EP2001291A1

EP2001291A1 - Penetration enhancers for insecticidal agents

Info

Publication number: EP2001291A1
Application number: EP07723689A
Authority: EP
Inventors: Hans-Peter Krause; Gerhard Schnabel; Rainer Süssmann; Peter Baur; Udo Bickers; Kerstin Hesse
Original assignee: Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 2006-03-29
Filing date: 2007-03-28
Publication date: 2008-12-17
Also published as: US20110021575A1; WO2007112905A1; BRPI0709632A2; JP2009531362A

Abstract

The invention relates to the polyalkylene oxide derivatives of formula (I), wherein the symbols and indices are defined as follows: Ra is a C8-C30 hydrocarbon group; Rb is a C8-C30 hydrocarbon group such as C8-C30 alkyl, C8-C30 alkenyl, C8-C30 alkinyl; a is 0 or 1; b is 0 or 1; c is 0 or 1 and A represents one or more alkylene oxide entities. The derivatives according to the invention are suitable for enhancing penetration of insecticidal agents into plants.

Description

description

Penetration promoter for insecticidal active ingredients

The invention relates to the field of chemical crop protection, in particular the use of special surfactants as penetration promoters for insecticidal active ingredients and insecticidal agents containing these surfactants.

Substances which increase the penetration of agrochemical active substances through the cuticle of the plant, so-called penetration promoters, are valuable auxiliaries in chemical crop protection. Although various classes of substances are already known as penetration enhancers (see, for example, WO 2005/104844), there is a further need for compounds having such properties from a variety of viewpoints.

The object of the invention is therefore to provide further substances with penetration-promoting properties for insecticidal active ingredients.

Surfactants from the group of polyalkylene oxide dialkanoates and their use in crop protection are known: in the field of herbicides, for example from WO 01/97614 A, WO 01/97615 A2 and WO 02/49432 A1, the latter two documents surfactants with at least 10 or Use 12 alkylene oxide units; in the field of fungicides from WO 98/48628 A1 as wetting agent; in the field of insecticides from JP 3272105 B2 as wetting agent in an aerosol application.

In addition, the use of surfactants from the group of polyalkylene oxide dialkanoates is hitherto known only for the physical stabilization of

Microemulsion concentrates (WO 02/45507 A2), for the preparation of storage-stable solid formulations (JP 11100301 A) ₁ for the emulsification of externally applied adjuvants based on oil (WO 94/24858 A1, WO 03/094613 A1). It has now been found that special surfactants from this group are suitable as penetration promoters for insecticidal active ingredients.

The invention therefore provides the use of polyalkylene oxide derivatives of the formula (I)

R * - (CO). [O] _c - A (CO) - ^Rb (I)

to promote the penetration of insecticidal active substances into plants, the

Symbols and indices in the following formula (I) have: R ^a is a Cs-Cao-hydrocarbon radical, preferably C ₈ -C ₃ -alkyl, C ₈ -C ₃ O- alkenyl or C ₈ -C ₃ o alkynyl;

R ^b is a Cs-Cso-hydrocarbon radical, such as C ₈ -C ₃ -alkyl, C ₈ -C ₃ -alkenyl, C ₈ - C ₃₀ alkynyl; a is 0 or 1; b is 0 or 1; c is 0 or 1 and

A is one or more alkylene oxide units.

Hydrocarbon radical preferably denotes an aliphatic, saturated or presaturated hydrocarbon radical, more preferably alkyl, alkenyl and

Alkynyl, in particular alkyl, having preferably 4 to 24, particularly preferably 8 to 18 C-atoms, which is optionally substituted by halogen, preferably F and Cl, or (CrC ₄ ) - alkoxy groups.

The term alkylene oxide units is preferably understood as meaning units of C ₂ -C ₁₀ -alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or hexylene oxide, it being possible for the units within the surfactant to be identical or different from one another. Particularly preferred are units of ethylene oxide and propylene oxide, most preferably ethylene oxide. If the surfactant (I) contains different alkylene oxide units, these may be arranged alternately, in blocks or randomly.

Preferably contain the compounds of the formula A _n alkylene oxide units, where n> 1 and <600, preferably> 3 and <400, more preferably> 5 and <100, most preferably> 5 and <80, is.

The surfactant of the formula (I) preferably contains alkylene oxide units A of the formula

(H).

