WO2005056548A1 - Epoxiconazole enantiomeriquement pur et ses utilisations en tant qu'agent phytosanitaire - Google Patents

Epoxiconazole enantiomeriquement pur et ses utilisations en tant qu'agent phytosanitaire Download PDF

Info

Publication number
WO2005056548A1
WO2005056548A1 PCT/DK2004/000858 DK2004000858W WO2005056548A1 WO 2005056548 A1 WO2005056548 A1 WO 2005056548A1 DK 2004000858 W DK2004000858 W DK 2004000858W WO 2005056548 A1 WO2005056548 A1 WO 2005056548A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
enantiomers
formula
composition according
general structure
Prior art date
Application number
PCT/DK2004/000858
Other languages
English (en)
Inventor
Niels Jacobsen
Anders Lohse
Harald Bernhard Teicher
Original Assignee
Cheminova A/S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cheminova A/S filed Critical Cheminova A/S
Publication of WO2005056548A1 publication Critical patent/WO2005056548A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • Epoxiconazole Enantiomerically pure Epoxiconazole and its use as crop protection agent
  • the invention relates to compositions comprising the compound (la) and the use of said compound in the control of harmful phytopathogenic fungi.
  • the inven- tion also relates to compositions comprising the compound (lb) and the use of said compositions for influencing the growth of plants.
  • the present invention further relates to a process for the preparation of the enantiomerically pure compound (la) which is (2S,3R)-l-[3-(2-chlorophenyl)-2-(4- fluorophenyl)oxiranyl]methyl-lH-[l,2,4]triazole or the compound (lb) which is (2R,3S)-l-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiranyl]methyl-lH- [l,2,4]triazole
  • the compound of formula (I), which is l-[3-(2-chlorophenyl)-2-(4- fluorophenyl)oxiranyl]methyl-lH-[l,2,4]triazole, is known as a fungicide from United States patent no. 4,906,652 and its use as a plant growth regulator known from European patent no. 315850- A2.
  • the compound can exist as four difference isomers, i.e. a pair of diastereomers having either the E- or Z-form, also known as the trans or cis form respectively, each consisting of two enantiomers.
  • a pair of diastereomers having either the E- or Z-form, also known as the trans or cis form respectively, each consisting of two enantiomers.
  • United States patent no. 4,906,652 it is possible to produce exclusively the Z-form (2RS,3SR diastereomer, compound 8 in said patent) consisting of a 1:1 racemic mixture of the (2R,3S) and (2S,3R) forms.
  • Epoxiconazole This racemic mixture is commer- cially known as Epoxiconazole (for instance sold under the trademark OPUS) and is used in the control of harmful phytopathogenic fungi.
  • Epoxiconazole belongs to the class of pesticides termed "triazoles" generally known for their fungicidal and plant growth regulating effect. Many of these compounds possesses one or more asymmetric carbon atoms and hence exists in several structurally different isomeric forms. As illustrated by Spindler et al. in Chirality in Agrochemicals - Wiley 1998, p. 157-173, the fungicidal activity for a given compound can in some instances be restricted to a single enantiomer (e.g.
  • Triadimenol, 4 enantiomers Triadimenol, 4 enantiomers
  • each enantiomer show varying relative activity towards different target organisms (e.g. Propiconazole, 4 enantiomers).
  • the most active isomer out of 4 possible of the triazole fungicide Diclobutrazol has the 2R,3R configuration whereas in the structural closely related compound Triadimenol the most active isomer in contrast has the 2S,3R configuration as stated by Baldwin et al. in Pesticide Science, 1984, p. 157-166. Sugavanam in Pesticide Science, 1984, p.
  • the present invention contributes vitally to plant dis- ease control and to cultivation of more resistive plant in the fields of agriculture and horticulture. For instance, application of a more active chemical substantially free from any inactive isomer forms is connected to adequate application of a smaller amount of the chemical, which leads to the improvement in economics of the processes of manufacture, transportation and field application and to the expectation of minimising the environmental pollution as well as the improvement in safety.
  • optically pure compound (lb) has a significantly higher influence on plant growth than the corresponding racemic Z-form or the enantiomerically pure (2S,3R)-enantiomer (compound la).
  • the present invention provides a composition suitable for controlling harmful fungi, comprising a solid or liquid carrier and the compound (la) substantially free from the compound (lb) or any of the other enantiomers having the general structure (I).
