WO2008122396A2

WO2008122396A2 - Method of improving the growth of a plant

Info

Publication number: WO2008122396A2
Application number: PCT/EP2008/002614
Authority: WO
Inventors: Max Angst; Michael Schade; Christoph Vock; Ana Cristina Dutton
Original assignee: Syngenta Participations Ag
Priority date: 2007-04-04
Filing date: 2008-04-02
Publication date: 2008-10-16
Also published as: WO2008122396A3; CL2008000972A1; UY31003A1; AR065929A1; TW200904332A

Abstract

The present invention relates to a novel method of improving the growth of a plant, especially yield and vigor, comprising treating the plant or its propagation material with an effective amount of a compound of formula I wherein the substituents are defined as in claim 1.

Description

Method of improving the growth of a plant

The present invention relates to the improvement of the growth of a plant, especially increasing yield and vigor (greening enhancement, stress shield), and more particularly to a method of increasing the yield and vigor of agronomic plants by treatment of the plant or its propagation material with insecticidally active bisamide derivatives optionally in admixture with further active agents.

Certain methods of improving plant growth are described in the literature. These methods are usually based on conventional fertilizing. The biological effects of those known methods are however not entirely satisfactory in the area of agriculture. There is therefore still a need to improve the growth of the plants basically for obtaining higher crop yields, as well as the reduction of the use of fertilizers needed.

Early vigor is considered an essential component of plant development under most environmental conditions. Plants, especially cotton, maize, wheat, barley, rice, potato, soybeans, brassica , tomato, peper, chili, eggplant, cucurbits: melons, cucumbers, onion, spinache, lettuce, sugar cane , sugar beet, beans, tobacco, coffee, citrus, apple, pear, stone fruits, nuts, bananas, vine, rape and sunflower, with early seedling vigor and good stand establishment tend to maximize use of available soil water, resulting in increased dry matter accumulation and improved grain yield.

Bisamide derivatives with insecticidal action are known and described, for example, in WO 04/067528, WO 2005/085234, WO 03/015519, WO 2006/111341 , WO07/020050, WO06/040113 and PCT/EP2007/001283. US-A-6,753,296 discloses a method of improving the growth of a plant which is essentially free of insects, comprising applying to the plants or the locus thereof at least one compound selected from the class of the neonicotinoids.

There have now been found that certain bisamide derivatives have the capability of improving the growth of a plant, especially the yield and vigor of the plant.

The present invention accordingly relates to a novel method of improving the growth of a plant comprising treating the plant or its propagation material with an effective amount of a compound of formula I

wherein

X is a bivalent group selected from

R₁ is hydrogen, CrC₄alkyl or C^^alkyl substituted with one or two groups selected from C₃- C₆cycloalkyl and cyano; or R₁ is C₃-C₆cycloalkyl or C₃-C₆cycloalkyl substituted by C₃- C₆cycloalkyl; with the proviso that R₁ is different from unsubstituted C_rC₄alkyl if X is X₁ and R₄ is cyano;R₂ is halogen, C₁-C₄alkoxy, C_rC₄haloalkyl or C_rC₄haloalkoxy; R₃ is C_!-C₄alkyl or halogen; and R₄ and R₅ independently from each other, are hydrogen, d-C₄alkyl, C₁-C₄BIkOXy, cyano, nitro, or halogen; and agronomically acceptable salts/isomers/enantiomers/tautomers/N- oxides of those compounds.

Compounds I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as d-C₄alkanecarboxylic acids which are unsubstitu- ted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as CrC₄alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mor- pholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. Where appropriate, the corresponding internal salts can furthermore be formed. Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also encompasses salts which have disadvantage for agrochemical use, for example salts which are toxic to bees or fish, and which are employed, for example, for the isolation or purification of free compounds I or agrochemically utilizable salts thereof. Owing to the close relationship between the compounds I in free form and in the form of their salts, for the purposes of the invention the free compounds I or their salts hereinabove and hereinbelow are respectively to be understood as including, where appropriate, the corresponding salts or the free compounds I. The same applies analogously to tautomers of compounds I and salts thereof. In general, the free form is preferred in each case.

