WO2013007550A1

WO2013007550A1 - Fungicide mixtures

Info

Publication number: WO2013007550A1
Application number: PCT/EP2012/062831
Authority: WO
Inventors: Camilla Corsi; Carla Bobbio; Peter Schneiter
Original assignee: Syngenta Participations Ag
Priority date: 2011-07-08
Filing date: 2012-07-02
Publication date: 2013-01-17
Also published as: AR087086A1; UY34189A

Abstract

A composition suitable for control of diseases caused by phytopathogens comprising (A) a compound of formula (I) wherein wherein the substituents have the definitions as defined in claim 1 or a salt or a oxide thereof and (B) at least one compound selected from compounds known for their fungicidal activity; and a method of controlling diseases on useful plants.

Description

FUNGICIDE MIXTURES

The present invention relates to novel compositions of fungicides comprising isoxazole containing compounds and a further fungicidial active ingredient, their use and methods for the control and/or prevention of microbial infection, particularly fungal infection, in plants.

The incidence of serious microbial infections, particularly fungal infections, either systemic or topical, continues to increase for plants. Fungicides are compounds, of natural or synthetic origin, which act to protect plants against damage caused by fungi. Current methods of agriculture rely heavily on the use of fungicides. In fact, some crops cannot be grown usefully without the use of fungicides. Using fungicides allows a grower to increase the yield of the crop and consequently, increase the value of the crop. Numerous fungicidal agents have been developed. However, the treatment of fungal infestations continues to be a major problem. Furthermore, fungicide resistance has become a serious problem, rendering these agents ineffective for some agricultural uses. As such, a need exists for the development of new fungicidal compositions with optionally synergistical effect. The present invention provides composition suitable for control of diseases caused by phytopathogens comprising a component (A) and a component (B).

Accordingly, the present invention provides a synergistically active fungicidal composition comprising a component (A) and a component (B) wherein the component (A) is selected from at least one compound of formula I:

wherein:

Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro;

R₂ is heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro;

R₃ is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano, nitro; heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro; or alkylsilyl; and

R4 is H or acyl, benzoyl and phenylacetyl and the component (B) is selected from at least one selected from the group consisting of

Isopyrazam, N-[9-(dichloromethylene)-l ,2,3,4-tetrahydro-l ,4-methanonaphthalen-5-yl]-3- (difluoromethyl)- 1 -methyl- 1 H-pyrazole-4-carboxamide, 3 -(Difluoromethyl)-N-methoxy- 1 - methyl-N-[l -methyl -2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide, Bixafen, Boscalid, Fluxapyroxad, Penthiopyrad, Fluopyram, Prothioconazole, Propiconazole,

Difenconazole, Ipconazole, Cyproconazole, Epoxiconazole, Metconazole, Tebuconazole, Prochloraz, Flusilazole, Flutriafol, Fluquinconazole, Azoxystrobin, Trifloxystrobin,

Pyraclostrobin, Fluoxastrobin, Picoxystrobin, Kresoxim-methyl, Dimoxystrobin,

Famoxadone, Cyprodinil, Chlorothalonil, Fludioxonil, Metrafenone, Proquinazid,

Cyflufenamid, Fenpropidin, Fenpropimorph, Spiroxamine, Trinexapac-ethyl, Thiamethoxam, Clothianidin, Imidaclodprid, or Tefluthrin. It has been found that the use of component (B) in combination with component (A) surprisingly and substantially may enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the method of the invention is effective against a wider spectrum of such fungi that can be combated with the active ingredients of this method, when used solely.

Therfore a further aspect of present invention provides a composition comprising a combination of components (A) and (B) in a synergistically effective ratio between the component (A) and component (B).

A further aspect of the present invention provides a method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a combination of components (A) and (B) in as synergistically effective amount and ratio between the component (A) and component (B).

The present invention accordingly further relates to the method of controlling

phytopathogenic diseases on useful plants or plant propagation material thereof, which comprises applying to said plant propagation material a fungicidally effective amount of a composition comprising the component (A) and the component (B).

Further the composition according to the invention is especially suitable to increase the yield and/or quality of useful plants, such as crop yield of crop plants.

Accordingly the present invention also relates to a method of protecting plant propagation material and organs that grow at a later point in time against damage phytopathogenic diseases, which method comprises applying to said propagation material a fungicidally effective amount of a composition comprising the component (A) and the component (B).

Accordingly the present invention further relates to a method of improving the growing characteristics of a plant, which method comprises applying to said propagation material a fungicidally effective amount of a composition comprising the component (A) and the component (B).

Accordingly the present invention further relates to a method of controlling or preventing fungal diseases in a growing plant or growing plant tissue said method comprising applying onto the seed before planting or sowing thereof and effective amount of a composition comprising the component (A) and the component (B).

In one group of mixtures, component B is a SDHI fungicide.

In one group of mixtures, component B is a strobilurin fungicide.

In one group of mixtures, component B is an azole fungicide, preferably selected from a triazole fungicide, or a pro-triazole fungicide.

In one group of mixtures, component B is DMI fungicide.

In one group of mixtures, component B is a morpholine fungicide.

In one group of mixtures, component B is an anilinopyrimidine fungicide.

In one group of mixtures, component B is a sterol biosynthesis inhibitor fungicide.

In a further preferred embodiment the component B is Isopyrazam. In a further preferred embodiment the component B is N-[9-(dichloromethylene)- 1,2,3, 4-tetrahydro- 1,4- methanonaphthalen-5-yl]-3-(difluoromethyl)-l-methyl-lH-pyrazole-4-carboxamide. In a further preferred embodiment the component B is 3-(Difluoromethyl)-N-methoxy-l-methyl- N-[l-methyl-2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide. In a further preferred embodiment the component B is Bixafen. In a further preferred embodiment the component B is Boscalid. In a further preferred embodiment the component B is

Fluxapyroxad. In a further preferred embodiment the component B is Penthiopyrad. In a further preferred embodiment the component B is Fluopyram. In a further preferred embodiment the component B is Prothioconazole. In a further preferred embodiment the component B is Propiconazole. In a further preferred embodiment the component B is Difenconazole. In a further preferred embodiment the component B is Ipconazole. In a further preferred embodiment the component B is Cyproconazole. In a further preferred embodiment the component B is Epoxiconazole. In a further preferred embodiment the component B is Metconazole. In a further preferred embodiment the component B is Tebuconazole. In a further preferred embodiment the component B is Prochloraz. In a further preferred embodiment the component B is flusilazole. In a further preferred embodiment the component B is Flutriafol. In a further preferred embodiment the component B is Fluquinconazole. In a further preferred embodiment the component B is Azoxystrobin. In a further preferred embodiment the component B is Trifloxystrobin. In a further preferred embodiment the component B is Pyraclostrobin. In a further preferred embodiment the component B is Fluoxastrobin. In a further preferred embodiment the component B is Picoxystrobin. In a further preferred embodiment the component B is Kresoxim-methyl. In a further preferred embodiment the component B is dimoxystrobin. In a further preferred embodiment the component B is famoxadone. In a further preferred embodiment the component B is

Cyprodinil. In a further preferred embodiment the component B is Chlorothalonil. In a further preferred embodiment the component B is fludioxonil. In a further preferred embodiment the component B is Metrafenone. In a further preferred embodiment the component B is

Proquinazid. In a further preferred embodiment the component B is cyflufenamid. In a further preferred embodiment the component B is Fenpropidin. In a further preferred embodiment the component B is Fenpropimorph. In a further preferred embodiment the component B is spiroxamine. In a further preferred embodiment the component B is Trinexapac-ethyl. In a further preferred embodiment the component B is Thiamethoxam. In a further preferred embodiment the component B is Clothianidin. In a further preferred embodiment the component B is Imidaclodprid. In a further preferred embodiment the component B is Tefluthrin. In a preferred embodiment the component (A) is not the same compound as the compound of the component (B). In a preferred embodiment the component (B) is not a compound according to formula (I). The term sterol biosynthesis inhibitor fungicide is well known to the person skilled in the art, and includes, for example, Spiroxamine, Fenpropimorph, Tridemorph, Fenpropidin, Fenhexamid, Terbinafme, Naftifine

The term triazole fungicide is well known to the person skilled in the art, and includes, for example, Cyproconazole, Difenoconazole, Metconazole, Propiconazole, Epoxiconazole, Tebuconazole, Flutriafol, Ipconazole and l-(2-chlorophenyl)-2-(l-chlorocycloprop-l-yl)-3- (l,2,4-triazol-l-yl)propan-2-ol [CAS number 120983-64-4]. Preferred triazole fungicide compounds are Cyproconazole, Difenoconazole, Metconazole and Tebuconazole. Even more preferred is Cyproconazole.

The term pro-triazole fungicide is well known to the person skilled in the art and includes, for example, prothioconazole.

The term DMI fungicides is well known to the person skilled in the art and includes, for example, Prothioconazole, Propiconazole, Difenconazole, Ipconazole, Cyproconazole, Epoxiconazole, Metconazole, Tebuconazole.

The term SDHI fungicide is well known to the person skilled in the art and includes, for example, N-[9-(dichloromethylene)-l ,2,3,4-tetrahydro-l ,4-methanonaphthalen-5-yl]-3- (difluoromethyl)- 1 -methyl- 1 H-pyrazole-4-carboxamide, 3 -(Difluoromethyl)-N-methoxy- 1 - methyl-N-[l -methyl -2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide,

Isopyrazam, Sedaxane, Boscalid Fluxapyroxad, Penthiopyrad, Penflufen, Bixafen,

Fluopyram, benodanil, carboxin, fenfuram, flutolanil, furametpyr, mepronil, oxycarboxin, penthiopyrad and thifluzamid and Fluxapyroxad. Preferred SDHI fungicides are N-[9- (dichloromethylene)- 1,2,3 ,4-tetrahydro- 1 ,4-methanonaphthalen-5 -yl] -3 -(difluoromethyl)- 1 - methyl- 1 H-pyrazole-4-carboxamide, 3 -(Difluoromethyl)-N-methoxy- 1 -methyl-N- [ 1 -methyl - 2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide, Isopyrazam.

In general, the weight ratio of component (A) to component (B) is from 2000 : 1 to 1 : 1000. A non-limiting example for such weight ratios is compound of formula I : compound of formula B-2 is 10: 1. The weight ratio of component (A) to component (B) is preferably from 100 : 1 to 1 : 100; more preferably from 20 : 1 to 1 : 50. The active ingredient mixture of component (A) to component (B) comprises compounds of formula I and a further, other biocidally active ingredients or compositions preferably in a mixing ratio of from 1000: 1 to 1 : 1000, 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.

It has been found, surprisingly, that certain weight ratios of component (A) to component (B) are able to give rise to synergistic activity. Therefore, a further aspect of the invention are compositions, wherein component (A) and component (B) are present in the composition in amounts producing a synergistic effect. This synergistic activity is apparent from the fact that the fungicidal activity of the composition comprising component (A) and component (B) is greater than the sum of the fungicidal activities of component (A) and of component (B). This synergistic activity extends the range of action of component (A) and component (B) in two ways. Firstly, the rates of application of component (A) and component (B) are lowered whilst the action remains equally good, meaning that the active ingredient mixture still achieves a high degree of phytopathogen control even where the two individual components have become totally ineffective in such a low application rate range. Secondly, there is a substantial broadening of the spectrum of phytopathogens that can be controlled.

A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture

X = % action by active ingredient A) using p ppm of active ingredient

Y = % action by active ingredient B) using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredients A)+B) using

X · Y

p+q ppm of active ingredient is E = X + Y

⁶ 100

If the action actually observed (O) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to a positive value for the difference of (O-E). In the case of purely complementary addition of activities (expected activity), said difference (O-E) is zero. A negative value of said difference (O-E) signals a loss of activity compared to the expected activity.

However, besides the actual synergistic action with respect to fungicidal activity, the compositions according to the invention can also have further surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, 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.

Some compositions according to the invention have a systemic action and can be

used as foliar, soil and seed treatment fungicides.

With the compositions according to the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms. The compositions according to the invention can be applied to the phytopathogenic microorganisms, the useful plants, the locus thereof, the propagation material thereof, storage goods or technical materials threatened by microorganism attack. The compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, storage goods or technical materials by the microorganisms .

A further aspect of the present invention is a method of controlling diseases on useful plants or on propagation material thereof caused by phytopathogens, which comprises applying to the useful plants, the locus thereof or propagation material thereof a composition according to the invention. Preferred is a method, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, more preferably to the useful plants. Further preferred is a method, which comprises applying to the propagation material of the useful plants a composition according to the invention.

The components (B) are known for example from "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition (New edition (02 Nov 2003)); Editor: C. D. S. Tomlin; The British Crop Protection Council, ISBN- 10: 1901396134; ISBN-13: 978- 1901396133] or its electronic version "e-Pesticide Manual V4.2" or from the website http://www.alanwood.net/pesticides/. Where the components (B) are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition;

Editor: C. D. S. Tomlin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular component (B); for example, the compound "abamectin" is described under entry number (1). Most of the components (B) are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular component (B); in that case, the IUPAC name, the IUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "develoment code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed.

Throughout this document the expression "composition" stands for the various mixtures or combinations of components (A) and (B), 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 components (A) and (B) is not essential for working the present invention.

The compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component (A). An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole.

The Mixtures of the present invention may also act as plant grow regulators. Plant growth regulators can, for example, reduce plant height, stimulate seed germination, induce flowering, darken leaf coloring, change the rate of plant growth and modify the timing and efficiency of fruiting. In addition, PGRs may exhibit pronounced growth-regulating properties which can result in an increase in the yield of cultivated plants or harvested crops.

PGRs may also have a growth inhibiting action which is dependent on concentration. The growth of both monocots and dicots may be inhibited. Inhibition of the vegetative growth of many cultivated plants permits more plants to be sown in a crop area, so that a higher yield may be obtained per unit of area. Inhibition of the vegetative growth of monocot plants, e.g. cultivated plants such as cereals, is sometimes desirable and advantageous. Such a growth inhibition is of economic interest. The use of PGRs for inhibiting the growth in height of cereals is also important, as shortening the stalks diminishes or completely eliminates the danger of lodging before harvesting.

Additionally, PGRs are able to bring about a strengthening of the stalks in crops of cereals and this too counteracts lodging.

Furthermore, the present invention also provides compositions comprising the isoxazole derivatives of the present invention that improve plants, a process which is commonly and hereinafter referred to as "plant health". For example, advantageous properties that may be mentioned are improved crop

characteristics including: emergence, crop yield, protein content, increased vigour, faster/delayed maturation, increased speed of seed emergence, improved nutrient utilization efficiency, improved nitrogen utilization efficiency, improved water use efficiency, improved oil content and /or quality, improved digestibility, faster/more even ripening, improved flavor, improved starch content, more developed root system (improved root growth), improved stress tolerance (e.g. against drought, heat, salt, light, UV, water, cold), reduced ethylene (reduced production and/or inhibition of reception), tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input needed (such as fertilizers or water), less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, enhanced plant vigor, increased plant stand and early and better germination.

Advantageous properties obtained, especially from treated seeds, include, for example, improved germination and field establishment, better vigor and more homogeneous field establishment.

Advantageous properties obtained, especially from foliar and/or in-furrow application include, for example, improved plant growth and plant development, better growth, more tillers, greener leafes, largers leaves, more biomass, better roots, improved stress tolerance of the plants, more grain yield, more biomass harvested, improved quality of the harvest (content of fatty acids, metabolites, oil etc), more marketable products (e.g. improved size), improved process (e.g. longer shelf-life, better extraction of compounds), improved quality of seeds (for being seeded in the following seasons for seed production); or any other advantages familiar to a person skilled in the art.

