Patent Application
20240023555
The present invention relates to a composition comprising a combination of insecticidal active ingredients, to the preparation of such compositions, and to a method of using such a composition to control pests in crops of useful plants.
Insecticidal compositions containing combinations of the insecticidal active ingredient spiropidion with another active ingredient are known, eg, from WO 2013/107793. However, in certain compositions for use in insect control on crop plants, the chemical instability of the active ingredient (eg, spiropidion) may be an issue which results in a loss of insecticidal performance. Accordingly, there remains a strong motivation to develop insecticidal compositions where for practical purposes the active ingredient component retains long-term chemical stability.
According to the present invention, there is provided a pesticidal composition comprising:
(a) 2 to 7% by weight of an alkali metal sulfate and/or an alkaline earth metal sulfate, and
The pesticidal compositions of the invention have, for practical purposes, a very advantageous level of activity in controlling insect pests in crops of useful plants after foliar or soil application, whilst also maintaining acceptable crop safety (phytotoxicity) outcomes. By activity, it is meant that the compositions of the invention are capable of killing or controlling insects, retarding the growth or reproduction of insects, reducing an insect population, and/or reducing damage to plants caused by insects.
Furthermore, surprisingly it has been found for the present invention that the addition of an organic acid (eg, citric acid) to certain compositions comprising spiropidion and acetamiprid, significantly improves the chemical stability of the spiropidion active ingredient component and thus the useful storage life of compositions containing these two active ingredients.
Further according to the invention, there is provided an aqueous composition comprising the pesticidal composition according the invention, optionally further comprising one or more adjuvants or carriers.
Still further according to the invention, there is provided a (non-therapeutic) method of combating and controlling pests which comprises applying to a pest, to a locus of a pest, or to a crop of a useful plant susceptible to attack by a pest a composition according to the invention.
Spiropidion ([3-(4-chloro-2,6-dimethyl-phenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl]ethyl carbonate. CAS no.: 1229023-00-0) is known inter alia from WO 2010/066780, WO 2018/114648 and WO 2018/114649. Acetamiprid ((1E)-N-[(6-chloro-3-pyridyl)methyl]-1V-cyano-N-methyl-acetamidine. CAS no.: 135410-20-7) is known inter alia from EP 0 456 826. Certain pesticidal mixtures comprising spiropidion and acetamiprid as active ingredients are known from WO 2013/107793.
Preferably, the compositions according to the invention comprise as the pesticidal active ingredient component (i) 28 to 32% by weight of spiropidion and (ii) 22 to 26% by weight of acetamiprid, and more preferably (i) 29 to 31% by weight of spiropidion and (ii) 23 to 25% by weight of acetamiprid.
The compositions according to the invention comprise as the pesticidal active ingredient component spiropidion and acetamiprid, respectively, in a weight ratio of 5:6 to 7:4, and preferably a weight ratio of 1:1 to 3:2.
Preferably, the compositions according to the invention comprise 4.5 to 8% by weight of a buffering agent, of which based on the total composition comprises 4 to 6% by weight of an alkali metal sulfate, and 0.5 to 2.5% by weight of an organic acid. Most preferably, the compositions according to the invention comprise 4.5 to 6.5% by weight of a buffering agent, of which based on the total composition comprises 4 to 6% by weight of an alkali metal sulfate, and 0.5 to 1.5% by weight of an organic acid.
More preferably, the compositions according to the invention comprise 4.5 to 8% by weight of a buffering agent, of which based on the total composition comprises 4 to 6% by weight of an alkali metal sulfate, and 0.5 to 2.5% by weight of citric acid. Most preferably, the compositions according to the invention comprise 4.5 to 6.5% by weight of a buffering agent, of which based on the total composition comprises 4 to 6% by weight of an alkali metal sulfate, and 0.5 to 1.5% by weight of citric acid.