The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl. - H -

Halogen is generally fluorine, chlorine, bromine or iodine.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1-difluoro- 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, 2,2,2- trifluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2-chloroethoxy, pentafluoroethoxy, 2,2,3,3-tetrafluoroethoxy and 2,2,2-trichloroethoxy; preferably dif luorochloromethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy and 2,2,2- trifluoroethoxy.

Alkoxy groups preferably have a preferred chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.

The cycloalkyl groups have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The present invention also relates to a novel method of improving the growth of a plant which is essentially free of insects comprising treating the plant or its propagation material with an effective amount of a compound of formula I as mentioned above.

Surprisingly, it has been found that the application of the compounds of the formula I to the plants or the locus thereof results in a quite unexpectedly enhanced plant growth. It has now been found, that the action of the compounds of the formula I goes far beyond their well- known pesticidal action. It has been shown, that the compounds of the formula I exhibit an action termed plant growth in the frame of the instant invention. Under the term plant growth there are understood various sorts of improvements of plants which are not connected to the control of pests with the said compound I. For example such advantageous properties that may be mentioned are improved crop characteristics including: emergence, crop yields, protein content, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination; or any other advantages familiar to a person skilled in the art.

Especially preferred is the use of the compounds of formula I in a method for the improvement of the growth plants which are essentially free of insects and representatives of the order Acarina.

It has been shown, that compounds of formula I have a good effect on the plant growth. As a rule, a good effect means at least 10% earlier emergence, crop yields, more developed root system, increase in plant height, bigger leaf blade, less fertilizers needed, less seeds needed increased shoot growth, improved plant vigor etc.

A further aspect of the invention is a method of using a compound of formula I in a method for Improving the growth of plants.

A further aspect of the invention is the use of a compound of formula I in a method for improving the growth of plants.

Still a further aspect of the invention is a method of using a composition comprising a compound of formula I in a method for improving the growth of plants. Crops which can be improved according to the present method include cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, for example pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g. strawberries, raspberries and blackberries; leguminous fruits, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucurbitaceae, such as marrows, cucumbersand melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruit, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocados, cinnamon and camphor; and also tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals; especially rice, beans, soybeans, rape.

Especially suitable compounds according to the present invention are selected from the compounds of formula I, wherein a) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is bromine, R₃ is methyl, R₄ is CN and X is X₁; b) Ri is methyl substituted by cyclopropyl, R₂ is CF₃, R₃ is methyl, R₄ is Cl and X is X₁; c) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is CF₃, R₃ is methyl, R₄ is Cl and X is X₁; d) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is CF₃, R₃ is methyl, R₄ is CN and X is X₁; e) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is OCH₂CF₃, R₃ is methyl, R₄ is CN and X is X₁; f) R₁ is isopropyl, R₂ is methoxy; R₃ is methyl, R₄ is hydrogen and X is X₈ ; g) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is chlorine, R₄ is hydrogen and X is X₈; h) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is methyl, R₄ is hydrogen and X is X₈; i) R₁ is methyl, R₂ is bromine, R₃ is methyl, R₄ is Cl and X is X₁; j) R₁ is methyl, R₂ is trifluoromethyl, R₃ is Cl, R₄ is Cl and X is X₂; k) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is bromine, R₃ is Cl, R₄ is

Br and X is X₂;

I) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is methyl, R₄ is methyl and X is X₃; m) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is Cl, R₄ is trifluoromethyl and X is X₄; n) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is Cl, R₄ is methoxy and X is X₅; and o) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is methyl and X is X₇; in particular from a) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is bromine, R₃ is methyl, R₄ is CN and X is X₁; b) R₁ is methyl substituted by cyclopropyl, R₂ is CF₃, R₃ is methyl, R₄ is Cl and X is X₁; c) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is CF₃, R₃ is methyl, R₄ is Cl and X is X₁; d) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is CF₃, R₃ is methyl, R₄ is CN and X is X₁; e) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is OCH₂CF₃, R₃ is methyl, R₄ is CN and X is X₁; f) R₁ is isopropyl, R₂ is methoxy; R₃ is methyl, R₄ is hydrogen and X is X₈ ; g) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is chlorine, R₄ is hydrogen and X is X₈; h) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is methyl, R₄ is hydrogen and X is X₈; i) R₁ is methyl, R₂ is bromine, R₃ is methyl, R₄ is Cl and X is X₁;

The compounds of formula I can be prepared analogously to known processes, for example as described, for example, in WO 04/067528, WO 2005/085234, WO 2006/111341 , WO 2007/020050 and PCT/EP2007/001283.