- (EO) _x (RO) _y (EO) ₂ - (II)

wherein

EO is an ethylene oxide unit, RO is a unit - CHR ^x -CHR ^y -O -, where R ^x , R ^y independently of one another are H or (C 1 -C ₄ ) alkyl, preferably H, methyl, ethyl, in particular RO is a propylene oxide unit (PO) x is an integer from 0 to 600, preferably from 1 to 50, y is an integer from 0 to 600, z is an integer from 0 to 600, where the sum (x + y + z)> 2 and <600, preferably> 3 and <400, more preferably> 5 and <100.

The abbreviations EO and PO in formula (II) mean an ethylene oxide unit and a propylene oxide unit, respectively, also as far as they are used elsewhere in the description.

Preferably used surfactants (I) are surfactants of the following formulas 1-1) to

I-3), 1-1) R ^a -OAR ^b, wherein R ^a, A and R ^b are as defined in formula (I), preferably (C ₈ -C ₃ o) alkyl-O - [(EO) _x (PO) _y] - (C ₈ -C ₃ o) alkyl, 1-2) R ^a CO-OAR, ^b wherein R ^a, A and R ^b are as defined in formula (I), preferably (C ₈ -C ₃ o) alkyl-CO-0 - [(EO) χ ( PO) _x HC ₈ -C _{3 O} ) AIkVl,

1-3) R ^a -CO-OA-CO-R ^b, wherein R ^a, A and R ^b are as defined in formula (I), preferably (C ₈ -C ₃ o) alkyl-CO-O - [( EO) _x (PO) _y ! -CO- (C ₈ -C ₃₀ ) alkyl, where x is an integer from 0 to 600, y is an integer from 0 to 600, and x + y is an integer> 1 and < 600, preferably from 3 to 400, more preferably 5 to 100, most preferably from 5 to 80.

Particularly preferably used are surfactants

1-11) (C ₁₀ -C ₂₄ ) alkyl-O - [(EO) _x (PO) _y HCio-C ₂ 4) alkyl

I-22) (C ₉ -C ₂₃ ) alkyl-CO-O - [(EO) _x (PO) _y ] - (C ₁₀ -C ₂₄ ) alkyl

I-33) (C ₉ -C ₂₃ ) alkyl CO-O - [(EO) _x (PO) _y ] CO (C ₉ -C ₂₃ ) alkyl, wherein x is an integer from 0 to 600, y is a integer from 0 to 600, and x + y is an integer> 1 and <600, preferably from 3 to 400, more preferably from 5 to 100, most preferably from 5 to 80,

Surfactants of the formula (I) are known from the literature, for. From McCutcheon ^'s ,

Emulsifiers & Detergents 1994, Vol. 1: North American Edition and Vol. 2,

International Edition; McCutcheon Division, Glen Rock NJ. The herein mentioned

Surfactants are incorporated herein by reference. In addition, surfactants of formula (I) are also commercially available, for. B. under the brand names

Cithrol ^® by Croda or by known synthetic reactions to the

Professional easily accessible.

Particularly preferred polyalkylene oxide derivatives of the formula (I) are those of the formula (III). O

R - C 0 - (CH ₂ -CH ₂ -O) -X (III)

wherein the symbols and indices have the following meanings: R is an oleyl, stearyl or lauryl radical; n is a natural number from 2 to 20 and X is H or -C (O) R.

Such compounds are for example commercially available from the Cithrol ^® series from Croda.

Preferred compounds of the formula (III) are, for example:

Very particular preference is given to polyalkylene oxide derivatives of the formula I where the indices a and b are equal to one. The commercially available products are generally mixtures of compounds of the formula (I), in particular with different contents of alkylene oxide groups A, so that the value n usually represents an average value.

Examples of surfactants of the formula (I) are listed in Tables 1 to 3 below:

Table 1: Surfactants of the formula 1-1 R ^a -OAR ^b

Table 2: Surfactants of the formula I-2 R ^a -CO-OAR ^b

Table 3: Surfactants of the formula I-3 R ^a -CO-OA-CO-R ^b

The term penetration enhancer is understood to mean compounds which promote the uptake of insecticidal substances through the cuticle of a plant into the plant, i. Accelerate the rate of absorption and / or increase the amount of drug absorbed into the plant.

Since the mechanism of action of the surfactants (I) as a penetration promoter is basically independent of the type of agrochemical active used, all insecticides come into question whose biological effectiveness can be increased by increased penetration into a crop.

Preferably mentioned are insecticides, acaricides, nematicides, molluscicides, rodenticides and repellents, which have systemic properties, as well as combination partners in question contact agents. In the following, the term insecticides includes insecticides as well as acaricides, nematicides, molluscicides, rodenticides and repellents - unless the context otherwise indicates.