  • the present invention also provides a method of controlling harmful fungi, which comprises treating the fungi or the materials, plants, soil or seed to be protected from fungal attack with an active amount of a compound formula (la) substantially free from the compound (lb) or any of the other enantiomers having the general structure (I).
  • the present invention provides a composition suitable for influencing the growth of plants, comprising a solid or liquid carrier and the compound (lb) substantially free from the compound (la) or any of the other enantiomers having the general structure (I).
  • the present invention also provides a method for influencing the growth of plants, which comprises treating the plants, soil of seed with an active amount of a compound (lb) substantially free from the compound (la) or any other enantiomers having the general structure (I).
  • the composition contains a greater proportion or percentage of the compound (la) or (lb), on a weight basis, in relation to the any other enantiomer of the formula (I), these percentages being based on the total amount of the compound (I) present.
  • the term “substantially free from” as used herein means that the composition contains at least 70% by weight of the compound (la) or (lb), and 30% by weight or less of the other enantiomers having the general structure (I).
  • the term “substantially free from” means that the composition contains at least 80% by weight of the compound (la) or (lb) in relation to the any other enantiomer of the formula (I). In a still more preferred embodiment, the term “substantially free from” means that the composition contains at least 90% by weight of the compound (la) or (lb) in relation to the any other enantiomer of the formula (I). In an even more preferred embodiment, the term “substantially free from” means that the composition contains at least 99% by weight of the compound (la) or (lb) in relation to the any other enantiomer of the formula (I).
  • the present invention provides a method for the preparation of the compounds (la) and (lb) in substantially enantiomerically pure form.
  • the invention further relates to said compounds prepared by the method described herein or isolated in substantially enantiomerically pure form from the racemic Z-mixture or from a racemic mixture of both the Z and E form.
  • substantially enantiomerically pure form of the active compound as used herein, means that the desired isomer is synthesised or isolated at 95-100%, preferably 100%o, purity relative to any of the other enantiomers having the general struc- ture (I).
  • the present invention also relates to novel intermediates, which are precursors to the compounds (la) and (lb). Said intermediates and the compounds (la) and (lb) may serve as starting materials for the preparation of other active compounds in enantiomerically pure form for either agrochemical or pharmaceu- tical use.
  • the compound (la) is synthesised in substantially enantiomerically pure form in a process, which comprises the following steps:
  • L represents a leaving group other than OH; d) reacting the compound (IVa) in the presence of a base with lH-l,2,4-triazole or one of its salts.
  • the configuration of the asymmetric carbon atoms are classified as "R” or "S” in accordance with the Cahn-Ingold-Prelog rules, and although changes in the assignment of configuration are seen during the course of the above steps, the two phenyl groups on the oxiran ring maintain their orientation in space during the above procedure, and the change in assignment of configuration is merely a result of these rules.
  • the compound (lb) is synthesised in the same manner using the above step a) and onwards utilising the (2S,3S) isomer (compound lib) whereby intermediate compounds of the formula (Illb) and (INb) occur.
  • the acid-salt forming resolving agent employed in step a) is preferably an opti- cally active amine and in particular an optically active amine of the following formula (V)
  • R 1 and R 2 are different and each represent C ⁇ -8 alkyl optionally substituted with one or more phenyl groups; phenyl or naphtyl which may be substituted with one or more C 1-4 alkyl groups. It is most preferred to use either one of the optical active isomers of 1-methylbenzyl amine.
  • the salt of (S)- 1-methylbenzyl amine and the (2R,3R) enantiomeric form of compound (II) is considerably less soluble than the diastereomer salt from (S)- 1-methylbenzyl amine and the (2S,3S) enantiomeric form of compound (II)).
  • the salts that are diastereomers to each other show sufficiently large differences in solubility in numerous solvents.
  • water belongs to this class of solvents.
  • solvents primary or secondary alcohols having up to 6 carbon atoms or ethers and among these solvents especially those, which are miscible with water.
  • hexanol, butanol, methyl t-butyl ether and especially methanol, ethanol, propan-2-ol, dioxane and tetrahydrofuran can be used.
  • Other solvents include propanol, butan-2-ol, 2-methyl-propanol.