It is therefore an object of the present invention to provide compositions and methods suitable for addressing the opportunities outlined above. The present invention provides plant-protecting active ingredients that are isoxazole compounds of formula (I) according to the invention, in particular the individual isoxazole compounds described in the description as being preferred, and mixtures with increased efficacy and to a method of improving the health of plants by applying said compounds and mixtures to the plants or the locus thereof.

The action of the compounds of formula (I) is separate to any fungicidal action. The isoxazole compounds of formula (I) according to the invention, in particular the individual isoxazole compounds described in the above description as being preferred compounds exhibit plant health properties.

The present invention also concerns compositions comprising or consisting essentially of an active compound as described herein in combination with a suitable carrier (e.g., an agricultural carrier). The foregoing and other objects and aspects of the present invention are explained in greater detail below. Unless otherwise stated, the substituents are unsubstituted or substituted, preferably the substituents are unsubstituted or substituted by the substituents given below. Unless otherwise stated, the following terms used in the specification and claims have the meanings given below: "Alkyl" as used herein refers to a saturated hydrocarbon radical which may be straight-chain or branched-chain or cyclic (cycloalkyl) and contains from 1 to 24 carbon atoms. This definition applies both when the term is used alone and when it is used as part of a compound term, such as haloalkyl and similar terms. Preferred straight chain and branched alkyl groups may contain 1 to 8 carbon atoms, more preferably 1 to 4 carbons, even more preferably, 1 to 4 carbon atoms. Representative alkyl groups include, for example, methyl, ethyl, isopropyl, n- propyl, n-butyl, t-butyl, t-amyl, and 2,5-dimethylhexyl. Preferred cycloalkyl groups may contain 3 to 12 carbon atoms, more preferably 4 to 10 carbons, even more preferably, 5 to 8 carbon atoms and most preferably 5 or 6 carbon atoms. Preferred cycloalkyl groups include, for example, cyclobutyl, cyclopropyl, cyclopentyl and cyclohexyl.

"Alkenyl" as used herein, refers to a straight or branched chain hydrocarbon containing from 2 to 24 carbons, more preferably 2 to 8 carbons, yet more preferably, 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and containing at least one carbon-carbon double bond. Representative alkenyl groups include, for example, ethenyl, 2-propenyl, 2 -methyl -2- propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-l-heptenyl and 3-decenyl.

"Alkynyl" as used herein, refers to a straight or branched chain hydrocarbon group containing from 2 to 24 carbons, more preferably 2 to 8 carbons, yet more preferably, 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and containing at least one carbon-carbon triple bond. Representative alkynyl groups include, for example, acetylenyl, 1-propynyl, 2- propynyl, 3-butynyl, 2-pentynyl and 1-butynyl.

Representative alkoxy groups include, for example, methoxy, ethoxy and t-butoxy.

Representative alkylthio groups include, for example, methylthio, ethylthio, t-butylthio and hexylthio.

"Heterocyclyl", as used herein refers to a saturated or partially unsaturated cyclic hydrocarbon containing from 3 to 10 ring-atoms up to 4 of which may be hetero-atoms such as nitrogen, oxygen and sulfur. Examples of heterocyclyl groups are oxiranyl, azetidinyl,

tetrahydrofuranyl, thiolanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, sulfolanyl, dioxolanyl, dihydropyranyl, tetrahydropyranyl, piperidinyl, pyrazolinyl, pyrazolidinyl, dioxanyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, azepinyl, oxazepinyl, thiazepinyl, thiazolinyl and diazapanyl.

"Aryl" refers to an aromatic substituent which may be a single ring or multiple rings which are fused together, linked covalently or linked to a common group such as an ethylene or methylene moiety. The aromatic rings may each contain heteroatoms and hence aryl encompasses heteroaryl as used herein. Aryl moieties may be optionally substituted with 1 to 4 substituents independently selected from halogen, nitro, alkylcarboxyl, alkoxy and phenoxy. Representative examples of aryl include phenyl azulenyl, indanyl, indenyl, naphthyl, tetrahydronaphthyl, biphenyl, diphenylmethyl, 2,2-diphenyl-l -ethyl, thienyl, pyridyl and quinoxalyl. Most preferably, aryl is phenyl.

"Heteroaryl" means a cyclic, aromatic hydrocarbon containing 3 to 10 ring-atoms including 1 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur. Preferred heteroaryl groups are five and six membered rings and contain from one to three heteroatoms independently selected from nitrogen, oxygen and sulphur. Heteroaryl moieties may be optionally substituted with 1 to 4 substituents independently selected from halogen, nitro, alkylcarboxyl, alkoxy and phenoxy. Examples of heteroaryl groups include furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyranyl, pyridazinyl, tetrazolyl, triazinyl.

In addition, the term heteroaryl includes fused heteroaryl groups, for example benzimidazolyl, benzoxazolyl, imidazopyridinyl, benzoxazinyl, benzothiazinyl, oxazolopyridinyl,

benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, benzothiazolyl, phthalimido,

benzofuranyl, benzodiazepinyl, indolyl, isoindolyl, isobenzofuranyl, chromenyl, xanthenyl, indolizinyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, phthalazinyl, naphthyridinyl and benzo[b]thienyl.

Acyl includes any readily hydrolysable acyl groups, and comprises, for example, C(0)R⁵, C(0)OR⁵, C(0)NHR⁵ and C(0)NR⁵R⁶, wherein R⁵ and R⁶ are each independently selected from alkyl, alkenyl, akynyl, heterocyclyl, aryl and heteroaryl. Acyl groups may be optionally substituted with one or more, for example 1, 2, 3 or 4, halo or OR⁵ groups. Preferred acyl groups are acetyl, benzoyl and phenylacetyl. "Halo" or "halogen" means fluoro, chloro, bromo and iodo and is preferably fluoro or chloro.

"Haloalkyl" includes monohaloalkyl, polyhaloalkyl and perhaloalkyl, for example, chloromethyl, 2-bromoethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, chlorodifluoromethyl, trichloromethyl, trifluoromethyl, pentafluoroethyl and 2-chloro-3-fluoropentyl.

"Organic base" as used herein includes, for example, triethylamine, triisobutylamine, triiooctylamine, triisodecylamine, diethanolamine, triethanolamine, pyridine, morpholine, and mixtures thereof. A preferred category of organic base is organic amines. "Inorganic base" as used herein includes, for example, sodium carbonate, sodium

bicarbonate, potassium carbonate, and mixtures thereof.

"Inert solvent" as used herein includes any suitable inert solvent including, for example, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, toluene, dimethyl ether, methyl t-butyl ether and dioxane, methylene chloride, chloroform, 1 ,2-dichloroethane, and mixtures thereof.

"Protic solvent" as used herein may be any suitable protic solvent including, for example, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, methyl Cellosolve, ethyl Cellosolve, cyclohexanol, glycerol, diethylene glycol, triethanolamine, polyethylene glycol, sec-butanol, n-propanol and tert-butanol.

"Optionally substituted" means substituted by one or more substituents, in particular, one, two, three or four substituents. In the case where groups may be selected from a number of alternative groups, the selected groups may be the same or different.

"Agriculturally acceptable salt" means a salt the cation of which is known and accepted in the art for the formation of salts for agricultural or horticultural use. Preferably the salts are water-soluble.

The compounds of formula (I) may exist in different geometric or optical isomeric forms or in different tautomeric forms. One or more centres of chirality may be present, in which case compounds of the formula (I) may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds present in the molecule, such as C=C or C=N bonds, in which case compounds of formula (I) may exist as single isomers of mixtures of isomers. Centres of tautomerisation may be present. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.

Suitable salts of the compounds of formula (I), include acid addition salts such as those with an inorganic acid such as hydrochloric, hydrobromic, sulphuric, nitric or phosphoric acid, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulphonic acid such as methane, benzene or toluene sulphonic acid. Other examples of organic carboxylic acids include haloacids such as trifluoroacetic acid.

N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen containing heteroaromatic compounds. They are described in many books for example in "Heterocyclic N-oxides" by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton, Florida, 1991. In another aspect, the present invention provides a method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a compound of formula (I) as defined herein.

The preferred embodiments of the invention as defined below apply equally to each aspect and preferred aspects thereof of the invention as defined herein.

In a preferred embodiment, Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, nitro; or heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano or nitro.

Preferably, Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen.

More preferably, Ri is phenyl optionally substituted with halogen, Ci-C₆-alkyl, C₂-C₆- alkenyl, C₂-C₆-alkynyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, Ci-C₆-alkylthio, Ci-C₆-haloalkoxy, phenoxy, methoxypropargyl, cyano, or nitro; or furanyl, thienyl, pyridyl, or benzothienyl, each optionally substituted with halogen.

Most preferably, Ri is 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 4-trifluoro-methylphenyl, 4-trifluoromethoxyphenyl, 2-fluoro-4-chlorophenyl or 2-thienyl.

In a preferred embodiment, R₂ is heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano or nitro. Preferably, R₂ is pyridyl, pyrimidinyl or isoquinolyl, each optionally substituted with halogen, Ci-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, Ci-C₆- alkylthio, Ci-C₆-haloalkoxy, cyano, or nitro.

More preferably, R₂ is 2-, 3- or 4-pyridyl or 5-pyrimidinyl, each optionally substituted with halogen, Ci-C₆-haloalkyl, Ci-C₆-alkoxy or Ci-C₆-alkylthio.

Most preferably, R₂ is 3 -pyridyl, 4-pyridyl, or 5-pyrimidinyl, each optionally substituted with methyl, chloro, fluoro, methoxy, thiomethoxy or trifluoromethyl.

Preferably, R₃ is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano or nitro; heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano or nitro; or alkylsilyl.

More preferably, R₃ is phenyl optionally substituted with halogen, Ci-C₆-alkyl, Ci-C₆- haloalkyl, Ci-C₆-alkoxy, Ci-C₆-alkylthio, methoxypropargyl, cyano or nitro; furanyl, thienyl or pyridyl, each optionally substituted with halogen, Ci-C₆-alkyl or Ci-C₆-alkoxy; or Ci-C₆- alkylsilyl.

More preferably, R₃ is phenyl, 3-chlorophenyl, 4-chlorophenyl, 4-fluorophenyl,

3,5-difluorophenyl, 4-methylphenyl, 2,4-difluorophenyl, 2-thienyl, 5-chloro-2-thienyl, 5- methyl-2-thienyl, 3-thienyl, t-butyl or trimethylsilyl.

In a preferred embodiment, R₄ is H, acetyl.

Most preferably, R₄ is H.

In one preferred aspect of the present invention: Ri is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, phenoxy, alkoxyalkynyl, cyano, or nitro; or heteroaryl optionally substituted with halogen;

R3 is aryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, alkoxyalkynyl, cyano, nitro; heteroaryl optionally substituted with halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, cyano, or nitro; or alkylsilyl; and

R₄ is H or acetyl.

Most preferably, R₄ is H.

In a more preferred aspect of the present invention;

Ri is phenyl optionally substituted with halogen, Ci-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, Ci-C₆-alkylthio, Ci-C₆-haloalkoxy, phenoxy,

methoxypropargyl, cyano, or nitro; or furanyl, thienyl, pyridyl, or benzothienyl, each optionally substituted with halogen;

R₂ is pyridyl or pyrimidinyl, each optionally substituted with halogen, Ci-C₆-alkyl,

C₂-C₆-alkenyl, C₂-C₆-alkynyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, Ci-C₆-alkylthio, Ci-C₆- haloalkoxy, cyano, or nitro;

R₃ is Ci-C₆-alkyl; Ci-C₆-alkoxy; phenyl optionally substituted with halogen, Ci-C₆-alkyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, Ci-C₆-alkylthio, methoxypropargyl, cyano or nitro; furanyl, thienyl or pyridyl, each optionally substituted with halogen, Ci-C₆-alkyl or Ci-C₆-alkoxy; or Ci-C₆-alkylsilyl; and P IS H.

In the more preferred embodiment

Ri is phenyl, which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from halogen, haloalkyl, haloalkoxy and cyano;

P 2 is pyridyl;

wherein R³ is phenyl, which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from halogen, haloalkyl, haloalkoxy and cyano, and;

R₄ is H

In the even more preferred embodiment

Ri is phenyl, which is substituted with 1 , 2 or 3 substituents selected from F or CI;

R₂ is pyridyl;

wherein R³ is phenyl, which is unsubstituted or substituted with 1 , 2 or 3 substituents selected from from F or CI, and;

R₄ is H

Preferred compounds of formula (I) for use according to the methods of the present invention are selected from:

3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]- isoxazole (compound 144);

3-(4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole (compound 145);

3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-isoxazole (compound 146);

3-(2,4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole

(compound 147); 3-(2-nuoro-4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole (compound 148);

3-(4-chlorophenyl)-5-(2-methoxypyridine)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole (compound 149);

3-(4-chlorophenyl)-5-(4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole

(compound 150);

3-(4-chlorophenyl)-5-(2,4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole

(compound 151);

3-(2,4-fluoro-4-chlorophenyl)-5-(2-chloro-4-fluorophenyl)-4-[(3pyridyl)hydroxymethyl]- isoxazole (compound 152); and

(5)-3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole (compound 154);

and salts thereof. In a preferred embodiment the compound of formula (I) is 3-(4-Chloro-2-fluoro-phenyl)-5 - (2,4-difluoro-phenyl)-isoxazol-4-yl]-pyridin-3-yl-methanol.

In a preferred embodiment the compound of formula (I) is (¾)-[3-(4-Chloro-2-fluoro-phenyl)- 5 -(2,4-difluoro-phenyl)-isoxazol-4-yl]-pyridin-3-yl-methanol and In a further aspect, the present invention provides a method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a compound of formula (I) as defined herein, wherein said method comprises one or more applications of one or more compounds as defined herein alone or in conjunction with one or more customary plant protection formulating auxiliaries.

In a further aspect, the present invention provides a method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a compound of formula (I) as defined herein, wherein two or more applications are carried out in sequence, and wherein the two or more applications have the same or different concentration or combinations of compounds as defined herein or both.

In a preferred embodiment of the invention, the crops of useful plants are selected from cereals, rice, beets, leguminous plants, oil plants, cucumber plants, fibre plants, vegetables, plantation crops, ornamentals, vines, bushberries, caneberries, cranberries, peppermint, rhubarb, spearmint, sugar cane and turf grasses.

In a preferred embodiment of the invention, the plant growth regulating effect is an inhibition or a retardation of the plant growth.

In a further aspect, the present invention provides an agricultural composition comprising one or more compounds of formula (I) as defined herein and one or more customary plant protection auxiliaries.

The compound of formula (I) exists as racemate comprising (R) and (S)-enantiomers. The (S)-enantiomer has been found to have significantly greater fungicidal activity compared to the (R)-enantiomer

In a further aspect, the present invention is directed to the (5)-enantiomers of the compounds of formula (I), designated (S)-(I)

wherein R_{l s} R₂, R₃ and R₄ are as defined herein; and salts thereof. The stereo center described in the expression " 5)-enantiomer of the compound of formula

(I) " is the carbon atom in the methanol moiety which is marked with a star (*) in the formula (S)-(I). The present invention provides the compound of formula (S)-(I) as a single enantiomer having an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%. Preferred compounds of formula (5)-(I) include the (S)-enantiomers of compounds 1 to 153 of Table 1.

In a further aspect, the present invention also relates to an agricultural composition comprising a compound of formula (S)-(I) a defined herein, or an agrochemically acceptable salt thereof, and an agrochemically acceptable diluent or carrier.

In a further aspect, the present invention also relates to an isoxazole compounds of formula

(II) , derived from compound 146, exhibit unexpected fungicidal activity and are therefore suitable for use in agriculture as crop protection agents to combat or prevent fungal infestations, or to control other pests such as weeds, insects, or acarids that are harmful to crops.