Further preferred are systemic active substances, ie those which are taken up by the plant through the leaves or via the roots and passed on in the juice stream, the transport system or plant. Particular preference is given to those active substances which have a log P value of ≦ 4 (determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC ₁ gradient method, acetonitrile / 0.1% aqueous phosphoric acid), in particular those with a Log P value of <4 and> 0.1.

Examples of individual insecticides are:

Acetylcholinesterase (AChE) inhibitors carbamates, for example alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, bendodi carb, benfuracarb, bufencarb, butacarb, butocarboxime, butoxycarboxime,

Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Dimetilane, Ethiofencarb, Fenobucarb, Fenothiocarb, Formetanate, Furathiocarb, Isoprocarb, Metam-sodium, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Thiodicarb, Thiofanox, Trimethacarb, XMC, Xylylcarb, Triazamate organophosphates, for example acephates, azamethiphos, azinphos (-methyl, -ethyl), bromo-phos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion, chloroethoxyfos, chlorfenvinphos, chloroformes, chlorpyrifos (-methyl) ethyl), coumaphos, cyanofenphos, cyanophos, chlorfenvinphos, demeton-S-methyl, demeton-S-methylsulphon, dialifos, diazinon, dichlorofluithine, dichlorvos / DDVP, dicrotophos, dimethoates, dimethylvinphos, dioxabenzofos, disulphoton, EPN, ethion , Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitrothion, Fensulfothion, Fenthion, Flupyrazofos, Fonofos, Formothion, Fosmethilan, Fosthiazate, Heptenophos, iodofenphos, Iprobenfos, Isazofos, Isofenphos, Isopropyl O-salicyla te, isoxathione, malathion, mecarbam, methacrifos, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion (-methyl / -ethyl), phenthoates, phorates, phosalones, phosmet, phosphamidone, phospho - Carb, Phoxim, Pirimiphos (-methyl / -ethyl), Profenofos, Propaphos, Propetamphos, Prothiofos, Prothoates, Pyraclofos, Pyridaphenthion, Pyridathion, Quinophos, Sebufos, Sulfotep, Sulprofos, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometone, triazophos, triclorfone, vamidothion Sodium-channel Modulators / Voltage-Dependent Sodium Channel Blockers Pyrethroids, for example, acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, biphenol, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioethanomethrin , Biopermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrine, cycloprothrin, cyfluthrin, cyhalothrin, cyperethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, Deltamethrin, pententhrin (1R isomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinates, flucythrinates, flufenprox, fluethrin, fluvalinate, fubfenprox, gamma-cyhalothrin, imiprothrin, kadethrin, lambda-cyhalothrin, Metofluthrin, permethrin (cis-, trans-), phenothhrin (1R-trans isomer), prallethrin, profuthrin, protrifenbutene, pyresmethrin, resmethrin, RU 15525, silafluofen, tau-fluvalinate, tefluthrin, terallethrin, tetramethrin (-1R isomer), tralomethrin, transfluthrin, ZXI 8901, pyrethrin

(pyrethrum) DDT

Oxadiazines, for example Indoxacarb Semicarbazone, for example Metaflumizone (BAS3201)

Acetylcholine receptor agonists / antagonists

Chloronicotinyls, for example acetamipride, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazines, thiacloprid, thiamethoxam nicotine, bensultap, cartap

Acetylcholine receptor modulators Spinosyne, for example spinosad GABA-Directed Chloride Channel Antagonists Organochlorines, for example, Camphechlor, Chlordane, Endosulfan, Gamma-HCH, HCH, Heptachlor, Lindane, Methoxychlor Fiprole, for example, Acetoprole, Ethiprole, Fipronil, Pyrafluprole, Pyriprole, Vaniliprole

Chloride channel activators Mectins, for example Abamectin, Emamectin, Emamectin benzoate, Ivermectin, Lepimectin, Milbemycin

Juvenile hormone mimetics, for example, diofenolan, epofenonans, fenoxycarb, hydroprene, kinoprene,

Methoprene, pyriproxifen, triprene

Ecdysone agonists / disruptors

Diacylhydrazines, for example chromafenozide, Halofenozide, Methoxyfenozide, Tebufenozide