Salts of compounds I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

Salts of compounds I can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.

Salts of compounds I can be converted in a manner known per se into other salts of compounds I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds I, which have salt- forming properties can be obtained in free form or in the form of salts.

The compounds I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.

Diastereomer mixtures or racemate mixtures of compounds I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high- performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is com- plexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.

The compounds I according to the invention are known as preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, a good activity corresponding to a destruction rate (mortality) of at least 50 to 60%.

The term "useful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bi ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bi) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransf erase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature- Gard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait) and Protecta®.

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs₁ see e.g. EP-A-O 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-O 392 225, WO 95/33818, and EP-A-O 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.

The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.

The term "plants which are essentially free of insects" means plants in locations where the level of insect infestation is below that indicating the need for the use of an insecticide for insect control purposes.

The compounds of formula I can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation. When the subject method is described herein as "increasing the yield" of an agronomic plant, what is meant is that the yield of a product of the plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the subject method. It is preferred that the yield be increased by at least about 0.5%, more preferred that the increase be at least about 1 %, even more preferred is about 2%, and yet more preferred is about 4%, or more.

When the subject method is described herein as "increasing the vigor" of an agronomic plant, what is meant is that the vigor rating, or the plant weight, or the plant height, or the plant canopy, or the visual appearance, or any combination of these factors, is increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the subject method. It is preferred that such factor(s) is increased or improved by a significant amount.

The compounds of formula I can be applied in the form of pesticidal compositions such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients of formula I according to the invention and which are to be selected to suit the intended aims and the prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C₈ to C₁₂ of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-me- thylpyrrolid-2-one, dimethyl sulfoxide or N.N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.

Solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly disperse silicas or highly disperse absorbtive polymers. Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand. In addition, a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.

Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.

Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cyc- loaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopo- lypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylpheno- xypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate. The cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethyl- ammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are the alkali, alkaline earth or (un- substituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. As a rule, the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutyl- naphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate. Also possible are, furthermore, suitable phosphates, such as salts of the phosphoric ester of a p- nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants(% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient. Preferred compositions are composed in particular as follows (% = percent by weight):

Emulsifiable concentrates: active ingredient: 1 to 95%, preferably 5 to 20% surfactant: 1 to 30%, preferably 10 to 20 % solvent: 5 to 98%, preferably 70 to 85%

Dusts: active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates: active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%

Wettable powders: active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 99%, preferably 15 to 98%

Granulates: active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

Formulation examples (% = percent by weight)

Example F1 : Emulsion concentrates a) b) c)

Active ingredient 25 % 40 % 50 %

Calcium dodecylbenzenesulfonate 5 % 8 % 6 %

Castor oil polyethylene glycol ether (36 mol of EO) 5 % - -

Tributylphenoxypolyethylene glycol ether (30 mol of EO) - 12 % 4 %

Cyclohexanone - 15 % 20 %

Xylene mixture 65 % 25 % 20 % Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

Example F2: Solutions a) b) c) d)

Active ingredient 80 % 10 % 5 % 95 %

Ethylene glycol monomethyl ether 20 % - - -

Polyethylene glycol MW 400 - 70 % - -

N-Methylpyrrolid-2-one - 20 % - -

Epoxidized coconut oil - - 1 % 5 %

Petroleum ether (boiling range: 160-190°) - - 94 % -

The solutions are suitable for use in the form of microdrops.

Example F3: Granules a) b) c) d)

Active ingredient 5 % 10 % 8 °/ > 21 ' %

Kaolin 94 % - 79 ' Vo 54 " Vo

Highly disperse silica 1 % - 13 ' Vo 7 %

Attapulgite 90 % 18 ^« Vo

The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.

Example F4: Dusts a) b)

Active ingredient 2 % 5 %

Highly disperse silica 1 % 5 %

Talc 97 % _

Kaolin - 90 %

Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.