Accordingly, in an additional aspect, the present invention provides a compound of formula (II)

or an agrochemically acceptable salt thereof.

In a preferred embodiment, the present invention provides the compound formula (iS)-(II)

wherein R⁴ is H or acyl;

or an agrochemically acceptable salt thereof.

Most preferably, the present invention provides the compound (5)-[3-(4-chloro-2- fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]pyridin-3-yl-methanol (compound (S)- (146)).

Preferably, the compounds of formula (S)-(II), and preferably (5)-(146), are provided as single enantiomers having an enantiomeric excess (e.e.) of at least 40%, for example, at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, yet more preferably at least 98% and most preferably at least 99%. Accordingly there is provided a composition comprising a compound of formula (5)-(II), and preferably (5)-(146), and an agriculturally acceptable diluent or carrier. The compound of formula (S)-(II), and preferably (S)-(146), and compositions thereof are suitable for controlling and preventing plant pathogenic microorganisms, especially fungal organisms, including those disclosd in International Patent Application WO 2006/031631.

In particular, the present invention provides a method for controlling or preventing infestation of cultivated plants by pathogenic microorganisms, comprising applying a compound of formula (S)-(II), and preferably (5)-(146), to said plants, parts thereof or the locus thereof in an amount effective to control said microorganisms. Preferably, the organism is a fungal organism and more preferably, said fungal organism is selected from the group consisting of Septoria tritici, Stagonospora nodorum, Phytophthora infestans, Botrytis cinerea, Sclerotinia homoeocarpa and Puccinia recondita.

In a further embodiment the fungal organism is Botryotinia fuckeliana {Botrytis cinerea) (Gray mould). In a further embodiment the fungal organism is Glomerella lagenarium

(Colletotrichum lagenarium) (Anthracnose). In a further embodiment the fungal organism is F urium culmorum (Head blight). In a further embodiment the fungal organism is

Gaeum an n omyces graminis (Take-all of cereals). In a further embodiment the fungal organism is Mycosphaerella arachidis (Cercospora arachidicola) (early leaf spot). In a further embodiment the fungal organism is Mycosphaerella graminicola (Septoria tritici) (Septoria blotch) Furthermore, the compositions according to the invention are suitable for controlling the following plant diseases: Alternaria species on vegetables, oilseed rape, sugar beet and fruit and rice, such as, for example, A. solani or A. alternata on potatoes and tomatoes;

Aphanomyces species on sugar beet and vegetables; Ascochyta species on cereals and vegetables; Bipolaris and Drechslera species on corn, cereals, rice and lawns, such as, for example, D. maydis on corn; Blumeria graminis (powdery mildew) on cereals; Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and grapevines; Bremia lactucae on lettuce; - Cercospora species on corn, soybeans, rice and sugar beet; Cochliobolus species on corn, cereals, rice, such as, for example, Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice; Colletotricum species on soybeans and cotton; Drechslera species, Pyrenophora species on corn, cereals, rice and lawns, such as, for example, D. teres on barley or D. tritici-repentis on wheat; Esca on grapevines, caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum and Formitipora punctata (syn. Phellinus punctatus); Exserohilum species on corn; Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumbers; - Fusarium and Verticillium species on various plants, such as, for example, F. graminearum or F. culmorum on cereals or F. oxysporum on a multitude of plants, such as, for example, tomatoes;

Gaeumanomyces graminis on cereals; Gibberella species on cereals and rice (for example Gibberella fujikuroi on rice); - Grainstaining complex on rice; Helminthosporium species on corn and rice; Michrodochium nivale on cereals; Mycosphaerella species on cereals, bananas and groundnuts, such as, for example, M. graminicola on wheat or M.fijiensis on bananas; - Peronospora species on cabbage and bulbous plants, such as, for example, P. brassicae on cabbage or P. destructor on onions; Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans; Phomopsis species on soybeans and sunflowers; Phytophthora infestans on potatoes and tomatoes; - Phytophthora species on various plants, such as, for example, P. capsici on bell pepper; Plasmopara viticola on grapevines; Podosphaera leucotricha on apples;

Pseudocercosporella herpotrichoides on cereals; - Pseudoperonospora on various plants, such as, for example, P. cubensis on cucumber or P. humili on hops; Puccinia species on various plants, such as, for example, P. triticina, P. strifor- mins, P. hordei or P. graminis on cereals or P. asparagi on asparagus; Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae,

S.attenuatum, Entyloma oryzae on rice; - Pyricularia grisea on lawns and cereals; Pythium spp. on lawns, rice, corn, cotton, oilseed rape, sunflowers, sugar beet, vegetables and other plants, such as, for example, P. ultiumum on various plants, P. aphanidermatum on lawns; Rhizoctonia species on cotton, rice, potatoes, lawns, corn, oilseed rape, pota- toes, sugar beet, vegetables and on various plants, such as, for example, R. so- lani on beet and various plants; Rhynchosporium secalis on barley, rye and triticale; Sclerotinia species on oilseed rape and sunflowers; Septoria tritici and Stagonospora nodorum on wheat; - Erysiphe (syn. Uncinula) necator on grapevines; Setospaeria species on com and lawns; Sphacelotheca reilinia on com; Thievaliopsis species on soybeans and cotton; Tilletia species on cereals; - Ustilago species on cereals, corn and sugar cane, such as, for example, U. may- dis on corn; Venturia species (scab) on apples and pears, such as, for example, V. inaequalis on apples. The inventive compositions are furthermore suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In the protection of wood, particular attention is paid to the following harmful fungi: Ascomycetes, such as Ophiostoma spp., Cerato- cystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Peni- cillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes, such as Mucor spp., additionally in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae.

The present invention also encompasses compositions, combinations and plants as described herein and in International Patent Application WO2006/031631. In a another aspect, the present invention is directed to novel compounds of formula (I) selected from:

(compound 147);

3-(2-fluoro-4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole (compound 148);

3-(4-chlorophenyl)-5-(4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole

(compound 150); 3-(4-chlorophenyl)-5-(2,4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole

(compound 151);

(5)-3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole (compound 153);

and salts thereof.

"Plant propagation material" means the generative parts of a plant including seeds of all kinds (fruit, tubers, bulbs, grains etc), roots, rhizomes, cuttings, cut shoots and the like. Plant propagation material may also include plants and young plants which are to be transplanted after germination or after emergence from the soil.

"Locus" means the fields on which the plants to be treated are growing, or where the seeds of cultivated plants are sown, or the place where the seed will be placed into the soil.

The crops of useful plants to be protected typically comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, maize (including field corn, pop corn and sweet corn), rice, sorghum and related crops); beet (sugar beet and fodder beet); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, sunflowers); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); vegetables (spinach, lettuce, asparagus, cabbages, carrots, eggplants, onions, pepper, tomatoes, potatoes, paprika, okra); plantation crops (bananas, fruit trees, rubber trees, tree nurseries), ornamentals

(flowers, shrubs, broad-leaved trees and evergreens, such as conifers); as well as other plants such as vines, bushberries (such as blueberries), caneberries, cranberries, peppermint, rhubarb, spearmint, sugar cane and turf grasses including, for example, cool-season turf grasses (for example, bluegrasses {Poa L.), such as Kentucky bluegrass {Poa pratensis L.), rough bluegrass {Poa trivialis L.), Canada bluegrass {Poa compressa L.) and annual bluegrass {Poa annua L.); bentgrasses {Agrostis L.), such as creeping bentgrass {Agrostis palustris Huds.), colonial bentgrass {Agrostis tenius Sibth.), velvet bentgrass {Agrostis canina L.) and redtop (Agrostis alba L.); fescues (Festuca L.), such as tall fescue (Festuca arundinacea Schreb.), meadow fescue {Festuca elatior L.) and fine fescues such as creeping red fescue {Festuca rubra L.), chewings fescue {Festuca rubra var. commutata Gaud.), sheep fescue {Festuca ovina L.) and hard fescue {Festuca longifolia); and ryegrasses {Lolium L.), such as perennial ryegrass {Lolium perenne L.) and annual (Italian) ryegrass {Lolium multiflorum Lam.)) and warm-season turf grasses (for example, Bermudagrasses {Cynodon L. C. Rich), including hybrid and common Bermudagrass; Zoysiagrasses {Zoysia Willd.), St.

Augustinegrass {Stenotaphrum secundatum (Walt.) Kuntze); and centipedegrass {Eremochloa ophiuroides (Munro.) Hack.)).

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 or PPO (protoporphyrinogen-oxidase) 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® , Herculex I® 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.

Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CryIIIB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CryIIIB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (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 (Btl 1 corn borer (CB) trait), Agrisure® RW (corn rootworm 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" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. 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 compounds of formula I can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.

The term "plant" or "useful plants" as used herein includes seedlings, bushes and trees. The term "crops" is to be understood as including also crop 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.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vipl, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect- specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome- inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by δ-endotoxins, for example CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced

recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl- type deoxyribonucleic acids and their preparation are known, for example, from WO

95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

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 CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a CrylFa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cryl Ac toxin); Bollgard I® (cotton variety that expresses a Cryl Ac toxin); Bollgard II® (cotton variety that expresses a Cryl Ac and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a Cryl Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate -tolerant trait), Agrisure® CB Advantage (Btl 1 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bill Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer {Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cryl Ab toxin. Btl 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Btl76 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur,

France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer {Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Btl 76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects. 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-l 160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry IF for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.

7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-l 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cryl Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.

Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate. Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

The agrochemical compositions of the present invention will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula (I), 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.

Suitably, the agrochemical compositions of the present invention are applied prior to disease development. Rates and frequency of use of the formulations are those conventionally used in the art and factors such as the developmental stage of the plant and on the location, timing and application method. Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from lOg to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient rates of application are from lOmg to lg of active substance per kg of seeds.

In practice, as indicated above, the agrochemical compositions comprising a compound of formula (I) are applied as a formulation containing the various adjuvants and carriers known to or used in the industry. They may therefore be formulated as granules, wettable or soluble powders, emulsifiable concentrates, coatable pastes, dusts, flowables, solutions, suspensions or emulsions, or as controlled release forms such as microcapsules. These formulations are described in more detail below and may contain from 0.5% to 95% or more by weight of the active ingredient. The optimum amount will depend on formulation, application equipment and nature of the plant to be treated.

Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti- foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent. Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins. Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.

Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers,

polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.

Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.

Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Ν,Ν-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1- trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n- hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o- xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N-methyl-2 -pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1% to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccmate salts, such as sodium di(2-ethylhexyl) sulfosuccmate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride;

polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.

Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.

In addition, further, other biocidally active ingredients or compositions may be combined with the compound of formula (I) and used in the methods of the invention and applied

simultaneously or sequentially with the compound of formula (I). When applied

simultaneously, these further active ingredients may be formulated together with the compound of formula (I) or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.

Accordingly, in one aspect, the present invention provides a composition comprising a compound of formula (I), which is selected from compounds 1 to 156 of Table 1 , and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator. Additionally, the present invention provides for the use of a composition in the methods of the present invention, said composition comprising a compound of formula (I), which is selected from compounds 1 to 156 of Table 1 , and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.

In a further aspect, the present invention provides a composition comprising a compound of formula (I), which is the (5)-enantiomer of formula (5)-(Ι) and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.

Additionally, the present invention provides for the use of a composition in the methods of the present invention, said composition comprising a compound of formula (I), which is the (S)- enantiomer of formula (5)-(I), and (i) a further fungicide, (ii) a herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide and/or (vii) a plant growth regulator.

In addition, the compounds of the invention may also be applied with one or more systemically acquired resistance inducers ("SAR" inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

The present invention relates additionally to mixtures comprising at least a compound of formula I and at least a further, other biocidally active ingredient and optionally further ingredients. The further, other biocidally active ingredient are known for example from "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition (New edition (02 Nov 2003)); Editor: C. D. S. Tomlin; The British Crop Protection Council, ISBN- 10: 1901396134; ISBN-13 : 978-1901396133] or its electronic version "e-Pesticide Manual V4.2" or from the website http://www.alanwood.net/pesticides/ or preferably one of the further pesticides listed below. The following mixtures of the compounds of TX with a further active ingredient (B) are preferred (the abbreviation "TX" means a compound encompassed by the compounds of formula I, or preferably the term "TX" refers to a single compound selected from the Table I. In a preferred embodiment "TX" has the meaning of [3-(4-chloro-2-fluorophenyl)-5-(2,4- difluorophenyl)isoxazol-4-yl]pyridin-3-yl-methanol. In a further preferred embodiment "TX" has the meaning of (5)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4- yl]pyridin-3-yl -methanol (Table 1, compound 153: (S)- 146)). an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628) + TX,

an acaricide selected from the group of substances consisting of l,l-bis(4-chlorophenyl)-2- ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenyl benzenesulfonate

(IUP AC/Chemical Abstracts name) (1059) + TX, 2-fhioro-N-methyl-N- 1 -naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981 ) + TX, abamectin (1) + TX, acequinocyl (3) + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, alpha-cypermethrin (202) + TX, amidithion (870) + TX, amidofiumet [CCN] + TX, amidothioate (872) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, aramite (881) + TX, arsenous oxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azocyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alternative name) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, bifenthrin (76) + TX, binapacryl (907) + TX, brofenvalerate (alternative name) + TX, bromocyclen (918) + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butocarboxim (103) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, calcium polysulfide (IUPAC name) ( 111 ) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl (115) + TX, carbofuran (118) + TX, carbophenothion (947) + TX, CGA 50'439 (development code) (125) + TX, chinomethionat (126) + TX, chlorbenside (959) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenethol (968) + TX, chlorfenson (970) + TX, chlorfensulphide (971) + TX, chlorfenvinphos ( 131 ) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentezine (158) + TX, closantel (alternative name) [CCN] + TX, coumaphos (174) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos (1010) + TX, cufraneb (1013) + TX, cyanthoate (1020) + TX, cyflumetofen (CAS Reg. No.: 400882-07-7) + TX, cyhalothrin (196) + TX, cyhexatin (199) + TX, cypermethrin (201) + TX, DCPM (1032) + TX, DDT (219) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton-0 (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton- S -methyl (224) + TX, demeton-S- methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diazinon (227) + TX, dichlofluanid (230) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicofol (242) + TX, dicrotophos (243) + TX, dienochlor (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dinactin (alternative name) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinocton (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathion (1102) + TX, diphenyl sulfone (IUPAC name) (1103) + TX, disulfiram (alternative name) [CCN] + TX, disulfoton (278) + TX, DNOC (282) + TX, dofenapyn (1113) + TX, doramectin

(alternative name) [CCN] + TX, endosulfan (294) + TX, endothion (1121) + TX, EPN (297) + TX, eprinomectin (alternative name) [CCN] + TX, ethion (309) + TX, ethoate- methyl (1134) + TX, etoxazole (320) + TX, etrimfos (1142) + TX, fenazaflor (1147) + TX, fenazaquin (328) + TX, fenbutatin oxide (330) + TX, fenothiocarb (337) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fenpyroximate (345) + TX, fenson (1157) + TX, fentrifanil (1161) + TX, fenvalerate (349) + TX, fipronil (354) + TX, fluacrypyrim (360) + TX, fluazuron (1166) + TX, flubenzimine (1167) + TX,

flucycloxuron (366) + TX, flucythrinate (367) + TX, fluenetil (1169) + TX, flufenoxuron (370) + TX, flumethrin (372) + TX, fluorbenside (1174) + TX, fluvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, gamma- HCH (430) + TX, glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC/Chemical Abstracts name) (1216) + TX, hexythiazox (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos

(alternative name) (473) + TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (430) + TX, lufenuron (490) + TX, malathion (492) + TX, malonoben (1254) + TX, mecarbam (502) + TX, mephosfolan (1261) + TX, mesulfen (alternative name) [CCN] + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methidathion (529) + TX, methiocarb (530) + TX, methomyl (531) + TX, methyl bromide (537) + TX, metolcarb (550) + TX, mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naled (567) + TX, NC-184 (compound code) + TX, NC-512 (compound code) + TX, nifiuridide (1309) + TX, nikkomycins (alternative name) [CCN] + TX, nitrilacarb (1313) + TX, nitrilacarb 1 : 1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250

(compound code) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, parathion (615) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, phenkapton (1330) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, pirimiphos-methyl (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alternative name) (653) + TX, proclonol (1350) + TX, profenofos (662) + TX, promacyl (1354) + TX, propargite (671) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothoate (1362) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, quinalphos (711) + TX, quintiofos ( 1381 ) + TX, R- 1492 (development code) ( 1382) + TX, RA- 17 (development code) (1383) + TX, rotenone (722) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, sophamide (1402) + TX, spirodiclofen (738) + TX, spiromesifen (739) + TX, SSI-121 (development code) (1404) + TX, sulfiram (alternative name) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphur (754) + TX, SZI-121 (development code) (757) + TX, tau-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbam (alternative name) + TX, tetrachlorvinphos (777) + TX, tetradifon (786) + TX, tetranactin (alternative name) (653) + TX, tetrasul (1425) + TX, thiafenox (alternative name) + TX, thiocarboxime (1431) + TX, thiofanox (800) + TX, thiometon (801) + TX, thioquinox (1436) + TX, thuringiensin (alternative name) [CCN] + TX, triamiphos ( 1441 ) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alternative name) (653) + TX, vamidothion (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX, an algicide selected from the group of substances consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,

an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,

an avicide selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4 -amine (IUPAC name) (23) and strychnine (745) + TX, a bactericide selected from the group of substances consisting of 1 -hydroxy- lH-pyridine-2- thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargaphen (alternative name) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX,

a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis

(alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternative name) (300) + TX, Helicoverpa zea NPV (alternative name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433) + TX, Hippodamia convergens (alternative name) (442) + TX, Leptomastix dactylopii (alternative name) (488) + TX, Macrolophus caliginosus (alternative name) (491) + TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternative name) (575) + TX, Orius spp. (alternative name) (596) + TX, Paecilomyces fumosoroseus (alternative name) (613) + TX, Phytoseiulus persimilis (alternative name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternative name) (742) + TX, Steinernema carpocapsae (alternative name) (742) + TX, Steinernema feltiae (alternative name) (742) + TX, Steinernema glaseri (alternative name) (742) + TX, Steinernema riobrave (alternative name) (742) + TX, Steinernema riobravis (alternative name) (742) + TX, Steinernema scapterisci (alternative name) (742) + TX, Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and Verticillium lecanii (alternative name) (848) + TX,

a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX,

a chemosterilant selected from the group of substances consisting of apholate [CCN] + TX, bisazir (alternative name) [CCN] + TX, busulfan (alternative name) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alternative name) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholate [CCN] + TX, morzid [CCN] + TX, penfluron (alternative name) [CCN] + TX, tepa [CCN] + TX, thiohempa (alternative name) [CCN] + TX, thiotepa (alternative name) [CCN] + TX, tretamine (alternative name) [CCN] and uredepa (alternative name) [CCN] + TX,

an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-l-yl acetate with (E)-dec-5-en-l-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-l-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)- tetradeca-4,10-dien-l-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-l-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-l 1-enal (IUPAC name) (436) + TX, (Z)-hexadec- 1 1 -en- 1 -yl acetate (IUPAC name) (437) + TX, (Z)-hexadec- 13 -en- 1 1 -yn- 1 -yl acetate (IUPAC name) (438) + TX, (Z)-icos-13-en-10-one (IUPAC name) (448) + TX, (Z)- tetradec-7-en- 1 -al (IUPAC name) (782) + TX, fZ)-tetradec-9-en- 1 -ol (IUPAC name) (783) + TX, (Z)-tetradec-9-en-l-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-l- yl acetate (IUPAC name) (283) + TX, (9Z, 1 lE)-tetradeca-9, 1 1 -dien- 1 -yl acetate (IUPAC name) (780) + TX, (9Z 12E)-tetradeca-9,12-dien-l-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-l-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol with 4- methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name)

[CCN] + TX, brevicomin (alternative name) [CCN] + TX, codlelure (alternative name) [CCN] + TX, codlemone (alternative name) (167) + TX, cuelure (alternative name) (179) + TX, disparlure (277) + TX, dodec-8-en-l -yl acetate (IUPAC name) (286) + TX, dodec-9- en-l-yl acetate (IUPAC name) (287) + TX, dodeca-8 + TX, 10-dien-l-yl acetate (IUPAC name) (284) + TX, dominicalure (alternative name) [CCN] + TX, ethyl 4-methyloctanoate (IUPAC name) (317) + TX, eugenol (alternative name) [CCN] + TX, frontalin (alternative name) [CCN] + TX, gossyplure (alternative name) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdienol (alternative name) [CCN] + TX, ipsenol (alternative name) [CCN] + TX, japonilure (alternative name) (481) + TX, lineatin (alternative name) [CCN] + TX, litlure (alternative name) [CCN] + TX, looplure (alternative name) [CCN] + TX, medlure [CCN] + TX, megatomoic acid (alternative name) [CCN] + TX, methyl eugenol (alternative name) (540) + TX, muscalure (563) + TX, octadeca-2,13-dien-l-yl acetate (IUPAC name) (588) + TX, octadeca-3,13-dien-l-yl acetate (IUPAC name) (589) + TX, orfralure (alternative name) [CCN] + TX, oryctalure (alternative name) (317) + TX, ostramone (alternative name) [CCN] + TX, siglure [CCN] + TX, sordidin (alternative name) (736) + TX, sulcatol (alternative name) [CCN] + TX, tetradec-1 1-en-l-yl acetate (IUPAC name) (785) + TX, trimedlure (839) + TX, trimedlure A (alternative name) (839) + TX, trimedlure Bi (alternative name) (839) + TX, trimedlure B₂ (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX, an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,

an insecticide selected from the group of substances consisting of 1-dichloro-l-nitroethane (IUPAC/Chemical Abstracts name) (1058) + TX, l,l-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), + TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1- bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-l- (3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2,2-dichlorovinyl 2- ethylsulphinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(l,3-dithiolan-2- yl)phenyl dimethylcarbamate (IUPAC/ Chemical Abstracts name) (1109) + TX, 2-(2- butoxyethoxy)ethyl thiocyanate (IUPAC/Chemical Abstracts name) (935) + TX, 2-(4,5- dimethyl-l,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984) + TX, 2-imidazolidone (IUPAC name) (1225) + TX, 2-isovalerylindan-l,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2- ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-l-chloroprop-l-ene (IUPAC name) (917) + TX, 3- methyl-l-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop- 2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name) (1285) + TX, 5,5-dimethyl-3- oxocyclohex-l-enyl dimethylcarbamate (IUPAC name) (1085) + TX, abamectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, acethion (alternative name) [CCN] + TX, acetoprole [CCN] + TX, acrinathrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, aldrin (864) + TX, allethrin (17) + TX, allosamidin (alternative name) [CCN] + TX, allyxycarb (866) + TX, alpha-cypermethrin (202) + TX, alpha-ecdysone (alternative name) [CCN] + TX, aluminium phosphide (640) + TX, amidithion (870) + TX, amidothioate (872) + TX, aminocarb (873) + TX, amiton (875) + TX, amiton hydrogen oxalate (875) + TX, amitraz (24) + TX, anabasine (877) + TX, athidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alternative name) (41) + TX, azamethiphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azothoate (889) + TX, Bacillus thuringiensis delta endotoxins (alternative name) (52) + TX, barium hexafluorosilicate (alternative name) [CCN] + TX, barium polysulfide

(IUPAC/Chemical Abstracts name) (892) + TX, barthrin [CCN] + TX, Bayer 22/190 (development code) (893) + TX, Bayer 22408 (development code) (894) + TX, bendiocarb (58) + TX, benfuracarb (60) + TX, bensultap (66) + TX, beta-cyfluthrin (194) + TX, beta-cypermethrin (203) + TX, bifenthrin (76) + TX, bioallethrin (78) + TX, bioallethrin S-cyclopentenyl isomer (alternative name) (79) + TX, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, bioresmethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluron (83) + TX, borax (86) + TX, brofenvalerate (alternative name) + TX, bromfenvinfos (914) + TX, bromocyclen (918) + TX, bromo-DDT

(alternative name) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, bufencarb (924) + TX, buprofezin (99) + TX, butacarb (926) + TX, butathiofos (927) + TX, butocarboxim (103) + TX, butonate (932) + TX, butoxycarboxim (104) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, calcium arsenate [CCN] + TX, calcium cyanide (444) + TX, calcium polysulfide (IUPAC name) (111) + TX, camphechlor (941 ) + TX, carbanolate (943) + TX, carbaryl ( 115) + TX, carbofuran (118) + TX, carbon disulfide (IUPAC/Chemical Abstracts name) (945) + TX, carbon

tetrachloride (IUPAC name) (946) + TX, carbophenothion (947) + TX, carbosulfan (119) + TX, cartap (123) + TX, cartap hydrochloride (123) + TX, cevadine (alternative name) (725) + TX, chlorbicyclen (960) + TX, chlordane (128) + TX, chlordecone (963) + TX, chlordimeform (964) + TX, chlordimeform hydrochloride (964) + TX, chlorethoxyfos (129) + TX, chlorfenapyr (130) + TX, chlorfenvinphos (131) + TX, chlorfluazuron (132) + TX, chlormephos (136) + TX, chloroform [CCN] + TX, chloropicrin (141) + TX, chlorphoxim (989) + TX, chlorprazophos (990) + TX, chlorpyrifos (145) + TX, chlorpyrifos-methyl (146) + TX, chlorthiophos (994) + TX, chromafenozide (150) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, cis-resmethrin

(alternative name) + TX, cismethrin (80) + TX, clocythrin (alternative name) + TX, cloethocarb (999) + TX, closantel (alternative name) [CCN] + TX, clothianidin (165) + TX, copper acetoarsenite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, coumithoate (1006) + TX, crotamiton (alternative name) [CCN] + TX, crotoxyphos ( 1010) + TX, crufomate ( 1011 ) + TX, cryolite (alternative name) (177) + TX, CS 708 (development code) (1012) + TX, cyanofenphos (1019) + TX, cyanophos (184) + TX, cyanthoate (1020) + TX, cyclethrin [CCN] + TX, cycloprothrin (188) + TX, cyfluthrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cyphenothrin (206) + TX, cyromazine (209) + TX, cythioate (alternative name) [CCN] + TX, (i-limonene (alternative name) [CCN] + TX, -tetramethrin (alternative name) (788) + TX, DAEP (1031) + TX, dazomet (216) + TX, DDT (219) + TX, decarbofuran (1034) + TX, deltamethrin (223) + TX, demephion (1037) + TX, demephion-0 (1037) + TX, demephion-S (1037) + TX, demeton (1038) + TX, demeton-methyl (224) + TX, demeton- O (1038) + TX, demeton-O-methyl (224) + TX, demeton-S (1038) + TX, demeton-S- methyl (224) + TX, demeton- S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dialifos (1042) + TX, diamidafos (1044) + TX, diazinon (227) + TX, dicapthon (1050) + TX, dichlofenthion (1051) + TX, dichlorvos (236) + TX, dicliphos (alternative name) + TX, dicresyl (alternative name) [CCN] + TX, dicrotophos (243) + TX, dicyclanil (244) + TX, dieldrin (1070) + TX, diethyl 5 -methylpyrazol-3-yl phosphate (IUP AC name) (1076) + TX, diflubenzuron (250) + TX, dilor (alternative name) [CCN] + TX, dimefhithrin [CCN] + TX, dimefox (1081) + TX, dimetan (1085) + TX, dimethoate (262) + TX, dimethrin (1083) + TX, dimethylvinphos (265) + TX, dimetilan (1086) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX, dinoprop (1093) + TX, dinosam (1094) + TX, dinoseb (1095) + TX, dinotefuran (271) + TX, diofenolan (1099) + TX, dioxabenzofos (1100) + TX, dioxacarb (1101) + TX, dioxathion (1102) + TX, disulfoton (278) + TX, dithicrofos (1108) + TX, DNOC (282) + TX, doramectin (alternative name) [CCN] + TX, DSP (1115) + TX, ecdysterone (alternative name) [CCN] + TX, EI 1642 (development code) ( 1118) + TX, emamectin (291 ) + TX, emamectin benzoate (291 ) + TX, EMPC (1120) + TX, empenthrin (292) + TX, endosulfan (294) + TX, endothion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, epofenonane (1124) + TX, eprinomectin (alternative name) [CCN] + TX, esfenvalerate (302) + TX, etaphos

(alternative name) [CCN] + TX, ethiofencarb (308) + TX, ethion (309) + TX, ethiprole (310) + TX, ethoate-methyl ( 1134) + TX, ethoprophos (312) + TX, ethyl formate (IUPAC name) [CCN] + TX, ethyl-DDD (alternative name) (1056) + TX, ethylene dibromide (316) + TX, ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, etofenprox (319) + TX, etrimfos ( 1142) + TX, EXD ( 1143) + TX, famphur (323) + TX, fenamiphos (326) + TX, fenazaflor (1147) + TX, fenchlorphos (1148) + TX, fenethacarb (1149) + TX, fenfiuthrin (1150) + TX, fenitrothion (335) + TX, fenobucarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, fenpirithrin (1155) + TX, fenpropathrin (342) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fenthion (346) + TX, fenthion-ethyl [CCN] + TX, fenvalerate (349) + TX, fipronil (354) + TX, flonicamid (358) + TX, fhibendiamide (CAS. Reg. No.: 272451-65-7) + TX, fhicofuron (1168) + TX, flucycloxuron (366) + TX, fiucythrinate (367) + TX, fluenetil (1169) + TX, f ufenerim [CCN] + TX, flufenoxuron (370) + TX, flufenprox (1171) + TX, fhimethrin (372) + TX, fiuvalinate (1184) + TX, FMC 1137 (development code) (1185) + TX, fonofos ( 1191 ) + TX, formetanate (405) + TX, formetanate hydrochloride (405) + TX, formothion (1192) + TX, formparanate (1193) + TX, fosmethilan (1194) + TX, fospirate ( 1195) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furathiocarb (412) + TX, furethrin ( 1200) + TX, gamma-cyhalothrin ( 197) + TX, gamma-HCH (430) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, GY-81 (development code) (423) + TX, halfenprox (424) + TX, halofenozide (425) + TX, HCH (430) + TX, HEOD (1070) + TX, heptachlor (1211) + TX, heptenophos (432) + TX, heterophos [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydramethylnon (443) + TX, hydrogen cyanide (444) + TX, hydroprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, imiprothrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX, IPSP (1229) + TX, isazofos (1231) + TX, isobenzan (1232) + TX, isocarbophos (alternative name) (473) + TX, isodrin (1235) + TX, isofenphos (1236) + TX, isolane (1237) + TX, isoprocarb (472) + TX, isopropyl O-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473) + TX, isoprothiolane (474) + TX, isothioate (1244) + TX, isoxathion (480) + TX, ivermectin (alternative name) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, juvenile hormone I (alternative name) [CCN] + TX, juvenile hormone II (alternative name) [CCN] + TX, juvenile hormone III (alternative name) [CCN] + TX, kelevan (1249) + TX, kinoprene (484) + TX, lambda- cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepimectin (CCN) + TX, leptophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lufenuron (490) + TX, lythidathion (1253) + TX, m-cumenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, malathion (492) + TX, malonoben (1254) + TX, mazidox (1255) + TX, mecarbam (502) + TX, mecarphon (1258) + TX, menazon (1260) + TX, mephosfolan (1261) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metam (519) + TX, metam- potassium (alternative name) (519) + TX, metam- sodium (519) + TX, methacrifos (1266) + TX, methamidophos (527) + TX, methanesulphonyl fluoride (IUPAC/Chemical Abstracts name) (1268) + TX, methidathion (529) + TX, methiocarb (530) + TX, methocrotophos (1273) + TX, methomyl (531) + TX, methoprene (532) + TX, methoquin-butyl (1276) + TX, methothrin (alternative name) (533) + TX, methoxychlor (534) + TX,

