(-)-enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2 - hydroxypropyl]-2,4-dihydro-[1, 2,4]-triazole-3-thione and its production method

 

(57) Abstract:

New (-)-enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxy-propyl]-2,4-dihydro-[1,2,4]-triazole-3-thione of the formula (I)

and how to obtain it. 1 C.p. f-crystals, 5 PL.

The present invention relates to a new (-)-enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione, the method of its production and its use as microbicide.

It is well known that the racemate of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione has fungicidal properties (see WO 96-16048). The effectiveness of this substance is good, but at a very low cost in some cases leaves much to be desired.

Now found a new (-)-enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione of the formula

Under (-)-enantiomer is accordingly such an enantiomer that rotates to the left oscillating plane-polarized light (D line of sodium.

It was further found that (-)-enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione of the formula (1) receive, if

a) the racemate of 2-[">chromatographic on chiral stationary phase of kieselguhr-gel based optical active monomer N-methacryloyl-L-leucine-3-(2,4-dimethylpentyl)amide with ethyl acetate as eluent at a temperature of from 20 to 25°C.

b) the eluate evaporated under reduced pressure and

c) drop-down when this product is recrystallized from toluene.

Finally found that the new (-)-enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione of the formula (I) has a very good microbicide properties and can be used as a fungicide for crop protection and in the protection of materials for controlling undesirable microorganisms.

(-)-Enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-tion of the formula (I) according to the invention unexpectedly discovered considerably better fungicidal effect than the corresponding (+)-enantiomer and the corresponding racemate, which have high efficiency recognized as biologically active substances with fungicidal properties.

(-)-Enantiomer according to the invention may be fully or partially match the form of “tion” by the formula (I)

or “tion”.

In formulas (I) and (Ib) asymmetric carbon atom, respectively denoted by *.

The racemate of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione of the formula (Ia), which is required as starting material for the implementation of the method of receiving according to the invention are known (see WO 96-16048).

When implementing the method of receiving according to the invention use the methods of preparative chromatography, preferably the method is highly effective liquid chromatography (HPLC). With the applicable separation materials are known (see EP-A 0397917).

The content of the substance in the eluate set photometrische analysis. Collected erwerbende faction investigate analytically on the content of the enantiomeric components. Faction, which respectively contain the same enantiomers, gather together and under reduced pressure evaporated. Then the obtained product is recrystallized from toluene.

The initial product elution is a (-)-enantiomer according to the invention. Further, later leaked fractions can be used to isolate the corresponding (+)-enantiomer.

The biologically active substance according to the invention has a strong microsized and bactericide, for protection of plants and materials.

Fungicidal properties can be used for plant protection in the fight against plasmodiophoromycota, oomycetes, they, zygomycete, records of Ascomycetes, basidiomycetes and deuteromycetes.

Bactericidal properties can be used for plant protection in the fight against pseudomonadaceae, rhizobiaceae, Enterobacteriaceae, corynebacteriaceae, streptomycetaceae.

Examples that fall under the above common generic term, not limiting, however, existing fungal and bacterial diseases include the following:

the genus Xanthomonas, as, for example, Xanthomonas campestris, subspecies oryzae;

the genus Pseudomonas, such as Pseudomonas syringae, subspecies lachrymans;

the genus Erwinia, as, for example, Erwinia amylovora;

the genus Pythium, as, for example, Pythium ultimum;

the genus Phytophthora, as, for example, Phytophthora infestans;

the genus Pseudoperonospora, as, for example, Pseudoperonospora humuli or Pseudop-eronospora cubensis;

genus Plasmopara, as, for example, Plasmopara viticola;

the genus Bremia, as, for example, Bremia lactucae;

the genus peronospora., as, for example, Peronospora. pisi or P. brassicae;

the genus Erysiphe, as, for example, Erysiphe graminis;

the genus Sphaerotheca, as, for example, Sphaerotheca fuliginea;

the genus Podosphaera, as, for example, Podosphaera leucotricha;

genus Ve Helminthosporium);

the genus Cochliobolus, as, for example, Cochliobolus sativus (form conidia Cereals, synonym Helminthosporium);

the genus Uromyces as, for example, Uromyces appendiculatus;

www.indexfungorum.org, as, for example, Puccinia recondita;

the genus Sclerotinia, as, for example, Sclerotinia sclerotiorum;

the genus Tilletia, as, for example, Tilletia caries;

