WO2003106436A1

WO2003106436A1 - Nematicidal tetrazole-containing trifluorobutenes

Info

Publication number: WO2003106436A1
Application number: PCT/EP2003/006170
Authority: WO
Inventors: Yukiyoshi Watanabe; Jun Mihara; Akihiko Yanagi; Yuichi Otsu; Katsuhiko Shibuya; Akira Emoto
Original assignee: Bayer Cropscience Ag
Priority date: 2002-06-14
Filing date: 2003-06-12
Publication date: 2003-12-24
Also published as: JP2004018430A; AU2003242682A1

Abstract

The present invention relates to novel tetrazole-containing trifluorobutene derivatives of the formula (I) wherein R represents alkyl, alkenyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl, optionally substituted phenyl or optionally substituted arylalkyl, and n represents 1 or 2, to a process for their preparation and to their use as nematicides.

Description

Nematicidal tetrazole-containing trifluorobutenes

The present invention relates to novel tetrazole-containing trifluorobutene derivatives, to a process for their preparation and to their use as nematicides.

U. S. Patent No. 3,513,172 describes that certain kinds of trifluorobutenyl compounds have a nematicidal activity. WO 86/07590 Al also describes that certain kinds of polyhaloalkene compounds have a nematicidal activitiy. Further, British Laid-open Patent Specification No. 2 293 380 A describes that, certain kinds of heterocyclic compounds have a nematicidal activity. WO 95/04727 Al describes a process for the preparation of certain nematicidally active fluoroalkenylthioheterocy- clic derivatives, and WO 95/24403 Al describes that 4,4-difluorobutenyl compounds have a nematicidal activity.

There have now been found tetrazole-containing trifluorobutene derivatives of the formula (I)

wherein

R represents alkyl, alkenyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl, optionally substituted phenyl or optionally substituted arylalkyl, and

n represents 1 or 2. The compounds of the formula (I) can be synthesized, for example, by the preparation process a) when

compounds of the formula (II)

wherein

R has the aforementioned me-ιning,

are oxidized in the presence of inert solvents,

The compounds of the formula (I) of the present invention are distinguished by a strong nematicidal activitiy and a good compatibility with various crops.

The compounds of the formula (I) according to the present invention show a surprisingly strong nematicidal activity compared with the compounds described in the aforementioned prior art.

In the present specification "halogen" represents fluoro, chloro, bromo or iodo, preferably represents fluoro, chloro or bromo and particularly preferably represents chloro or bromo.

The term "alkyl" alone or within the terms "alkoxy" and "alkylthio" represents a straight-chain or branched-chain alkyl such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc., preferably represents Cι-₈ alkyl, more preferably represents Cι-₆-alkyl and particularly preferably represents Cι-₄-alkyl.

The term "haloalkyl" corresponds to the above-mentioned term "alkyl", which is substituted with the above-mentioned "halogen", preferably represents mono-, di- or trifluoro-, chloro- and/or bromo-substituted Cι- -alkyl and particularly preferably represents 2-chloroethyl, 2,2,2-trifluoroethyl or 3-bromopropyl.

The terms "alkoxyalkyl" and "alkylthioalkyl", wherein the term "alkyl" has the abovementioned meaning, preferably represent C₂.₈ (total carbon number)- alkoxyalkyl and C -₈ (total carbon number)-alkyltbioalkyl, more preferably represent C₂.₆ (total carbon number)-alkoxyalkyl and C₂.₆ (total carbon number)-alkylthioalkyl, and particularly preferably represent 2-methoxyethyl, 2-ethoxyethyl or 2-methyl- thioethyl.

The term "alkenyl" represents alkenyl moieties such as vinyl, allyl, 1-propenyl, 1-, 2- or 3-butenyl, etc., preferably represents C₃.₄-alkenyl and particularly preferably represents allyl or 2-butenyl.

The term "cycloalkyl" represents cycloalkyl moieties, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., preferably represents C₃.₆ cycloalkyl, and particularly preferably represents cyclopropyl, cyclopentyl or cyclohexyl.

The term "arylalkyl" represents C₇-ι₂ (total carbon number)-arylalkyl, wherein the aryl part is p enyl or naphthyl and the alkyl part is methyl or ethyl, such as benzyl, phenethyl, α-methylbenzyl, α- or- β-naphthylmethyl, α- or β-naphthylethyl, etc. The term "arylalkyl" preferably represents benzyl.