methoxyfenozide (535) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, methylchloroform (alternative name) [CCN] + TX, methylene chloride [CCN] + TX, metofiuthrin [CCN] + TX, metolcarb (550) + TX, metoxadiazone (1288) + TX,

mevinphos (556) + TX, mexacarbate (1290) + TX, milbemectin (557) + TX, milbemycin oxime (alternative name) [CCN] + TX, mipafox (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, morphothion (1300) + TX, moxidectin (alternative name) [CCN] + TX, naftalofos (alternative name) [CCN] + TX, naled (567) + TX, naphthalene (IUPAC/Chemical Abstracts name) (1303) + TX, NC-170 (development code) (1306) + TX, NC- 184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (578) + TX, nifiuridide ( 1309) + TX, nitenpyram (579) + TX, nithiazine ( 1311 ) + TX, nitrilacarb ( 1313) + TX, nitrilacarb 1 : 1 zinc chloride complex ( 1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, novaluron (585) + TX, novifiumuron (586) + TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate (IUPAC name) (1057) + TX, O-diethyl 0-4-methyl-2-oxo-2H- chromen-7-yl phosphorothioate (IUP AC name) ( 1074) + TX, O, O-diethyl <3-6-methyl-2- propylpyrimidin-4-yl phosphorothioate (IUP AC name) ( 1075) + TX, 0, 0, 0 O'-tetrapropyl dithiopyrophosphate (IUP AC name) (1424) + TX, oleic acid (IUP AC name) (593) + TX, omethoate (594) + TX, oxamyl (602) + TX, oxydemeton-methyl (609) + TX, oxydeprofos (1324) + TX, oxydisulfoton (1325) + TX, pp'-DDT (219) + TX, para-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, penfluron (alternative name) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oils (alternative name) (628) + TX, PH 60-38 (development code) (1328) + TX, phenkapton (1330) + TX, phenothrin (630) + TX, phenthoate (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosnichlor (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX, pirimicarb (651) + TX, pirimiphos-ethyl (1345) + TX, pirimiphos-methyl (652) + TX, polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, polychloroterpenes (traditional name) (1347) + TX, potassium arsenite [CCN] + TX, potassium thiocyanate [CCN] + TX, prallethrin (655) + TX, precocene I (alternative name) [CCN] + TX, precocene II (alternative name) [CCN] + TX, precocene III (alternative name) [CCN] + TX, primidophos (1349) + TX, profenofos (662) + TX, profluthrin [CCN] + TX, promacyl (1354) + TX, promecarb (1355) + TX, propaphos (1356) + TX, propetamphos (673) + TX, propoxur (678) + TX, prothidathion (1360) + TX, prothiofos (686) + TX, prothoate (1362) + TX, protrifenbute [CCN] + TX, pymetrozine (688) + TX, pyraclofos (689) + TX, pyrazophos (693) + TX, pyresmethrin (1367) + TX, pyrethrin I (696) + TX, pyrethrin II (696) + TX, pyrethrins (696) + TX, pyridaben (699) + TX, pyridalyl (700) + TX, pyridaphenthion (701) + TX, pyrimidifen (706) + TX, pyrimitate (1370) + TX, pyriproxyfen (708) + TX, quassia (alternative name) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinothion (1380) + TX, quintiofos (1381) + TX, R-1492 (development code) (1382) + TX, rafoxanide (alternative name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525

(development code) (723) + TX, RU 25475 (development code) (1386) + TX, ryania (alternative name) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabadilla (alternative name) (725) + TX, schradan (1389) + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, silafluofen (728) + TX, SN 72129 (development code) (1397) + TX, sodium arsenite

[CCN] + TX, sodium cyanide (444) + TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenoxide (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, sophamide (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX,

spirotetrmat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulphonyl fluoride (756) + TX, sulprofos

(1408) + TX, tar oils (alternative name) (758) + TX, tau-fluvalinate (398) + TX, tazimcarb ( 1412) + TX, TDE ( 1414) + TX, tebufenozide (762) + TX, tebufenpyrad (763) + TX, tebupirimfos (764) + TX, tefiubenzuron (768) + TX, tefluthrin (769) + TX, temephos (770) + TX, TEPP ( 1417) + TX, terallethrin ( 1418) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachloroethane [CCN] + TX, tetrachlorvinphos (777) + TX, tetramethrin (787) + TX, theta-cypermethrin (204) + TX, thiacloprid (791) + TX, thiafenox (alternative name) + TX, thiamethoxam (792) + TX, thicrofos (1428) + TX, thiocarboxime (1431) + TX, thiocyclam (798) + TX, thiocyclam hydrogen oxalate (798) + TX, thiodicarb (799) + TX, thiofanox (800) + TX, thiometon (801) + TX, thionazin (1434) + TX, thiosultap (803) + TX, thiosultap-sodium (803) + TX, thuringiensin

(alternative name) [CCN] + TX, tolfenpyrad (809) + TX, tralomethrin (812) + TX, transfluthrin (813) + TX, transpermethrin (1440) + TX, triamiphos (1441) + TX, triazamate (818) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, trichlorfon (824) + TX, trichlormetaphos-3 (alternative name) [CCN] + TX, trichloronat (1452) + TX, trifenofos (1455) + TX, triflumuron (835) + TX, trimethacarb (840) + TX, triprene (1459) + TX, vamidothion (847) + TX, vaniliprole [CCN] + TX, veratridine (alternative name) (725) + TX, veratrine (alternative name) (725) + TX, XMC (853) + TX, xylylcarb (854) + TX, YI-5302 (compound code) + TX, zeta-cypermethrin (205) + TX, zetamethrin (alternative name) + TX, zinc phosphide (640) + TX, zolaprofos (1469) and ZXI 8901 (development code) (858) + TX, cyantraniliprole [736994-63-19] + TX, chlorantraniliprole [500008-45-7] + TX, cyenopyrafen [560121-52-0] + TX, cyflumetofen [400882-07-7] + TX, pyrifiuquinazon [337458-27-2] + TX, spinetoram [187166-40-1 + 187166-15-0] + TX, spirotetramat [203313-25-1] + TX, sulfoxaflor [946578-00-3] + TX, fiufrprole [704886-18-0] + TX, meperfluthrin [915288-13-0] + TX, tetramethylfluthrin

[84937-88-2] + TX,

a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetoarsenite [CCN] + TX, copper sulfate (172) + TX, fentin (347) + TX, ferric phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-olamine (576) + TX, pentachlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, tazimcarb ( 1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, trifenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX,

a nematicide selected from the group of substances consisting of AKD-3088 (compound code) + TX, l,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045) + TX, 1 ,2-dichloropropane (IUPAC/ Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4- dichlorotetrahydrothiophene 1,1 -dioxide (IUPAC/Chemical Abstracts name) (1065) + TX, 3- (4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-l,3,5- thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxycarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinins (alternative name) (210) + TX, dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dichlofenthion (1051) + TX, dicliphos (alternative name) + TX, dimethoate (262) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fosthietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidofos (1230) + TX, isazofos (1231) + TX, ivermectin (alternative name) [CCN] + TX, kinetin (alternative name) (210) + TX, mecarphon (1258) + TX, metam (519) + TX, metam-potassium (alternative name) (519) + TX, metam-sodium (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, Myrothecium verrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, sebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX,

tetrachlorothiophene (IUPAC/ Chemical Abstracts name) (1422) + TX, thiafenox

(alternative name) + TX, thionazin (1434) + TX, triazophos (820) + TX, triazuron (alternative name) + TX, xylenols [CCN] + TX, YI-5302 (compound code) and zeatin (alternative name) (210) + TX, fluensulfone [318290-98-1] + TX,

a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,

a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX,

a rodenticide selected from the group of substances consisting of 2-isovalerylindan-l,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminium phosphide (640) + TX, antu

(880) + TX, arsenous oxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoum (89) + TX, bromadiolone (91) + TX, bromethalin (92) + TX, calcium cyanide (444) + TX, chloralose (127) + TX, chlorophacinone (140) + TX, cholecalciferol (alternative name) (850) + TX, coumachlor (1004) + TX, coumafuryl (1005) + TX, coumatetralyl (175) + TX, crimidine (1009) + TX, difenacoum (246) + TX, difethialone (249) + TX, diphacinone (273) + TX, ergocalciferol (301) + TX, fiocoumafen (357) + TX, fluoroacetamide (379) + TX, flupropadine (1183) + TX, flupropadine hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, norbormide (1318) + TX, phosacetim (1336) + TX, phosphine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX,

scilliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fiuoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX,

a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(l,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alternative name) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421

(development code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,

an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetates (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX,

a virucide selected from the group of substances consisting of imanin (alternative name)

[CCN] and ribavirin (alternative name) [CCN] + TX,

a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,

and biologically active compounds selected from the group consisting of azaconazole (60207- 31-0] + TX, bitertanol [70585-36-3] + TX, bromuconazole [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenbuconazole [1 14369-43-6] + TX, fluquinconazole [136426-54-5] + TX, flusilazole [85509-19-9] + TX, flutriafol

[76674-21-0] + TX, hexaconazole [79983-71-4] + TX, imazalil [35554-44-0] + TX, imibenconazole [86598-92-7] + TX, ipconazole [125225-28-7] + TX, metconazole

[1251 16-23-6] + TX, myclobutanil [88671-89-0] + TX, peflirazoate [101903-30-4] + TX, penconazole [66246-88-6] + TX, prothioconazole [178928-70-6] + TX, pyrifenox [88283- 41-4] + TX, prochloraz [67747-09-5] + TX, propiconazole [60207-90-1 ] + TX,

simeconazole [149508-90-7] + TX, tebuconazole [107534-96-3] + TX, tetraconazole

[ 1 12281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimenol [55219-65-3] + TX, trifhimizole [99387-89-0] + TX, triticonazole [131983-72-7] + TX, ancymidol [12771 -68- 5] + TX, fenarimol [60168-88-9] + TX, nuarimol [63284-71-9] + TX, bupirimate [41483- 43-6] + TX, dimethirimol [5221 -53-4] + TX, ethirimol [23947-60-6] + TX, dodemorph [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxamine [1 18134-30-8] + TX, tridemorph [81412-43-3] + TX, cyprodinil [121552-61 - 2] + TX, mepanipynm [ 1 10235-47-7] + TX, pyrimethanil [531 12-28-0] + TX, fenpiclonil [74738-17-3] + TX, fludioxonil [131341-86- 1] + TX, benalaxyl [71626- 1 1-4] + TX, furalaxyl [57646-30-7] + TX, metalaxyl [57837-19-1] + TX, R-metalaxyl [70630-17-0] + TX, ofurace [58810-48-3] + TX, oxadixyl [77732-09-3] + TX, benomyl [17804-35-2] + TX, carbendazim [10605-21-7] + TX, debacarb [62732-91-6] + TX, fuberidazole [3878- 19-1] + TX, thiabendazole [148-79-8] + TX, chlozolinate [84332-86-5] + TX,

dichlozoline [24201-58-9] + TX, iprodione [36734- 19-7] + TX, myclozoline [54864-61-8] + TX, procymidone [32809-16-8] + TX, vinclozoline [50471 -44-8] + TX, boscalid

[188425-85-6] + TX, carboxin [5234-68-4] + TX, fenfuram [24691-80-3] + TX, flutolanil [66332-96-5] + TX, mepronil [55814-41-0] + TX, oxycarboxin [5259-88-1] + TX, penthiopyrad [183675-82-3] + TX, thif uzamide [130000-40-7] + TX, guazatine [108173- 90-6] + TX, dodine [2439-10-3] [1 12-65-2] (free base) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, dimoxystrobin [149961-52-4] + TX, enestroburin {Proc. BCPC, Int. Congr., Glasgow, 2003, 1, 93 } + TX, fhioxastrobin [361377-29-9] + TX, kresoxim-methyl [ 143390-89-0] + TX, metominostrobin [133408-50-1] + TX,

trifloxystrobin [141517-21-7] + TX, orysastrobin [248593-16-0] + TX, picoxystrobin [117428-22-5] + TX, pyraclostrobin [175013-18-0] + TX, ferbam [14484-64-1] + TX, mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, metiram [9006-42-2] + TX, propineb [12071-83-9] + TX, thiram [137-26-8] + TX, zineb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol [2425-06-1] + TX, captan [133-06-2] + TX, dichlofluanid

[1085-98-9] + TX, fluoroimide [41205-21-4] + TX, folpet [133-07-3 ] + TX, tolylfluanid [731-27-1] + TX, bordeaux mixture [8011-63-0] + TX, copperhydroxid [20427-59-2] + TX, copperoxychlorid [1332-40-7] + TX, coppersulfat [7758-98-7] + TX, copperoxid [1317-39-1] + TX, mancopper [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dmocap [131-72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, edifenphos [17109-49-8] + TX, iprobenphos [26087-47-8] + TX, isoprothiolane [50512-35-1] + TX, phosdiphen [36519-00-3] + TX, pyrazophos [13457-18-6] + TX, tolclofos-methyl [57018-04-9] + TX, acibenzolar-S-methyl [135158-54-2] + TX, anilazine [101-05-3] + TX, benthiavalicarb [413615-35-7] + TX, blasticidin-S [2079-00-7] + TX, chinomethionat [2439-01-2] + TX, chloroneb [2675-77-6] + TX, chlorothalonil [1897-45-6] + TX, cyflufenamid [180409-60- 3] + TX, cymoxa il [57966-95-7] + ΎΧ, dichlone [117-80-6] + TX, diclocymet [139920- 32-4] + TX, diclomezine [62865-36-5] + TX, dicloran [99-30-9] + TX, diethofencarb [87130-20-9] + TX, dimethomorph [110488-70-5] + TX, SYP-LI90 (Flumorph) [211867- 47-9] + TX, dithianon [3347-22-6] + TX, ethaboxam [162650-77-3] + TX, etridiazole [2593-15-9] + TX, famoxadone [131807-57-3] + TX, fenamidone [161326-34-7] + TX, fenoxanil /775S52-4S-7/ + TX, fentin [668-34-8] + TX, ferimzone [89269-64-7] + TX, fluazinam [79622-59-6] + TX, fluopicolide [239110-15-7] + TX, flusulfamide [106917-52- 6] + TX, fenhexamid [126833-17-8] + TX, fosetyl-aluminium [39148-24-8] + TX, hymexazol [10004-44-1] + TX, iprovalicarb [140923-17-7] + TX, IKF-916 (Cyazofamid) [120116-88-3] + TX, kasugamycin [6980-18-3] + TX, methasulfocarb [66952-49-6] + TX, metrafenone [220899-03-6] + TX, pencycuron [66063-05-6] + TX, phthalide [27355-22-2] + TX, polyoxins [11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb

[25606-41-1] + TX, proquinazid [189278-12-4] + TX, pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, quintozene [82-68-8] + TX, sulphur [7704-34-9] + TX, tiadinil [223580-51-6] + TX, triazoxide [72459-58-6] + TX, tricyclazole [41814-78-2] + TX, triforine [26644-46-2] + TX, validamycin [37248-47-8] + TX, zoxamide (RH7281) [156052-68-5] + TX, mandipropamid [374726-62-2] + TX, isopyrazam [881685-58-1] + TX, sedaxane [874967-67-6] + TX, 3 -difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid (9-dichloromethylene-l,2,3,4-tetrahydro-l,4-methano-naphthalen-5-yl)-amide (dislosed in WO 2007/048556) + TX, 3-difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid [2- (2,4-dichlorophenyl)-2-methoxy-l-methyl-ethyl]-amide (disclosed in WO 2008/148570) + TX, l-[4-[4-[(5S)5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2- yl]piperidin-l-yl]-2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone + TX, l-[4-[4- [5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl]piperidin-l-yl]-2-[5- methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone [1003318-67-9], both disclosed in WO 2010/123791, WO 2008/013925, WO 2008/013622 and WO 2011/051243 page 20) +TX, and 3 -difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2- yl)-amide (dislosed in WO 2006/087343) + TX, 3-(difluoromethyl)-N-methoxy-l-methyl-N- [l-methyl-2-(2,4,6-trichlorophenyl)ethyl]-lH-Pyrazole-4-carboxamide + TX, 4-[(5<S)-5-(3,5- dichlorophenyl)-5 -(trifluoromethyl)-4H-isoxazol-3 -yl] -2-methyl-N-(thietan-3 -yl)benzamide (WO2011/104089) + TX, 4-[(5i?)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-2-methyl-N-(thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(55)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(cis-l-oxo-thietan-3- yl)benzamide (WO2011/104089) + TX, 4-[(5i?)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)- 4H-isoxazol-3-yl]-2-methyl-N-(cis-l-oxo-thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(55)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(trans-l- oxo-thietan-3-yl)benzamide (WO2011/104089) + TX, 4-[(5i?)-5-(3,5-dichlorophenyl)-5- (trifluoromethyl)-4H-isoxazol-3 -yl] -2-methyl-N-(trans- 1 -oxo-thietan-3 -yl)benzamide

(WO2011/104089) + TX, 4-[(55)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-N-(l,l-dioxothietan-3-yl)-2-methyl-benzamide (WO2011/104089) + TX, 4-[(5i?)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-(l,l-dioxothietan-3-yl)-2-methyl- benzamide (WO2011/104089) + TX, 4-[(55)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide

(WO2011/104089) + TX, 4-[(5i?)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-2-methyl-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]benzamide (WO2011/104089) + TX, Penflufen [494793-67-8] and TX, 5-[(5S)-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl]-2-(l,2,4-triazol-l-yl)benzonitrile (WO2007/075459) + TX, 5-[(5R)-5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-(l,2,4-triazol-l-yl)benzonitri (WO2007/075459) + TX. Throughout this document the expression "composition" stands for the various mixtures or combinations of components TX and (B), 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 components TX and (B) is not essential for working the present invention.

The compositions according to the invention may also comprise more than one of the active components (B), if, for example, a broadening of the spectrum of disease control is desired. For instance, it may be advantageous in the agricultural practice to combine two or three components (B) with component TX. An example is a composition comprising a compound of formula (I), azoxystrobin and cyproconazole.

In the above different lists of active ingredients to be mixed with a TX, the compound of the formula I is preferably a compound of Table 1.

In the above-mentioned mixtures of compounds of formula I, in particular a compound selected from said Table 1, with other insecticides, fungicides, herbicides, safeners, adjuvants and the like, the mixing ratios can vary over a large range and are, preferably 100: 1 to 1 :6000, especially 50: 1 to 1 :50, more especially 20: 1 to 1 :20, even more especially 10: 1 to 1 : 10.

Those mixing ratios are understood to include, on the one hand, ratios by weight and also, on other hand, molar ratios.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of TX with the mixing partner). Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.

The mixtures comprising a TX selected from Table 1 especialy the compounds 144,

145,147,148, 149, 150, 151, or 153, or (S)-146 (or 154) and one or more active ingredients 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 selected from Table Table 1 especialy the compounds 144, 145,147,148, 149, 150, 151, or 153, or (S)-146 (or 154), and the active ingredients as described above is not essential for working the present invention.

Compounds of formula (I) may be prepared using the methods below or according to WO2006031631, WO2010069881 and/or WO2010069882.

Compounds of formula (I) wherein R₄ = H may be prepared by a [3+2]-cycloaddition of a carboximidoyl chloride (II) with an acetylenic carbinol (III):

The reaction may be carried out in the presence of an organic base such as triethylamine in an inert solvent such as DCE (1,2-dichloroethane), or an inorganic base such as sodium bicarbonate in a protic solvent such as isopropanol. Time and temperature of the reaction is not critical but may be at temperatures ranging from 20 to 60° C for 1 to 24h.

The carboximidoyl chlorides (II) may be prepared from the corresponding oximes using chlorinating reagents such as N-chlorosuccinimide or sodium hypochlorite (bleach), or may be obtained from commercial sources.

The acetylenic carbinols (III) may be obtained by addition of an organometallic acetylene (IV) (M = Li, MgX; X = CI, Br) to an aldehyde R₂CHO (V), as shown below:

In certain cases, the [3+2]-cycloaddition proceeds more rapidly and in higher yield when the corresponding ketone (VI) of acetylenic carbinol (III) is used:

Compounds of formula (VII) are useful for making compounds of formula (I) as described below wherin the isoxazole (VII) is reduced (e.g. with sodium borohydride) to give (I). In some cases, the regioisomer (VIII) is produced along with (I) in the [3+2]-cycloaddition. This regioisomer (VIII) generally is less active than (I) in bioevaluation.

(VIII)

Acetylenic ketone (VI) can be prepared from (III) by oxidation, for example with IBX (o-iodosobenzoic acid) in an inert solvent such as DMSO (dimethylsulfoxide) at any suitable time and temperature (e.g. 20°C for 1 to 2h). Reduction of isoxazole (VII) with sodium borohydride in an alcoholic solvent (e.g. ethanol) at 0°C for 0.3 to 2h produces the isoxazole (I) (R₄ = H).

Isoxazoles in which R₄≠ H may be prepared from (I) (R₄ = H) using standard acylation or carbamoylation conditions. For example, the acetate derivative of (I) (R₄ = COCH₃) is synthesized from the alcohol (I) (R = H) by reaction with acetic anhydride and pyridine in ether solvent at room temperature overnight. Acylations may be carried out using either acid anhydrides (e.g. acetic anhydride, propionic anhydride) or acid chlorides (e.g. benzoyl chloride) in the presence of an organic base in an inert solvent (e.g. ether, dichloromethane). Carbamoylations are effected by treating alcohols (I) with a strong base such as sodium hydride followed by a carbamoyl chloride (e.g. N,N-dimethylcarbamoyl chloride) in an inert solvent such as DMF (dimethylformamide).

Conventional techniques for the preparation or isolation of individual enantiomers include chiral synthesis from a suitable optically pure precursor or resolution of the racemate (or the racemate of a salt or derivative) using, for example, chiral high performance liquid chromatography (HPLC). Alternatively, the racemate (or a racemic precursor) may be reacted with a suitable optically active compound, for example, a carboxylic acid, or, in the case where the compound of formula (I) contains an acidic or basic moiety, a base or acid such as 1-phenylethylamine or tartaric acid. The resulting diastereomeric mixture may be separated by chromatography and/or fractional crystallization and one or both of the diastereoisomers converted to the corresponding pure enantiomer(s) by means well known to a skilled person. Conventional techniques known to those skilled in the art -are disclosed in, for example, Stereochemistry of Organic Compounds by E. L. Eliel and S. H. Wilen (Wiley, New York, 1994).

The invention is illustrated by the following Examples.

Example 1 : 3-(2,6-Dichlorophenyl)-4-[(3-pyridyl)-hydroxymethyll-5-trimethylsilyl-isoxazole (Table 1, compound 1) and

3-(2,6-dichlorophenyl)-5-[(3-pyridyl)-hydroxymethyll-4-trimethylsilylisoxazole (Table 1 , compound 2)

A mixture of 55mg (0.24mmol) of 2,6-dichloro-N-hydroxybenzenecarboximidoyl chloride, 50mg (0.24mmol) of l-(3-pyridyl)-3-trimethylsilyl-2-propyn-l-ol, and 20mg (0.24mmol) of sodium bicarbonate in 2mL of isopropyl alcohol was heated at 55°C for 24h. The reaction mixture was diluted with ether. The ether layer was washed with saturated sodium chloride solution, and was dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by preparative thin layer chromatography (prep TLC), and two products were isolated.

The less polar product (lOmg, 0.025mmol) was identified as 3-(2,6-dichlorophenyl)-4-[(3- pyridyl)hydroxy-methyl]-5-trimethylsilylisoxazole. 1H NMR (CDC1₃): δ 0.45 (br s, 9), 5.82 (s, 1), and 7.40ppm (d, 1). MS m/z: 393.0 (M+H). The more polar product was 3-(2,6-dichlorophenyl)-5-[(3-pyridyl)hydroxymethyl]-4- trimethylsilylisoxazole. 1H NMR (CDC1₃): δ 0.20 (m, 9), 6.12 (s, 1), 7.80 (d, 1), and 7.87ppm (d, 1). MS m/z: 393.0 (M+H). Example 2: 5-(3-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-r(3-pyridyl) hydroxymethyll- isoxazole (Table 1 , compound 4)

A mixture of 53mg (0.24mmol) of 2,4-dichloro-N-hydroxybenzenecarboximidoyl chloride, 50mg (0.21mmol) of l-(3-pyridyl)-3-(3-chlorophenyl)-2-propyn-l-ol, and 26mg (0.31mmol) of sodium bicarbonate in 2.5mL of isopropyl alcohol was heated at 55°C on a rotary table shaker equipped with a heated sand bath. After 20h, an additional 20mg of 2,4-dichloro-N- hydroxybenzenecarboximidoyl chloride and lOmg of sodium bicarbonate was added, and the reaction mixture was stirred and heated for another 16h. The mixture was then diluted with ether, and the solution was washed with saturated sodium chloride and dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by prep TLC to give 15mg (0.035mmol) of 5-(3-chlorophenyl)-3- (2,4-dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]isoxazole.

1H NMR (CDC1₃): δ 5.92 (br s, 1), 7.04 (d of d, 1), 7.12 (d, 1), 7.72 (m, 1), 8.86 (br s, 1), and 8.29ppm (br s, 2). MS m/z: 430.9 (M+H).

Example 3 : 5-(3-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3-pyridyl)- acetoxymethyllisoxazole

To a solution of 43mg (O.lOmmol) of 5-(3-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)hydroxymethyl]isoxazole in 2mL of pyridine was added \9 iL (0.20mmol) of acetic anhydride. The reaction was stirred overnight at room temperature, and then the pyridine was removed under vacuum. The residue was taken up in ethyl acetate, washed with saturated sodium chloride, and the ethyl acetate fraction dried over magnesium sulfate. The drying agent was filtered off, and the ethyl acetate was removed by rotoevaporation. The crude product was purified by preparative thin layer chromatography (prep TLC) to give 35mg (0.074mmol) of 5-(3-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3-pyridyl)acetoxymethyl]- isoxazole.

Example 4: 3-(2,4-Dichlorophenyl)-5-(lJ-dimethylethyl)-4-r(3- pyridyDcarbonyllisoxazole

To a solution of 200mg (1.06mmol) of 4,4-dimethyl-l-pyridyl-2-pentyn-l-ol in 2.5mL of dimethyl sulfoxide (DMSO) was added 443mg (1.58mmol) of o-iodosobenzoic acid (IBX). The reaction mixture was stirred overnight at room temperature, and then the solid was removed by filtration. The filtrate was diluted with ether, and washed with saturated sodium chloride solution. The organic fraction was separated and dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The ketonic product, 4,4-dimethyl-l-(3-pyridyl)-2-pentyn-l-one (182mg) was used directly without any purification.

A mixture of 72mg (0.32mmol) of 2,4-dichloro-N-hydroxybenzenecarboximidoyl chloride, 60mg (0.32mmol) of 4,4-dimethyl-l-(3-pyridyl)-2-pentyn-l-one, and 32mg (0.38mmol, 1.2 equivalents) of sodium bicarbonate in 2.5mL of isopropyl alcohol was heated at 55°C for 16h on a rotary table shaker. A second addition of 25mg of carboximidoyl chloride and lOmg of sodium bicarbonate was followed by another 20h at 55 °C. The reaction mixture was cooled, diluted with ether, and then washed with saturated sodium bicarbonate. The ether fraction was dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by prep TLC to give 92mg of oily product, 3-(2,4-dichlorophenyl)-5-(l,l-dimethylethyl)-4-[(3-pyridyl)carbonyl]-isoxazole. 1H NMR (CDC1₃): δ 1.47 (s, 9), 7.90 (m, 1), 7.60 (br s, 1) and 8.72ppm (br s, 1). MS m/z: 375.0 (M+H).

Example 5 : 3-(2,4-Dichlorophenyl)-5-(l,l-dimethylethyl)-4-[(3- pyridyOhydroxymethyl] - isoxazole (Table 1 , compound 7) To a solution of 92mg (0.24mmol) of 3-(2,4-dichlorophenyl)-5-(l,l-dimethylethyl)-4-[(3- pyridyl)carbonyl]isoxazole in 5mL of ethanol at 0°C was added 20mg (0.53mmol) of sodium borohydride. After 2h, the reaction mixture was poured into water, and the product was extracted several times with ethyl acetate. The combined ethyl acetate fractions were washed with saturated sodium chloride and dried over magnesium sulfate. The drying agent was filtered off, and the ethyl acetate was removed by rotoevaporation. The crude product was purified by prep TLC to yield 68mg (0.18mmol) 3-(2,4-d.ichlorophenyl)-5-(l,l- dimethylethyl)-4-[(3-pyridyl)hydroxy-methyl]isoxazole. 1H NMR (CDC1₃): δ 1.52 (s, 9), 6.14 (br s, 1), 6.86 (d, 1), 7.38 (m, 1), 8.27 (br s, 1) and 8.33ppm (m, 1). MS m/z: 377.0 (M+H).

Example 6: 5-(2-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-r(3-pyridyl)hvdroxymethyl1- isoxazole (Table 1, compound 14)

To a solution of 655mg (4.8mmol) of 2-chlorophenylacetylene in lOmL of tetrahydrofuran (THF) cooled to -78°C under a nitrogen atmosphere was added 3.0mL (4.8mmol) of 1.6M n-butyllithium in hexane. The solution was stirred at -78°C for 2h, and then a solution of 514mg (4.8mmol) of 3-pyridinecarboxaldehyde in 2.5mL of tetrahydrofuran (THF) was added. After 3.5h, the reaction mixture was poured into water. The organic product was extracted with ether several times. Combined ether extracts were washed with saturated sodium bicarbonate and dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation to give the oily 3-(2-chlorophenyl)-l-(3-pyridyl)-2- propyn-l-ol.

A mixture of 52mg (0.23mmol) of 2,4-dichloro-N-hydroxybenzenecarboximidoyl chloride, 50mg (0.21mmol) of 3-(2-chlorophenyl)-l-(3-pyridyl)-2-propyn-l-ol, and 30mg (0.36mmol) of sodium bicarbonate in 3mL of isopropyl alcohol was heated at 55°C overnight with shaking. The reaction mixture was cooled, diluted with ether, and then washed with saturated sodium bicarbonate. The ether fraction was dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by prep TLC to give 15mg (0.035mmol) of 5-(2-chlorophenyl)-3-(2,4- dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]isoxazole. 1H NMR (CDC1₃): δ 5.80 (br s, 1). MS m/z: 431.0 (M+H).