  • the solvents can also be used in mixtures with each other or in mixtures with water, but the mixtures are suitably so selected that the solvents form a single phase.
  • the molar ratio of optically active acid-salt forming resolving agent to the compound of formula (II) is between 0.5 and 1.
  • the procedure is by fractional crystallisation in the customary manner. The mixture is either brought to elevated temperatures and subsequently the solution cooled for the crystallisation or a mixture of (II) is held at a fixed temperature for the crystallisation and the acid-salt forming compound in the same or different solvent is added gradually.
  • the salt of the (2R,3R)-acid is isolated by filtration and the (2R,3R) enantiomer, i.e. com- pound (Ha), separated from the salt by reaction with a mineral acid e.g. hydrochloric acid.
  • a mineral acid e.g. hydrochloric acid.
  • step b) the (2R,3R) enantiomer of the compound (II) is reacted with an alkoxycarbonyl chloride, preferably ethoxycarbonyl chloride to form the inter- mediate anhydride which is subjected to reduction by a reducing agent which may be selected among borohydrides, e.g. NaBH 4 ; aluminium hydrides e.g. those of formulae R R 4 A1H, M[R 3 R 4 A1H 2 ] or MA1H 4 , wherein R 3 and R 4 each independently of the other represents C 1- alkyl, and M is lithium or sodium.
  • a reducing agent which may be selected among borohydrides, e.g. NaBH 4 ; aluminium hydrides e.g. those of formulae R R 4 A1H, M[R 3 R 4 A1H 2 ] or MA1H 4 , wherein R 3 and R 4 each independently of the other represents C 1- alkyl, and M is lithium or sodium.
  • the intermediate anhydride is prepared at tem- peratures between -20 and 40 °C in an organic solvent, e.g CH 2 CI 2 , in the presence of a base such as an alkali metal hydroxide or a tertiary amine e.g. trialkyl amine such as triethyl amine.
  • a base such as an alkali metal hydroxide or a tertiary amine e.g. trialkyl amine such as triethyl amine.
  • a small molar excess of the alkoxy carbonyl chloride is preferably used.
  • the intermediate anhydride may be isolated but is advantageously treated directly with the reducing agent at temperatures between -20 and 40 °C.
  • the amount of reducing agent is in excess compared to the intermediate anhydride and usually in a molar excess between 2-6.
  • the compound (Hla) can be isolated and purified if desired, but may also be used without further purification.
  • the leaving group L may be any suitable leaving group known within the art. It is within the skills of an ordinary practitioner to select a suitable leaving group.
  • Typical leaving groups L includes halogen, preferably chlorine or bromine; C ⁇ -6 -alkylsulfonyloxy such as methylsulfonyloxy; C ⁇ -6 -haloalkylsulfonyloxy such as trifluoromethylsulfonyloxy; arylsulfonyloxy such as phenyl- or naphtylsulfonyloxy, where the aryl radical may, if appropriate, be substituted by one or more halogen or C ⁇ -6 -alkyl groups, such as phenyl- sulfonyloxy, -toluenesulfonyloxy and ⁇ -Cl-phenylsulfonyloxy.
  • L is preferably chlorine, bromine
  • the displacement agent may be any suitable displacement agent known within the art. It is within the skills of an ordinary practitioner to select a suitable displacement agent for a particular reaction.
  • Typical displacement agents include sulfonyl chlorides such as methansulfonyl chloride and p- toluensulfonyl chloride; thionyl chloride or bromide, phosphorus chlorides or bromides such as PC1 3 or PC1 5 ; phosphoryl chloride or bromide e.g. POCI 3 or POBr 3 .
  • the final step d) is carried out in the presence of a solvent, but may be performed without, at temperatures from 0 to 120 °C.
  • a solvent include ke- tones e.g. acetone, methyl ethyl ketone and cyclohexanone; nitriles e.g. acetoni- trile; esters e.g. ethyl acetate; ethers, e.g. diethyl ether, tetrahydrofuran and diox- ane; sulfoxides, e.g. dimethylsulfoxide (DMSO); amides, eg.
  • DMSO dimethylsulfoxide
  • the base may be chosen by example among alkali metal carbonates, e.g. sodium carbonate, potassium carbonate, sodium bicarbon- ate and potassium bicarbonate; alkali metal hydroxides e.g. lithium hydroxide, sodium hydroxide and potassium hydroxide.