Example F5: Wettable powders a) b) c)

Active ingredient 25 % 50 % 75 %

Sodium lignosulfonate 5 % 5 %

Sodium lauryl sulfate 3 % - 5 %

Sodium diisobutylnaphthalenesulfonate - 6 % 10 % Octylphenoxypolyethylene glycol ether (7-8 mol of EO) - 2 % -

Highly disperse silica 5 % 10 % 10 %

Kaolin 62 % 27 % -

The active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.

Example F6: Extruder granules

Active ingredient 10 %

Sodium lignosulfonate 2 %

Carboxymethylcellulose 1 %

Kaolin 87 %

The active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.

Example F7: Coated granules

Active ingredient 3 %

Polyethylene glycol (MW 200) 3 %

Kaolin 94 %

In a mixer, the finely ground active ingredient is applied uniformLy to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.

Example F8: Suspension concentrate

Active ingredient 40 % Ό

Ethylene glycol 10 %

Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6 %

Sodium lignosulfonate 10 %

Carboxymethylcellulose 1 %

37 % aqueous formaldehyde solution 0.2 %

Silicone oil (75 % aqueous emulsion) 0.8 %

Water 32 %

The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water. The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding other active ingredients. There have now been surprisingly found that certain members from the class of neonicotinoid insecticides are able to improve the the yield and vigor increasing properties of the compounds of formula I. Preferred compounds from the class of neonicotinoid insecticides are thiamethoxam (792) (available commercially as HELIX® and CRUISER®), imidacloprid (458) (available commercially as GAUCHO®) clothianidine (165), thiacloprid (791), dinotefuran (271 ), nitenpyram (579) and acetamiprid (4). Said compounds are described under the entry number given in round brackets hereinabove in the "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S. TomLin; The British Crop Protection Council]. Further preferred mixing partners for the compounds of formula I are selected from the group consisting of paclobutrazol (Chemical Abstracts Registry number 76738-62-0), acibenzolar-S-methyl (Chemical Abstracts Registry number 126448-41-7), bixafen (Chemical Abstracts Registry number 581809-46-3), fluopyram (Chemical Abstracts Registry number 658066-35-4) and the compound of formula A

p (formula A), described e.g. in WO98/46607.

Therefore, the present invention also relates to a method of improving the growth of a plant, especially yield and vigor, comprising treating the plant or its propagation material with an effective amount of a composition comprising as active ingredients a compound of formula I as mentioned above and at least one compound selected from the class of neonicotinoid insecticides, paclobutrazol, acibenzolar-S-methyl, bixafen, fluopyram and the compound of formula A (formula A),

preferably selected from the class of neonicotinoid insecticides, in particular thiamethoxam.

The active ingredient mixture of the compounds of formula I with the insecticides described above comprises a compound of formula I and an insecticide as described above preferably in a mixing ratio of from 100:1 to 1 :6000, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4:1 to 2:1 being likewise preferred, above all in a ratio of 1 :1 , or 5:1 , or 5:2, or 5:3, or 5:4, or 4:1 , or 4:2, or 4:3, or 3:1 , or 3:2, or 2:1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 :150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.

The mixtures comprising a compound of formula I and an insecticide as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I and the neonicotinoid insecticides as described above is not essential for working the present invention.

The compositions can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds I for the preparation of these compositions are also a subject of the invention.

The application methods for the compositions, such as spraying, atomizing, dusting, brushing on, dressing, scattering or pouring - which are to be selected to suit the intended aims of the prevailing circumstances - and the use of the compositions for controlling pests of the abovementioned type are other subjects of the invention. Typical rates of concentration are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The rate of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application).

The compositions according to the invention are also suitable for the use in plant propagation material, for example seeds. The propagation material can be treated with the compositions prior to planting, for example seed can be treated prior to sowing. Alternatively, the compositions can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. Biological examples:

Example 1 : Vigour effects on peas:

Five day old seedlings of Pea seedlings Pisum sativum Douce Provence were placed individually in glass 25ml vials which were filled with 12ml soil and 15.5ml water. For each compound 15 plants were used for each of the water or soil/water treatment. The seedlings were treated with 12.5 ppm of an active substance of formula I and placed in a complete randomized block design with border plants which were used for reducing possible border effects. Seedlings were kept in the growth chamber for 16 days at a temperature of 20⁰C, 60% relative humidity, light regime of 16:8 LD and watered as needed. After the 16 days plants were removed from vials, roots washed and plants placed to dry for six days at 55°C. Dry weight of roots, stem & leaves and whole plant were recorded (in mg). Results are given in Table B1.