Example 7: 5-(2-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3-pyridyl)hydroxymethyll- isoxazole (Table 1, compound 14)

A mixture of 56mg (0.25mmol) of 2,4-dichloro-N-hydroxybenzenecarboximidoyl chloride, 60mg (0.25mmol) of 3-(2-chlorophenyl)-l-(3-pyridyl)-2-propyn-l-one, and 30mg (0.36mmol) of sodium bicarbonate in 2.5mL of isopropyl alcohol was heated at 55°C overnight with shaking. An additional 30mg of carboximidoyl chloride and 15mg of sodium bicarbonate was then added, and the mixture was heated for another 20h.The reaction mixture was cooled, diluted with ether, and then washed with saturated sodium bicarbonate. The ether fraction was dried over magnesium sulfate. The drying agent was filtered off, and the ether was removed by rotoevaporation. The crude product was purified by prep TLC to give 90mg (0.2 lmmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3-pyridyl)carbonyl]isoxazole. 1H NMR (CDCI₃): 5 7.16 (m, 1), 7.60 (m,2), 7.92 (m, 1), 8.53 (br d, 1), and 8.74ppm (br s, 1). MS m/z: 428.9 (M+H).

To a solution of 80mg (0.19mmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)carbonyl]isoxazole in 3mL of ethanol at 0°C was added 40mg (1.06mmol) of sodium borohydride. The mixture was stirred for 2h and then diluted with ethyl acetate. The ethyl acetate solution was washed with saturated sodium chloride solution and dried over magnesium sulfate. The drying agent was filtered off, and the ethyl acetate was removed by rotoevaporation. The crude product was purified by prep TLC to give 65mg (0.1 mmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-isoxazole.

1H NMR (CDCI3): δ 5.80 (br s, 1), 6.97 (m, l), 8.23 (br s, 1), and 8.28ppm (br s, 1).

MS m/z: 431.0 (M+H). Example 8: 5-(2-Chlorophenyl)-3-(2,4-dichlorobenzyl)-4-[(3-pyridyl)hydroxymethyll- isoxazole (Table 1, compound 15)

A solution of 59mg (0.25mmol) of 2,4-dichlorobenzylcarboximidoyl chloride (prepared according to G. Kumaran and G. H. Kulkarni, J. Org. Chem. 1997, 62, 1516), 50mg (0.21mmol) of 3-(2-chlorophenyl)-l-(3-pyridyl)-2-propyn-l-one, and 43μί (0.31mmol) of triethylamine in mL of dichlorom ethane was heated at 55°C in a sealed vial overnight. The reaction mixture was cooled and diluted with ether, washed with saturated sodium chloride, and dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation. The crude product was purified by prep TLC to give 50mg (0.1 lmmol) 5-(2-chlorophenyl)-3-(2,4-dichlorobenzyl)-4-[(3-pyridyl)carbonyl]isoxazole. 1H NMR (CDC1₃): δ 4.23 (s, 2), 7.48 (d, 1), 7.88 (d of d, 1), 8.66 (br d, 1), 8.70ppm (br s, 1). MS m/z: 442.9 (M+H). To a solution of 50mg (0.1 lmmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorobenzyl)-4-[(3- pyridyl)carbonyl]isoxazole in 15mL of THF was added 21mg (0.56mmol) of sodium borohydride at room temperature. After 2h, the solution was diluted with ethyl acetate, washed with saturated sodium chloride, and dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation. The crude product was purified by prep TLC to give 39mg (0.088mmol) of 5-(2-chlorophenyl)-3-(2,4-dichlorobenzyl)-4-[(3- pyridyl)hydroxymethyl]isoxazole. 1H NMR (CDCI3): δ 3.91 (d, 1), 4.00 (d, 1), 6.97 (br s, 1), 7.64 (d, 1), 8.42ppm (br m, 2). MS m/z: 445.0 (M+H).

Example 9: 5-(3-Chlorophenyl)-3-(2-fluoro-5-trifluoromethylphenyl)-4-[(3-pyridyl)-hydroxyl- methyl]isoxazole (Table 1, compound 29)

To a solution of 643mg (3.10mmol) of 2-fluoro-5-trifluoromethylbenzaldehyde oxime in 5mL of dimethyl formamide (DMF) was added 456mg (3.4 lmmol) of N-chlorosuccinimide (see K.-C. Liu, B. R. Shelton, and R. K. Howe, J. Org. Chem. 1980, 45, 3916). The reaction mixture was stirred at room temperature overnight, and then diluted with ethyl acetate. The ethyl acetate solution was washed with saturated sodium chloride and dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation to give 675mg (2.79mmol) of pure white crystalline 2-fluoro-5-trifluoromethyl-N- hydroxybenzene-carboximidoyl chloride.

A mixture of 60mg (0.25mmol) of 2-fluoro-5-trifluoromethyl-N-hydroxybenzenecarbox- imidoyl chloride, 50mg (0.21mmol) of 3-(3-chlorophenyl) l-(3-pyridyl)-2-propyn-l-one (prepared similarly to procedures noted above from lithio 3-chlorophenylacetylide and 3-pyridinecarboxaldehyde, followed by IBX oxidation), and 26mg (0.36mmol) of sodium bicarbonate in 2.5mL of isopropyl alcohol was heated at 55°C overnight with shaking. An additional 30mg of carboximidoyl chloride and 15mg of sodium bicarbonate were added, and the reaction was heated for another 24h. The mixture was cooled and diluted with ether. The ether fraction was washed with saturated sodium chloride and dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation. The residue was purified by prepTLC to give 56mg (0.13mmol) of 5-(3-chlorophenyl)-3-(2-fluoro-5- trifluoromethylphenyl)-4-[(3-pyridyl)carbonyl]isoxazole. 1H NMR (CDC1₃): δ 7.10 (t, 1), 7.41 (m, 1), 7.52 (m, 1), 8.65 (br s, 1), and 8.86ppm (br s, 1). MS m/z: 447.0 (M+H).

To a solution of 56mg (0.13mmol) of 5-(3-chlorophenyl)-3-(2-fluoro-5-trifluoromethyl- phenyl)-4-[(3-pyridyl)carbonyl]isoxazole in 2mL of ethanol was added 24mg (0.63mmol) of sodium borohydride. After 2 h at room temperature, the reaction mixture was diluted with ethyl acetate. The solution was washed with saturated sodium chloride and was dried over magnesium sulfate. The drying agent was filtered off, and solvent was removed by rotoevaporation. The residue was purified by prepTLC to give 44mg (0.098mmol) of 5-(3- chlorophenyl)-3-(2-fluoro-5-trifluoromethylphenyl)-4-[(3-pyridyl)hydroxymethyl]isoxazole. 1H NMR (CDC1₃): δ 6.01 (s, 1), 7.01 (m, 1), 7.83 (m, 1), 8.27 (m, 1), and 8.35ppm (br s, 1). MS m/z: 449.0 (M+H).

Example 10: [3-(4-Chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yllpyridin- 3-yl-methanol (Table 1, compound 146) (i) Preparation of 3-(2,4-difluorophenyl)-l-pyridin-3-yl-propynone (3)

1 2 3 l-Ethynyl-2,4-difluorobenzene (24g, 0.17mol) was dissolved in THF (350ml) and the reaction mixture was cooled at -78°C. A solution of n-BuLi, 2.5 M in hexane, (76.5ml, 0.19mol) was added dropwise over 70 minutes maintaining the temperature below -70°C. The mixture was stirred at this temperature for a further 10 minutes after the addition was finished. A solution of the Weinreb amide 2 (prepared according to WO 05/097760, Letters in Organic Chemistry, 4, 20, 2007) (28.9g, 0.17mol) in THF (100ml) was added dropwise over 20 minutes to the solution above keeping the temperature below -70°C. The mixture was now warmed to -50°C obtaining a solution that was further stirred for 1 hour at this temperature. The reaction mixture was quenched with a saturated solution of ammonium chloride (100ml) and allowed to warm to room temperature. The reaction was then poured into a mixture of ethyl acetate/water. Successively, the aqueous phase was washed twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulphate, filtered and concentrated. The crude was recrystallised from diethyl ether obtaining 28g of the desired product. The mother liquors were concentrated and the residue was purified by column chromatography on alumina using a mixture of cyclohexane/ethyl acetate 3: 1. Totally, 29.8g (70%) of brown compound were obtained.

1H NMR (CDC1₃): δ 7. 02 (m, 1), 7.58 (m, 1), 7.71 (m, 1), 8.56 (m, 1) 8.90 (m, 1) and 9.48 ppm (m, 1). MS m/z: 244.0 (M+H).

(ii) Preparation of [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4- yl]pyridin-3-yl-methanone (5)

A mixture of 46.7g (0.22mol) of 2-fluoro-4-chloro-N-hydroxybenzenecarboximidoyl chloride (prepared by analogy to the method of preparation of 2-fluoro-5-trifluoromethyl-N- hydroxybenzene-carboximidoyl chloride Example 9), 42g (0.17mol) of 3-(2,4- difluorophenyl)-l-pyridin-3-yl-propynone (3), and 21.76g (0.26mol) of sodium bicarbonate in 500mL of isopropyl alcohol was heated at 85 °C for 21 hours. The reaction mixture was diluted with ethyl acetate and washed successively with saturated ammonium chloride, water, and saturate sodium chloride solution, and was dried over magnesium sulfate. The drying agent was filtered off and the ethyl acetate was removed by rotoevaporation. The crude was recrystallised from diethyl ether obtaining the desired product as a yellowish solid (50.28g, 70.2%). 1H NMR (CDC1₃): δ 6.75 (m, 1), 7.05 (m, 2), 7.27 (m, 2), 7.67 (t, 1), 7.80 (m, 1), 8.03 (m, 1), 8.66 (m, 1) and 8.82 ppm (d, 1). MS m/z: 415 (M+H).

(iii) Preparation of [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4- yl]pyridin-3-yl -methanol (6)

To a solution of 5 (26.5g, 63.9mmol) in a mixture of THF/methanol (400ml/40ml) at 0°C was added 2.42g (63.7mmol) of sodium borohydride. The mixture was stirred for 1.5 hours and then diluted with ethyl acetate. The ethyl acetate solution was washed with saturated sodium chloride solution and dried over magnesium sulfate. The drying agent was filtered off and the ethyl acetate was removed by rotoevaporation. The reaction mixture was purified by column chromatography using a mixture of heptane/ethyl acetate 1 : 1. The desired compound was obtained as white crystals (17.5g, 66%). mp= 138-140°C.

1H NMR (CDC1₃): δ 4.19 (bs, 1), 5.89 (s, 1), 6.99 (m, 5), 7.28 (t, 1), 7.43 (d, 1), 7.59 (q, 1), and 8.19 (d, 1) and 8.23 ppm (d, 1). MS m/z: 417 (M+H).

Example 1 1 : (6 -r3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4- yllpyridin-3-yl -methanol (Table 1 , compound 1 3 : (S)-146))

Each enantiomer was isolated by preparative chromatography using the racemic mixture 6 as starting material.

Preparative method:

Column: 250x76 mm CHIRALPAK^® AD 20 μιη;

Mobil phase: n-heptane/ethanol 70/30 (v/v)

Flow rate: 270 ml/min

Detection: UV 280 nm

Temperature: 25°C

Analytical method:

Column: 250x4.6 mm CHIRALPAK^® AD-H 5 μιη;

Mobil phase: n-heptane/ethanol/diethylamine 70/30/0.1 (v/v/v)

Flow rate: 1 ml/min Detection: UV 230 nm

Temperature: 25°C

The first eluting enantiomer had a retention time of 7.6 min ([a]= +58.07, C= 0.025 M, THF) while the second enantiomer had a retention time of 9.9 min ([a]= -57.59, C= 0.025 M, THF). The first eluting enantiomer is the ( ?)-enantiomer. The second eluting enantiomer is the (iS)-enantiomer. The compounds of formula (I) in Table 1 may be prepared by analogous methods. Table 1

Compound

Structure Chemical Name

No.

5-(3-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(2,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- phenylisoxazole

3-(2,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (2-thienyl)isoxazole

3-(2,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (3 -thienyl)isoxazole

5-(2-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(2- trifluoromethylphenyl)-isoxazole

4-[(3 -Pyridyl)hydroxymethyl] -3 -(4- trifluoromethoxyphenyl)-5-(2-trifluoromethylphenyl)- isoxazole

4-[(3 -Pyridyl)hydroxymethyl] -3 -(3 - trifluoromethylphenyl)-5-(2-trifluoromethylphenyl)- isoxazole

3-(3,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (2-trifluoromethylphenyl)-isoxazole

3-(2,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (2-trifluoromethylphenyl)-isoxazole

3-(4-Chlorophenyl)-5-(4-methylphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(4-Methylphenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluoromethoxyphenyl)-isoxazole

5-(4-Methylphenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(3- trifluoromethylphenyl)-isoxazole

3-(3,4-Dichlorophenyl)-5-(4-methylphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(2,4-Dichlorophenyl)-5-(4-methylphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5 - (3 -Chloropheny 1) - 3 - (2 - fluoro -5 - trifluoromethylphenyl)-4-[(3-pyridyl)liydroxymetliyl]- isoxazole

5-(3-Chlorophenyl)-3-(4-cyanophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(2-Chlorophenyl)-3-(4-cyanophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(4-Chlorophenyl)-3-(2,4-dichlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(3- trifluoromethylphenyl)-isoxazole

4-[(3-Pyridyl)hydroxymethyl]-3-(4- trifluoromethoxyphenyl) -5 -(3 -trifluoromethylphenyl) - isoxazole

4-[(3-Pyridyl)hydroxymethyl]-3-(3- trifluoromethylphenyl) -5 -(3 -trifluoromethylphenyl) - isoxazole

3-(3,4-Dichlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (3-trifluoromethylphenyl)-isoxazole

3 -(4-Chlorophenyl)-5 -phenyl-4-[(3 - pyridyl)hydroxymethyl] -isoxazole

5-Phenyl-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluoromethoxyphenyl)-isoxazole

5-Phenyl-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluoromethylphenyl)-isoxazole

3-(2,4-Dichlorophenyl)-5-phenyl-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3 -(3 ,4 -Dichlorophenyl) -5 -pheny 1-4- [(3 - pyridyl)hydroxymethyl] -isoxazole

5-(3-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluoromethoxyphenyl)-isoxazole

5-(3 -Chlorophenyl)-4-[(3 -pyridyl)hydroxymethyl] -3 -(3 - trifluoromethylphenyl)-isoxazole

5-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(2- thienyl)isoxazole

5-(4-Chlorophenyl)-3-(2-fluoro-4- trifluoromethylphenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole

3 - (2 -F luoro -4 -trifluoromethy lpheny 1) -4 - [ (3 - pyridyl)hydroxymethyl]-5-(3-thienyl)isoxazole

4-[(3-Pyridyl)hydroxymethyl] -3-(2-thienyl)-5-(3- thienyl)-isoxazole

5-(3 -Chlorophenyl)-3 -phenyl-4-[(3 - pyridyl)hydroxymethyl] -isoxazole

5-(4-Methylphenyl)-3-phenyl-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(4-Methylphenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(3- thienyl)isoxazole

5-(3 -Chlorophenyl)-4-[(3 -pyridyl)hydroxymethyl] -3 -(3 - thienyl)isoxazole

5-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(3- thienyl)isoxazole

3-(4-Chlorophenyl)-5-(3-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3 - (2 -F luoro -5 -trifluoromethy lpheny 1) -4 - [ (3 - pyridyl)hydroxymethyl]-5-(3-thienyl)isoxazole

5-(4-Chlorophenyl)-3-(2-fluoro-5- trifluoromethylphenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole

3 -(4-Chlorophenyl)-5 -phenyl-4-[(2- pyridyl)hydroxymethyl] -isoxazole

5-(3-Chloro-4-methylphenyl)-3-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(3-Chloro-4-fluorophenyl)-3-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-5-(2-methoxyphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5 -(3 -Chlorophenyl)-3 -(4-methylphenyl-4-[(3 - pyridyl)hydroxymethyl] -isoxazole

