CN1175945A - 1-arylpyrazoles pesticide - Google Patents

Abstract

The present invention discloses compounds of formula (I), wherein: each of R<2> and R<6>, which are identical or different, is hydrogen, halogen, CN, alkyl, haloalkyl or alkylthio; R<4> is lower alkyl; n is 0, 1 or 2; each of R<1> and R<3>, which are identical or different, is H, lower allkyl, lower alkyl-S(O)n, formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl or alkylcarbonyl, the alkyl portion of which radicals is optionally substituted by one or more R<5>; or R<1> and R<3> are joined so as together to form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene; R<5> is cyano, nitro, alkoxy, haloalkoxy, R<7>S(O)n, alkoxycarbonyl, alkylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; and R<7> is lower alkyl or lower haloalkyl, pesticidal compositions comprising them and related methods of controlling pests.

Description

1-arylpyrazole insecticides

Background of the invention

1. Field of invention

The present invention relates to novel 4-(sulfur-containing substituent) derivatives of 1-arylpyrazoles, and derivatives thereof. The present invention also relates to the composition of the compound and the method of using the compound to prevent and control pests such as arthropods, nematodes, intestinal worms or protozoa, especially relates to the application of the compound or the composition as an insecticide in agricultural methods. It is used to control arthropods, especially to kill pests through systemic action.

2. Relevant prior art

International Patent Publication No. WO93/06089 (and related U.S. Patent No. 5,451,598) and WO94/21606 describe 1-(4-SF5 substituted phenyl) heterocyclic insecticides which may be pyrrole and imidazoles or pyrazoles.

The object of the present invention is to provide 1-arylpyrazole insecticide compound and its preparation method.

A second object of the present invention is to provide insecticide compositions and use these pyrazole compound insecticides to kill arthropods (especially insects) especially in crops or horticultural crops, forestry, veterinary medicine or livestock breeding or public health. , plant nematodes or intestinal worms or protozoa) method.

A third object of the present invention is to provide compounds with improved systemic absorption, ie with improved systemic activity. High systemic absorption gives these compounds good efficacy even under dry conditions.

A fourth object of the present invention is to provide compounds with improved mammalian safety, ie less toxicity.

These and other objects of the present invention will be apparent from the following description of the present invention, and can be fully or partially achieved by the present invention.

Summary of invention

The present invention provides improved pyrazole insecticides having the general formula: in:

R and ^R can be the same or different, each being hydrogen, halogen, CN, alkyl, haloalkyl ^or alkylthio;

R ⁴ is lower alkyl;

n is 0, 1 or 2;

R ¹ and R ³ may be the same or different, each being H, lower alkyl, lower alkyl-S(O) _n , formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl or alkyl Carbonyl, the alkyl portion of which may be optionally substituted by one or more R ⁵ ;

Or ^R and ^R are linked together to form a divalent group having 4 to 6 atoms in the chain, the divalent group being an alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene ;

R ⁵ is cyano, nitro, alkoxy, haloalkoxy, R ⁷ S(O) _n , alkoxycarbonyl, alkylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl, or dialkylaminosulfonyl; and

R ⁷ is lower alkyl or lower haloalkyl.

These compounds show excellent performance against important pests such as aphids and whiteflies in foliar applications and cotton leaf aphids (Aphis gossypii) and wheat aphids (Schizaphis graminum) in systemic applications .

Detailed description of the invention

In the present invention, some words used have the following specific meanings:

The term "aminocarbonyl" refers to carbamoyl, a group of formula -C(=O) _NH2 . Likewise, the term "alkylaminocarbonyl" refers to an alkylcarbamoyl group, i.e. a group of the formula -C(=O)NH-alkyl; the term "dialkylaminocarbonyl" refers to a dialkylcarbamoyl group, That is, a group of formula -C(=O)N(alkyl) ₂ , wherein the alkyl moieties may be the same or different.