In the buffering agent component of the compositions of the invention, there may be included an alkali metal sulfate or an alkaline earth metal sulfate, or else a combination of an alkali metal sulfate and an alkaline earth metal sulfate. Preferably, the alkali metal sulfate used in the compositions of the invention is potassium sulfate or sodium sulfate, and most preferably sodium sulfate.
Preferably, the organic acid used in accordance with the present invention is an organic acid that contains 1, 2 or 3 carboxylic acid groups. More preferably, the organic acid is a tricarboxylic acid (ie, contains three carboxylic acid groups). Even more preferably, the organic acid is citric acid, or a salt thereof, such as the sodium or potassium salt of citric acid (sodium citrate or potassium citrate). Most preferably, the organic acid is citric acid.
In preferred embodiments, the compositions of the invention further comprise based on the total weight of the composition (ie, up to 100% by weight):
In other preferred embodiments, the compositions of the invention may comprise 1 to 3% by weight of an anti-foaming agent, and preferably 1.5 to 2.5% by weight of an anti-foaming agent.
In other preferred embodiments, the compositions of the invention may comprise 15 to 25% by weight of a filler, and preferably 18 to 22% by weight of a filler.
Preferably, the composition of the invention is a water-dispersible granule (WG), which may be defined as a solid, granular formulation which can disperse or dissolve quickly when added to water in a spray tank, thus providing a fine particle suspension comprising a pesticidal active ingredient or ingredients. A water-dispersible granule comprising the composition according to the present invention may be prepared according to standard methods. The water-dispersible granule may take the form of an extruded granule or a spray-agglomerated granule.
Preferably, in an aqueous composition according to the invention (eg, a tank mix preparation for applying to a crop), the adjuvant is selected from a mineral oil, a vegetable oil, an esterified vegetable oil, a methylated vegetable oil or an alkyl ester phosphate-based adjuvant. A pesticide adjuvant may be defined as a substance present in a pesticidal composition (eg, a concentrated active ingredient formulation diluted in water in a tank for a foliar spray application on a crop), which improves pesticidal active ingredient performance, for example by facilitating the spreading of the active ingredient on a leaf surface or penetration into the leaf of the crop plant.
Examples of adjuvant classes, which may be used in accordance with the present invention include a mineral oil, a vegetable oil, an esterified vegetable oil, a methylated vegetable oil or an alkyl ester phosphate-based adjuvant. Commercially-available adjuvant products which may be tank-mixed to yield a spray formulation with the composition of the present invention include HASTEN™ (Victorian Chemical Co. Pty. Ltd.-blend of an esterified vegetable oil and non-ionic surfactants), OCHIMA® (Syngenta—alkyl ester of phosphoric acid (EC formulation)), LEDNA™ (Polaquimia—EC formulation comprising a methyl ester of soybean oil), Atplus® 463 (CRODA Europe Limited—60% parafin oil with surfactant blend), Actirob® B (Bayer AG—rapeseed oil methyl ester (esterified vegetable oil)), Destiny® HC (Winfield Solutions LLC—methylated soybean oil), DYNE-AMIC® (HELENA—blend of (methylated) vegetable oil and organosilicone-based nonionic surfactants), and FS Optique™ (GROVVMARK, Inc—methyl ester of canola oil).
If an alkyl ester phosphate-based adjuvant is used in conjunction with the pesticidal composition according to the invention (ie, in a tank mix), the alkyl ester phosphate of the adjuvant is preferably tris-(2-ethylhexyl) phosphate, preferably in combination with ethoxylated sorbitol, hexaoleate, eg, OCHIMA®—EC, Syngenta.
A dispersant or a dispersing agent is typically a surfactant substance, which when added to a suspension of solid particles in a liquid better enables the separation of the particles to avoid their settling or clumping together. Dispersants which may be used in accordance with the present invention include, but are not limited to, lignosulphonate salts (eg, Ufoxane 3A, Borregard AS; Borresperse NA, Borregard AS; Polyfon™ H, Ingevity; Marasperse CBOS-4 powder, LignoTech), naphthalene sulfonic acid salts (eg, Dispergator B Gran, TFL Ledertechnik GmbH), a co-polymer of 2,5-furandione and 2,4,4-trimethylpentene (eg, Geropon® Ta/72, Solvay).