The present invention preferably relates to compounds of the formula (I) wherein R .. represents Cι-₈-alkyl, C₂.₆-alkenyl, Cι-₄-haloalkyl, C₂.₆ (total carbon number)- alkoxyalkyl, C₂.₆ (total carbon number)-all y'lthioalkyl or C₃.₈-cycloalkyl, or .

represents optionally halogen-,

Cι-₄-alkylthio- or Ci- ₄-haloalkyl-substituted phenyl, or

represents optionally halogen-, Cι-₄-alkyl-, C_M-alkoxy-,

or Ci. ₄-haloalkyl-substituted benzyl, and

n represents 1 or 2.

The present invention particularly preferably relates to compounds of the formula (I) wherein

R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n- pentyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-chloroethyl, 2,2,3,3,3- pentafluoropropyl, 2,2,2-trifluoroethyl, 3-bromopropyl, 2-methoxyethyl, 2- ethoxyethyl, 2-methylthioethyl, allyl, 2-butenyl, phenyl which is optionally substituted by one or two substituents which may be the same or different and which are selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, isopropyl, trifluoromethyl, methoxy and methylthio, or benzyl which is optionally substituted by one or two substituents which may be the same or different and which are selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, isopropyl, trifluoromethyl, methoxy and methylthio, and

n represents 1 or 2.

Preference according to the invention is also given to compounds of the formula (I) wherein R has one of the aforementioned meanings, and

n represents 1.

Preference according to the invention is also given to compounds of the formula (I) wherein

R has one of the aforementioned meanings, and

n represents 2.

The abovementioned general or preferred radical definitions apply both to the end products of formula (I) and correspondingly to the starting materials or intermediates required for their preparation.

Using, for example, l-methyl-5-(3',4',4'-trifluoro-3'-butenylthio)tetrazole as starting material and m-chloroperbenzoic acid as oxidizing agent, process a) for the preparation of the compounds of the formula (I) of the present invention can be illustrated by the following reaction scheme:

m-chloroperbenzoic acid

The compounds of the formula (II), used as starting material in the aforementioned preparation process a), can be easily obtained by reacting a compound of the formula

Cm)

wherein

R has the aforementioned meaning,

with 4-bromo- 1 , 1 ,2-trifluoro- 1 -butene.

The compounds of the abovementioned formula (111) include the known compounds described in, for example, Can. J. Chem. Vol. 37, pp.101-105, 1959 and can be easily synthesized according to the process described, for example, in US Patent No.

4,297,489 or in US Patent No. 3,843,668.

The process according to the invention for preparing compounds of the formula (II) can be carried out in the presence of an adequate diluent. Suitable diluents for carrying out the process according to the invention are especially aliphatic, alicyclic and aromatic hydrocarbons, such as, for example, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, etc.; ethers, such as, for example, diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, dioxane, tetrahydrofuran, etc.; ketones, such as, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; nitriles, such as, for example, acetonitrile, propionitrile etc.; acid amides, such as, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. The reaction can be carried out in the presence of an acid binder. Suitable acid binders for carrying out the process according to the invention are especially hydroxides, carbonates and alcoholates, etc. alkali metals, tertiary amines, such as, for example, Iriethylamine, diethylaniline, pyridine, 4-dimethylaminopyridine, 1,4- diazabicyclo[2,2,2]octane (DABCO), l,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc.

When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0°C and 180 C, preferably between 20°C and 120 C.

The process according to the invention is generally carried out under normal (atmospheric) pressure. However, it is also possible to carry out the process according to the invention under elevated pressure or under reduced pressure, for example between 0.1 bar and 10 bar.

Compounds of the corresponding formula (II) can be obtained, for example, by reacting 0.8-1.5 moles of 4-bromo-l,l,2-trifluoro-l-butene with 1 mole of a compound of the formula (HI) in a diluent, for example, acetonitrile in the presence of 1-1.3 moles of an acid binder, for example, potassium carbonate, under reflux.

Specific examples of the compounds of the formula (III) are, for example, 5- mercapto-1-methyltetrazole, l-ethyl-5-mercaptotetrazole, l-cyclopropyl-5- mercaptotetrazole, l-allyl-5-mercaptotetrazole, l-benzyl-5-mercaptotetrazole, l-(2- methoxyethyl) -5-mercaptotetrazole, 5-mercapto-l-phenyltetrazole and l-(2- chlorophenyl) -5-mercaptotetrazole.