Table B1 : Vigor effect for the compound of formula I, wherein R₁ is isopropyl, R₂ is methoxy; R₃ is methyl, R₄ is hydrogen and X is X₈ (Compound A) and the compound of formula I, wherein R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is methyl, R₄ is hydrogen and X is X₈ (Compound B);

The results show that compounds of formula I are suitable to significantly improve the plant growth of the crop plant pea.

Claims

What is claimed is:

1. A method of improving the growth of a plant, comprising treating the plant or its propagation material with an effective amount of a compound of formula I

wherein

X is a bivalent group selected from

Ri is hydrogen, CrC₄alkyl or C^^alkyl substituted with one or two groups selected from C₃- C₆cycloalkyl and cyano; or R₁ is C₃-C₆cycloalkyl or C₃-C₆cycloalkyl substituted by C₃- C₆cycloalkyl; with the proviso that R₁ is different from unsubstituted C₁-C₄SIkVl if X is X₁ and

R₄ is cyano;

R₂ is halogen, Cr^alkoxy, C!-C₄haloalkyl or C_rC₄haloalkoxy;

R₃ is C_rC₄alkyl or halogen; and

R₄ and R₅ independently from each other, are hydrogen, Ci-C₄alkyl, C₁-C₄alkoxy, cyano, nitro, or halogen; and agronomically acceptable salts/isomers/enantiomers/tautomers/N- oxides of those compounds.

2. The method according to claim 1 , wherein the compound of formula I is selected from the group of compounds wherein a) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is bromine, R₃ is methyl, R₄ is CN and X is X₁; b) R₁ is methyl substituted by cyclopropyl, R₂ is CF₃, R₃ is methyl, R₄ is Cl and X is X₁; c) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is CF₃, R₃ is methyl, R₄ is Cl and X is X₁; d) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is CF₃, R₃ is methyl, R₄ is CN and X is X₁; e) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is OCH₂CF₃, R₃ is methyl, R₄ is CN and X is X₁; f) R₁ is isopropyl, R₂ is methoxy; R₃ is methyl, R₄ is hydrogen and X is X₈ ; g) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is chlorine, R₄ is hydrogen and X is X₈; h) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is methyl, R₄ is hydrogen and X is X₈; and i) R₁ is methyl, R₂ is bromine, R₃ is methyl, R₄ is Cl and X is X₁ ; j) R₁ is methyl, R₂ is trifluoromethyl, R₃ is Cl, R₄ is Cl and X is X₂; k) R₁ is cyclopropyl substituted by cyclopropyl at the 1 -position, R₂ is bromine, R₃ is Cl, R₄ is

Br and X is X₂;

I) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is methyl, R₄ is methyl and X is X₃; m) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is Cl, R₄ is trifluoromethyl and X is X₄; n) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is Cl, R₄ is methoxy and X is X₅; and o) R₁ is isopropyl, R₂ is trifluoromethyl, R₃ is methyl and X is X₇.

3. The method according to claim 1 , wherein the plant or its propagation material is treated with a compound of formula I in admixture with a compound selected from the class of neonicotinoids.

4. The method according to claim 3, wherein the neonicotinoid is thiamethoxam.

5. The method according to claim 1 , wherein the plant or its propagation material is treated with a compound of formula I in admixture with a compound selected from thiamethoxam, imidacloprid, clothianidine, thiacloprid, dinotefuran, nitenpyram, acetamiprid, paclobutrazol, acibenzolar-S-methyl, bixafen, fluopyram and the formula A

p (formula A).

6. The method according to claim 1 , wherein the plant is selected from the group consisting of corn, cereals, cotton, maize, wheat, barley, rice, potato, soybeans, brassica , tomato, peper, chili, eggplant, cucurbits: melons, cucumbers, onion, spinache, lettuce, sugar cane , sugar beet, beans, tobacco, coffee, citrus, apple, pear, stone fruits, nuts, bananas, vine, rape and sunflower.