An anti-foaming agent is a chemical additive that reduces and hinders the formation of foam in a composition, such as a pesticidal formulation. Anti-foaming agents which may be used in accordance with the present invention include, but are not limited to, polydimethylsiloxanes (eg, XIAMETER™ ACP-1500, Dow, Inc; Antifoam MSA, Univar; Xiameter ACP-0001, Dow Brasil; Xiameter ACP-0100, Dow Chemical).
Fillers which may be used in accordance with the present invention include, but are not limited to, a polymethyl urea resin (Pergopak® M, Huber Engineered Materials; Cropal UF100H, Yoo Sung Chem R&T Co. Ltd), lactose monohydrate (Pharmatose® 200M, DFE Pharma; lactose monohydrate, Foremost Farms USA; Excipress™, Armor Pharma; Excipure™, Armor Pharma; lactose anhydrous, Kerry Inc).
Examples of pests which may be controlled in accordance with the compositions of the present invention include those:
Examples of soil-inhabiting pests, which can damage a crop in the early stages of plant development, are:
In particular, the compositions of the invention may be applied against insects from the order Homoptera (in particular, white flies, aphids, psyllids and armoured and soft scales), Thysanoptera (thrips), Acarina (mites) and Lepidoptera (butterflies and moths, and larva thereof). Preferably, the compositions of the invention may be applied against white flies, aphids, thrips.
Crops of useful plants in which the compositions according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, watermelon, okra, onion, leek, pepper, potato, pumpkin, squash, rhubarb, spinach and tomato; and vines for example grapes. The compositions of the invention can also be applied on turf, lawn and pastures.
Preferably, the compositions of the invention may be applied to a crop of a useful plant selected from:
Preferably, the composition of the invention may be applied to a crop of a useful plant selected from cucumber, squash, pepper, melon, watermelon, tomato, aubergine, courgette or gourd.
The rate at which the agrochemical compositions of the invention are applied will depend upon the particular type of insect, etc, to be controlled, the degree of control required and the timing and method of application and can be readily determined by the person skilled in the art. In general, the compositions of the invention can be applied at an application rate of between 0.005 kilograms/hectare (kg/ha) and about 5.0 kg/ha, based on the total amount of active ingredient in the composition. An application rate of between about 0.1 kg/ha and about 1.5 kg/ha is preferred, with an application rate of between about 0.3 g/ha and 0.8 kg/ha being especially preferred.
The pesticidal compositions of the present invention may be used as an insecticide to control pests on cotton plants or soybean plants, in particular for the control of insects from the order Homoptera (in particular, white flies, aphids, psyllids and armoured and soft scales), Thysanoptera (thrips) and Acarina (mites).
In particular, transgenic cotton events expressing useful traits which may be used in combination with the compositions of the invention, include BXN10211, BXN10215, BXN10222, BXN10224, COT102, COT67B, GHB614, GHB119, LLCotton25, MON531, MON757, MON15985, MON1445, MON88913, MON1076, MON1698, MON88701, T304-40, 281-24-236, 3006-210-23, 31707, 31803, 31808, 42317, and the like. Such combinations of the compositions of the invention with cotton events expressing one or more useful traits may provide more durable yield protection, provide a resistance management strategy for target pest control, and reduce farmer inputs, saving considerable expense in time and monetary value.
Furthermore, transgenic soybean plants expressing toxins, for example insecticidal proteins such as delta-endotoxins, e.g. Cry1Ac (Cry1Ac Bt protein) may be used in combination with the compositions of the invention. Accordingly, this may include transgenic soybean plants comprising event MON87701 (see U.S. Pat. No. 8,049,071 and related applications and patents, as well as WO 2014/170327 A1 (eg, see paragraph reference to Intacta RR2 PRO™ soybean)), event MON87751 (US. Patent Application Publication No. 2014/0373191) or event DAS-81419 (U.S. Pat. No. 8,632,978 and related applications and patents).