  • alkali metal carbonates e.g. sodium carbonate, potassium carbonate, sodium bicarbon- ate and potassium bicarbonate
  • alkali metal hydroxides e.g. lithium hydroxide, sodium hydroxide and potassium hydroxide.
  • the starting compound (II), mainly in its Z-form, is prepared by known methods.
  • the main area in which the compound of formula (la) is used is in the control of harmful phytopathogenic fungi.
  • the compound of formula (la) has, for practical field application purposes, a very advantageous curative, preventive and systemic action for protecting cultivated plants without having undesired side-effects on such plants.
  • cultivated plants are, for example, cereals (wheat, barley, rye, oats, rice); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sun- flowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (cucumber, marrows, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika) or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas, avocados and natural rubber plants, as well
  • the compound of formula (la) is effective especially against the phytopathogenic fungi belonging to the following classes: Ascomycetes e.g. Erysiphe, Ven- turia, Pyrenophora, Calonectria graminicola; Basidiomycetes, e.g. rusts (Puc- cinia) and smuts (Tilletia and Ustilago); Deuteromycotina, e.g. Helminthospo- rium, Fusarium, Septoria, Cercospora.
  • Ascomycetes e.g. Erysiphe, Ven- turia, Pyrenophora, Calonectria graminicola
  • Basidiomycetes e.g. rusts (Puc- cinia) and smuts (Tilletia and Ustilago)
  • Deuteromycotina e.g. Helminthospo- rium, Fusarium, Septoria, Cercospora
  • the pathogens that are controlled are especially those attacking cereals at any stage of development, whether it be on emergence, on bushing, on ripening or on sowing.
  • Cereal types which may be mentioned are, for example, wheat, rye, barley, oats, rice, maize and sorghum.
  • the following important pathogens inter alia are controlled by the compound (la):
  • Tilletia caries barley, wheat, rye
  • Drechslera teres barley, wheat
  • Fusarium nivale rye
  • Fusarium culmorum wheat
  • Erysiphe graminis cereals
  • Uncinula necator (vines) Puccinia graminis (wheat, barley, rye, oats)
  • Rhizoctonia solani (cotton, lawns)
  • Helminthosporium gramineum barley, wheat
  • Helminthosporium oryzae rice
  • Botrytis cinerea (gray mold - strawberries and vines)
  • the compound of formula (la) is particular useful for the control of diseases caused by Ascomycetes (e.g. Mildew); Basidiomycetes (e.g. Rusts), and Deu- teromycetes (Septoria) on cereals and in particularly on wheat and barley. Further, the compound of formula (la) may be used in the dressing of seeds to protect against such diseases as Fusarium, Septoria, Tilletia, Ustilago and Helminthosporium on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice
  • the compound of formula (la) or (lb) can be converted into the customary for- mulations, such as solutions, emulsions, suspensions, dusts, powders, pastes or granules.
  • the use forms here depend on the particular intended use.
  • the formulations are prepared in a known manner, eg. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispers- ants, where if water is used as a diluent other organic solvents can also be used as auxiliary solvents.
  • Suitable auxiliaries for this purpose are mainly: solvents such as aromatics (eg. xylene), chlorinated aromatics (eg. chloroben- zenes), paraffins (eg. petroleum fractions), alcohols (eg. methanol, butanol), ke- tones (eg. cyclohexanone), amines (eg. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (eg. kaolins, aluminas, talc, chalk) and ground synthetic minerals (eg. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.
  • solvents such as aromatics (eg. xylene), chlorinated aromatics (eg
  • Suitable surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, eg. lignosulfonic, phenolsulfonic, naphthalenesulfonic and dibutylnaphthalenesulfonic acid, and also of fatty acids, alkyl- and alkylarylsulfonates, alkyl-, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphe- nol ether, ethoxylated isooctyl
  • Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by addition of water.
  • the substrates can be homogenized in water as such or dissolved in an oil or solvent, by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of active substance, wetting agent, adhesive, dispersant or emulsifier and possibly solvent or oil can also be prepared which are suitable for dilution with water.
  • Powder, scattering and dusting compositions may be prepared by mixing or joint grinding of the active substances with a solid carrier.
  • Granules eg. coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
  • Solid carriers are mineral earths such as silica gel, silicic acids, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark meal, wood meal and nutshell meal, cellulose powder or other solid carriers.