4-Bromo-l,l,2-trifluoro-l-butene, another starting material used in the process for the preparation of the compounds of the formula (II), is a known compound described in, for example, WO 86/07590 Al. Specific examples of the compounds of the formula (IT) are, for example, l-methyl-5- (3',4',4'-trifluoro-3'-butenylthio)tetrazole, l-ethyl-5-(3',4',4'-trifluoro-3'-butenyl- thio)tetrazole, l-cyclopropyl-5-(3',4',4'-trifluoro-3'-butenylthio)tetrazole, l-allyl-5- (3 4 4'-trifluoro-3'-butenyltmo)tetrazole, l-(2-methoxyethyl)-5-(3',4',4'-trifluoro- 3'-butenylthio)tetrazole and l-(2-chlorophenyl)-5-(3',4',4'-trifluoro-3'-butenyl- thio)tetrazole.

Oxidizing agents used for oxidation of the compounds of the aforementioned formula (II) in the preparation process a) are those which are usually used in the field of organic chemistry, for example, hydrogen peroxide, m-chloroperbenzoic acid, peracetic acid, perbenzoic acid, magnesium monoperoxyphthalate, potassium peroxy- monosulfate, urea-hydrogen peroxide etc.

The reaction of the aforementioned process a) can be carried out in the presence of an adequate diluent. Diluents which can be used are, for example, aliphatic, alicyclic and aromatic hydrocarbons (which are optionally chlorinated), such as, for example, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene, etc.; ethers, such as, for example, diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, dioxane, tetrahydrofuran, etc.; alcohols, such as, for example, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.; esters, such as, for example, ethyl acetate, amyl acetate, etc.; acid amides, such as, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.; carboxylic acids, such as, for example, formic acid, acetic acid, etc.

The compounds of the formula (I) according to the invention can be obtained, for example, by reacting 0.8-3 moles of m-chloroperbenzoic acid with 1 mole of a compound of the formula (II) in a diluent, for example, methylene chloride at room temperature. The compounds of the formula (I) of the present invention show a strong nematicidal activity. They can, therefore, be efficiently used as nematicidal agents, for example, in the field of agriculture and forestry. Remarkably, the compounds of the formula (I) of the present invention are not phytotoxic while at the same time they are effectively controlling harmful nematodes. .

The compounds according to the invention can be used, for example, against nematodes such as Pratylenchus spp., Globodera spp., such as Globodera rostochiensis wollenweber, Heterodera spp., such as Heterodera glycines ichinohe, Meloidogyne spp., Aphelenchoides spp., such as Aphelenchoides basseyi christie, Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp., such as Bursaphelenchus xylophilis etc.

The compounds according to the invention are especially useful for combating

Pratylenchus spp., Globodera rostochiensis wollenweber, Heterodera glycines ichinohe, Meloidogyne spp., Aphelenchoides basseyi christie, Bursaphelenchus xylophilis.

However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other nematodes.

The active compounds of the present invention can be used also in a mixture with other active compounds, for example, insecticides, bactericides, miticides, _. fungicides, etc. in the form of their commercially useful formulations or in the application forms prepared from such formulations. Insecticides which can be used are, for example, organophosphorous agents, carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals, chloronicotinyl type chemicals, insecticidal substances produced by microbes, etc. The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to widen, for example, the activity spectrum or to prevent the development of resistance. In many cases, this results in synergistic effects, i.e. the activity of the mixture exceeds the activity of the individual components. Such formulations and application forms are commercially and ecologically especially useful as generally lower amounts of active ingredients can be used. A synergist, however, must not necessarily be active itself, as long as it enhances the action of the active compound.

The content of the active compounds of the present invention in a commercially useful formulation or application form can be varied in a wide range. The active- compound content of the use forms prepared from the commercial formulations can vary within wide limits. The active-compound concentration of the use forms can be from 0.0000001 to 100 % by weight of active compound, preferably between 0.0001 and 1 % by weight.