Other transgenic soybean plants may comprise event SYHT0H2—HPPD tolerance (U.S. Patent Application Publication No. 2014/0201860 and related applications and patents), event MON89788-glyphosate tolerance (U.S. Pat. No. 7,632,985 and related applications and patents), event MON87708 dicamba tolerance (U.S. Patent Application Publication No. US 2011/0067134 and related applications and patents), event DP-356043-5-glyphosate and ALS tolerance (U.S. Patent Application Publication No. US 2010/0184079 and related applications and patents), event A2704-12-glufosinate tolerance (U.S. Patent Application Publication No. US 2008/0320616 and related applications and patents), event DP-305423-1-ALS tolerance (U.S. Patent Application Publication No. US 2008/0312082 and related applications and patents), event A5547-127-glufosinate tolerance (U.S. Patent Application Publication No. US 2008/0196127 and related applications and patents), event DAS-40278-9-tolerance to 2,4-dichlorophenoxyacetic acid and aryloxyphenoxypropionate (see WO 2011/022469, WO 2011/022470, WO 2011/022471, and related applications and patents), event 127-ALS tolerance (WO 2010/080829 and related applications and patents), event GTS 40-3-2-glyphosate tolerance, event DAS-68416-4-2,4-dichlorophenoxyacetic acid and glufosinate tolerance, event FG72-glyphosate and isoxaflutole tolerance, event BPS-CV127-9-ALS tolerance and GU262-glufosinate tolerance or event SYHTO4R-HPPD tolerance.
In an aqueous composition comprising the pesticidal composition according to the invention (eg, a tank-mix composition) there may be added a further component comprising a pesticidal active ingredient selected from one or more of:
Abamectin, Acequinocyl, Acetoprole, Acrinathrin, Acynonapyr, Afidopyropen, Afoxalaner, Alanycarb, Allethrin, Alpha-Cypermethrin, Alphamethrin, Amidoflumet, Aminocarb, Azocyclotin, Bensultap, Benzoximate, Benzpyrimoxan, Betacyfluthrin, Beta-cypermethrin, Bifenazate, Bifenthrin, Binapacryl, Bioallethrin, Bioallethrin S)-cyclopentylisomer, Bioresmethrin, Bistrifluron, Broflanilide, Brofluthrinate, Bromophos-ethyl, Buprofezine, Butocarboxim, Cadusafos, Carbaryl, Carbosulfan, Cartap, CAS number: 1472050-04-6, CAS number: 1632218-00-8, CAS number: 1808115-49-2, CAS number: 2032403-97-5, CAS number: 2044701-44-0, CAS number: 2128706-05-6, CAS number: 2249718-27-0, Chlorantraniliprole, Chlordane, Chlorfenapyr, Chloroprallethrin, Chromafenozide, Clenpirin, Cloethocarb, Clothianidin, 2-chlorophenyl N-methylcarbamate (CPMC), Cyanofenphos, Cyantraniliprole, Cyclaniliprole, Cyclobutrifluram, Cycloprothrin, Cycloxaprid, Cycloxaprid, Cyenopyrafen, Cyetpyrafen (or Etpyrafen), Cyflumetofen, Cyfluthrin, Cyhalodiamide, Cyhalothrin, Cypermethrin, Cyphenothrin, Cyproflanilide, Cyromazine, Deltamethrin, Diafenthiuron, Dialifos, Dibrom, Dicloromezotiaz, Diflovidazine, Diflubenzuron, dimpropyridaz, Dinactin, Dinocap, Dinotefuran, Dioxabenzofos, Emamectin, Empenthrin, Epsilon-momfluorothrin, Epsilon-metofluthrin, Esfenvalerate, Ethion, Ethiprole, Etofenprox, Etoxazole, Famphur, Fenazaquin, Fenfluthrin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyroxymate, Fensulfothion, Fenthion, Fentinacetate, Fenvalerate, Fipronil, Flometoquin, Flonicamid, Fluacrypyrim, Fluazaindolizine, Fluazuron, Flubendiamide, Flubenzimine, Flucitrinate, Flucycloxuron, Flucythrinate, Fluensulfone, Flufenerim, Flufenprox, Flufiprole, Fluhexafon, Flumethrin, Fluopyram, Flupyradifurone, Flupyrimin, Fluralaner, Flupentiofenox, Fluvalinate, Fluxametamide, Fosthiazate, Gamma-Cyhalothrin, Gossyplure™, Guadipyr, Halofenozide, Halofenozide, Halofenprox, Heptafluthrin, Hexythiazox, Hydramethylnon, Imicyafos, Imidacloprid, Imiprothrin, Indoxacarb, Iodomethane, Iprodione, Isocycloseram, Isothioate, Ivermectin, Kappa-bifenthrin, Kappa-tefluthrin, Lambda-Cyhalothrin, Lepimectin, Lufenuron, Metaflumizone, Metaldehyde, Metam, Methomyl, Methoxyfenozide, Metofluthrin, Metolcarb, Mexacarbate, Milbemectin, Momfluorothrin, nicofluprole Niclosamide, Nitenpyram, Nithiazine, Omethoate, Oxamyl, Oxazosulfyl, Parathion-ethyl, Permethrin, Phenothrin, Phosphocarb, Piperonylbutoxide, Pirimicarb, Pirimiphos-ethyl, Polyhedrosis virus, Prallethrin, Profenofos, Profenofos, Profluthrin, Propargite, Propetamphos, Propoxur, Prothiophos, Protrifenbute, Pyflubumide, Pymetrozine, Pyraclofos, Pyrafluprole, Pyridaben, Pyridalyl, Pyrifluquinazon, Pyrimidifen, Pyrimostrobin, Pyriprole, Pyriproxyfen, Resmethrin, Sarolaner, Selamectin, Silafluofen, Spinetoram, Spinosad, Spirodiclofen, Spiromesifen, Spirotetramat, Sulfoxaflor, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Tefluthrin, Temephos, Tetrachloraniliprole, Tetradiphon, Tetramethrin, Tetramethylfluthrin, Tetranactin, Tetraniliprole, Theta-cypermethrin, Thiacloprid, Thiamethoxam, Thiocyclam, Thiodicarb, Thiofanox, Thiometon, Thiosultap, Tioxazafen, Tolfenpyrad, Toxaphene, Tralomethrin, Transfluthrin, Triazamate, Triazophos, Trichlorfon, Trichloronate, Trichlorphon, Triflumezopyrim, Tyclopyrazoflor, Zeta-Cypermethrin.
The Examples which follow serves to illustrate the invention and in particular demonstrate the surprising effect of the use of specific amounts of the organic acid citric acid as a buffering component on spiropidion stability in a heat storage test and thus demonstrate a viable composition for commercial pest control uses. Compositions according to the present invention are prepared according to known formulation methods, eg, for a water-dispersible (wettable) granule.
Referring to Table 1 below, Composition A is a composition as a water-dispersible granule not according to the invention (without citric acid present) and Composition B is a composition as a water-dispersible granule according to the invention (with citric acid present). Composition A and Composition B are identical with the exception of the inclusion of citric acid and a slightly lower filler amount present for Composition B to compensate for the inclusion of the citric acid component.
To test the robustness of chemical stability of the active ingredients (spiropidion and acetamiprid), samples of Composition A and Composition B were slurried in 50% by weight of water and stored at 54° C. for 2 weeks.
As can be seen at Table 2 below, after slurrying, Composition B according to the invention remains within a 5% degradation limit for spiropidion which is considered acceptable, whereas Composition A not according to the invention relates to an unacceptable degradation of spiropidion (greater than 20% loss).
| Number | Date | Country | Kind |
|---|---|---|---|
| 20210432.9 | Nov 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/083127 | 11/26/2021 | WO |