the genus Ustilago, as, for example, Ustilago nuda or Ustilago avenae;

the genus Pellicularia, as, for example, Pellicularia sasakii;

the genus Pyricularia, as, for example, Pyricularia oryzae;

the genus Fusarium, such as, for example, Fusarium culmorum;

the genus Botrytis, as, for example, Botrytis cinerea,

the genus Septoria, as, for example, Septoria nodonim;

the genus Leptosphaeria as, for example, Leptosphaeria nodorum;

the genus Cercospora, as, for example, Cercospora canescens;

the genus Alternaria, such as Alternaria brassicae;

genus Pseudocercosporelta, as, for example, Pseudocercosporella herpotrichoides.

Good compatibility with plants biologically active substances in concentrations required for combating plant diseases, permits to handle the aerial parts of plants, planting materials, seeds and soil.

With great success, you can use the biologically active substance according to the invention for combating diseases in viticulture, horticulture and vegetable growing, such as, for example against fungi powdery mildew, as Sphae Otsa diseases of cereals, such as the genus Erysiphe, Leptosphaeria or Pyrenophora and diseases of rice, such as the genus Pyricularia.

The biologically active substance according to the invention is suitable for increasing the yield. In addition, it has a moderate toxicity and shows a good compatibility with plants.

The biologically active substance according to the invention can be used in materials science for the protection of technical materials from damage and destruction by unwanted microorganisms.

Under the technical materials you should understand this combined notion of inanimate materials that are used in the technique. For example, these technical materials that must be protected biologically active substance according to the invention from microbial change or destruction include adhesives, sizing agents, paper and cardboard, textiles, leather, wood, coating and plastics, lubricants and other materials that may be damaged or degraded by microorganisms. Within the protected materials are also considered part of the industrial equipment, for example, the coolant, which may be detrimental to the reproduction of microorganisms. Within the materials, paper and cardboard, leather, wood, coating, grease and liquid fluids, most preferably wood.

The microorganisms that can cause destruction or modification of technical materials, include, for example, bacteria, fungi, yeasts, algae and slime. The biologically active substance according to the invention preferably act against fungi, in particular against fungi, mushrooms, changing color and destroy wood (Basidiomceten), as well as against broccoli and seaweed.

For example, known microorganisms of the following types:

Alternaria, as Alternaria tenuis,

Aspergillus as Aspergillus niger,

Chaetomium, as Chaetomium globosum,

Coniophora, as Coniophora puetana,

Lentinus as Lentinus tigrinus,

Penicillium, as Penicillium glaucum,

Polyporus, as Polyporus versicolor,

Aureobasidium, as Aureobasidium pullulans,

Sclerophoma, as Sclerophoma pityophila,

Trichoderma as Trichoderma viride,

Escherichia as Escherichia coli

Pseudomonas as Pseudomonas aeruginosa,

Staphylococcus as Staphylococcus aureus.

The biologically active substance may be used in the usual form, in the form of solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, fine capsules in polymeric substances and in coating samplename, for example, by mixing a bioactive substance with a carrier, and a solvent, under pressure directed liquefied gases and/or solid inert substances, if necessary with the use of surface-active substances, emulsifiers and/or dispersants and/or foam. If necessary, for example, water can be used as a carrier, and an organic solvent as an auxiliary solvent. As the liquid solvent can be significant aromatic compounds such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chlorethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example fractions distilled oil, alcohols such as butanol or glycol, and also ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents, such as dimethylformamide and dimethylsulfoxide, and water. By liquefied gaseous media or inert substances are liquids at normal temperature and normalac Bhutan, propane, nitrogen, carbon dioxide. As solid carriers are set to, for example, the Cretaceous rocks, such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic Cretaceous rocks, as highly dispersed silicic acid, alumina or silicates. As solid carriers for granules are set to, for example, bulk and fractionated natural rocks such as calcite, marble, pumice, thick, dolomite, and also synthetic granules of inorganic and organic chalk, and also granules of organic material such as sawdust, Coco shells, husks of maize and tobacco stems. As emulsifiers and/or foaming agents have a value of, for example, nonionic and anionic emulsifiers, fatty acid esters and polyethylene oxide, esters of fatty alcohols and polyethylene oxide, for example alkylarylsulphonates ether, alkylsulfonate, alkylsulfate, arylsulfonate and albumin hydrolysates. As a dispersant have a value of, for example, lignosulfonates and methylcellulose.