  • the active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges.
  • compositions contain from 0.0001 to 95% by weight of active compound.
  • Formulations containing more than 95% by weight of active compound can be applied highly successfully in the ultra-low volume process
  • compositions are applied in amounts sufficient as to provide a fungicidal active amount of the compound (la). Such amount are usually from 0.02 to 1 kg or more of active ingredient per hectar.
  • compositions When used to influence the growth of plants the compositions are applied in amounts sufficient as to provide a plant growth influencing active amount of the compound (lb). Such amounts are usually from 0.01 to 5 kg or more of active ingredient per hectare.
  • the active compound of formula (la) according to the invention can also be used as a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, for example to widen the spectrum of action or to prevent the build-up of resistance.
  • known fungicides, bactericides, acaricides, nematicides or insecticides for example to widen the spectrum of action or to prevent the build-up of resistance.
  • synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.
  • particularly advantageous mixtures are the following compounds.
  • fenbuconazole fenfuram, fenhexamid, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumo ⁇ h, fluoromide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, iprovali- carb, iso
  • Bactericides bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamy- cin, octhilinone, furanecarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • Insecticides/ Acaricides/Nematicides abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, azadirachtin, azinphos, azocyclotin,
  • Especially preferred (synergistic) mixture partners are benzimidazole fungicides
  • imidazole/triazole fungicides e.g. azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, paclobutrazol, penconazole, propiconazole, prochloraz, prothioconazole, tebuconazole, tetraconazole, tridi- mefon, triadimenol, triticonazole, uniconazole), carboxamide fungicides (e.g.
  • mo ⁇ holine fungicides e.g. dimethomo ⁇ h, dodemo ⁇ h, fenpropimo ⁇ h, fenpropidin, flumo ⁇ h, spiroxamine, tridemo ⁇ h
  • neonicotinoid insecticides e.g. acetamiprid, clothianidin, dinotefuran, imida- cloprid, nitenpyram, thiacloprid, thiamethoxam
  • phenylamide fungicides e.g.
  • organophos- phate insecticides e.g. chlo ⁇ yrifos, chlo ⁇ yrifos-methyl, dimethoate, malathion, phosalone
  • pyrethroid type insecticides e.g.
  • azox- ystrobin dimoxystrobin, famoxadone, fenamidone, fluoxastrobin, kresoxim- methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin), abamectin, ca ⁇ ropamide, captan, chlorothalonil, cyprodinil, fenhexamid, fipronil, fluazinam, folpet, fosethyl-al, iprodione, iprovahcarb, mancozeb, maneb, metiram, metrafenone, pyrimefhanil, quinoxyfen, sulfur, thiophanate- methyl, thiram, tolylfluanid, vinclozolin, zineb, and zoxamide.
  • a mixture with other known active compounds, such as herbicides or with fertil- izers or growth regulators (e.g. mepiquat and salts there of) is also possible.
  • the active compound of formula (lb) according to the invention can also be used as a mixture with known plant growth regulators, fungicides, bactericides, acaricides, nematicides or insecticides. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.
  • antiauxins clofibric acid, 2,3,5-tri-iodobenzoic acid, auxins: 4-CPA, 2,4-D, 2,4-DB, 2,4-DEP, dichlo ⁇ rop, fenoprop, IAA, IBA, naphthaleneacetamide, ⁇ -naphthaleneacetic acid, 1-naphthol, naphthoxyacetic acid, potassium naphthenate, sodium naphthenate, 2,4,5-T cytokinins: 2iP, benzyladenine, kinetin, zeatin defoliants: calcium cyanamide, dimethipin, endothal, ethephon, me ⁇ hos, me- toxuron, pentachlorophenol, thidiazuron, tribufos ethylene inhibitors: aviglycine, 1-methylcyclopropene ethylene releasers: ACC, et reviewingl, ethephon, glyoxime, growth inhibitors: absc
  • Example 1 preparation of the starting material (II) To a stirred solution of 60.0 g (0.22 mol) 3-(2-chlorophenyl)-2-(4- fluorophenyl)oxiranecarbaldehyde (94 % (Z)-isomer) in 200 ml acetonitrile was added 1.6 g NaH 2 PO 4 dissolved in 20 mL water. The mixture was cooled with ice and 20 ml 35% H 2 O 2 was added in one portion. A solution of 32 g 80% pure NaClO 2 in 280 mL water was then added with stirring at 8 - 10 °C during 2 hours.