3-(4-?er?-Butylphenyl)-5-(3-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(3-Chlorophenyl)-3-(4-isopropoxyphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(3-Chlorophenyl)-3-(4-butoxyoxyphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(3-Chlorophenyl)-3-(4-phenoxyphenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-5-(5-methyl-3-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(2,4-Dichlorophenyl)-5-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3 -(2-Chlorophenyl)-5 -(4-fluorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-5-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(4-Chlorophenyl)-3-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(2-Chlorophenyl)-3-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-5-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-5-(2-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Fluorophenyl)-5-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(3- thienyl)isoxazole

5-(4-Chlorophenyl)-3-(5-chloro-2-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(3-Chlorophenyl)-3-(5-chloro-2-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(5-Chloro-2-thienyl)-4-[(3-pyridyl)hydroxymethyl]-5- (3 -thienyl)isoxazole

5-(4-Chlorophenyl)-3-(5-chloro-3-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(3-Chlorophenyl)-3-(5-chloro-3-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(3-Chlorophenyl)-3-(2,5-dichloro-3-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(4-Chlorophenyl)-3-(2,5-dichloro-3-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3 -(4-Chlorophenyl)-5 -(3 ,5 -difluorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole

3-(5-Chloro-2-thienyl)-5-(3,5-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-5-(3-chlorophenyl)-4-[(5- pyrimidinyl)hydroxymethyl] -isoxazole

5-(3-Chlorophenyl)-3-(5-chloro-2-thienyl)-4-[(5- pyrimidinyl)hydroxymethyl] -isoxazole

3-(5-Bromo-2-thienyl)-5-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3 -(5-Bromo-2-thienyl)-5 -(3 -chlorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole

3-(2-Chlorophenyl)-5-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(2-Chlorophenyl)-5-(3-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(3-Chlorophenyl)-5-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3 -(3 -Chlorophenyl)-5-(3 -chlorophenyl)-4-[(3 - pyridyl)hydroxymethyl] -isoxazole

5-(4-Butylphenyl)-3-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(2- thienyl)isoxazole

5-(3-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluorophenyl)isoxazole

5-(4-Chlorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3-(4- trifluorophenyl)isoxazole

5-(3-Chlorophenyl)-3-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(4-Chlorophenyl)-3-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-5-(5-chloro-2-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(5-Chloro-2-thienyl)-5-(5-chloro-2-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(4-Chlorophenyl)-3-(3,5-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(4-Chlorophenyl)-5-(5-methyl-2-thienyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(2,4-Difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (2-thienyl)isoxazole

5-(5-Chloro-2-thienyl)-3-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(2,4-Difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5- (3 -thienyl)isoxazole

3-(2,4-Difluorophenyl)-5-(4-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

3-(5-Chloro-2-thienyl)-5-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl] -isoxazole

5-(2,4-Difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-3- (3-thienyl)isoxazole

5-(5-Bromo-2-thienyl)-3-(2,4-difluorophenyl)-4-[(3- pyridyl)hydroxymethyl]-isoxazole

5-(5-Bromo-2-thienyl)-3-(4-chlorophenyl)-4-[(3- pyridyl)hydroxymethyl]-isoxazole

5-(4-Chlorophenyl)-3-(2-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl]-isoxazole

5-(3,5-Diflorophenyl)-3-(2-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl]-isoxazole

5-(5-Chloro-2-thienyl)-3-(2-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl]-isoxazole

5-(5-Bromo-2-thienyl)-3-(2-fluorophenyl)-4-[(3- pyridyl)hydroxymethyl]-isoxazole

3-(2-Fluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(2- thienyl)isoxazole

3-(2-Fluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-5-(3- thienyl)isoxazole

3-(2-Fluoro-4-Chlorophenyl)-5-(2,4-difluorophenyl)-4- [(3-pyrimidyl)hydroxymethyl]-isoxazole

3-(4-Chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3- pyrimidyl)hydroxymethyl]-isoxazole

3-(2-Fluoro-4-Chlorophenyl)-5-(2,4-difluorophenyl)-4- [(3-pyridyl)hydroxymethyl]-isoxazole

3-(2,4-Chlorophenyl)-5-(2-Chlorophenyl)- 4-[(3- pyrimidyl)hydroxymethyl]-isoxazole

3-(2-Fluoro-4-Chlorophenyl)-5-(2-Chlorophenyl)- 4-[(3- pyrimidyl)hydroxymethyl]-isoxazole

3-(4-Chlorophenyl)-5-(2-Methoxypyridine)- 4-[(3- pyrimidyl)hydroxymethyl]-isoxazole

3-(4-Chlorophenyl)-5-(4-Fluorophenyl)- 4-[(3- pyrimidyl)hydroxymethyl]-isoxazole

3-(4-Chlorophenyl)-5-(2,4-Fluorophenyl)- 4-[(3- pyrimidyl)hydroxymethyl]-isoxazole

3-(2,4-Diluoro)-5-(2-Chloro-4-Fluorophenyl)-4-[(3- pyridyl)hydroxymethyl]-isoxaz»le

(S -3-(2-Fluoro-4-Chlorophenyl)-5-(2,4-difluorophenyl)- 4-[(3-pyridyl)hydroxymethyl]-isoxazole

Biological examples: This fungicidal properties of compound (146) (=3-(2-Fluoro-4- Chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-isoxazole) were demonstrated in the following examples.

Botryotini fuckeliana (Botrytis cinerea) I liquid culture (Gray mould)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application and percent antifungal activity relative to the untreated check is calculated.

Glomerella lagenarium (Colletotrichum lasenariuni) I liquid culture (Anthracnose)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application and percent antifungal activity relative to the untreated check is calculated. Fusarium culmorum I liquid culture (Head blight)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application and percent antifungal activity relative to the untreated check is calculated.

Gaeumannomyces graminis I liquid culture (Take-all of cereals)

Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores iss added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application and percent antifungal activity relative to the untreated check is calculated. Mycosphaerella arachidis (Cercospora arachidicola) I liquid culture (early leaf spot)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application and percent antifungal activity relative to the untreated check is calculated.

Mycosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch)

The component (B)-l is 3-(difluoromethyl)-N-methoxy-l-methyl-N-[l-methyl-2-(2,4,6- trichlorophenyl)ethyl] - 1 H-Pyrazole-4-carboxamide

Septoria tritici in PDB

Compounds in mg ai/l (ppm)

%

activity % expected

compound (146) component (B)-l

observed efficacy action

(Colby)

0.00781 46.2% 46.2

0.00391 16.5% 16.5

0.00198 1.6% 1.6

0.006250 78.8% 78.8 0.003125 73.8% 73.8 0.001563 47.3% 47.3

0.00781 0.006250 97.7% 97.7 88.6 0.00391 0.003125 93.0% 93.0 78.1 0.00198 0.001563 72.6% 72.6 48.2

Fusarium culmorum in PDB

Compounds in mg ai/l (ppm) activity % expected compound (146) component (B)-l

observed efficacy action

(Colby)

0.03125 6.9% 6.9

0.025000 34.3% 34.3

0.03125 0.025000 44.7% 44.7 38.8

CoUetotrichum lagenarium in PDB

Compounds in mg ai/l (ppm) activity % expected compound (146) component (B)-l

observed efficacy action

(Colby)

1.00000 53.1% 53.1

0.25000 34.4% 34.4

0.12500 32.2% 32.2

0.050000 0.0% 0.0

0.025000 0.0% 0.0

1.00000 0.050000 61.5% 61.5 53.1 0.25000 0.050000 39.5% 39.5 34.4 0.12500 0.025000 37.3% 37.3 32.2 Botrytis cinerea in Vogels Media

Compounds in mg ai/l (ppm)

%

activity % expected

compound (146) component (B)-l

observed efficacy action

(Colby)

0.03125 41.8% 41.8

0.001563 1.4% 1.4

0.03125 0.001563 55.1% 55.1 42.6

The component (B)-2 is N-[9-(dichloromethylene)-l,2,3,4-tetrahydro-l,4- methanonaphthalen-5 -yl] -3 -(difluoromethyl)- 1 -methyl- 1 H-Pyrazole-4-carboxamide

Septoria tritici in PDB

Compounds in mg ai/l (ppm)

% activity % expected compound (146) component (B)-2

observed efficacy action

(Colby)

0.00781 47.3% 47.3

0.000391 0.0% 0.0

0.00781 0.000391 58.2% 58.2 47.3

Botrytis cinerea in Vogels Media Compounds in mg ai/l (ppm) activity expected compound (146) component (B)-2

observed efficacy action

(Colby)

0.03125 17.5% 17.5

0.003125 0.6% 0.6

0.001563 0.0% 0.0

0.03125 0.001563 72.4% 72.4 17.5 0.03125 0.003125 48.0% 48.0 18.0

Septoria tritici in PDB

Compounds in mg ai/l (ppm)

% activity % expected compound (146) isopyrazam

observed efficacy action

(Colby)

0.00781 47.7% 47.7

0.00391 15.2% 15.2

0.00198 3.7% 3.7

0.031250 42.4% 42.4

0.015625 17.8% 17.8

0.003906 1.7% 1.7

0.00781 0.003906 56.8% 56.8 48.6

0.00391 0.031250 70.9% 70.9 51.1

0.00198 0.015625 54.2% 54.2 20.8

CoUetotrichum lagenarium in PDB

Compounds in mg ai/l (ppm) activity expected compound (146) isopyrazam

observed efficacy action

(Colby)

1.00000 54.1% 54.1

0.12500 22.0% 22.0

1.000000 22.4% 22.4

0.500000 0.0% 0.0

0.062500 4.4% 4.4

1.00000 0.500000 59.9% 59.9 54.1

0.12500 0.062500 54.3% 54.3 25.5

1.00000 1.000000 79.6% 79.6 64.4

0.12500 1.000000 67.2% 67.2 39.5

Claims

1 . a synergistically active fungicidal composition comprising a component (A) and a component (B) wherein the component (A) is selected from at least one compound of formula I:

wherein:

R4 is H or acyl, benzoyl and phenylacetyl and the component (B) is selected from at least one selected from the group consisting of Isopyrazam, N-[9-(dichloromethylene)-l ,2,3,4-tetrahydro-l ,4-methanonaphthalen-5-yl]-3- (difluoromethyl)- 1 -methyl- 1 H-pyrazole-4-carboxamide, 3 -(Difluoromethyl)-N-methoxy- 1 - methyl-N-[l -methyl -2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide, Bixafen, Boscalid, Fluxapyroxad, Penthiopyrad, Fluopyram, Prothioconazole, Propiconazole,

Pyraclostrobin, Fluoxastrobin, Picoxystrobin, Kresoxim-methyl, Dimoxystrobin,

Famoxadone, Cyprodinil, Chlorothalonil, Fludioxonil, Metrafenone, Proquinazid,

Cyflufenamid, Fenpropidin, Fenpropimorph, Spiroxamine, Trinexapac-ethyl, Thiamethoxam, Clothianidin, Imidaclodprid, or Tefluthrin.

2. A composition suitable for control of diseases caused by phytopathogens according to claim 1 wherein the at least one further compound the component (B) is selected from the group Isopyrazam, N-[9-(dichloromethylene)-l ,2,3,4-tetrahydro-l ,4-methanonaphthalen-5- yl]-3-(difluoromethyl)-l-methyl-lH-pyrazole-4-carboxamide and 3 -(Difluoromethyl) -N- methoxy-1 -methyl -N-[l-methyl-2-(2,4,6-trichlorophenyl)ethyl]-lH-pyrazole-4-carboxamide.

3. A composition suitable for control of diseases caused by phytopathogens according to claim 1 wherein Ri is phenyl optionally substituted with halogen, Ci-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, Ci-C₆-alkylthio, Ci-C₆-haloalkoxy, phenoxy, methoxypropargyl, cyano, or nitro; or furanyl, thienyl, pyridyl, or benzothienyl, each optionally substituted with halogen.

4. A composition suitable for control of diseases caused by phytopathogens according to claim 3 wherein Ri is 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2-fluorophenyl,

2,4-difluorophenyl, 3,5-difluorophenyl, 4-trifluoro-methylphenyl, 4-trifluoromethoxyphenyl, 2-fluoro-4-chlorophenyl or 2-thienyl.

5. A composition suitable for control of diseases caused by phytopathogens according to any one of claims 3 or 4 wherein R₂ is pyridyl, pyrimidinyl or isoquinolyl, each optionally substituted with halogen, Ci-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, Ci-C₆-haloalkyl, Ci-C₆- alkoxy, Ci-C₆-alkylthio, Ci-C₆-haloalkoxy, cyano, or nitro.

6. A composition suitable for control of diseases caused by phytopathogens according to claim 4 to 6 wherein R₂ is 3-pyridyl, 4-pyridyl, or 5-pyrimidinyl, each optionally substituted with methyl, chloro, fluoro, methoxy, thiomethoxy or trifluoromethyl

7. A composition suitable for control of diseases caused by phytopathogens according to claim 3 to 6 wherein R₃ is phenyl, 3-chlorophenyl, 4-chlorophenyl, 4-fluorophenyl, 3,5- difluorophenyl, 4-methylphenyl, 2,4-difluorophenyl, 2-thienyl, 5-chloro-2-thienyl, 5-methyl-

2- thienyl, 3-thienyl, t-butyl, or trimethylsilyl.

8. A composition suitable for control of diseases caused by phytopathogens according to claims 3 to 7 wherein R₄ is H.

9. A composition suitable for control of diseases caused by phytopathogens according to claim 1 wherein the compound of formula (I) is selected from:

3- (2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]- isoxazole;

3-(4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;

3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]-isoxazole;

3-(2,4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;

3-(2-fluoro-4-chlorophenyl)-5-(2-chlorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;

3-(4-chlorophenyl)-5-(2-methoxypyridine)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;

3-(4-chlorophenyl)-5-(4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;

3-(4-chlorophenyl)-5-(2,4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;

3-(2,4-difluorophenyl)-5-(2-chloro-4-fluorophenyl)-4-[(3pyridyl)hydroxymethyl]-isoxazole; and

(5)-3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole; and salts thereof.

10. A composition suitable for control of diseases caused by phytopathogens according to claim 1 wherein the compound of formula (I) is selected from:

3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]- isoxazole;

3-(4-chlorophenyl)-5-(4-fluorophenyl)-4-[(3-pyrimidyl)hydroxymethyl]-isoxazole;

(5)-3-(2-fluoro-4-chlorophenyl)-5-(2,4-difluorophenyl)-4-[(3-pyridyl)hydroxymethyl]- isoxazole;

and salts thereof.

11. A method of regulating plant growth of crops of useful plants, which comprises applying to said plants, to one or more parts of said plants, or to the locus thereof or plant propagation material, a mixtures as defined in any one of claims 1 to 10.

12. A method according to claim 11, which comprises one or more applications of one of more compounds of formula (I) alone or in conjunction with one or more customary plant protection formulating auxiliaries.

13. A method according to claim 10 wherein two or more applications are carried out in sequence, and wherein the two or more applications have the same or different concentration or combinations of mixtures as defined in any one of claims 1 to 10 or both.

14. A method according to any one of claims 11 to 13 wherein the useful crop plants are selected from the group consting of cereals, rice, beets, leguminous plants, oil plants, cucumber plants, fibre plants, vegetables, plantation crops, ornamentals, vines, bushberries, caneberries, cranberries, peppermint, rhubarb, spearmint, sugar cane and turf grasses.

15. An agricultural composition comprising mixtures as defined in any one of claims 1 to 10, and one or more customary plant protection auxiliaries.