Can be used in the compositions of auxiliary tools, such as carboxymethylcellulose, natural and manufactured the t, the polyvinyl acetate, and also natural phospholipids, such as cephalin or lecithins, and synthetic phospholipids. Then we can apply the additives of mineral or vegetable oil.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide, ferrocen blue, and organic dyes type alizarin, azo and metalphthalocyanine, and trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The content of biologically active substances in the compositions is about 0.1-95 wt.%, preferably 0.5 to 90 wt.%.

The biologically active substance according to the invention can also be used separately or in the form of mixtures with known fungicides, bactericides, acaricides, nematicides or insecticides, for example, to extend the limits of applicability or prevent resistance development of drug action. In many cases, this apparent synergistic effect, i.e. the effectiveness of the mixture is higher than the efficiency of individual components.

As components of mixtures are set to the following fungicides:

Aldemar, aspropirgos, aerophilately, andapril, anilazine, azaconazole, the sludge, bitertanol, blasticidin, bromuconazole, bupirimate, butiaba,

the calcium polysulfide, kapsimalis, captafol, Captan, carbendazim, carboxin, carvon, chinomethionat (quinomethionate), clobetasone, chlorbenzol, chloroneb, chlorpicrin, CHLOROTHALONIL, chlozolinate, hasilkan, kurane, having cymoxanil, cyproconazole, cyprodinil, zipform,

debaker, dichlorophen, diclobutrazol, dichlofluanid, declomycin, dicloran, dietphenterm, difenoconazol, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, datalists, dithianon, dodemont, Dodin, drazoxolon,

edifenphos, epoxiconazol, itaconate, ethirimol, etridiazole,

famoxadone, verapamil, fenarimol, fenbuconazole, fanforum, penetapan, fenpiclonil, fenpropidin, fenpropimorph, fentiazac, fistinginaction, ferbam, verison, fluazinam, flamethower, fluorone, fluquinconazole, flurried, flusilazol, flutolanil, flutolanil, flutriafol, folpet, fosetyl-aluminum, fosetyl-sodium, phtalic, fuberidazole, parallaxis, parameter, percarbonic, vorconizole, vorconizole-CIS, pharmacyclics, guazatine,

hexachlorobenzene, hexaconazole, hymexazol,

imazalil, kabekona, iminoctadine, iminoctadine. P CLASS="ptx2">kasugamycin, kresoximmethyl, derivatives of copper such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, the oxides of copper and Bordeaux mixture,

marcopper, MANCOZEB, MANEB, severinson, mepanipyrim, mepronil, metalaxyl, metconazole, metasurfaces, mefenoxam, metiram, matomela, metalhawk, millionizer, myclobutanil, mickleton,

the Nickel dimethyldithiocarbamate, nitroanisole, nuarimol,

furac, oxadixyl, oxamate, oxolinic, oxycarboxin, oxidation, paclobutrazol, peyratout, penconazole, pencycuron, forgiven, pimaricin, piperalin, polyoxin, palikari, provenzal, prochloraz, procymidone, propamocarb, propanoic sodium, propiconazol, propineb, pyrazophos, pirivenas, Pyrimethanil, pyroquilon, proxyfor,

quinceanos, quintozene (PCNB), quinoxyfen,

sulfur and sulfur derivatives,

the tebuconazole, telital, tecnazene, tetcyclacis, tetraconazole, thiabendazol, tilian, leflunomid, methylthiophenol, thiram, dioxime, metalloscope, tolylfluanid, triadimefon, triadimenol, triazolyl, triazoxide, trihemic, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, uniconazole, validamycin And, vinclozolin, viceconsul,-(2,4-dichlorophenyl)-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,

-(2,4-dichlorophenyl)--methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,

-(5-methyl-1,3-dioxane-5-yl)--[[4-(trifluoromethyl)phenyl]methylene]-1H-1,2,4-triazole-1-ethanol,

(5S,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazole-1-yl)-3-octanone,

(E)-and(methoxyimino)-N-methyl-2-phenoxyphenylacetic,

{2-methyl-1-[[[1-(4-were)ethyl]amino]carbonyl]propyl}karamanova acid-1-isopropyl ether

1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazole-1-yl)-alanon-O-(phenylmethyl)oxime,