  • Example A Control effect on Septoria nodorum and Septoria triticii (Deu- teromycetes) on agar medium. Standard formulations were prepared by mixing under stirring the following ingredients (all amounts in grams):
  • Table 1 Control effect on Septoria nodorum and Septoria triticii (Deuteromy- cetes) on agar medium. Values are average diameters in cm of fungal-free zone around site of application.
  • Example B Control effect on Puccinia recondita (Basidiomycetes) on wheat.
  • Wheat Triticum aestivum L.
  • four leaves (second leaf) from four separate seedlings were divided into 4 regions using a non-toxic marker. Region 1 was toward the leaf base, while region 4 was the leaf tip area.
  • the seedlings were inoculated with a fungal suspension of Puccinia recondita. The inoculated seedlings were incubated for a period of 24h at 18°C.
  • Example C Control effect on Puccinia recondita on wheat (climate chamber).
  • Wheat Triticum aestivum L.
  • the seedlings were inoculated with a fungal suspension of Puccinia recondita.
  • the inoculated seedlings were incubated for a period of 24h at 18°C.
  • Plants were sprayed with the racemic and chiral solutions at rates of 0.3, 1, 3, 10, 30, 100 or 300g/Ha, respectively.
  • Fungicidal effect was determined visually as the absence or presence of the fungus on the leaves. By fitting the effect data to a sigmoidal dose-response curve the ED50 value was determined.
  • Table 3 Control effect on Puccinia recondita on wheat (climate chamber).
  • Example D Control effect on Puccinia recondita on wheat (semi-field trials).
  • Wheat Triticum aestivum L.
  • Plants were sprayed with the racemic and chiral solutions at rates of 0.3, 1, 3, 10, 30, 100 or 300g/Ha, respectively.
  • One day after spraying the seedlings were inoculated with a fungal suspension of Puccinia recondita.
  • the inoculated seedlings were incubated for a period of 24h at 18°C.
  • plants where transferred to a semi-field plot, consisting of a greenhouse table erected in the immediate vicinity of a wheat field. Fungi- cidal effect was determined visually as the absence or presence of the fungus on the leaves.
  • the effect data was fitted to a sigmoidal dose-response curve the ED50 value was determined.
  • Example E Effect of seed treatment on germination and seedling emergence (greenhouse).
  • Table 5 Average plant height, seven days after sowing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des compositions renfermant le composé (Ia) et l'utilisation dudit composé dans la lutte contre des champignons phytopathogéniques nuisibles, ainsi qu'un procédé de préparation du composé (Ia) constitué de (2S, 3R)-1[3-(22-chloro-phényl)-2(4-fluoro-phényl)-oxiranyl]méthyl-1H[1,2,4] triazole ou du composé (Ib) constitué de (2R, 3S)-1[3-(2-chloro-phényl)-2(4-fluoro-phényl)-oxiranyl]méthyl-1H-[1,2,4]triazole, sous une forme énantiomère pure. Cette invention a aussi pour objet des compositions contenant le composé (Ib) et l'utilisation dudit composé de manière à influencer la croissance desdits végétaux.