Inhibitors of chitin biosynthesis Benzoylureas, for example bistrifluron, chlofluazuron, diflubenzuron, fluazuron, fiucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, triflumuron buprofezin cyromazine Inhibitors of oxidative phosphorylation, ATP disruptors

diafenthiuron

Organotin compounds, for example azocyclotin, cyhexatin, fenbutatin oxides

Decoupling of oxidative phosphorylation by interruption of the H proton gradient

Pyrroles, for example Chlorfenapyr dinitrophenols, for example binapacyrl, dinobutone, dinocap, DNOC

Site I electron transport inhibitors

METI ¹ S, for example fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad hydramethylnone dicofol

Site II electron transport inhibitors Rotenone

Site III electron transport inhibitors

Acequinocyl, Fluacrypyrim

Insect intestinal membrane microbial disruptors Bacillus thuringiensis strains

Inhibitors of fatty synthesis tetronic acids, for example spirodiclofen, spiromesifen Tetramic acids, for example spirotetramat

Carboxamides, for example flonicamide

Octopaminergic agonists, for example, amitraz

Inhibitors of magnesium-stimulated ATPase, propargite

Nereistoxin analogs, for example thiocyclam hydrogen oxalate, thiosultap-sodium

Agonists of the ryanodine receptor, benzoic acid dicarboxamides, for example flubendiamide

Anthranilamides, for example DPX E2Y45 (3-bromo-N- {4-chloro-2-methyl-6-)

[(methylamino) carbonyl] phenyl} -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide)

Biologics, hormones or pheromones

Azadirachtin, bacillus spec, beauveria spec, codlemone, metarrhicon spec, paecilomyces spec, thuringiensin, verticillium spec.

Active substances with unknown or nonspecific action mechanisms, feed inhibitors, for example cryolites, flonicamide, pymetrozine mite growth inhibitors, for example, clofentezine, etoxazole, hexythiazox

Amidoflumet, benclothiazole, benzoximate, bifenazate, bromopropylate, buprofezin, quinomethionate, chlordimeform, chlorobenzilate, chloropicrin, cinothiazoben, cycloprene, cyflumetofen, dicyclanil, fenoxacrim, fentrifanil, flumbenimine, flufenerim, flutenzin, gossyplaine, hydramethylnone, japonilurane,

Metoxadiazone, Petroleum, Piperonyl butoxide, Potassium oleate, Pyralidyl, Sulfluramid, Tetradifon, Tetrasul, Triarathene.Verbutin.

The invention further relates to insecticidal compositions containing at least one insecticidal active ingredient (A) and at least one surfactant (B) of the formula (I). The insecticidal compositions according to the invention exhibit an excellent action and in a preferred embodiment superadditive effects. Due to the improved control of the harmful organisms by the insecticidal compositions according to the invention, it is possible to reduce the application rate and / or to increase the safety margin. Both are economically as well as ecologically sensible. The choice of the amounts to be used by components (A) + B) and the ratio of components (A): (B) depend on a whole series of factors.

The formulation types in question include all formulations which are applied to plants or their propagation material. The processes used for their preparation are generally known to the person skilled in the art and are described, for example, in Winnacker-Kuchler, "Chemische Technologie" Volume 7, C. Hanser Verlag Munich, 4th ed., 1986, JW van Valkenburg, "Pesticide Formulations", Marcel Dekker NY, 1973, K. Martens, "Spray Drying Handbook", 3rd ed., 1979, G. Goodwin Ltd., London, or Mollet, Grubenmann, "Formulation Technology", Wiley-VCH-Verlag, Weinheim, 2000.

Examples of formulation types are those mentioned in the "Manual on development and use of FAO and WHO specifications for pesticides" (FAO and WHO, 2002, appendix E) (each using the GCPF formulation codes with English abbreviation and designation): AL Any other liquid; AP Any other Powder; CF Capsule Suspension for Seed Treatment; CG Encapsulated Granule; CL Contact liquid or gel; CP contact powder; CS capsule suspension; DC Dispersible concentrate; DP Dustable powder; DS Powder for dry seed treatment; EC Emulsifiable concentrate; ED Electrochargeable liquid; EC Emulsifiable Granules; EO emulsion, water in oil; EP emulsifiable powder; ES Emulsion for seed treatment; EW emulsion, oil in water; FG fine granule; FS Flowable concentrate for seed treatment; GF Gel for Seed Treatment; GG Macrogranule; GL emulsifiable gel; GP flo-dust; GR Granule; GS Grease; GW Water soluble gel; HN Hot fogging concentrate; KK Combi-pack solid / liquid; KL Combi-pack liquid / liquid; KN CoId fogging concentrate; KP Combi-pack solid / solid; LA Lacquer; LS Solution for seed treatment; OD oil dispersion; Oxygen miscible flowable concentrate / oil miscible suspension; OL OiI miscible liquid; OP OiI dispersible powder; PA paste; PC gel or paste concentrate; PO Pour-on; PR Plant rodlet; PT pellet; SA spot-on; SC suspension concentrate; SD suspension concentrate for direct application; SE suspo-emulsion; SG Water Soluble Granule; SL Soluble concentrate; SO Spreading oil; SP Water soluble powder; SS Water soluble powder for seed treatment; ST Water soluble tablet; SU ultra-low volume (ULV) suspension; TB tablet; TC Technical material; TK Technical concentrate; UL Ultra-low volume (ULV) liquid; WG Water dispersible granules; WP Wettable powder; WS Water dispersible powder for slurry seed treatment; WT Water dispersible tablet; XX Others.