The term "hydroxycarbonyl" refers to a carboxyl group, ie -COOH. _The term "sulfamoyl" refers to the sulfamoyl group, ie _-SO2NH2 . Likewise, the term "alkylaminosulfonyl" refers to an alkylsulfamoyl group, i.e., a group of formula -SO ₂ NH-alkyl; while the term "dialkylaminosulfonyl" refers to a dialkylsulfamoyl Groups with the general formula -SO ₂ N(alkyl) ₂ , where the alkyl moieties may be the same or different.

The term "alkylcarbonyl" refers to an alkanoyl group, ie a group of formula -C(=O)-alkyl.

The term "halo" preceding a group name means that the group is partially or fully halogenated, that is, substituted by F, Cl, Br or I in any combination, preferably by F or Cl. The term "halogen" refers to F, Cl, Br or I.

The term "aroyl" refers to an arylcarbonyl group, i.e. a group of formula -C(=O)-aryl, wherein "aryl" is an aromatic group, preferably phenyl, which may optionally be One or more substituents such as halogen, methyl and methoxy; most preferably the aroyl is a benzoyl, methylbenzoyl, halobenzoyl or xylylcarbonyl group.

Each aliphatic hydrocarbon moiety, i.e., groups and moieties having an acyclic, nonaromatic hydrocarbon backbone (e.g., alkyl moieties of alkenyl, alkynyl, alkoxycarbonyl, and alkylthiocarbonyl, etc.) typically has up to 7 carbon atoms. Use of the term "lower" before the name of the aliphatic hydrocarbon moiety means that the moiety has up to 4 carbon atoms; for example "lower alkyl" means _C1 - _C4 alkyl. Unless otherwise stated, each aliphatic hydrocarbon moiety is preferably a lower group.

When the name of a substituent is repeated, it has the same meaning unless otherwise stated.

When R ¹ and R ³ are linked together to form a divalent group, it is preferred that -NR ¹ R ³ together form morpholino, pyrrolidino, piperidino or piperazinyl.

Particularly preferred compounds of formula (I) above are those wherein R is ^methyl , ethyl or ^propyl , and/or R is ^hydrogen , R is hydrogen or alkyl, and ^/ or R and ^R can be the same or Different, those compounds each being H, Cl, Br or F.

Compounds of formula (I) wherein n is 0 or 1 are also preferred.

Preferred compounds of formula (I) are those wherein:

R ^{and R} are each hydrogen;

R ^{and R} are each chlorine;

R ⁴ is methyl or ethyl;

n is 0, 1 or 2.

Listed below are representative compounds of formula (I) of the present invention. In the tables below, Et represents ethyl (CH ₂ CH ₃ ). Compound R ¹ R ² R ⁶ R ³ R ⁴ n No.

1 HCl Cl H CH ₃ 0

2 HCl Cl H CH ₃ 1

3 H Et 0 Cl Cl Cl H Et 0

4 H Et 1 Cl Cl Cl H Et 1

5 H Et 2 Cl Cl Cl H Et 2

6 HCl Cl H CH ₃ 2

7 HCl Br H CH ₃ 0

8 HCl Br H CH ₃ 1

9 CH ₃ Cl Cl H CH ₃ 1

10 CH ₃ Cl Cl H Et 1

11 Et Cl Cl Cl H Et 1

_{12EtClClHCH31}

13 CH ₂ CH ₂ CN Cl Cl H Et 1

14 CH ₂ CH ₂ CN Cl Cl H CH ₃ 1

15 CH ₂ CH ₂ COOCH ₃ Cl Cl H CH ₃ 1

16 CH ₂ CH ₂ COOCH ₃ Cl Cl H Et 1

17 CH ₂ CH ₂ C(=O)NH ₂ Cl Cl H Et 1

18 CH ₂ CH ₂ C(=O)NH ₂ Cl Cl H CH ₃ 1

19 CH ₂ CH ₂ COOEt Cl Cl H Et 0

20 CH ₂ COOEt Cl Cl H Et 0

21 H Cl H H CH ₃ 1

22 H H Et 1

23 H Et 1

24 -CH=CH(OCH ₃ ) Cl Cl H Et 1

25 CH ₂ CH ₂ S(=O)CH ₃ Cl Cl H Et 1

26 CH ₂ OCH ₃ Cl Cl H Et 1

resolve resolution

Compounds of formula (I) can be prepared as described in International Patent Publication Nos. WO94/21606 and WO93/06089 or International Patent Publication No. WO87/03781 and European Patent Publication No. 0295117 and U.S. Patent No. 5,232,940 to Hatton et al. method for preparation. Those skilled in the art can select appropriate initial reactants among these known methods, and adopt these known methods to obtain the corresponding desired products.

其中R²、R⁴和R⁶的定义如上。The first method is according to the following reaction scheme:

wherein R ² , R ⁴ and R ⁶ are as defined above.

The reactant of the above formula (II) can also be described as follows:

The conversion of (II) to (III) can be achieved by reducing the disulfide (II) to an intermediate sulfide or thiolate with a suitable reducing agent (such as sodium borohydride), and then reacting the intermediate with a suitable alkyl oxidizing agent (such as alkyl halide or dialkyl sulfate) in a suitable solvent (such as ethanol, water or ether or a mixture thereof) to achieve. The reaction can be carried out at a temperature of from about -20°C to about 150°C, preferably at room temperature.

其中R²、R⁶和R⁴如式(I)所定义，X是卤素。The second method for the preparation of compounds of formula (III) proceeds according to the following scheme:

wherein R ² , R ⁶ and R ⁴ are as defined in formula (I), and X is halogen.

Compounds of formula (IV) can be converted to compounds of formula (III) by direct alkylation of an appropriate alkylsulfenyl halide such as methylthio chloride or ethylthio chloride.

Alkylthio halides can be prepared in a separate reactor, or they can be prepared in situ in the reaction medium used to alkylate analogous compounds of formula (IV). The solvent used may be protic or aprotic, or a mixture of both.

Examples of aprotic solvents used in the above methods are: amides, such as dimethylformamide (DMF); ethers, such as methyl tert-butyl ether, diethyl ether, tetrahydrofuran, and dimethoxyethane; alkyl halides, such as dichloromethane; and aromatic solvents such as toluene and chlorobenzene. Examples of protic solvents used in the present invention are: alcohols, such as methanol and ethanol; amines; and water. The reaction may be carried out in the presence of a catalyst such as a basic catalyst such as a carbonate, a metal hydride such as sodium hydride or a metal hydroxide such as sodium hydroxide. The reaction temperature may be about -20 to 150°C, preferably about 0 to 100°C.

Compounds of formula (I) in higher oxidation states (ie compounds where n is 1 or 2) can be synthesized by oxidation of the corresponding compounds of formula (III). Alternatively, the compound of formula (IV) (wherein R ² , R ⁶ and R ⁴ are as defined above for formula (I) can be directly alkylated with the appropriate alkylthio halide R ⁴ S(O) _n'X as follows, n' is 1 or 2, X is a halogen (Cl, Br, I or F)):

to obtain compounds of formula (IIIa) in higher oxidation states. Examples of alkylating agents include _CH3S (O)Cl, _CH3CH2S (O)Cl, and ( _CH3 ) _{2CHS (} O) _2Br . The reaction conditions and solvents used to carry out the conversion are the same as those described above for the alkylation.

With regard to the synthesis of 5-alkylamino analogues, including monoalkylamino and dialkylamino derivatives of formula (I) and cyclic amino compounds of formula (I) (i.e. compounds where R ^{and R} are linked together) In other words, three basic approaches are suitable. The first method involves the direct alkylation of a precursor compound of formula (III) or formula (III') with an alkylating agent. The second method involves a two-step procedure: synthesis of iminoethers followed by reduction. The third preparation method is by conjugate addition, such as Michael type addition. R and/ ^or R can be prepared using one or more of the methods described in International Publication Nos. WO94/21606, WO93/06089, and WO87/03781, European Patent Publication No. 0295117, and U.S. Patent No. ^5,232,940 to Hatton et al. A compound of formula (I) that is lower alkyl-S(O) _n , formyl, alkenyl, alkynylalkoxycarbonyl, alkylthiocarbonyl, aroyl or alkylcarbonyl.

Precursor compounds of formula (II) and (IV) can be synthesized using various known methods, such as those described in GB8531485 and GB9201636 and US Patent No. 5,232,940 to Hatton et al.

The present invention provides a method of controlling pests in a locus, comprising applying an insecticidally effective amount of a compound of formula (I) to said locus. The compound of formula (I) may conveniently be used in the form of a composition consisting of said compound and an inert agriculturally acceptable carrier. In a preferred embodiment, the pest to be controlled is an arthropod and an arthropodicidally effective amount of the compound is applied to the locus. In the best example, the arthropods to be controlled are insects, for which the present invention provides a method for controlling insects in a locus, comprising applying an insecticidally effective amount of a compound of formula (I) to said locus, or applying an insecticidally effective amount An amount of an insecticidal composition consisting of an insecticidally effective amount of a compound of formula (I) and an agriculturally acceptable inert carrier. In another preferred example, nematodes are required to be controlled, for which the present invention provides a method for controlling nematodes in a place, comprising applying a nematicidal amount of a compound of formula (I) to said place, or applying an effective nematicidal amount An amount of a nematicidal composition consisting of a nematicidally effective amount of a compound of formula (I) and an agriculturally acceptable inert carrier. Preferably, the place where the effective insecticide, especially arthropodicide (especially insecticide) or nematicide amount is applied is a crop or a crop growth area (that is, the area where the crop is growing or the area where the crop has been grown, or areas where crops will be planted, especially those that will be or have begun to be infested by insects).

The composition of the invention which can be used in the present invention for killing pests, especially arthropods (especially insecticides) or nematodes may comprise about 0.001-95% of the active ingredient of formula (I). As used herein, unless otherwise stated, the term "active ingredient of formula (I)" or "active ingredient" refers to a compound of formula (I) as defined above.

Dilute liquid formulations for application to loci where crops are subject to pests usually comprise about 0.001-3%, preferably about 0.1-0.5%, active ingredient of formula (I).

Solid formulations for application to said locus or crops usually comprise about 0.1-8%, preferably about 0.5-1.5%, active ingredient of formula (I).

Concentrated compositions are compositions intended for sale or transport or storage. For use on plants, it is usually diluted with water and applied in this diluted form. Both dilute and concentrated forms are part of the invention.

Concentrated formulations usually comprise from about 5-95%, preferably from about 10-50%, of the active ingredient of formula (I).

The pesticidal composition of the present invention may be applied once, or more than once, or throughout the entire pest season. The pesticidal composition of the present invention is usually applied to the crop area (or the place where pests will (have) occurred) at a rate of about 0.04-1 kg active ingredient/ha, preferably about 0.1-0.5 kg/ka.

The concentrated pesticidal compositions of the present invention may be in solid form, such as dusts, granules or wettable powders, preferably in liquid form, such as emulsifiable concentrates or true solutions.

The compositions of the present invention will usually comprise from about 0.5% to about 95% active ingredient. The remaining ingredients of the composition include the carrier and various additives such as those mentioned below.

"Carrier" herein means an organic or inorganic substance, which may be natural, artificial or synthetic, which is added to the active ingredient and which facilitates its application to the crop or locus to be treated. Such carriers are therefore generally inert and should be agriculturally acceptable, especially for the locus or crop being treated or treated. Carriers can be solid (clays, silicates, silica, resins, waxes, fertilizers, etc.) or liquid (water, alcohols, ketones, oil solvents, saturated or unsaturated hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc. ).

Among many additives, the present invention may include surfactants and other components, such as dispersants, adhesives, defoamers, antifreeze agents, colorants, thickeners, viscous agents, protective colloids, penetrants, stabilizers, additives, deflocculants, corrosion inhibitors, pigments and polymers.

In general, all kinds of solid or liquid additives known in the field of pesticidal and pesticidal treatments can be included in the compositions of the present invention.

Surfactants can be emulsifying or wetting, ionic or nonionic. Suitable surfactants are polyacrylic acid or lignosulfonate; phenolsulfonic acid or naphthalenesulfonate; ethylene oxide with fatty alcohols, fatty acids, fatty amines or substituted phenols (especially alkylphenols or arylphenols) sulfosuccinates; taurine derivatives such as alkyl taurates; phosphoric acid esters; or esters of alcohols or polyoxyethylated phenols. When the spray vehicle is water, it is generally necessary to use at least one surfactant since the active ingredient is not water soluble.

The method of application of the compositions of the invention is generally by spraying a mixture previously prepared by diluting the more concentrated formulations of the invention.

Solid compositions may be powders for spraying or dispersion (in which the active ingredient content can be up to 100%) and granules, especially extruded or compressed granules, or granules prepared by impregnation of the powder (this The content of the active ingredient in the powder may be about 1-80%).

Liquid compositions or compositions which are liquid upon application include solutions, water-soluble concentrates, emulsifiable concentrates, emulsions, wettable powders or slurries or water-dispersible granules.

Emulsifiable concentrates usually contain about 10-80% active ingredient; applied emulsions usually contain about 0.01-20% active ingredient.

For example, the emulsifiable concentrate may include a solvent and, if desired, about 2-20% of suitable additives such as stabilizers, surfactants, penetrants, corrosion inhibitors, or other additives as described.

These concentrates are often diluted in containers with water to obtain a thin liquid suitable for spraying.

Concentrated suspensions can also be applied by spraying, which must be fluidized so that the solids do not separate and sink to the bottom. Usually it comprises about 1-75% (preferably about 2-50%) active ingredient, about 0.5-15% surfactant, about 0.1-10% thickener and about 0-10% other suitable above-mentioned additives, the rest An organic liquid that is insoluble or of low solubility in water or active ingredients.

Wettable powders usually include active ingredient (about 1-95%, preferably about 2-80%), solid carrier, wetting agent (about 0-5%), dispersing agent (about 3-10%) and as required 0- 10% other additives such as stabilizers and other additives mentioned above.

To obtain these wettable powders or dusting powders, the active ingredient and additives are mixed thoroughly, preferably by grinding, for example in a ball mill or similar.

Dispersible granules are generally prepared by agglomerating the powder and subsequently using a suitable granulation method.

The emulsions described herein may be of the oil-in-water or water-in-oil type. They have a somewhat thick consistency, even approaching the viscosity of a gel.

Those skilled in the art can select the most suitable composition or formulation according to specific treatment conditions among these many compositions or formulations.

The compounds or compositions of the present invention may also be used in combination with other insecticides, such as insecticides, acaricides or herbicides.

The present invention will be illustrated by the following examples, and these examples should not be regarded as limiting the present invention, but only to better implement the present invention.

Example 1

Preparation of 1-(2,6-dichloro-4-pentafluorothio)phenyl-3-cyano-4-methylthio-5-aminopyrazole (Compound 1)

1) prepare methylthio chloride:

To 3.16 g of dimethyl disulfide was added 40 ml of methyl tert-butyl ether followed by 1.48 g of sulfuryl chloride. The mixture was stirred at room temperature for 5 hours. A 0.6 ml aliquot of the resulting solution was used in the following reactions.

II) Methylthiolation:

A mixture of 40 mg of 1-(2,6-dichloro-4-pentafluorosulfanyl)phenyl-3-cyano-5-aminopyrazole in 5 ml of methyl tert-butyl ether was heated to reflux under an inert atmosphere. Methylthio chloride (0.6 ml of a solution in methyl tert-butyl ether) was added and the mixture was heated to reflux for 4 hours. The mixture was cooled to room temperature, then partitioned between saturated aqueous sodium bicarbonate and dichloromethane. The organic layer was washed with water. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off. The residue was purified by preparative TLC (thin layer chromatography) using 40% ethyl acetate in hexane as eluent to give 1-(2,6-dichloro-4-pentafluorosulfanyl) Phenyl-3-cyano-4-methylthio-5-aminopyrazole. H-1 NMR (CDCl ₃ ): d 7.8 ppm (2H, s), 2.3 ppm (3H, s).

1-(2,6-Dichloro-4-pentafluorothio)phenyl-3-cyano-4-ethylthio-5-aminopyrazole (Compound 3) was obtained in the same manner. m.p.164-167°C.