PCT/DK2004/000858 2003-12-11 2004-12-10 Epoxiconazole enantiomeriquement pur et ses utilisations en tant qu'agent phytosanitaire WO2005056548A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DKPA200301830 2003-12-11
DKPA200301830 2003-12-11
DKPA200400265 2004-02-20
DKPA200400265 2004-02-20

Publications (1)

Publication Number Publication Date
WO2005056548A1 true WO2005056548A1 (fr) 2005-06-23

Family

ID=34680190

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DK2004/000858 WO2005056548A1 (fr) 2003-12-11 2004-12-10 Epoxiconazole enantiomeriquement pur et ses utilisations en tant qu'agent phytosanitaire

Country Status (1)

Country Link
WO (1) WO2005056548A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011069894A1 (fr) 2009-12-08 2011-06-16 Basf Se Composés triazoles, leur utilisation et agents les contenant
WO2011069912A1 (fr) 2009-12-07 2011-06-16 Basf Se Composés triazole, leur utilisation et produits les contenant
WO2011069916A1 (fr) 2009-12-08 2011-06-16 Basf Se Composés triazoles, leur utilisation comme fongicides et agents les contenant
WO2011113820A1 (fr) 2010-03-16 2011-09-22 Basf Se Procédé utilisant des réactifs de grignard
WO2012041858A1 (fr) 2010-09-30 2012-04-05 Basf Se Procédé de synthèse de composés contenant des groupes thio-triazolo
EP2484210A1 (fr) 2011-02-08 2012-08-08 Basf Se Compositions pesticides
WO2012130823A1 (fr) 2011-03-30 2012-10-04 Basf Se Concentrés en suspension
CN105085439A (zh) * 2015-08-31 2015-11-25 江苏七洲绿色化工股份有限公司 一种氟环唑中间体的制备方法
CN106279067A (zh) * 2016-08-16 2017-01-04 江苏七洲绿色化工股份有限公司 一种氟环唑中间体的制备方法及氟环唑的制备方法
WO2018060090A1 (fr) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Dérivés d'imidazolylméthyloxirane à substitution en position 5 en tant que fongicides
CN113321622A (zh) * 2021-06-28 2021-08-31 上海晋鲁医药科技有限公司 一种1-甲基-1h-1,2,4-***-3-甲酸甲酯的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0315850A2 (fr) * 1987-11-07 1989-05-17 BASF Aktiengesellschaft Procédé pour influencer la croissance des plantes par des azolylméthyloxiranes
EP0379081A2 (fr) * 1989-01-18 1990-07-25 BASF Aktiengesellschaft Procédé pour la préparation de 1-hydroxyméthyl-oxirannes Z-substitués en position 2
EP0409049A2 (fr) * 1989-07-18 1991-01-23 BASF Aktiengesellschaft ProcédÀ© pour la fabrication stéréosélective de chlorures d'allyle-Z-1,2-diaryle et leur conversion en azolylméthyloxiranes et intermédiaires
WO1998015180A1 (fr) * 1996-10-08 1998-04-16 Isagro S.P.A. Compositions fongicides et leur utilisation pour lutter contre les champignons phytopathogenes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0315850A2 (fr) * 1987-11-07 1989-05-17 BASF Aktiengesellschaft Procédé pour influencer la croissance des plantes par des azolylméthyloxiranes
EP0379081A2 (fr) * 1989-01-18 1990-07-25 BASF Aktiengesellschaft Procédé pour la préparation de 1-hydroxyméthyl-oxirannes Z-substitués en position 2
EP0409049A2 (fr) * 1989-07-18 1991-01-23 BASF Aktiengesellschaft ProcédÀ© pour la fabrication stéréosélective de chlorures d'allyle-Z-1,2-diaryle et leur conversion en azolylméthyloxiranes et intermédiaires
WO1998015180A1 (fr) * 1996-10-08 1998-04-16 Isagro S.P.A. Compositions fongicides et leur utilisation pour lutter contre les champignons phytopathogenes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUTTA M ET AL: "Liquid chromatographic method development for determination of fungicide epoxiconazole enantiomers by achiral and chiral column switching technique in water and soil", JOURNAL OF CHROMATOGRAPHY A, ELSEVIER SCIENCE, NL, vol. 959, no. 1-2, 14 June 2002 (2002-06-14), pages 143 - 152, XP004360283, ISSN: 0021-9673 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011069912A1 (fr) 2009-12-07 2011-06-16 Basf Se Composés triazole, leur utilisation et produits les contenant
