0/0/0 Comments to Table 10 As shown in Table 10, the formulations according to the invention meet the requirements of having sufficient cold stability and sufficient dilution spontaneity. The improvement of technical properties is due to the introduction of a dialkyl sulfoxide and a lactic acid ester. This can be seen when comparing comparative examples 1 to 4 with formulations according to the invention 9 to 19: in these cases, the dialkyl carbonate has been completely replaced by a mixture of a dialkyl sulfoxide and a lactic acid ester, while maintain the use of an alkyl polypropylene polyethylene glycol. This ensures that the formulations are cold stable between 0°C and -10°C, and that the formulations can be properly dispersed in water (spontaneity of the dispersion process between 1 and 4). Alternatively, the dialkyl carbonate can be partially replaced by a mixture of dialkyl sulfoxide and lactic acid ester (examples 7 to 8): the technical properties of these formulations are also improved with respect to those of the comparative formulations 1 to 6.

Claims

BCS233049 FC -45- Flupyradifurone Biological Testing The formulations according to the invention were tested as described in the methods section. The formulations tested biologically are presented in Table 11. Table 11: Formulations according to the invention tested biologically Formul ation Alkyl Flupyradi Examp polypro furone Dialk % lacti % Dialk le pylene (Composi g/ yl % c % Antif w yl % accordi w glycol tion Mod L Carb / olyeth w/w acid oam / Sulfo ng to p w/w w/w A : Mod onate ester w xide the w ylene B) inventi glycol on Flupyradi furone Prop Dime 3 1 Pura To (68 ylene Antarox SAG 0. thyl 20 % 0 3. 27.0 solv 17.0 100 mod A: Carb B/848 1572 1 Sulfo 0 4 BL %/1L 32% mod onate xide B) Flupyradi furone Prop Dime 3 1 Pura To ( ylene Antarox SAG 0. thyl 21 68% 0 1. 27.0 solv 17.0 100 mod A: Carb B/848 1572 1 Sulfo 0 9 BL %/1L 32% mod onate xide B) BCS233049 FC -46- The results of the biological testing of the formulations according to the invention in Table 11 is presented in Table 12. Table 12: Biological Efficacy of formulations according to the invention Formulation FPF Rate % Control % Control % Control % Control Example (g/ha) Systemic contact Systemic contact MYZUPE MYZUPE APHIGO APHIGO after 7 days after 7 days after 7 days after 7 days FPF SL 200¹⁾ 204 100 100 100 100 (state of the art) 20 204 98 100 100 100 (according to the invention) 21 100

(according to the invention) ¹⁾: commercially available SL formulation containing 200 g/l flupyradifurone (17.1% by weight), > 10% by weight propylene carbonate and > 25% by weight butanol EO/PO block copolymer) FPF: Flupyradifurone MYZUPE: Myzus persicae APHIGO: Aphis gossypii Comments to Table 12 The biological efficacy of the formulations according to the invention is comparable to that of the state of the art formulation. BCS233049 FC -47- Claims: 1. A water-soluble liquid concentrate formulation comprising a) flupyradifurone, b) an alkyl polypropylene glycol polyethylene glycol, c) a lactic acid ester and d) a dialkyl sulfoxide. 2. A water-soluble liquid concentrate formulation according to claim 1, wherein the concentration of flupyradifurone is within the range of from 225 g/l to 350 g/l. 3. A water-soluble liquid concentrate formulation according to claim 1 comprising a) 225-350 g/l flupyradifurone, b) 15-35% by weight alkyl polypropylene glycol polyethylene glycol, c) 10-25% by weight lactic acid ester, d) at least 9% by weight dialkyl sulfoxide. 4. A water-soluble liquid concentrate formulation according to claim 3, comprising components a) to d) in the following concentrations: a) 275-325 g/l b) 21-29% by weight c) 13-21% by weight d) at least 21% by weight. 5. A water-soluble liquid concentrate formulation according to any of the preceding claims, further comprising e) an antifoam. 6. A water-soluble liquid concentrate formulation according to claim 5, wherein component e) is present in a concentration range of 0.01-0.5% by weight, preferably 0.02-0.25% by weight, more preferably in the range 0.03-0.1% by weight, most preferably in the range 0.04-0.06% by weight. BCS233049 FC -48- 7. A water-soluble liquid concentrate formulation according to any of the preceding claims, characterized in that (b) is selected from the group “alkyl polypropylene glycol polyethylene glycol” exemplified by the structure in Formula 3: Formula 3 where R is a linear or branched C1-C4 alkyl fragment, A is a polypropylene glycol fragment containing between 10-40 propylene oxide (PO) units (Formula 4), and B is a polyalkylene glycol fragment containing between 10-50 ethylene oxide (EO) units (Formula 5) together with 0-10 propylene glycol (PO) units, wherein when both PO unit and EO units are present, said PO and EO units are present in randomly copolymerized form, Formula 4 Formula 5 8. A water-soluble liquid concentrate formulation according to claim 7, wherein R, A and B in formula 3 are defined as follows: R is a linear or branched C3-C4 alkyl fragment, A is a polypropylene glycol fragment containing between 15-35 propylene oxide (PO) units, and B is a fragment containing between 20-40 ethylene oxide (EO) units together with 0-8 propylene glycol (PO) units. 9. A water-soluble liquid concentrate formulation according to claim 7, wherein R, A and B in formula 3 are defined as follows: R is a linear C4 alkyl fragment, A is a polypropylene glycol fragment containing between 20-30 propylene oxide (PO) units, and B is a fragment containing between 30-40 ethylene oxide (EO) units together with 0-5 propylene glycol (PO) units.