1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,

1-(3,5-dichlorophenyl)-3-(2-propenyl)-2.5-pyrrolidinedione,

1-[(diiodomethyl)sulfonyl]-4-methylbenzol,

1-[[2-(2,4-dichlorophenyl)-1,3-dioxolane-2-yl]methyl]-1H-imidazole,

1-[[2-(4-chlorophenyl)-3-phenyloxirane]methyl]-1H-1,2,4-triazole

1-[1-[2-[(2,4-dichlorophenyl)methoxy]phenyl]ethynyl]-1H-imidazole,

1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidino,

2',6'-dibromo-2-methyl-4'-triptoreline-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,

2,2-dichloro-N-[1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclohexanecarboxylic,

2,6-dichloro-5-(methylthio)-4-pyrimidinediamine,

2,6-dichloro-N-(4-trifloromethyl)benzamid,

2,6-dichloro-N-[[4-(trifluoromethyl)fil)-1,3,4-thiadiazole,

2-[[6-deoxy-4-O-(4-O-methyl-D-glycopyranosyl)-a-D-glucopyranosyl]amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2 aminobutane,

2-bromo-2-(methyl bromide)pentagonite,

2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

2-chloro-N-(2,6-dimetilfenil)-N-(isothiocyanates)ndimethylacetamide,

2-phenylphenol (ORR),

3,4-dichloro-1-[4-(deformedarse)phenyl]-1H-pyrrole-2,5-dione,

3,5-dichloro-N-[cyan[(1-methyl-2-PROPYNYL)oxy]methyl]benzamide,

3-(1,1-dimethylpropyl)-1-oxo-1H-inden-2-carbonitril,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidine]pyridine,

4-chloro-2-cyan-N,N-dimethyl-5-(4-were)-1H-imidazole-1-sulfonamide,

4-methyltetrazole[1,5-a]quinazolin-5(4H)-he,

8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4,5]decane-2-methanamine,

8-hydroxyanisole,

N-xanthene-9-carboxylic acid 2-[(phenylamine)carbonyl]hydrazide,

bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)oxy]-2,5-thiophencarboxylic,

CIS-1-(4-chlorophenyl)-2-(1H-1,2,4-triazole-1-yl)cycloheptanol,

CIS-4-[3-[4-(1,1-dimethylpropyl)phenyl-2-methylpropyl]-2,6-dimethylmorpholine,

ethyl-[(4-chlorophenyl)azo]ciancetta,

caligiuricarlton, metanarration sodium is enyl)-N-(5-isoxazolidinone)-DL-alaninate,

methyl-N-(chloroacetyl)-N-(2,6-dimetilfenil)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxylic

N-(2,6-dimetilfenil)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)ndimethylacetamide,

N-(2,6-dimetilfenil)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)ndimethylacetamide,

N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitrobenzenesulfonamide,

N-(4-cyclohexylphenol)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(5-chloro-2-were)-2-methoxy-N-(2-oxo-3-oxazolidinyl)ndimethylacetamide,

N-(6-methoxy)-3-pyridinyl)cyclopropanecarboxamide,

N-[2,2,2-trichloro-1-[(chloroacetyl)amino]ethyl]benzamide,

N-[3-chloro-4,5-bis-(2-propenyloxy)phenyl]-N'-methoxyethylamine,

N-formyl-N-hydroxy-DL-alanine sodium salt,

O,O-diethyl-[2-(dipropylamino)-2-oxoethyl]ethylphosphonothiolothionate

O-methyl-S-phenyl-phenylpropionamide,

S-methyl-1,2,3-benzothiadiazole-7-carbothioic,

Spiro[2H]-1-benzopyran-2,1'(3 N)-isobenzofuran]-3'-he.

Antibacterial (bactericidal) tools:

bronopol, dichlorophen, nitrapyrin, Nickel dimethyldithiocarbamate, kasugamycin, Actelion, francebuy acid, oxytetracycline, provenzal, streptomycin, streaming is, is Zefat, acetamiprid, acrinathrin, alankar, aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadiractin, azamethiphos, azinphos And, azinphos M, azocyclotin,

the home had a drink, the home sphaericus, the home subtilis, the home of thuringiensis, baculovirus, beauveria of bassiana, beauveria tenella, bendiocarb, benfuracarb, bensultap, benoxinate, betacyfluthrin, bifenazate, bifenthrin, biomonomers, bioprotein, VRMS, bromophos And, bofenkamp, buprofezin, butamifos, butocarboxim, butylparaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, cloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinfos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, glavatartsi, CIS-resmethrin, CIS-permethrin, claritin, cloethocarb, clofentezine, cyanophos, zipopen, cicloprofen, cyfluthrin, cigalotrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylene, giovanola, disulfoton, docusate-sodium, dienen,

althusian, emamectin, empenthrin, endosulfan, entomophthora spp.,

esfenvalerate, ethiofencarb, ation, ethoprophos, etofenprox, fenoxycarb, fenpropathrin, feneral, generatin, fenpyroximate, fenvalerate, fipronil, fluazuron, lubricant, flucycloxuron, flucythrinate, flufenoxuron, lotensin, fluvalinate, fonofos, tomatlan, fosthiazate, tupfenrock, furathiocarb,

granulopenia,

halogenated, HCH (hexachlorocyclohexane, HCH), heptenophos, hexaflumuron,

hexythiazox, hydroprene,

Imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,

caroleehalloran,

lambda-cigalotrin, lufenuron,

Malathion, mecarbam, metaldehyde, metamidophos, Metarhizium anisopliae, Metarhizium flavoviride, mitigation, methiocarb, methomyl, methoxyfenozide, metolcarb, methoxamine, mevinphos, milbemectin, monocrotophos,

naled, nitenpyram, nithiazine, novaluron,

omethoate, oxamyl, oxydemeton M

paecilomyces fumosoroseus, parathion And parathion M, permethrin, penhoat, Fort, fozalon, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos And, pirimiphos M, profenofos, promecarb, propoxur, prothiofos, procoat, PI merosin, pyraclofos, prismatron, feverfew, pyridaben, predation, PI-imidiwan, pyriproxifen,

quinalphos,

ribavirin

coalition, sabots, forces teflubenzuron, tefluthrin, temephos, timelines, terbufos, tetrachlorvinphos, tealpirate, thiacloprid, thiamethoxam, tiopronin, tiatives, tollemache, thiodicarb, thiofanox, thuringiensis, telocity, tralomethrin, triuralin, triazamate, triazophos, treasure, trichloride, trichlorfon, triflumuron, trimeter, vamidothion,

unilibro, netrillium lecane,

YI 5302,

Zeta-cypermethrin, colaprete,

(1R-CIS)-[5-(phenylmethyl)-3-furanyl]methyl-3-[(dihydro-2-oxo-3(2H)-furylidene)methyl]-2,2-dimethylcyclopropanecarboxylate,

(3-phenoxyphenyl)methyl-2,2,3,3-tetramethylcyclopropanecarboxylate,

1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-Imin,

2-(2-chloro-6-forfinal)-4-[4-(1,1-dimethyl)phenyl]-4,5-dihydrooxazolo,

2-(atomic charges)-3-Diezel-1,4-naphthalenedione,

2-chloro-N-[[[4-(phenylethane)phenyl]amino]carbonyl]benzamide,

2-chloro-N-[[[4-(2,2-dichloro-1,1-diflorasone)phenyl]amino]carbonyl]benzamide,

3-methylphenylcarbinol,

4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxybenzoyl,

4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,

4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodine-3-pyridinyl)methoxy]-3(2H)-pyrid is otiv Bacillus thuringiensis,

benzoic acid, 2-benzoyl-1-(1,1-dimethylethyl)hydrazide,

butane, 2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4,5]Dec-3-EN-4-yl-ether

dihydro-2-(nitromethylene)-2H-1,3-thiazin-3(4H)-carboxaldehyde

ethyl-[2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]carbamate,

N-(3,4,4-Cryptor-1-oxo-3-butenyl)glycine

N-(4-chlorophenyl)-3-[4-deformedarse)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,

N-[(2-chloro-5-thiazolyl)methyl]-N'-methyl-N"-nitroguanidine,

N-methyl-N'-(1-methyl-2-propenyl)-1,2-hydrazinecarbothioamide,

N-methyl-N'-2-propenyl-1,2-hydrazinecarbothioamide,

O,O-diethyl-[2-(dipropylamino)-2-oxoethyl]ethylphosphonothiolothionate.

It is also possible mixing with other known biologically active substances, such as herbicides or fertilizers and growth regulators.

The biologically active substance may also be applied directly itself or in the form of widespread forms of use, such as ready-to-use solutions, suspensions, powders, pastes, soluble powders, dusts and granules. Use is done with conventional methods, for example by watering, spraying, spraying, spreading, Rapaniana, almatymetrostroi biologically active substances, or itself biologically active substance applied to the soil. You can also handle seed.