WO2011069916A1 (fr) 2009-12-08 2011-06-16 Basf Se Composés triazoles, leur utilisation comme fongicides et agents les contenant
WO2011069894A1 (fr) 2009-12-08 2011-06-16 Basf Se Composés triazoles, leur utilisation et agents les contenant
US9167817B2 (en) 2010-03-16 2015-10-27 Basf Se Process using Grignard reagents
WO2011113820A1 (fr) 2010-03-16 2011-09-22 Basf Se Procédé utilisant des réactifs de grignard
US8729272B2 (en) 2010-03-16 2014-05-20 Basf Se Process using grignard reagents
WO2012041858A1 (fr) 2010-09-30 2012-04-05 Basf Se Procédé de synthèse de composés contenant des groupes thio-triazolo
EP2484210A1 (fr) 2011-02-08 2012-08-08 Basf Se Compositions pesticides
WO2012130823A1 (fr) 2011-03-30 2012-10-04 Basf Se Concentrés en suspension
CN105085439A (zh) * 2015-08-31 2015-11-25 江苏七洲绿色化工股份有限公司 一种氟环唑中间体的制备方法
CN105085439B (zh) * 2015-08-31 2018-03-16 江苏七洲绿色化工股份有限公司 一种氟环唑中间体的制备方法
CN106279067A (zh) * 2016-08-16 2017-01-04 江苏七洲绿色化工股份有限公司 一种氟环唑中间体的制备方法及氟环唑的制备方法
WO2018060090A1 (fr) 2016-09-29 2018-04-05 Bayer Cropscience Aktiengesellschaft Dérivés d'imidazolylméthyloxirane à substitution en position 5 en tant que fongicides
CN113321622A (zh) * 2021-06-28 2021-08-31 上海晋鲁医药科技有限公司 一种1-甲基-1h-1,2,4-***-3-甲酸甲酯的制备方法
CN113321622B (zh) * 2021-06-28 2022-06-24 上海晋鲁医药科技有限公司 一种1-甲基-1h-1,2,4-***-3-甲酸甲酯的制备方法

Similar Documents

Publication Publication Date Title
US10111433B2 (en) Fungicidal compositions
US9278941B2 (en) Azole derivative and uses thereof
CA2838586C (fr) Derive azole, son procede de fabrication, compose intermediaire et agent chimique agricole ou horticole et agent de protection de matiere industrielle
EP2315752A1 (fr) Dérivés de 5-benzyl-4-azolylméthyl-4-spiro[2.4]heptanol, leurs procédés de fabrication et agents pour l agriculture et l horticulture et agents de protection de matériel industriel correspondants
EP2509958A1 (fr) Dérivés d'azole, leurs procédés de production, leur intermédiaire, agents à usage agricole et horticole
EP0832083A1 (fr) (mercapto-triazolylmethyl)-dioxacycloalcanes microbicides
MX2011000077A (es) Mezclas fungicidas que comprenden 1-metilpirazol-4-ilcarboxanilida s sustituidas.
EP2509959A1 (fr) Dérivés azole et leurs procédés de production, composés intermédiaires pour synthétiser les dérivés et leurs procédés de production, et agents agro-horticoles et agents de protection de produits industriels contenant les dérivés
WO2005056548A1 (fr) Epoxiconazole enantiomeriquement pur et ses utilisations en tant qu'agent phytosanitaire
US9241488B2 (en) Azole derivative, method for producing azole derivative, and intermediate compound
RU2656550C2 (ru) Композиция стереоизомеров дифеноконазола с пониженной фитотоксичностью
KR102497895B1 (ko) 아졸 유도체, 아졸 유도체의 제조 방법, 및 농원예용 약제 및 공업용 재료 보호제
EP2719281A1 (fr) Agent chimique pour l'agriculture ou l'horticulture, composition pour lutter contre les maladies des plantes, procédé pour lutter contre les maladies des plantes et produit pour lutter contre les maladies des plantes
WO2010074021A1 (fr) Dérivé de 1-(1-chlorocyclopropyle)-2-(1h-1,2,4-triazole-1-yle)-2-propène-1-ole substitué, son procédé de production, et produit chimique employé en agriculture/horticulture et agent de protection des équipements industriels contenant celui-ci
EP3750888A1 (fr) Forme cristalline a de 1,4-diméthyl-2-[2-(pyridine-3-yl)-2h-indazol-5-yl]-1,2,4-triazolidine-3,5-dione
WO1994029281A1 (fr) Cyclobutylazoles
US9253983B2 (en) Triazole compound and use thereof
WO1996041798A1 (fr) (mercapto-triazolylmethyl)-ethanols microbicides
JP2011246380A (ja) ピリダジン化合物ならびにその用途
DK201400182U1 (da) Et kombinationsprodukt
DE4412358A1 (de) Cyclopropyl-ethyl-azole
DE4412332A1 (de) Silyloxy-cyclopropyl-azolyl-Derivate
JP2011231037A (ja) ピリダジン化合物ならびにその用途
WO1995008537A1 (fr) Thioesters de pyridin-3-imino et leur utilisation comme fongicides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase