JP2005089383A - New thiadiazole-containing difluoroalkenes and utilization as pest-controlling agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide new thiadiazole-containing difluoroalkenes having high pest-controlling activities. <P>SOLUTION: The thiadiazole-containing difluoroalkenes are represented by the formula (wherein, R is hydrogen, a halogen, an alkyl, a cycloalkyl, an alkoxyalkyl, an alkylthioalkyl, a haloalkyl, an alkoxy, an alkylthio, a phenyl which may optionally be substituted, a benzyl which may optionally be substituted, or a heteroaryl which may optionally be substituted and which contains at least one heteroatom selected from N, O and S; m is an integer of 3-10; and n is 0, 1 or 2). The utilization of the compound as the pest-controlling agent is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to novel thiadiazole-containing difluoroalkenes and their use as pest control agents.

  Patent Document 1 describes that certain polyhaloalkene compounds have nematicidal activity.

Furthermore, Patent Document 2 discloses that certain trifluorobutenyl compounds have nematocidal activity; Patent Document 3 discloses that certain heterocyclic compounds have nematocidal activity; A method for producing nematocidal fluoroalkenylthioheterocyclic derivatives; Patent Document 5 discloses that 4,4-difluorobutenyl compounds have nematocidal activity; and Patent Document 6 discloses that difluoroalkene derivatives exhibit pest control activity. Each of them is described as having.
WO 86/07590 brochure U.S. Pat. No. 3,513,172 British Patent Publication No. 2,293,380 WO 95/4727 brochure WO 95/24403 brochure Japanese Patent Application Laid-Open No. 11-349557

  The present inventors have now found that thiadiazole-containing difluoroalkenes represented by the following formula (I) have excellent nematocidal activity and herbicidal activity.

  formula

Where
R is hydrogen, halogen, alkyl, cycloalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkoxy, alkylthio, optionally substituted phenyl, optionally substituted benzyl, or optionally substituted A heteroaryl comprising at least one heteroatom selected from N, O and S,
m represents an integer of 3 to 10, and n represents 0, 1 or 2.

The compound of the said formula (I) is compoundable by the following manufacturing method a) and manufacturing method b), for example.
Production method a) : When n is 0

In the formula, R is as defined above.
In the formula _M-SO 2 -O- the compound represented _{(CH 2) mCH = CF 2} (III)
Where
M represents methyl or p-tolyl,
m is as defined above,
The method of making it react with the compound represented by these.
Production method b) : When n is 1 or 2

In the formula, R and m are as defined above.
A method for oxidizing a compound represented by the formula:

  The compound of the formula (I) of the present invention has strong nematocidal activity and herbicidal activity, and exhibits good affinity for various crops.

  According to the present invention, the compounds of formula (I) surprisingly exhibit a very superior nematocidal action and herbicidal action compared to compounds similar to the compounds of the invention described in the above-mentioned known literature. .

In this specification;
“Halogen” refers to fluoro, chloro, bromo and iodo, preferably fluoro, chloro and bromo.

“Alkyl” is, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl. , N-decyl, n-undecyl, n-dodecyl and the like linear or branched C _1-12 alkyl, preferably C _1-6 alkyl.

“Cycloalkyl” represents, for example, C _3-8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., particularly preferably C _3-6 cycloalkyl.

  Examples of each alkyl moiety of “alkoxyalkyl”, “alkylthioalkyl”, “haloalkyl”, “alkoxy”, and “alkylthio” are the same as those described above for alkyl.

  “Heteroaryl” refers to an aromatic heterocyclic group containing at least 1, preferably 1 to 3 heteroatoms selected from N, O and S, preferably furyl, thienyl, pyridyl, pyrimidinyl, pyrazinyl, etc. The 5- or 6-membered aromatic heterocyclic group can be exemplified.

In the compound of formula (I) of the present invention,
R is hydrogen, chloro, fluoro, bromo, C _1-6 alkyl, C _3-8 cycloalkyl, C _2-6 (total carbon number) alkoxyalkyl, C _2-6 (total carbon number) alkylthioalkyl, chloro- or Fluoro-substituted C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, optionally substituted phenyl, optionally substituted benzyl, or optionally substituted And heteroaryl containing at least one heteroatom selected from N, O and S, wherein phenyl and benzyl substituents are halogen, C _1-4 alkyl, C _1-4 alkoxy, C _{1- At} least one group selected from the group consisting of ₄ alkylthio, halogen-substituted C _1-4 alkyl and nitro, The aryl substituent is at least one group selected from the group consisting of halogen, C _1-4 alkyl, C _1-4 alkoxy and halogen-substituted C _1-4 alkyl;
m represents an integer of 3 to 10 and n represents 0, 1 or 2;
The compounds of the case can be mentioned as suitable.

Among them, in the compound of formula (I)
R is hydrogen, chloro, fluoro, bromo, _C1-4 alkyl, _C3-6 cycloalkyl, _C2-4 (total carbon number) alkoxyalkyl, _C2-4 (total carbon number) alkylthioalkyl, chloro- or Fluoro-substituted C _1-2 alkyl, C _1-3 alkoxy, C _1-3 alkylthio, optionally substituted phenyl, optionally substituted benzyl, or optionally substituted And heteroaryl containing at least one heteroatom selected from N, O and S, wherein the phenyl and benzyl substituents are chloro, fluoro, bromo, methyl, methoxy, methylthio, trifluoromethyl and nitro. And at least one group selected from the group consisting of, and the heteroaryl substituent is bromo and meso. At least one group selected from the group consisting of Le, further, heteroaryl is furyl, thienyl, pyridyl, pyrimidinyl or pyrazinyl,
m represents an integer of 3 to 8 and n represents 0, 1 or 2;
Especially preferred are compounds of the case.

  The production method a) for producing the compound of the formula (I) of the present invention includes, for example, 5-mercapto-1,2,4-thiadiazole and 1-methanesulfonyloxy-6,6-difluoro-5- When hexene is used, it can be represented by the following reaction formula.

Similarly, the production method b) uses, for example, 5- (6,6-difluoro-5-hexenylthio) -1,2,4-thiadiazole as a raw material and m-chlorobenzoic acid as an oxidizing agent. It can be represented by a reaction formula.

  The compound of the formula (II) used as a raw material in the production method a) includes, for example, known compounds described in JP-A-1-308270, WO 86/07590 pamphlet and WO 95/24403 pamphlet. The compound of the formula (II) is a known compound described in, for example, German Patent Publication No. 4239727, JP-A-60-255782, JP-A-1-308270, JP-A-5-194449, and the like. It is easily obtained by the method.

  Typical examples of the compound of the formula (II) include those described below.

5-mercapto-1,2,4-thiadiazole,
5-mercapto-3-methyl-1,2,4-thiadiazole,
5-mercapto-3-tert-butyl-1,2,4-thiadiazole,
5-mercapto-3-methoxy-1,2,4-thiadiazole,
5-mercapto-3-phenyl-1,2,4-thiadiazole,
3-ethyl-5-mercapto-1,2,4-thiadiazole,
5-mercapto-3-n-propyl-1,2,4-thiadiazole,
3-isopropyl-5-mercapto-1,2,4-thiadiazole,
5-mercapto-3-n-butyl-1,2,4-thiadiazole,
5-mercapto-3-sec-butyl-1,2,4-thiadiazole,
5-mercapto-3-n-pentyl-1,2,4-thiadiazole,
3-cyclopropyl-5-mercapto-1,2,4-thiadiazole,
3-cyclopentyl-5-mercapto-1,2,4-thiadiazole,
3-cyclohexyl-5-mercapto-1,2,4-thiadiazole,
5-mercapto-3-methoxymethyl-1,2,4-thiadiazole,
3-ethoxymethyl-5-mercapto-1,2,4-thiadiazole,
3-isopropoxy-5-mercapto-1,2,4-thiadiazole,
5-mercapto-3-methylthiomethyl-1,2,4-thiadiazole,
3-ethylthiomethyl-5-mercapto-1,2,4-thiadiazole,
3-isopropylthiomethyl-5-mercapto-1,2,4-thiadiazole,
3-chloromethyl-5-mercapto-1,2,4-thiadiazole,
3- (2-chloroethyl) -5-mercapto-1,2,4-thiadiazole,
3-trifluoromethyl-5-mercapto-1,2,4-thiadiazole,
5-mercapto-3-pentafluoroethyl-1,2,4-thiadiazole,
3-ethoxy-5-mercapto-1,2,4-thiadiazole,
3-isopropoxy-5-mercapto-1,2,4-thiadiazole,
5-mercapto-3-methylthio-1,2,4-thiadiazole,
3-ethylthio-5-mercapto-1,2,4-thiadiazole,
3-isopropylthio-5-mercapto-1,2,4-thiadiazole,
3-benzyl-5-mercapto-1,2,4-thiadiazole,
3- (4-fluorobenzyl) -5-mercapto-1,2,4-thiadiazole,
3- (2-chlorobenzyl) -5-mercapto-1,2,4-thiadiazole,
3- (4-bromobenzyl) -5-mercapto-1,2,4-thiadiazole,
5-mercapto-3- (3-trifluoromethylbenzyl) -1,2,4-thiadiazole,
5-mercapto-3- (4-trifluoromethylbenzyl) -1,2,4-thiadiazole,
5-mercapto-3- (4-methylbenzyl) -1,2,4-thiadiazole,
5-mercapto-3- (4-methoxybenzyl) -1,2,4-thiadiazole,
5-mercapto-3- (4-methylthiobenzyl) -1,2,4-thiadiazole,
3- (2,4-dichlorobenzyl) -5-mercapto-1,2,4-thiadiazole,
3- (2,4-dimethylbenzyl) -5-mercapto-1,2,4-thiadiazole,
3- (2-fluorophenyl) -5-mercapto-1,2,4-thiadiazole,
3- (3-fluorophenyl) -5-mercapto-1,2,4-thiadiazole,
3- (4-fluorophenyl) -5-mercapto-1,2,4-thiadiazole,
3- (2-chlorophenyl) -5-mercapto-1,2,4-thiadiazole,
3- (3-chlorophenyl) -5-mercapto-1,2,4-thiadiazole,
3- (4-chlorophenyl) -5-mercapto-1,2,4-thiadiazole,
3- (4-bromophenyl) -5-mercapto-1,2,4-thiadiazole,
5-mercapto-3- (4-trifluoromethylphenyl) -1,2,4-thiadiazole,
5-mercapto-3- (3-tolyl) -1,2,4-thiadiazole,
5-mercapto-3- (4-tolyl) -1,2,4-thiadiazole,
5-mercapto-3- (4-methoxyphenyl) -1,2,4-thiadiazole,
5-mercapto-3- (4-methylthiophenyl) -1,2,4-thiadiazole,
3- (2,4-dichlorophenyl) -5-mercapto-1,2,4-thiadiazole,
3- (2,4-dimethylphenyl) -5-mercapto-1,2,4-thiadiazole,
3-bromo-5-mercapto-1,2,4-thiadiazole,
3- (2-furyl) -5-mercapto-1,2,4-thiadiazole,
5-mercapto-3- (2-thienyl) -1,2,4-thiadiazole,
5-mercapto-3- (3-thienyl) -1,2,4-thiadiazole,
3- (5-bromothiophen-2-yl) -5-mercapto-1,2,4-thiadiazole,
5-mercapto-3- (5-methylthiophen-2-yl) -1,2,4-thiadiazole,
3- (4,5-dibromothiophen-2-yl) -5-mercapto-1,2,4-thiadiazole,
5-mercapto-3- (2-pyridyl) -1,2,4-thiadiazole,
5-mercapto-3- (3-pyridyl) -1,2,4-thiadiazole,
5-mercapto-3- (4-pyridyl) -1,2,4-thiadiazole,
5-mercapto-3- (6-methylpyridin-2-yl) -1,2,4-thiadiazole,
3- (4,6-dimethyl-pyridin-2-yl) -5-mercapto-1,2,4-thiadiazole,
5-mercapto-3- (2-pyrimidinyl) -1,2,4-thiadiazole,
5-mercapto-3- (4-pyrimidinyl) -1,2,4-thiadiazole,
5-mercapto-3- (2-pyrazinyl) -1,2,4-thiadiazole and the like.

  The compound of the formula (III) is a known compound described in JP-A-11-349557.

  Specific examples of the compound of the formula (III) include those described below.

1-methanesulfonyloxy-5,5-difluoro-4-pentene,
1-methanesulfonyloxy-6,6-difluoro-5-hexene,
1-methanesulfonyloxy-7,7-difluoro-6-heptene,
1-methanesulfonyloxy-8,8-difluoro-7-octene,
1-methanesulfonyloxy-9,9-difluoro-8-nonene,
1-methanesulfonyloxy-10,10-difluoro-9-decene,
1-methanesulfonyloxy-11,11-difluoro-10-undeken,
1-methanesulfonyloxy-12,12-difluoro-11-dodecene and the like.

  The compound of the formula (Ia) used as a raw material in the said manufacturing method b) corresponds to the compound in case n shows 0 in the compound of the formula (I) of this invention, For example, it can synthesize | combine according to the said manufacturing method a). it can.

  As the oxidizing agent used for the oxidation of the compound of formula (Ia) in the production method b), those usually used in the field of organic chemistry, for example, hydrogen peroxide, m-chloroperbenzoic acid, peracetic acid, Examples thereof include perbenzoic acid, magnesium monoperoxyphthalic acid, and potassium peroxymonosulfate.

  The reaction of the production method a) can be carried out in the presence of a suitable diluent. Examples of diluents that can be used in this case include, for example, aliphatic, cycloaliphatic and aromatic hydrocarbons such as , Hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, etc .; ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, dioxane, tetrahydrofuran, etc .; ketones such as acetone , Methyl ethyl ketone, methyl isobutyl ketone, and the like; nitriles such as acetonitrile, propionitrile, acrylonitrile, and the like; acid amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

  The reaction can be carried out in the presence of an acid binder. Examples of the acid binder that can be used in this case include alkali metal hydroxides, carbonates and alcoholates, and tertiary amines such as Triethylamine, diethylaniline, pyridine, 4-dimethylaminopyridine, 1,4-di-azabicyclo [2,2,2] octane (DABCO), 1,8-di-azabicyclo [5,4,0] undec-7- En (DBU) and the like.

  The reaction can be carried out in a substantially wide temperature range, but generally a temperature in the range of about 0 to about 180 ° C, preferably about 20 to about 120 ° C is suitable. In addition, the reaction is preferably performed under normal pressure, but in some cases, the reaction can also be performed under pressure or reduced pressure.

  And, for example, from 0.7 to 1.2 moles of the compound of formula (III) per mole of the compound of formula (II), the presence of 0.9 to 1.1 moles of acid binder, such as potassium carbonate. The compound of formula (I) of the present invention can be obtained by reacting under heating in a diluent such as acetonitrile under heating.

  The reaction of the production method b) can be carried out in the presence of a suitable diluent. Examples of diluents that can be used in this case include, for example, aliphatic, cycloaliphatic and aromatic hydrocarbons (in the case of May be chlorinated, for example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene, etc .; ethers such as diethyl ether , Methyl ethyl ether, di-iso-propyl ether, dibutyl ether, dioxane, tetrahydrofuran, etc .; alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol, etc .; esters such as ethyl acetate, amyl acetate, etc. Acid amides, such as Dimethylformamide, dimethylacetamide, N- methylpyrrolidone and the like; carboxylic acids, for example, may be mentioned formic acid, acetic and the like.

  The reaction of process b) can be carried out within a substantially wide temperature range, but generally a temperature in the range of about -20 to about 100 ° C, preferably about 0 to about 80 ° C is suitable. In addition, the reaction is preferably performed under normal pressure, but in some cases, the reaction can also be performed under pressure or reduced pressure.

  In carrying out process b), for example, by reacting 0.8 to 3 mol of m-chloroperbenzoic acid with 1 mol of the compound of formula (Ia) at room temperature in a diluent such as methylene chloride. The corresponding target compound of formula (I) can be obtained.

  The compound of the formula (I) of the present invention exhibits a strong control action against nematodes and weeds. Therefore, they can be used effectively as nematocides and herbicides, for example, in the field of agriculture and forestry. And the compound of the formula (I) of the present invention does not cause phytotoxicity to crops, and can exert an accurate control effect against harmful nematodes and weeds. In the present specification, animals and plants harmful to humans, including harmful nematodes and weeds, are referred to as pests.

  Examples of nematodes to which the active compound of formula (I) of the present invention can be applied include, for example, Nematosa nematodes (Pratylenchus spp.), Potato cyst nematodes (Globodera rostochiensis Wollenweber), soybean cyst nematodes (Heterodera glycines Ichinohe), and root-knot nematodes Examples include, but not limited to, Meloidogyne spp., Aphelenchoides basseyi Christie, and Bursaphelenchus Xylophilus.

Similarly, as the weeds to which the active compound of the formula (I) of the present invention can be applied, for example,
Genus of dicotyledonous weeds: Sinapis, Lepidium, Yamgra Kinutasou (Galium), Stellaria, Red-headed Arita (Chenopodium), Nettle (Urtica), Hangonso Noborgiku Kion (Senecio) , Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsium, Schus, Sonchu Potatoes (Solanum), Inugarashi (Rorippa), Odrichospodium (Lamium), Stag beetle Inoufuguri (Veronica), Datura, Violet pansy (Viola), Chishimadoro (Galeopsis), Poppy (Capaver), Centaurea , Galinsoga, Rotala, Aze (Lindernia), etc.,
The genus of monocotyledons: Echinochloa, Enokoro Awa (Setaria), Millet (Panicum), Barkeye (Digitaria), Agaea Timothy (Phleum), Strawberry Tuna Suzumenokatabira (Poa), Ushikokegusa Toboshigara (Festuca) Eurysine, Lolium, Vulture, Bromus, Oat (Avena), Cyperus, Papyrus, Cyperus, Sronhum, Sorghum, Sorghum Monochoria, Tenbuki (Fimbristylis), Omodaka Kwai (Sagittaria), Harii Krogwai (Eleocharis), Firefly Ukiyagura Futui (Scirpus), Paspalum, Platypus (Ischaemum), Nusabo (Agro) Alopecurus) Cynodon etc. But are lower, the use of the compounds of the present invention is not limited to the above plant. In addition, the compound of the present invention acts as a non-selective or selective herbicide depending on the concentration used, and can be used either before germination or after germination.

  The active compounds of the present invention are in the form of their commercially useful formulations or use forms prepared from these formulations, with other active compounds such as insecticides, fungicides, acaricides, fungicides etc. It can also be present as a mixture. Here, examples of the insecticide include organic phosphorous agents, carbamate agents, carboxylate agents, chlorinated hydrocarbon agents, chloronicotinyl agents, insecticides produced by microorganisms, and the like.

  Furthermore, the active compounds according to the invention can also be present as admixtures with synergists, and such formulations and use forms can also be mentioned as being commercially useful. The synergist need not be active per se, but is a compound that enhances the action of the active compound.

  The content of the active compounds of the invention in commercially useful formulations or use forms can be varied within wide limits. The use concentration of the active compounds of the formula (I) according to the invention as nematocides can generally be in the range from 0.000001 to 100% by weight, preferably from 0.0001 to 1% by weight. The concentration in use as a herbicide can be exemplified as the amount of active ingredient per hectare within the range of about 0.05 kg to about 4 kg, preferably about 0.1 kg to about 2 kg.

  The active compounds of the invention can be in the form of conventional preparations. The forms include, for example, liquids, emulsions, wettable powders, granular wettable powders, suspensions, powders, foams, pastes, granules, active compound infiltration-natural and synthetic, microcapsules, fumigants, etc. Can be mentioned.

  These preparations can be produced in a manner known per se, for example by converting the active compound into a developing agent, ie a liquid, liquefied gas or solid diluent or carrier, and optionally a surfactant. I.e. by mixing with emulsifiers and / or dispersants and / or foam formers. When water is used as the developing agent, for example, an organic solvent can be used as an auxiliary solvent.

  Examples of the liquid diluent or carrier include aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides). , Methylene chloride, etc.), aliphatic hydrocarbons [eg, cyclohexane, etc., paraffins (eg, mineral oil fraction, etc.)], alcohols (eg, butanol, glycol and their ethers, esters, etc.), ketones (eg, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strong solvents (for example, dimethylformamide, dimethyl sulfoxide, etc.), water and the like.

  The liquefied gaseous diluent or carrier is a liquefied substance that is gaseous at normal temperature and pressure, and examples thereof include butane, propane, nitrogen gas, carbon dioxide, and halogenated hydrocarbons. And aerosol sprays.

  Examples of solid diluents include ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapul guide, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates). Etc.).

  Solid carriers for powders include, for example, crushed and separated rocks (for example, calcite, marble, pumice, gypsum, dolomite, etc.), synthetic grains of inorganic and organic powders, organic substances (for example sawdust) Coconut husks, corn cobs, tobacco stems, etc.).

  Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (for example, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfate, Aryl sulfonates, etc.)], albumin hydrolysis products, and the like.

  Dispersants include, for example, lignin sulfite waste liquor, methylcellulose and the like.

  Fixing agents can also be used in preparations (powder, granules, emulsions). Examples of the fixing agents that can be used include carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate, etc.) Can be mentioned.

  Colorants can also be used, such as inorganic pigments (eg iron oxide, titanium oxide, Prussian blue, etc.), alizarin dyes, organic dyes such as azo dyes or metal phthalocyanine dyes, and further And trace elements such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, and zinc.

  The preparation can generally contain the active ingredient in a proportion within the range of 0.1 to 95% by weight, preferably 0.5 to 90% by weight.

  Next, the production and use of the compounds of the present invention will be described more specifically with reference to the following examples and test examples. However, the present invention should not be limited to these examples. “Parts” means “parts by weight” unless otherwise specified.

Synthesis example 1

5-mercapto-1,2,4-thiadiazole (0.35 g), 1-methanesulfonyloxy-6,6-difluoro-5-hexene (0.7 g) and potassium carbonate (0.5 g) in acetonitrile (100 ml). ) And heated to reflux for 4 hours. The reaction solution was cooled to room temperature and suction filtered, and the filtrate was distilled off under reduced pressure. The residue was purified by column chromatography (elution solvent ethyl acetate: hexane = 1: 9) and colorless oily 5- (6,6-difluoro-5-hexenylthio) -1,2,4-thiadiazole (0.55 g). Yield 79%, n _D ²⁰ = 1.5093).
Synthesis example 2

After dissolving 5- (6,6-difluoro-5-hexenylthio) -1,2,4-thiadiazole (0.4 g) in dichloromethane (100 ml), m-chloroperbenzoic acid ( 0.9 g, purity about 70%) was added, and the mixture was stirred at room temperature for 20 hours. The reaction solution was washed twice with a saturated aqueous sodium hydrogen carbonate solution (50 ml), and the organic layer was dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by column chromatography (elution solvent ethyl acetate: hexane = 1: 9), and colorless oily 5- (6,6-difluoro-5-hexenylsulfonyl) -1,2, 4-thiadiazole (0.25 g, yield 55%, n _D ²⁰ = 1.4999) was obtained.
Synthesis example 3

5- (6,6-Difluoro-5-hexenylthio) -3-methyl-1,2,4-thiadiazole (0.5 g) was dissolved in dichloromethane (100 ml) and m-chloroperoxygen was dissolved under ice-cooling. Benzoic acid (0.5 g, purity about 70%) was added and stirred at room temperature for 20 hours. The reaction solution was washed twice with a saturated aqueous sodium hydrogen carbonate solution (50 ml), and the organic layer was dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by column chromatography (elution solvent ethyl acetate: hexane = 1: 4) and colorless oily 5- (6,6-difluoro-5-hexenylsulfenyl) -3-methyl. -1,2,4-thiadiazole (0.5 g, 94% yield, n _D ²⁰ = 1.5110) was obtained.

  The compounds of the present invention obtained by the same method as above are shown in Table 1 below together with the compounds of Synthesis Examples 1, 2, and 3.

In the table, Me is methyl, Et is ethyl,
n-Pr is n-propyl, iso-Pr is isopropyl,
n-Bu is n-butyl, sec-Bu is sec-butyl,
t-Bu is tert-butyl, n-Pen is n-pentyl,
cy-Pr is cyclopropyl, cy-Pen is cyclopentyl,
cy-Hex represents cyclohexyl, and ph represents phenyl.

Synthesis example 4 (synthesis of raw materials)

To ethanol (100 ml) were added potassium ethylxanthate (32 g) and formamidine hydrochloride (10.4 g), and the mixture was stirred for 30 minutes. A solution prepared by dissolving 6.4 g of sulfur in 100 ml of carbon disulfide was slowly added dropwise to this mixture, and the mixture was heated to reflux for 30 hours. After completion of the reaction, the solvent was distilled off under reduced pressure at 40 ° C. or lower, and water (150 ml) and 6N aqueous sodium hydroxide solution (50 ml) were added to the residue, followed by stirring for 10 minutes. Insoluble material was collected by filtration, and the filtrate was allowed to stand at room temperature for one day, and then concentrated hydrochloric acid was added under ice cooling to adjust the pH to 3. After extracting three times with ethyl acetate (100 ml), the organic layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by column chromatography (elution solvent ethyl acetate: hexane = 1: 4). 5-mercapto-1,2,4-thiadiazole (1.25 g, yield 11%) was obtained.
Synthesis Example 5 (Synthesis of raw materials)

1,5-pentanediol (55.6 g, 533.8 mmol) and triethylamine (61 g, 603 mmol) were dissolved in tetrahydrofuran (230 ml), and p-chlorobenzoyl chloride (46.7 g, 266.9 mmol) was added to this solution under ice cooling. ) Was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, water (150 ml) was added to the reaction solution, and the mixture was extracted with toluene. The toluene layer is washed with water and dried over anhydrous sodium sulfate, and the residue is subjected to column chromatography (n-hexane: ethyl acetate = 1: 1) to give 1- (p-chlorobenzoyloxy) -5-pentanol. (58.89 g) was obtained. n _D ²⁰ = 1.5212, 91% yield.
Synthesis Example 6 (Synthesis of raw materials)

Oxalyl chloride (54.82 g, 431.93 mmol) was dissolved in dichloromethane (500 ml), and a solution of dimethyl sulfoxide (37.5 g, 479.92 mmol) in dichloromethane (100 ml) was added dropwise to this solution at −60 ° C. Next, a solution of 1- (p-chlorobenzoyloxy) -5-pentanol (58.24 g, 239.96 mmol) in dichloromethane (80 ml) was added dropwise and stirred for 15 minutes. Triethylamine (121.41 g, 1.2 mol) was added dropwise to this solution and stirred for 5 minutes, and then the reaction solution was returned to room temperature. Water (500 ml) was added to the reaction solution, and the dichloromethane layer was separated. After the dichloromethane layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The residue was subjected to column chromatography (n-hexane: ethyl acetate = 7: 2) to give 1- (p-chlorobenzoyloxy) -5-pentanal (51 g). n _D ²⁰ = 1.5220, yield 88%.
Synthesis Example 7 (Synthesis of raw materials)

Dibromodifluoromethane (66.52 g, 317 mmol) was dissolved in tetrahydrofuran (300 mol), and tris- (dimethylamino) phosphine (103.47 g, 634 mmol) was added dropwise at −78 ° C. to this solution. After completion of dropping, the mixture was stirred for 30 minutes, and the reaction solution was returned to room temperature. A solution of 1- (p-chlorobenzoyloxy) -5-pentanal (38.15 g, 158.5 mmol) in tetrahydrofuran (200 ml) was added dropwise and stirred for 2 hours. Water (600 ml) was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to column chromatography (n-hexane: ethyl acetate = 18: 1) to obtain 1- (p-chlorobenzoyloxy) -6,6-difluoro-5-hexene (36.11 g). n _D ²⁰ = 1.5315, 83% yield.
Synthesis Example 8 (Synthesis of raw materials)
HO— (CH ₂ ) ₄ CH═CF ₂
An aqueous solution of sodium hydroxide (5.99 g, 149.86 mmol) in a solution of 1- (p-chlorobenzoyloxy) -6,6-difluoro-5-hexene (36.11 g, 131.45 mmol) in ethanol (80 ml). (40 ml) was added dropwise and the mixture was stirred at 50 ° C. for 1 hour. After cooling, water (200 ml) was added and extracted with ether. The ether layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography (n-hexane: ethyl acetate = 2: 1) to give 1-hydroxy-6,6-difluoro-5-hexene (15 g). n _D ²⁰ = 1.3985, 84% yield.
Synthesis Example 9 (Synthesis of raw materials)
_{H 3 C-S (O)} 2 -O- (CH 2) 4 CH = CF 2
1-Hydroxy-6,6-difluoro-5-hexene (22.14 g, 162.62 mmol) and triethylamine (18 g, 178.89 mmol) were dissolved in dichloromethane (400 ml), and this solution was cooled to ice with methanesulfonyl chloride. (20.48 g, 178.89 mmol) was added dropwise. After stirring at room temperature for 30 minutes, water (300 ml) was added and the organic layer was separated. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to column chromatography (n-hexane: ethyl acetate = 3: 1) to obtain 1-methanesulfonyloxy-6,6-difluoro-5-hexene (27.43 g). n _D ²⁰ = 1.4210, yield 79%.
Test Example 1: Test for root-knot nematode (soil pot test)
Preparation of reagent:
1 part of active compound is impregnated with 99 parts of pumice to give a granule.
Test method:
The reagent preparation prepared as described above was added to the contaminated soil of sweet potato nematode to a dose of 10 ppm, and the mixture was stirred and mixed uniformly to fill a 1/5000 are pot. About 20 seeds of tomato (variety: Kurihara) were sown per pot, cultivated at room temperature, extracted so that the roots would not be lost after 4 weeks, and evaluated for damage according to the following criteria. The control effect was determined.

Damage degree 0: Does not create a bump (complete control)
1: Create a slight bump
2: Moderately grooving
3: Creates a bump in strength
4: Creates a knob with maximum strength (corresponding to no treatment)

As a result of the test, No. 4 and No. 5 are given as typical examples of compounds showing a control effect of 100% at an active ingredient concentration of 10 ppm.
Test Example 2 : Herbicidal activity test (pre-emergence soil treatment test for upland weeds)
Preparation of active compound preparation Carrier: Acetone 5 parts by weight Emulsifier: Benzyloxypolyglycol ether 1 part by weight The active compound preparation is prepared by mixing 1 part by weight of active compound with the above amount of carrier and emulsifier. Obtained as an emulsion. Dilute the prescribed amount of the preparation with water.
Test method:
In a greenhouse, 120 cm ² pot surface layer filled with field soil was seeded with various seeds of Inobie, Enocologosa, Aoubi and Inuta, and a predetermined dose dilution of each active compound prepared according to the above preparation method was added to each pot. It was sprayed uniformly on the soil surface. The degree of herbicidal effect was investigated 2 weeks after spraying.
result:
As a result, as a representative example, the compounds of Compound Nos. 5 and 6 each showed an herbicidal activity of 90% or more against Inubiae, Enocologosa, Aoubi and Inuta, at an active ingredient amount of 2 kg / ha.
Test Example 3 : Herbicidal activity test (post-emergence foliar treatment test for upland weeds)
Test method:
In the greenhouse, 120 cm ² pot surface layers filled with field soil were seeded with various seeds of Inobie, Enocologosa, Aoubi and Inuta. Ten days after sowing (on average weeds are in the second leaf stage), a predetermined dose dilution of each active compound prepared in the same manner as in Test Example 2 above was uniformly sprayed on the plant foliage of each pot. The degree of herbicidal effect was investigated 3 weeks after spraying.
result:
As a result, as a representative example, the compounds of Compound Nos. 6 and 86 each showed an herbicidal activity of 90% or more against Inbiebi, Enocologosa, Aoubi and Inuta, at an active ingredient amount of 2 kg / ha.
Formulation Example 1 (Granule)
25 parts of water is added to a mixture of 10 parts of the compound (No. 4) of the present invention, 30 parts of bentonite (montmorillonite), 58 parts of talc (talc) and 2 parts of lignin sulfonate, and then hatched well and extruded granulation. It is made into granules of 10 to 40 mesh by a machine, and dried at 40 to 50 ° C. to form granules.
Formulation Example 2 (Granule)
After 95 parts of clay mineral particles having a particle size distribution of 0.2 to 2 mm are placed in a rotary mixer and sprayed with 5 parts of the compound (No. 4) of the present invention together with a liquid diluent under rotation, the mixture is made uniform. , Dried at 40-50 ° C. to give granules.
Formulation Example 3 (Emulsion)
30 parts of the compound (No. 4) of the present invention, 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and stirred to obtain an emulsion.
Formulation Example 4 (Wetting agent)
15 parts of the compound of the present invention (No. 5), 80 parts of a mixture of white carbon (hydrous amorphous silicon oxide fine powder) and powdered clay (1: 5), 2 parts of sodium alkylbenzene sulfonate and sodium formalin sulfonate sulfonate formalin 3 parts of the condensate is pulverized and mixed to obtain a wettable powder.

  The novel thiadiazole-containing difluoroalkenes of the present invention can be easily synthesized by a general production method as shown in the above Examples and Test Examples, and exhibit useful effects as nematocides and herbicides.

Claims (4)

formula

Where
R is hydrogen, halogen, alkyl, cycloalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkoxy, alkylthio, optionally substituted phenyl, optionally substituted benzyl, or optionally substituted A heteroaryl comprising at least one heteroatom selected from N, O and S,
m represents an integer of 3 to 10, and n represents 0, 1 or 2;
A thiadiazole-containing difluoroalkene represented by the formula: R is hydrogen, chloro, fluoro, bromo, C _1-6 alkyl, C _3-8 cycloalkyl, C _2-6 (total carbon number) alkoxyalkyl, C _2-6 (total carbon number) alkylthioalkyl, chloro- or Fluoro-substituted C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, optionally substituted phenyl, optionally substituted benzyl, or optionally substituted And heteroaryl containing at least one heteroatom selected from N, O and S, wherein phenyl and benzyl substituents are halogen, C _1-4 alkyl, C _1-4 alkoxy, C _{1- At} least one group selected from the group consisting of ₄ alkylthio, halogen-substituted _C1-4 alkyl and nitro; The substituent of teroaryl is at least one group selected from the group consisting of halogen, C _1-4 alkyl, C _1-4 alkoxy and halogen-substituted C _1-4 alkyl;
m represents an integer of 3 to 10 and n represents 0, 1 or 2;
The compound of claim 1. R is hydrogen, chloro, fluoro, bromo, _C1-4 alkyl, _C3-6 cycloalkyl, _C2-4 (total carbon number) alkoxyalkyl, _C2-4 (total carbon number) alkylthioalkyl, chloro- or Fluoro-substituted C _1-2 alkyl, C _1-3 alkoxy, C _1-3 alkylthio, optionally substituted phenyl, optionally substituted benzyl, or optionally substituted And heteroaryl containing at least one heteroatom selected from N, O and S, wherein the phenyl and benzyl substituents are chloro, fluoro, bromo, methyl, methoxy, methylthio, trifluoromethyl and nitro. And at least one group selected from the group consisting of, and the heteroaryl substituent is bromo and meso. At least one group selected from the group consisting of Le, further, heteroaryl is furyl, thienyl, pyridyl, pyrimidinyl or pyrazinyl,
m represents an integer of 3 to 8 and n represents 0, 1 or 2;
The compound according to claim 1 or 2.   A pest control agent comprising the thiadiazole-containing difluoroalkene according to any one of claims 1 to 3 as an active ingredient.