Examples of advantageous mixing components are, for example, the following:

Fungicides

aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram, debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon, ediphenp os, epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole, flu rimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl- aluminium, fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox, guazatine, hexachlorobenzene, hexa- conazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione, irumamycin, isoprothiolane, isovaledione, kasugamycin, kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, aneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin, nickel dhnethyldithiocarbamate, mtrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxa ocarb, oxolinic acid, oxycarboxim, oxyfenthiin, paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, pro- pamocarb, propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox; pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quintozene (PCNB), sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole, thiabendazole, tbicyofen, thifluzamide, thiophanate-methyl, thira , tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, uni- conazole, validamycin A, vinclozolin, viniconazole, zarila ide, zineb, ziram and also Dagger G, OK-8705, OK-8801, α-(l,l-dimethylethyl)-β-(2-phenoxyethyl)-lH-l,2,4- triazole-1 -ethanol, α-(2,4-dichlorophenyl)-β-fluoro-b-propyl-lH-l,2,4-triazole-l- ethanol, α-(2,4-dichlorophenyl)-β-methoxy-a-methyl- 1H- 1 ,2,4-triazole- 1 -ethanol, α- (5-methyl-l,3-diox-ιn-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-lH-l,2,4- triazole-1 -ethanol, (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(lH-l,2,4-triazol-l- yl)-3-octanone, (E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide, isopropyl l-{2-methyl-l-[[[l-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}- carbamate, 1 -(2,4-dichlorophenyl)-2-(lH- 1 ,2,4-triazol- 1 -yl)-ethanone O-

(phenyl ethyl) oxime, l-(2-methyl-l-naphthalenyl)-lH-pyrrol-2,5-dione, l-(3,5- dichlorophenyl)-3 -(2-propenyl)-2, 5 -pyrrolidinedione, 1 - [(diiodomethyl)-sulphonyl] - 4-methyl-benzene, l-[[2-(2,4-dichlorophenyl)-l,3-dioxolan-2-yl]-methyl]-lH- imidazole, l-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-lH-l,2,4-triazole, 1-[1-

[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]- lH-imidazole, 1 -methyl-5- nonyl-2-(phenylmethyl)-3-pyrrolidinole, 2',6'-dibromo-2-methyl-4'-trifluoromethoxy- 4'-trifluoro-methyl- 1 ,3 -tMazole-5-carboxanilide, 2,2-dichloro-N-[ 1 -(4-chloroρhenyl)- ethyl]-l-ethyl-3-methyl-cyclopropanecarboxamide, 2,6-dichloro-5-(methylthio)-4- pyrimidinyl thiocyanate, 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 2,6- dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide, 2-(2,3,3-triiodo-2-pro- penyl)-2H-tetrazole, 2-[(l-methylethyl)-sulphonyl]-5-(trichloromethyl)-l,3,4-thi- adiazole, 2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-a-D-glucopyranosyl]- amino] -4-methoxy- 1 H-pyrrolo [2,3 -d]pyrimidine-5-carbonitrile, 2-aminobutane, 2- bromo-2-(bromomethyl)-pentanedinitrile, 2-chloro-N-(2,3-dihydro-l ,1 ,3-trimethyl- lH-inden-4-yl)-3-pyridinecarboxamide, 2-chloro-N-(2,6-dimethylphenyl)-N-(isothio- cyanatomethyl)-acetamide, 2-phenylphenol (OPP), 3,4-dichloro-l-[4-(difluoro- methoxy)-phenyl]-lH-pyrrol-2,5-dione, 3,5-dichloro-N-[cyano-[(l-methyl-2-pro- pynyl)-oxy] -methyl] -benzamide, 3 -( 1 , 1 -dimethylpropyl- 1 -oxo- 1 H-indene-2-carbo- nitrile, 3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine, 4-chloro-2-cyano-

N,N-dimethyl-5-(4-methylphenyl)-lH-imidazole-l-sulphonamide, 4-methyl-tetra- zolo [ 1 ,5-a]quinazolin-5 (4H)-one, 8-(l , 1 -dimethylethyl)-N-ethyl-N-propyl-l ,4-dioxa- spiro[4.5]decane-2-methanamine, 8-hydroxyquinoline sulphate, 9H-xanthene-2- [(phenylamino)-carbonyl]-9-carboxylic hydrazide, bis-(l-methylethyl) 3-methyl-4- [(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate, cis-l-(4-chlorophenyl)-2-(lH-