Example 2

Preparation of 1-(2,6-dichloro-4-pentafluorothio)phenyl-3-cyano-4-methylsulfinyl-5-aminopyrazole (compound 2)

Add 0.02 ml of sulfuric acid to a solution of 20 mg of 1-(2,6-dichloro-4-pentafluorothio)phenyl-3-cyano-4-methylthio-5-aminopyrazole in 5 ml of methanol at 4°C /isopropanol catalyst solution followed by 0.02 ml of 30% hydrogen peroxide. The mixture was stirred for 2 days while allowing to warm to room temperature. Additional sulfuric acid/isopropanol solution (0.02ml) and 0.02ml 30% hydrogen peroxide were added and stirred overnight at room temperature. The mixture was partitioned between dichloromethane and water. The organic layer was washed successively with a saturated aqueous solution of sodium hydrogensulfate, a saturated aqueous solution of sodium hydrogencarbonate and water. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off. The residue was purified by preparative TLC using 70% ethyl acetate in hexane as eluent to give the desired 1-(2,6-dichloro-4-pentafluorosulfanyl)phenyl-3- Cyano-4-methylsulfinyl-5-aminopyrazole. H-1 NMR (CDCl ₃ ): d 7.8 ppm (2H, s), 3.0 ppm (3H, s).

The following compounds can also be obtained by the same method:

1-(2,6-Dichloro-4-pentafluorothio)phenyl-3-cyano-4-ethylsulfinyl-5-aminopyrazole (Compound 4). m.p.186-187°C.

1-(2,6-Dichloro-4-pentafluorothio)phenyl-3-cyano-4-methylsulfonyl-5-aminopyrazole (Compound 6). m.p.263-264°C.

Representative compounds of the invention prepared above were applied using the following test procedures. Use the following species:

Species Genus Common Name Abbreviation

Aphis gossypii Cotton leaf aphid APHIGO

Schizaphis graminum gram aphid TOXOGY

Musca domestica Musca domestica MUSCDO

Spodoptera eridania Subtropical armyworm PRODER

Meloidogyne incognita Jute root wart nematode MELGIN

Soil Infiltration Test

In this test, representative compounds of the present invention and compounds known in the art 1-(2,6-dichloro-4-pentafluorothio)phenyl-3-cyano-4-trifluoromethylidene The sulfonyl-5-aminopyrazole and the corresponding 4-SO ₂ CF ₃ compounds (compounds 2 and 3 in WO93/06089, hereinafter referred to as compounds P1 and P2) were compared. Cotton and sorghum plants were grown in pots. The day before treatment, each pot was infested with a mixed population of approximately 25 aphids. Cotton plants were infected with the cotton leaf aphid and sorghum plants were infected with the two-handed aphid. Test compounds were applied to the soil surface as solutions at soil concentrations corresponding to 20, 5 and 1.25 ppm by weight. Count the number of aphids after 5DAT (days after treatment). The number of aphids on the treated plants was compared with the number of aphids on untreated control plants. The LC50 values of various compounds were calculated. The following results are obtained:

Result of LC50 (ppm)

type

Compound APHIGO TOXOGR

2 ＜10.0 ＜10.0

3 ＞10.0 6.0

4 3.57 0.55

6 1.39 1.55

P1 ＞20.0 4.83

P2 ＞10.0 ＞10.0

Nematode Soil Infiltration Test

The soil was treated with the test compound to give a soil concentration of 10.0 ppm. Juvenile nematodes were collected and isolated from infected tomato roots and placed in treated soil. Tomato seedlings or cotton seeds (both susceptible to nematode infestation) were sown in the treated nematode-infested soil. After an appropriate time has elapsed for plant growth and root wart formation, remove the plant from the soil and examine for root wart formation. Plants treated with the highly active test compound, and untreated, uninoculated plants showed no root warts on their roots.

Housefly bait/contact test

About 25 4-6 day old adult houseflies are anesthetized and housed in cages with a sugar water bait solution containing the test compound. The compound concentration in the bait solution was 100 ppm. After 24 hours, houseflies that did not respond to the stimulus were considered dead.

A representative compound of the invention obtained a mortality rate of 100%.