Preference is given to liquid formulation types. These include the formulation types DC (GCPF Formulation Code for Dispersible Concentrate); EC (GCPF Formulation Code for Emulsion Concentrate); EW (GCPF formulation code for oil-in-water emulsion); ES (GCPF Formulation Code for Emulsion Stain); FS (GCPF Formulation Code for Multiphase Concentrate for Seed Treatment); EO (GCPF formulation code for water in oil emulsion); OD (GCPF formulation code for oil dispersions); SE (GCPF formulation code for suspoemulsion); SL (GCPF formulation code for water-soluble concentrate); CS (Capsule Suspension GCPF Formulation Code) and AL (GCPF Formulation Code for ready-to-use liquid formulation, other liquids for undiluted use). Particular preference is given to emulsion concentrates (formulation type EC) and oil dispersions (formulation type OD).

Suitable additives which may be present in the preferably liquid formulations according to the invention are all customary formulation auxiliaries, such as organic solvents, defoamers, emulsifiers, dispersants, preservatives, acids and bases, dyes, fillers and also water.

Suitable defoamers are conventional defoamers present in formulations of agrochemical active compounds. Examples include silicone oils, dispersions of silicone oils, magnesium stearate, phosphinic and phosphonic acids, in particular Fluowet PL 80 ^® .

Suitable organic solvents or dispersants are all customary organic solvents. Aliphatic and aromatic, optionally halogenated hydrocarbons, such as toluene, xylene, Solvesso ^®, mineral oils such as white spirit, petroleum, alkylbenzenes and spindle oil, still carbon tetrachloride, chloroform, methylene chloride and methylene chloride, and also esters, such as ethyl acetate, lactates further lactones such as Butyrolactone, also lactams, such as N-methylpyrrolidone, N-octylpyrrolidone, N-dodecylpyrrolidone N-octylcaprolactam and N-methylcaprolactam, γ-butyrolactone, dimethylformamide and tributyl phosphate, triglycerides, such as animal and vegetable fats and oils, and their transesterification products, such as fatty acid alkyl esters ,

As emulsifiers are common, in formulations of agrochemical

Active substances existing surface-active substances in question. Examples which may be mentioned are ethoxylated nonylphenols, polyethylene glycol ethers of linear alcohols, end-capped and non-end-capped alkoxylated linear and branched, saturated and unsaturated alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols Fatty acid esters, end-capped and non-endcapped alkoxylated linear and branched, saturated and unsaturated fatty acids, alkyl sulfonates, alkyl sulfates, aryl sulfates, ethoxylated arylalkylphenols, such as tristyrylphenol ethoxylate having an average of 16 ethylene oxide units per molecule, ethoxylated and propoxylated arylalkylphenols and sulfated or phosphated arylalkylphenol ethoxylates or ethoxy and propoxylates.

Suitable dispersants are all substances customarily used in crop protection agents for this purpose. In addition to the examples mentioned above under emulsifiers, preference is also given to natural and synthetic, water-soluble polymers, such as gelatin, starch and cellulose derivatives, in particular cellulose esters and cellulose ethers, furthermore polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid and copolymers of (meth) acrylic acid and (meth) acrylic acid esters, and also neutralized with alkali metal hydroxide co-polymers of methacrylic acid and methacrylic acid ester, as well as ionic polymers such as lignosulfonates and condensation products of alkylnaphthalenesulfonates with formaldehyde. -

Suitable preservatives are all substances usually present in plant treatment compositions for this purpose. As examples may be mentioned Preventol® ^® and Proxel ^®.

Suitable dyes are all customary for the production of pesticides inorganic or organic dyes. Examples include titanium dioxide, carbon black, zinc oxide and blue pigments.