1 ,2,4-triazol- 1 -yl)-cycloheptanol, cis-4- [3 - [4-( 1 , 1 -dimethylpropyl)-phenyl-2-methyl- propyl]-2,6-dimethyl-morpholine hydrochloride, ethyl [(4-chlorophenyl)-azo]- cyanoacetate, potassium hydrogen carbonate, methanetetrathiol sodium salt, methyl l-(2,3-dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazole-5-carboxylate, methyl N- (2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate, methyl N-(chloro- acetyl)-N-(2,6-dimethylphenyl)-DL-alaninate, N-(2,3-dichloro-4-hydroxyphenyl)-l- melnyl-cyclohexanecarboxamide, N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro- 2-oxo-3 -ftιranyl)-acetamide, N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2- oxo-3 -thienyl)-acetamide, N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesul- phonamide, N-(4-cyclohexylphenyl)- 1 ,4,5,6-tetrahydro-2-pyrimidineamine, N-(4- hexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidineamine, N-(5-chloro-2-methylphenyl)-2~ methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide, N-(6-methoxy)-3-pyridinyl)-cyclo- propanecarboxamide, N-[2,2,2-trichloro-l-[(chloroacetyl)-amino]-ethyl]-benzamide, N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N'-methoxy-methanimidamide, N-form- yl-N-hydroxy-DL-alanine-sodium salt, O,O-diethyl [2-(dipropylamino)-2-oxoethyl]- ethylphosphoramidothioate, O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl l,2,3-benzothiadiazole-7-carbothioate, and spiro[2H]-l-benzopyran- 2,r(3'H)-isobenzofiιr--n]-3'-one.

Bactericides

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides / acaricide / nematicides

abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha- cypermethrin, alph-imethrin, amitraz, avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin, bifenazate, bifentl n, bioem--nomethrin, biopermethrin, BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlor- pyrifos, chlorpyrifos M, chlovaporthrin, cis-resmethrin, cispe-rnetlirin, clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalotiirin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoat, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn, eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp., esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimfos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron, flubrocylx-rinate, flucycloxuron, flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb, granulosis viruses, halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene, imidacloprid, isazofos, isofenphos, isoxathion, ivermectin, nuclear polyhedrosis viruses, 1-tmbda-cyhalothrin, lufenuron, malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathion, methiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, monocrotophos, naled, nitenpyram, nithiazine, novaluron, omethoat, dxamyl, oxydemethon M, Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoat, phorat, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur, prothiofos, prothoat, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen, pyriproxyfen, quinalphos, ribavirin, salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos, tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, theta-cypermethrin, . thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb, vamidothion, vamliprole, Nerticillium lecanii, YI 5302, zeta-cypermethrin, zolaprofos, (lR-cis)-[5-(phenylmethyl)-3-fi-r--nyl]-methyl 3-[(c-ihydro-2-oxo-3(2H)--x-ra^^ (3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, l-[(2- chloro-5-t azolyl)methyl]tetrahydro-3,5-dime yl-Ν-mtro-l,3,5-triazine-2(lH)- imine, 2-(2-cMoro-6-fluorophenyl)-4-[4-(l,l-dimethylethyl)phenyl]-4,5-dihydro- oxazole, 2-(acetlyoxy)-3-dodecyl-l,4-naphthalenedione, 2-chloro-N-[[[4-(l- phenylethoxy)-phenyl]---mino]-c--rbonyl]-ber-z--mide, 2-chloro-N-[[[4-(2,2-dichloro- l,l-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide, 3-methylphenyl propylcarbamate, 4-[4-(4-ethoxyphenyl)-4-methylpentyl]-l-fluoro-2-phenoxy- benzene, 4-chloro-2-(l , 1 -dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)- ethyl]thio]-3(2H)-pyridazrnone, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3- pyridinyl)methoxy]-3(2H)-pyridazinone, 4-chloro-5-[(6-chloro-3-pyridinyl)- methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone, Bacillus thuringiensis strain EG-2348, [2-benzoyl-l-(l,l-dimethylethyl)-hydrazinobenzoic acid, 2,2-dimethyl-3-

(2,4-dichlorophenyl)-2-oxo- 1 -oxaspiro [4.5] dec-3 -en-4-yl butanoate, [3 - [(6-chloro-3 - ρyridinyl)methyl]-2-thiazolidinylidene]-cyanamide, dihydro-2-(nitromethylene)-2H- l,3-thiazine-3(4H)-carboxaldehyde, ethyl [2-[[l,6-dihydro-6-oxo-l-(phenylmethyl)- 4-pyridazinyl]oxy]emyl]-carbamate, N-(3,4,4-trifluoro-l-oxo-3-butenyl)-glycine, N- (4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl- lH-pyrazole-

1 -carboxamide, N-[(2-chloro-5-t azolyl)me yl]-N'-methyl-N"-nitro-gu-ιnidine, N- methyl-N^,-(l-methyl-2-propenyl)-l,2-hydrazinedicarbothioamide, N-methyl-N'-2- propenyl- 1 ,2-hydrazinedicarbotbioamide, O,O-diethyl [2-(dipropylamino)-2- oxoethylj-ethylphosphoroamidothioate.

A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators is also possible.

The active compounds of the present invention can be converted into customary formulations such as solutions, emulsions, wettable powders, water-dispersible granules, suspensions, powders, foaming agents, pastes, granules, active compound- impregnated natural and synthetic substances, microcapsules, fumigants etc.

These formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid, liquefied gas or solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents. If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, mineral or vegetable oil, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo- hexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.

Liquid diluents or carriers can be, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride etc.), aliphatic hydrocarbons (for example, cyclohexane etc. or paraffins, such as, mineral oil fractions etc.), alcohols (for example, butanol, glycols and their ethers, esters etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulfoxide etc.), water etc.

Liquefied gas diluents or carriers are liquefied substances which are gases, at normal temperature and pressure. Liquefied gas diluents can be, for example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons, etc.

Solid diluents can be, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates etc.) etc. Solid carriers for granules can be, for example, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite etc.) synthetic granules of inorganic and organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks etc.) etc.

Emulsifiers and/or foam-forming agents can be, for example, nonionic and anionic emulsifiers, for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers, such as, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates etc., albumin hydrolysis products etc.

Dispersants include, for example, lignin sulfite waste liquor, methyl cellulose etc.

Tackifϊers can also be used in formulations (powders, granules, emulsifiable concentrates). As usable tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate etc.).

Colorants can also be used. Colorants can be, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue etc,), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further traces nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc etc.

Said formulations can contain the aforementioned active components in a range of generally 0.1-95 % by weight, preferably 0.5-90 % by weight.

The preparation and possible application forms of the compounds of the present invention will be described more specifically by the following examples. The present invention, however, should not be restricted to them in any way. "Parts" means "parts by weight" unless otherwise specified. Examples

Synthesis Example 1

1.5g (6.69mmol) of l-methyl-5-(3',4',4'-trifluoro-3'-butenylthio)tetrazole was dissolved in 30ml of dichloromethane and 1.62g (9.37mmol) of m-chloroperbenzoic acid (purity about 70%) were added little by little. After stirring at room temperature for 8 hours, it was washed with saturated sodium hydrogen carbonate and water and dried with anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was treated by column chromatography (n-hexane: ethyl acetate = 1:1) to obtain 1.18g of l-methyl-5-(3',4',4'-trifluoro-3'-butenylsulfinyl)tetrazole. n_D ²⁰: 1.4730. Yield: 73%.

Synthesis Example 2

1.5g (6.69mmol) of l-methyl-5-(3^,,4',4^,-trifluoro-3'-butenyltbio)tetrazole was dissolved in 30ml of dichloromethane and 3.23g (18.73mmol) of m-chloroperbenzoic acid (purity about 70%) were added little by little. After stirring at room temperature for 8 hours, it was washed with saturated sodium hydrogen carbonate and water and dried with anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was treated by column chromatography (n-hexane: ethyl acetate = 3:1) to obtain 0.64g of l-methyl-5-(3',4',4'-trifluoro-3'-butenylsulfonyl)tetrazole. n_D ²⁰: 1.4620. Yield: 37%.

Analogously to Synthesis Examples 1 and 2 and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds listed in the following Table 1. Synthesis Examples 1 and 2 are again shown in Table 1 (Examples 1 and 2).

In Table 1, Me represents methyl, Et represents ethyl, n-Pr represents n-propyl, iso-

Pr represents isopropyl, n-Bu represents n-butyl, sec-Bu represents sec-butyl, t-Bu represents tert-butyl, cy-Pr represents cyclopropyl, cy-Pen represents cyclopentyl, cy- Hex represents cyclohexyl, and Ph represents phenyl.

Table 1: Examples of the compounds of the formula (I)

Table 1: (continued)

Table 1 (continued)

Synthesis Reference Example 1 (formula (III))

To 27g (57mmol) of 15% aqueous solution of mercaptomethanol sodium salt, an ethanol solution (5ml) of 4.3g (44mmol) of cyclopropyl isothiocyanate was added drop by drop at room temperature under stirring. After stirring the mixed solution at room temperature for one night, it was acidified with 2N hydrochloric acid and extracted with ethyl acetate. After drying the obtained organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 6.2g (yield

96%) of N-cyclopropyl-S-methyl dithiocarbamate.