APHIGO blade/contact test

Aphid-infested cotton plants and green bean plants were placed on a rotating turntable and sprayed with a 100 ppm formulation of the compound of the invention to runoff. Survival and dead larvae were counted after 5 DAT. The treated APHIGO-infected plants were left for 3 days after treatment, after which the number of dead aphids was counted. A representative compound of the invention obtained a mortality rate of 100%.

Claims (12)

1. Compounds having the following general formula: in: R and ^R can be the same or different, each being hydrogen, halogen, CN, alkyl, haloalkyl ^or alkylthio; n is 0, 1 or 2; R ⁴ is lower alkyl; R ¹ and R ³ may be the same or different, each being H, lower alkyl, lower alkyl-S(O) _n , formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl or alkyl Carbonyl, the alkyl portion of which may be optionally substituted by one or more R ⁵ ; Or ^R and ^R are linked together to form a divalent group having 4 to 6 atoms in the chain, the divalent group being an alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene ; R ⁵ is cyano, nitro, alkoxy, haloalkoxy, R ⁷ S(O) _n , alkoxycarbonyl, alkylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl, or dialkylaminosulfonyl; and R ⁷ is lower alkyl or lower haloalkyl. 2. The compound according to claim 1, characterized in that R ² and R ⁶ can be the same or different, each being H, Cl, Br or F. 3. The compound according to claim 1 or 2, characterized in that R ⁴ is methyl, ethyl or propyl. 4. The compound according to claim 2 or 3, characterized in that R ² and R ⁶ are chlorine. 5. The compound according to any one of claims 1 to 4, characterized in that R ¹ is hydrogen, R ³ is hydrogen or lower alkyl. 6. Compounds according to any one of claims 1 to 5, characterized in that ^R1 and ^R3 are hydrogen. 7. The compound of claim 1, wherein ^R1 and ^R3 are each hydrogen; ^R2 and ^R6 are each chlorine; ^R4 is methyl or ethyl; n is 0, 1 or 2. 8. The compound of claim 1, which is: (a) 1-(2,6-dichloro-4-pentafluorothio)phenyl-3-cyano-4-methylthio-5-aminopyrazole; (b) 1-(2,6-dichloro-4-pentafluorothio)phenyl-3-cyano-4-methylsulfinyl-5-aminopyrazole; (c) 1-(2,6-dichloro-4-pentafluorothio)phenyl-3-cyano-4-ethylthio-5-aminopyrazole; (d) 1-(2,6-dichloro-4-pentafluorothio)phenyl-3-cyano-4-ethylsulfinyl-5-aminopyrazole; or (e) 1-(2,6-Dichloro-4-pentafluorothio)phenyl-3-cyano-4-methylsulfonyl-5-aminopyrazole. 9. A pesticide composition comprising a pesticidally effective amount of a compound of formula (I) as claimed in any one of claims 1 to 8 and an agriculturally acceptable inert carrier. 10. A method for controlling pests in a locus, comprising applying a pesticidally effective amount of the compound of formula (I) according to any one of claims 1 to 8 to the locus. 11. The method according to claim 10, characterized in that the compound is applied to the locus at an application rate of 0.04 to 1 kg/ha. 12. The method for preparing the compound as claimed in claim 1, said method comprising: (a) wherein n is O, R and ^R are hydrogen, so ^that the compound of formula (II): Wherein R ² and R ⁶ are defined as described in claim 1, react with reducing agent, then make the intermediate obtained react with sulfide or mercaptide and alkylating agent; (b) wherein R ^and R are ^hydrogen , such that the compound of formula (IV):

wherein R ⁴ and R ⁶ are as defined in claim 1, react with a compound of the formula R ⁴ S(O) _n X, wherein R ⁴ is as defined in claim 1, and X is a halogen compound; (c) wherein n is 1 or 2, oxidizes the corresponding compound of formula (I), wherein n is 0 or 1; or (d) wherein one or both of ^R1 and ^R3 is an alkyl group, or ^R1 and ^R3 are joined together to form a divalent group having 4 to 6 atoms in the chain, the divalent group being Alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene reacts the corresponding compound of formula (I), wherein R ^{or R} is hydrogen, with an alkylating agent.