When using the substances according to the invention as a fungicide can be varied within wide limits the amount used depending on the type of application. When processing parts of the plant used a number of biologically active substances, in General, is in the range between 0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha In the processing of seed material used number of biologically active substances, in General, is between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. If tillage is used, the number of biologically active substances, in General, is in the range between 0.1 and 10,000 g/ha, preferably between 1 and 5000 g/ha

For the protection of technical materials used tool containing a biologically active substance, in General, in an amount of from 1 to 95%, preferably from 10 to 75%.

Used the concentration of biologically active substances according to the invention corresponds to the mind and the presence of microorganisms against which the struggle as well as the composition of the protected materials. Optima is 0.001 to 5 wt.%, preferably from 0.05 to 1.0 wt.% relatively protected material.

The efficacy and spectrum of activity used biologically active substances according to the invention for protection of the materials, which respectively made as a means to concentrate or all of the total composition may be increased, if necessary, apply a further connection of antimicrobial action, fungicides, bactericides, herbicides, insecticides or other biologically active substances to broaden the spectrum of action or to achieve special effects, for example, adds additional protection from insects. These compounds can have a wide range of impacts as compounds according to the invention.

Preparation and application of biologically active substances according to the invention is shown in the following examples.

An example of a method of obtaining

300 g of racemate of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione share portions of 0.2 g of chiral stationary phase yeasty gel (HSF) on the basis of the optically active monomer N-methacryloyl-L-leucine-3-(2,4-dimethylphenyl)amide with ethyl acetate as eluent at room temperature (about 23°Hundred. Separately carry out preparative separation under the following conditions.

Column: HSF, as described above, the fraction is 10 microns, h mm (int. the diameter).

Eluent: ethyl acetate.

Fluid flow: 100 ml/min

Detector: UV, 254 nm.

The size of the sample of 0.2 g was dissolved in 20 ml of ethyl acetate.

Those fractions which contain the same every time enantiomer, unite and under reduced pressure evaporated. And, finally, the precipitated product is recrystallized from toluene.

In these conditions, eluted first levogyrate enantiomer, and then programalso enantiomer.

Receive 117 g of (-)-enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione in the form of a solid substance with a melting point of 123-S.

The specific ratio of rotation []20D=-55,5 (10 mg/1 ml chloroform).

Similar conditions obtain (+)-enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione in the form of a solid substance with a melting point 122-S.

The specific ratio of rotation []20D=-54,9° (10 mg/1 ml chloroform).

Examples of use

Example A. Cochliobolus sativus-EN the piece alkylarylsulphonates ether.

For the preparation of practical ready-effective product mix 1 weight part of the biologically active substance with a given amount of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To check on the effectiveness of protection spray young plants ready product in the given number. After drying of the sprayed layer, sprinkle the plants with a suspension of conidia of Cochliobolus sativus. Plants left for 48 hours at 20°C and a relative humidity of 100% in an incubation cabin.

Plants left in a greenhouse at a temperature of 20°C and relative humidity of 80%.

After 7 days of inoculation conduct the debriefing. The degree of efficiency of 0% corresponds to the control, while the degree of effectiveness of 100% means that in any case was not observed lesions.

Biologically active substances, the dose applied and experimental data are shown in table A.

Example Century. Podosphaera analysis (Apple)/protection.

Solvent: 47 weight parts of acetone.

Emulsifier: 3 weight parts alkylarylsulphonates.

For the preparation of practical ready-effective proclamator and dilute the concentrate with water to the desired concentration.

To check on the effectiveness of protection spray young plants ready product in the given number. After drying of the sprayed layer grafted plants with an aqueous suspension of spores of the pathogen of Apple powdery mildew Podosphaera leucotricha. Plants installed in the greenhouse at about 23°C and a relative humidity of about 70%.

After 10 days of inoculation conduct the debriefing. The degree of efficiency of 0% corresponds to the control, while the degree of effectiveness of 100% means that in any case was not observed lesions.

Biologically active substances, the dose applied and experimental data are shown in table C.

Example

Uncinula analysis (grape)/protection.

Solvent: 47 weight parts of acetone.

Emulsifier: 3 weight parts alkylarylsulphonates ether.

For the preparation of practical ready-effective product mix 1 weight part of the biologically active substance with a given amount of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To check on the effectiveness of protection spray young plants ready product in the which I set up in the greenhouse at about 23°C and a relative humidity of about 70%.