Then, after refluxing the mixture of 6.2g (42mmol) of the obtained N-cyclopropyl-S- methyl dithiocarbamate, 3.3g (50mmol) of sodium azide, 10 drops of IN aqueous solution of sodium hydroxide and water (50ml) for 3 hours, the reaction solution was washed with ethyl acetate. Then, the aqueous layer was acidified with 2N hydrochloric acid and extracted with ethyl acetate. After drying the obtained organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 5.1g of 5-mercapto-l-cyclopropyltetrazole. mp. 126-129°C, yield 85%.

Synthesis Reference Example 2 (formula (II))

2.32g (20mmol) of 5-mercapto-l-methyltetrazole, 3.59g (24mmol) of potassium carbonate and 4.54g (26mmol) of 4-bromo-l,l,2-trifluoro-l-butene were suspended in 50ml of acetonitrile and refluxed for 8 hours. After filtering the precipitates, the filtrate was concentrated under reduced pressure and the residue was purified by column chromatography (n-hexane: diethyl ether = 3:1) to obtain 3.78g of 1-methyl-

5-(3',4',4'-trifluoro-3'-butenylthio)tetrazole. n_D ²⁰: 1.4793. Yield: 94.6%.

Further examples of the compounds of the formula (II) obtained by the aforementioned process (Synthesis Reference Example 2) and in accordance with the general description of the preparation process according to the invention are:

1 -ethyl-5-(3 ' ,4 ' ,4 ' -trifluoro-3 ' -butenylthio)tetrazole (n_D ²⁰ : 1.4727), l-cycloproρyl-5-(3 ',4',4'-trifluoro-3 '-butenylthio)tetrazole (n_D ²⁰: 1.4895), l-allyl-5-(3',4',4'-trifluoro-3'-butenylthio)tetrazole (nD²⁰: 1.4837), l-(2-methoxyethyl)-5-(3 ',4 ',4 '-trifluoro-3 '-butenylthio)tetrazole (n_D ²⁰: 1.4750), l-(2-cωorophenyl)-5-(3 4 4'-trifluoro-3'-butenylt io)tetrazole (mp.: 66-67⁰C) l-ρhenyl-5-(3⁵,4',4'-trifluoro-3'-butenylthio)tetτazole (mρ.:85-86⁰C). l-(2,2,2-trifluoroethyl)-5-(3',4',4'-trifluoro-3'-butenylthio)tetrazole (n_D ²⁰: 1.4295) l-(2-hydroxyethyl)-5-(3',4',4'-trifluoro-3'-butenylthio)tetrazole (n_D ²⁰: 1.4905) l-benzyl-5-(3 ',4',4'-trifluoro-3 '-butenylthio)tetrazole (n_D ²⁰: 1.5298) l-isopropyl-5-(3',4',4'-trifluoro-3'-butenylthio)tetrazole (n_D ²⁰: 1.4675) l-n-propyl-5-(3 4 4'-trifluoro-3'-butenylthio)tetrazole (n_D ²⁰: 1.4735) l-n-butyl-5-(3',4',4'-trifluoro-3'-butenylthio)tetr--zole (nD²⁰: 1.4720) l-(2-ethyltMoethyl)-5-(3 4 4^,-trifluoro-3'-butenyltl-io)tetrazole (n_D ²⁰: 1.5047) l-(3-chlorophenyl)-5-(3 ',4',4'-trifluoro-3 '-butenylthio)tetrazole (mp. : 68-69°C) l-(4-chlorophenyl)-5-(3 4 4'-trifluoro-3'-butenylthio)tetrazole (mp.: 72-74°C) l-(2,2,3,3-tetrafluoro-2,3-dihydro-l,4-benzodioxin-6-yl)-5-(3',4',4'-trifluoro-3'- butenylthio)tetrazole (n_D ²⁰: 1.4990). Use Examples:

Example 1: Test against Meloidogyne spp. (Soil pot test)

Preparation of the test agent:

1 Part of the active compound is impregnated to 99 parts of pumice to produce fine granules.

Test method: The test agent prepared as mentioned above was added to the soil contaminated with

Meloidogyne incognita to provide for a concentration of lOppm of the active ingredient. The soil and the test agent were homogeneously mixed by stirring and a pot (1/5000 are) was filled with the soil. About 20 seeds of tomato (variety: Kurihara) were sown per pot. After cultivation in a greenhouse for 4 weeks, they were carefully pulled out not to damage the roots and the root knot index and the controlling effect were determined as follows:

Degree of damage No knots were formed (Complete control) A few knots were formed, Knots were formed to a medium extent. Knots were formed to an intense extent. Knots were formed to the most intense extent (which corresponds to non-treatment).

Σ (degree of damage x number of individuals)

Root knot index x lOO

Total number of tested individuals x 4 The controlling effect of the compounds tested can then be evaluated according to the following equation:

(Root knot index at (Root knot index at non-treated area) - treated area)

Controlling effect [%] = x 100

Root knot index at non-treated area

In the test described, the following compounds showed more than 90 % controlling effect at an effective concentration of 10 ppm: No. 1, 2, 3, 12, 19, 22 and 42.

Formulation Examples

Example 1 (Granules)

To a mixture of 10 parts of the compound of the present invention (No. 1), 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of ligninsulfonate salt, 25 parts of water was added, well kneaded, made into granules of 10-40 mesh by an extrusion granulator and dried at 40-50°C to obtain granules.

Example 2 (Granules)

95 Parts of clay mineral particles having particle diameter distribution of 0.2-2mm are put in a rotary mixer. While rotating it, 5 parts of the compound of the present invention (No. 1) are sprayed together with a liquid diluent, wetted uniformly and dried at 40-50°C to obtain granules.

Example 3 (Emulsifiable concentrate)

30 Parts of the compound of the present invention (No. 2), 55 parts of xylene, 8 parts of polyoxyethylene alkyl phenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and stirred to obtain an emulsifiable concentrate.

Example 4 (Wettable powder)

15 Parts of the compound of the present invention (No. 2), 80 parts of a mixture of white carbon (hydrous amorphous silicon oxide fine powders) and powder clay (1:5), 2 parts of sodium alkylbenzenesulfonate and 3 parts of sodium alkyl- naphthalenesulfonate-formalin-condensate are crushed and mixed to make a wettable powder.

Claims

Claims;

A compound of the formula (I)

wherein

R represents alkyl, alkenyl, haloalkyl, alkoxyalkyl, alkylthio alkyl, cycloalkyl, optionally substituted phenyl or optionally substituted arylalkyl, and

n represents 1 or 2.

2. A process for preparing compounds of the formula (I) according to claim 1,

comprising reacting a compound of the formula (II)

wherein

R has the aforementioned meaning,

with an oxidizing agent in the presence of inert solvents.

3. A compound of the formula (I) according to claim 1, characterized in that

R represents Cι-₈-alkyl, C₂-₆-alkenyl, Cι.₄-haloalkyl, C₂.₆ (total carbon number)-alkoxyalkyl, C .₆ (total carbon number)-a-kylthioalkyl or C . ₈-cycloalkyl, or

represents optionally halogen-, Ci-₄-alkyl-, C_M-alkoxy-, Cw alkylthio- or Cι-₄-haloalkyl-substituted phenyl, or

represents optionally halogen-, Cι-₄-alkyl-, C₁.₄-alkoxy-, Cι_₄- alkylthio- or C^-haloalkyl-substituted benzyl, and

n represents 1 or 2.

4. A compound of the formula (I) according to claim 1 or 2, charaterized in that

R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, n-pentyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-chloroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2-trifluoroethyl, 3-bromopropyl, 2- methoxyethyl, 2- ethoxyethyl, 2-methylthioethyl, allyl, 2-butenyl, phenyl which is optionally substituted by one or two substituents which may be the same or different and which are selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, isopropyl, trifluoromethyl, methoxy and methylthio, or benzyl which is optionally substituted by one or two substituents which may be the same or different and which are selected from the group consisting of fluoro, chloro, bromo, methyl, ethyl, isopropyl, trifluoromethyl, methoxy and methylthio, and

n represents 1 or 2.

5. A nematicidal composition comprising one or more compounds of the formula (I) according to claim 1 and customary extenders and/or surface active agents.

6. Use of one or more compounds of the formula (I) according to claim 1 for combating nematodes.

7. A method of combating nematodes comprising allowing an effective amount of a compound of the formula (I) according to claim 1 to act on said nematodes and/or their environment.

8. A process for preparing a nematicidal composition comprising mixing one or more compounds of the formula (I) according to claim 1 with extenders and/oder surface active agents.