Suitable fillers are all substances normally used for this purpose in crop protection agents. Preference is given to inorganic particles, such as carbonates, silicates and oxides having an average particle size of 0.005 to 5 .mu.m, more preferably from 0.02 to 2 microns. Examples include silicon dioxide, so-called highly disperse silica, silica gels, and natural and synthetic silicates and aluminosilicates. Suitable compounds which act as emulsion stabilizers and / or crystallization inhibitors are all substances conventionally used for this purpose in crop protection agents.

The content of the individual components can be varied within a substantial range in the formulations according to the invention.

The preparation of the plant protection agents according to the invention is carried out, for example. in such a way that the components are mixed together in the desired ratios. When the insecticidal active ingredient is a solid, it is generally employed either in finely ground form or in the form of a solution or suspension in an organic solvent or water. If the insecticidal active ingredient is liquid, it is often unnecessary to use an organic solvent. It is also possible to use a solid insecticidal active ingredient in the form of a melt.

The temperatures can be varied within a certain range when carrying out the process. It generally works at temperatures between 0 ⁰ C and 80 ⁰ C, preferably between 10 ⁰ C and 60 ⁰ C.

In general, the preparation of agents according to the invention is carried out by mixing the polyalkylene derivatives (I) with one or more active ingredients and optionally with additives. The order in which the components are mixed together is arbitrary.

For carrying out the process, customary devices are used, which are used for the preparation of insecticidal formulations.

As application forms, all methods known to those skilled in the art can be used; Examples include: spraying, diving,

Mist and a number of special processes for direct treatment above or below ground of whole plants or parts (seeds, root, stolons, Stem, stem, leaf), such as stem injection in trees or stalk bandages in perennial plants, and a number of specific indirect application methods.

The respective surface and / or object-related application rate of

Pesticides of different types of formulations for controlling the mentioned harmful organisms varies greatly. In general, the application media known to those skilled in the art as customary for the respective field of application are generally used in the customary amounts; for example, from several hundred liters of water per hectare in standard spraying over a few liters of oil per hectare in the "Ultra Low Volume" aircraft application to a few milliliters of a physiological solutions in injection procedures. The concentrations of the crop protection agents according to the invention in the corresponding application media therefore vary within a wide range and are dependent on the respective field of use. In general will be

Concentrations used, which are known to those skilled in the art for the respective field of application. Preference is given to concentrations of from 0.01% by weight to 99% by weight, particularly preferably from 0.1% by weight to 90% by weight.

The insecticidal formulations according to the invention may e.g. in the preparation forms customary for liquid preparations, either as such or after prior dilution with water, e.g. as emulsions, suspensions or solutions. The application is carried out by conventional methods, e.g. by spraying, pouring or injecting.

The application rate of the insecticidal formulations according to the invention can be varied within a relatively wide range. It depends on the particular insecticidal active ingredients and their content in the formulations.

The invention further provides a process for promoting the penetration of insecticidal active substances into plants, wherein the insecticidally active substance is applied simultaneously or sequentially applied to the plant with one or more polyalkylene oxide derivatives of formula (I).

The crop protection agents according to the invention are partly known and partly new.

The invention also relates to a crop protection agent containing

A) one or more agrochemical active substances from the group of insecticides,

B) one or more polyalkylene oxide derivatives of the formula (I)

R-- (CO) ₃ [O] _c - (A) _n - (CO) - R ^b (I)

wherein the symbols and indices have the meanings given above for the formula (I).

Preferred insecticides are those from the group of chloronicotinyls, in particular imidacloprid.

The insecticidal compositions according to the invention generally contain from 0.01 to 99% by weight, in particular from 0.1 to 95% by weight, of one or more insecticidal active compounds (A).

In wettable powders, the active ingredient concentration z. B. about 10 to 90 wt .-%, the remainder to 100 wt .-% consists of conventional formulation components and optionally surfactants (B). For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dusty formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

The surfactants (B) to be used according to the invention are generally applied together with the insecticidal active ingredient (A) or directly after one another, preferably in the form of a spray mixture containing the surfactants (B) and the insecticidal active compounds (A) in effective amounts and optionally contains other conventional auxiliaries. The spray mixture is preferably based on water and / or an oil, for. As a high-boiling hydrocarbon such as kerosene or paraffin produced. The compositions according to the invention can be realized as a tank mixture or via a "finished formulation".