After 14 days of inoculation conduct the debriefing. The degree of efficiency of 0% corresponds to the control, while the degree of effectiveness of 100% means that in any case was not observed lesions.

Biologically active substances, the dose applied and experimental data are shown in table C.

Example D. Venturia-analysis (Apple)/protection.

Solvent: 47 weight parts of acetone.

Emulsifier: 3 weight parts alkylarylsulphonates ether.

For the preparation of practical ready-effective product mix 1 weight part of the biologically active substance with a given amount of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test therapeutic effect of grafted young plants with an aqueous suspension of conidia of the pathogen of Apple scab Venturia inaequalis. Plants leave on one day at a temperature of about 20°C and a relative humidity of 100% in an incubation cabin, and then set in the greenhouse. After the given number of hours sprayed plants almost ready biologically active substance in the above amounts.

Plants installed in greenhouses is avodat conclusions. The degree of efficiency of 0% corresponds to the control, while the degree of effectiveness of 100% means that in any case was not observed lesions.

Biologically active substances, the dose applied and experimental data are shown in table D.

Example E. Pyricularia analysis (Fig)/protection.

Solvent: a 2.5 weight parts of acetone.

Emulsifier: 0,06 weight parts alkylarylsulphonates ether.

For the preparation of practical ready-effective product mix 1 weight part of the biologically active substance with a given amount of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To check on the effectiveness of protection spray young plants ready product in the given number. After drying of the sprayed layer grafted plants with an aqueous suspension of spores Pyricularia oryzae. Finally the plants are set in the greenhouse at a relative humidity of about 100% and about 25°C.

After 4 days of inoculation conduct the debriefing. The degree of efficiency of 0% corresponds to the control, while the degree of effectiveness of 100% means that in any case not nabludalos the

1. (-)-Enantiomer of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxy-propyl]-2,4-dihydro-[1,2,4]-triazole-3-thione of the formula

2. The method of obtaining biologically active (-)-enantiomer of formula (I) under item 1, characterized in that a) the racemate of 2-[2-(1-chlorocyclopropane)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione of the formula (1A)

chromatographic on chiral stationary phase of kieselguhr-gel based optical active monomer N-methacryloyl-L-leucine-3-(2,4-dimethylpentyl)amide with ethyl acetate as eluent at a temperature of from 20 to 25°C; (b) the eluate evaporated under reduced pressure, and c) drop-down when this product is recrystallized from toluene.

 

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The invention relates to new substituted phenyl derivatives, which are strong blockers chlorine ion channels and as such are useful in the treatment of sickle cell anemia, cerebral edema that accompanies ischemia or tumor, diarrhea, hypertension (diuretic), osteoporosis and to reduce the intraocular pressure for the treatment of disorders such as glaucoma

The invention relates to new amide derivatives of General formula (I) or their salts, where a means thiazolidin, imidazoline, triazoline, benzimidazolyl, benzothiazolyl, thiadiazolyl, imidazopyridine or imidazothiazole; X is a bond, -NR5-, -NR5CO-, -NR5CONH-, NR5SO2-, -NR5C(= NH)NH-; R1means H, lower alkyl, aryl, pyridyl, thienyl, furyl, thiazolyl, benzimidazolyl, imidazopyridine, triazolyl, thiadiazolyl, imidazolyl, imidazothiazoles, benzothiazolyl, cyclohexyl, which may be optionally substituted with halogen, lower alkyl, -OH, -CN, -NO2, -CF3, -NH2, -O-lower alkyl, and the Deputy of the lower alkyl may be substituted by phenyl, naphthyl, fullam, tanila or pyridium;2a, R2bmean H or lower alkyl; R3means hydrogen or lower alkyl; R4a, R4bmean H or HE, or taken together form a group =O or =N-O-lower alkyl; R5means H or lower alkyl

The invention relates to diphenylvinyl heterocyclic compounds of formula 1 in which Het denotes a fragment selected from the group consisting of (A) - (H)