The weight ratio of insecticidal active ingredients (A) to surfactant (B) can vary within a wide range and depends, for example, on B. on the effectiveness of the insecticidal active ingredient. It is usually in the range of 10: 1 to 1: 5000, preferably 4: 1 to 1: 2000, 4: 1 to 1: 200, 4: 1 to 1:50, 2: 1 to 1: 10, 2 : 1 to 1: 5, 2: 1 to 1: 2.

The application rates of the insecticidal active compounds (A) are generally between 10 and 2000 g AS / ha (AS = active substance, that is, application rate based on the active ingredient), preferably between 50 and 1000 g AS / ha. The

Application rates of surfactants (B) are generally between 1 and 5000 g of surfactant / ha, preference is given to 10 and 2000 g of surfactant / ha, in particular 20 to 1000 g of surfactant / ha, 20 to 500 g / ha, 50 to 500 g / ha.

The concentration of the surfactants (B) to be used according to the invention in a spray mixture is generally from 0.05 to 4% by weight, preferably 0.1 to 1% by weight, in particular 0.1 to 0.3% by weight. % Surfactant. In the case of harmful animals, application to plants to be protected from these harmful organisms is preferred. Methods for therapeutic use in humans and animals are excluded.

The invention further relates to a method for controlling harmful animals, preferably harmful arthropods, such as insects and arachnids, helminths and molluscs, particularly preferably harmful arthropods and helminths, wherein

A) one or more agrochemical active ingredients from the group of insecticides,

B) one or more polyalkylene oxide derivatives of the formula (I)

R "- (CO) ₃ [O] _c - (A) _n - (CO) -R" (I)

wherein the symbols and indices have the meanings given above, preferably in an effective amount, are applied to the harmful animals or their habitat, preferably on plants to be protected against these harmful animals plants. Methods for therapeutic use in humans and animals are excluded.

The crops treated according to the invention are all economically important, for example transgenic, crops of useful and ornamental plants, e.g. of cereals, such as wheat, barley, rye, oats, millet, rice, cassava and maize, or else cultures of peanut, sugarbeet, cotton, soya, rapeseed, potato, tomato, pea and other vegetables.

The invention is further illustrated by the examples without being limited thereto. Examples penetration test

In this test, the penetration of drugs was measured by enzymatically isolated cuticle of apple tree leaves.

Sheets were used, which were cut in the fully developed state of apple trees of the variety Golden Delicious. The isolation of the cuticles took place in such a way that

- First on the bottom with dye marked and punched

Leaf discs were filled by means of vacuum infiltration with a pectinase solution (0.2 to 2%) buffered to a pH between 3 and 4,

then sodium azide was added and

the treated leaf discs were allowed to stand until the original leaf structure had dissolved and the non-cellular cuticle detached.

Thereafter, only the cuticle openings and hairs of the cuticles were the

Leaf tops continue to be used. They were washed several times alternately with water and a pH 7 buffer solution. The resulting clean cuticles were finally grown on Teflon flakes and smoothed with a gentle jet of air and dried.

In the next step, the membrane membranes obtained for membrane transport studies were placed in diffusion cells (= transport chambers) made of stainless steel. For this purpose, the cuticles were placed with tweezers in the middle of the silicone grease-coated edges of the diffusion cells and sealed with a likewise greased ring. The arrangement was chosen so that the morphological outer side of the cuticles was directed outwards, ie towards the air, while the original inner side faces the interior of the diffusion cell was. The diffusion cells were filled with water or with a mixture of water and solvent.

To determine the penetration, in each case 9 μl of a spray mixture of the composition mentioned in the examples were applied to the outside of a cuticle.

Tap water was used in each spray liquor.

After applying the spray liquors, the water was allowed to evaporate, then each turned the chambers and placed them in thermostatically controlled baths, wherein air was blown on the outside of the cuticle with a defined temperature and humidity. The onset of penetration therefore took place at a relative humidity of 60% and a set temperature of 25 ° C. Drug penetration was measured with radiolabeled drug.

As can be seen from the examples shown in the tables examples, the presence of lead compounds of the formula (I) (as an example products from the Cithrol ^® series) to a significant increase in uptake compared to the formulations in which the compounds of formula (I ) are not available. The alternatives used for compounds of the formula (I) are examples of commercially available solvents for formulations.