The invention relates to novel triazole compounds of the General formula (1), where a denotes a linear or branched C1-C18-alkylenes group which may comprise at least one group which is selected from O, S, CONH, COO,3-C6-cycloalkene or double or triple bond; In denotes the radical of formula (a), (b) or (C); R1denotes H, NH2WITH3-C6-cycloalkyl or1-C8-alkyl, which is not substituted or substituted OS1-C8-alkyl; R2denotes H, HE, C1-C8-alkyl, C3-6-cycloalkyl, CF3, CN, NR3R4, SR3or CO2R3where R3denotes N or C1-C8-alkyl, a R4denotes H, C1-C8-alkyl, or COR3where R3stands WITH1-C8-alkyl; Ar represents naphthyl, phenyl with 1-2 substituent selected from C1-C8-alkyl, CF3, CHF2, NO2, SR3, SO2R3where R3means1-C8-alkyl; and pyridyl, pyrimidyl or triazinyl, which have from 1 to 3 substituents selected from C1-C8-alkyl, C2-C6-alkenyl, C2-C6-quinil, halogen, CN, CF3, OR4where R43-C6-lalouche possibly condensed, phenylalkylamine or 5-membered aromatic heterocycle with 1 to 2 nitrogen atoms, which may be condensed with a benzene ring

The invention relates to 2-[1',2',4'-triazole-3'-roximation] anilides formula I

< / BR>
in which the index and the substituents have the following meanings:

n means 0, 1, 2, 3 or 4, where the substituents R1may be different if n is greater than 1;

X represents a direct bond, O, or NRa;

Rameans hydrogen, alkyl, alkenyl, quinil, cycloalkyl or cycloalkenyl;

R1means nitro, cyano, halogen, optionally substituted alkyl, alkenyl, quinil, alkoxy, alkenylacyl, alkyloxy or

if n is 2, additionally represents associated with two adjacent ring atoms optionally substituted by a bridge containing three or four members from the group containing 3 or 4 carbon atoms, 1-3 carbon atoms and 1 or 2 nitrogen atom, oxygen and/or sulphur, and this bridge together with the ring to which it is linked, may form a partially unsaturated or aromatic radical;

R2means hydrogen, nitro, cyano, halogen, C1-C4alkyl, C1-C4halogenated, C1-C4alkoxy, C1-C4alkylthio or C1-C4alkoxycarbonyl; R3means optionally substituted is which, together with the carbon atoms may contain one to three heteroatoms as members of a cycle of the following: oxygen, sulfur and nitrogen, or an optionally substituted single or dual core aromatic radical, which together with the carbon atoms may contain as members of the cycle from one to four nitrogen atoms or one or two nitrogen atom and one oxygen atom or sulfur or one oxygen atom or sulfur;

R4means hydrogen, optionally substituted alkyl, alkenyl, quinil, cycloalkyl, cycloalkenyl, alkylaryl or alkoxycarbonyl;

R5means alkyl, alkenyl, quinil, cycloalkyl or cycloalkenyl or if X is NRaadditionally represents a hydrogen

The invention relates to new nitrogen-containing heterocyclic compounds possessing biological activity, in particular fungicidal activity, and more particularly to a derivative triazolyl, the way they are received and fungicidal tool

-methoxykynuramine acids" target="_blank">

The invention relates to a method of producing methylamino- methoxykynuramine acids of the formula I, where Y represents a C-organic radical through reaction of Pinner interaction achilleid formula II with an alcohol and subsequent interaction of the formed in the Pinner reaction of ester of the formula (IV) with hydroxylamine to obtain the oxime of the formula V by methylation of the oxime of the formula V to oximoula ether of the formula VI or b) somethingitaliano obtaining oximoula ester of formula VI, followed by interaction oximoula ester of formula VI with methylamine, characterized in that in the reaction of Pinner used alcohol of the formula III R-OH, boiling point above 75°C

The invention relates to the protection of grain crops

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention relates to new substituted benzoylketones of the general formula (I): , all possible tautomeric forms and possible salts that can represent active substance as a component of herbicide agent. In the formula (I) A means (C1-C4)-alkyl; R1 means cyclo-(C3-C6)-alkyl; R2 means hydrogen atom (H), cyano-group (CN); R3 means hydrogen atom (H), halogen atom, CF3, (C1-C4)-alkylsulfonyl; R4 means halogen atom; X means groups: or wherein R5 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, (C1-C4)-alkylthio-group, di-(C1-C6-alkyl)-amino-group; R6 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, cyclo-(C3-C6)-alkyl; n = 0 or 1 including all possible tautomeric forms and possible salts. Compounds of the formula (I) elicit herbicide activity and can be used in herbicide composition.

EFFECT: valuable properties of compounds.

3 cl, 1 sch, 3 tbl, 13 ex

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