Table 1

Cuticular penetration of imidacloprid with and without cithrol additives ⁸

Formulation / Imidacloprid Penetration * Penetration * Penetration ^*

Tenside concentration at 5 after 1 day after 2 days

[g / i] hours [%] [%] [%]

Imidacloprid (Ai) 0.3 0.1 0.3 0.5

(only active ingredient) Formulation / Imidacloprid Penetration * Penetration ^* Penetration *

Tenside concentration at 5 after 1 day after 2 days

[g / i] hours [%] [%] [%]

Ai + 0, 5 g / l 0, 2 8,9 22,2 30,6

Cithrol 2DO ^**

Ai + 0, 5 g / l 0, 2 46.3 60.0 65.8

Cithrol 4DL

Ai + 0, 5 g / l 0, 2 41, 8 67.8 76.2

Cithrol 4DO ^** ^{a means} of 5-8 repetitions

* at 2O ⁰ C, 60%

^* * Cithrol 2DO: PEG 200 dioleate, cithrol 4 DO: PEG 400 dioleate

Claims

claims

1. Use of polyalkylene oxide derivatives of the formula (I),

R 1 - (CO) ₃ [O] _c - A (CO) - R ^b (I)

to promote the penetration of insecticidal active substances into plants, the

Symbols and indices in the formula (I) have the following meanings:

R ^a is a Cβ-Cso-hydrocarbon radical, vorzugswie C ₈ -C ₃ -alkyl, C ₈ -C ₃₀ - alkenyl or C ₈ -C ₃₀ alkynyl;

R ^b is a Cβ-Cso-hydrocarbon radical, such as C ₈ -C ₃ -alkyl, C ₈ -C ₃ -alkenyl, C ₈ - C ₃₀ alkynyl; a is 0 or 1; b is 0 or 1; c is 0 or 1 and

A is one or more alkylene oxide units.

2. Use according to claim 1, wherein the polyalkylene oxide derivative of the formula (I) contains alkylene oxide units A of the formula (II),

- (EO) _x (RO) _y (EO) ₂ - (II)

wherein

EO represents an ethylene oxide unit; RO is a moiety - CHR ^x -CHR ^y -O-, where R ^x , R ^{y are} independently H or (dC-Oalkyl; x is an integer from 0 to 600; y is an integer from 0 to 600; z is an integer from 0 to 600, where the sum (x + y + z) is> 2 and <600.

3. Use according to claim 1 or 2, wherein the polyalkylene oxide derivatives are compounds of the following formulas 1-1) to I-3):

1-1) R ^a -OAR ^b , wherein R ^a , A and R ^{b are} as defined in formula (I) in claim 1; I-2) R ^a -CO-OAR ^b , wherein R ^a , A and R ^{b are} as defined in formula (I) in claim 1;

I-3) R ^a -CO-OA-CO-R ^b , wherein R ^a , A and R ^{b are} as defined in formula (I) in claim 1;

4. Use according to claim 3, wherein polyalkylene oxide derivatives of the formulas (1-11), (I-22) or (I-33) are used,

1-11) (C ₁₀ -C ₂₄ ) alkyl-O - [(EO) _x (PO) _y ] - (C ₁₀ -C ₂ 4) alkyl

I-22) (C ₉ -C ₂₃ ) alkyl CO-O - [(EO) _x (PO) _y HCio-C ₂₄ ) alkyl

I-33) (C ₉ -C ₂₃ ) alkyl CO-O - [(EO) _x (PO) _y ] CO (C ₉ -C ₂₃ ) alkyl, wherein x is an integer from 0 to 600; y is an integer from 0 to 600 and x + y is an integer> 1 and ≤600.

5. Use according to one or more of claims 1 to 4, wherein the polyalkylene oxide derivatives are those of the formula (III),

O R - C 0 - (CH ₂ -CH ₂ -O) _n -X ( ^{M |} )

6. A method for promoting the penetration of insecticidal active ingredients in plants, wherein the insecticidal active ingredient is administered simultaneously or sequentially with one or more a plurality of polyalkylene oxide derivatives of the formula (I) according to claim 1 applied to the plant.

7. Plant protection products containing A) one or more agrochemical active substances from the group of insecticides,

B) one or more polyalkylene oxide derivatives of the formula (I)

R "- (CO) ₃ [O] _c - (A) _n - (CO) - R ^b (I)

wherein the symbols and indices have the meanings given for the formula (I) in claim 1.

8. Method for controlling harmful animals, wherein

A) one or more agrochemical active ingredients from the group of insecticides,

B) one or more polyalkylene oxide derivatives of the formula (I)

R '- (CO) - [O] ₀ - (A) _n - (CO) - R ^b (I)

wherein the symbols and indices have the meanings given in formula (I) in claim 1, are applied to the harmful animals or their habitat.