JPH07505652A - Nitroethylenes and nitroguanidines with arthropodicidal action - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Nitroethylenes and nitroguanidines hopper for arthropodicide use Methyl-substituted cyclic nitroethylene and methyl-substituted cyclic nitroethylene as arthropodicides for combating and nitroguanidine.

GB 1,483,633 covers compounds of the invention as insecticides. It has been announced publicly. International Publication No. 91/17659 pamphlet describes the compound of the present invention. Comprehensive information on how to exterminate planthoppers and leafhoppers using objects is published. US patent No. 4,880,933 comprehensively describes the compounds of the present invention as intermediates for insecticides. It has been announced. There are no specific descriptions of the compounds of the present invention in these specifications. stomach.

Composition of the invention The present invention relates to compounds of formula (2) including all geometric and stereoisomers, suitable for agricultural salts thereof, agricultural compositions containing them, and agricultural and non-agricultural environments. their use for the control of arthropods, specifically planthoppers and leafhoppers, in use. The compound of formula ■ has the following structure: During the ceremony: R1 is HSCHICNSC+-C4 alkyl, C,-C4 haloalkyl, formi Le, C! -04 alkylcarbonyl, C, -C, alkoxycarbonyl, C, - C, alkoxyalkyl, C, -C, dialkoxyalkyl C, -C, alkenyl, C* C4 alkynyl, C, -C. alkylamino, C 2-C, dialkylamino or optionally Rz-substituted benzyl; R2 is halogen, C, -C, alkyl, C+-Cz haloalkyl, C. -C2a Rukoxy, C, -C, alkylthio, C, -C, haloalkylthio, C, -C2 Haloalkoxy, NOt or CN. And Z is CHNO or NNO2.

Preferred compounds A are those in which R1 is HSC, -C4 alkyl, formyl, CHI A compound of formula I that is S(0)z or CH,C(0). preferred compound For B, Z in the formula is CHNO! This is compound A. A preferred compound C has the formula This is a compound A in which Z is N　N　O　2.

Compounds that are particularly preferred for biological activity and ease of synthesis are each preferred. Compound B and preferred compound C, which are: 5-methyl-1-[2- (methylthio)ethyl)-2-tromethylene)-imidazolidine; and 5-Methyl-1-[2-(methylthio)ethyl)-N-nitro-2-imida It is zolidine imine.

Preferred compositions of the invention are those containing the preferred compounds described above.

The preferred method of controlling arthropod and nematode pests on leaves and soil is to A method using compounds and compositions.

Details of the invention In the above definitions, alone or “alkylthio” or “haloalkyl” The word “alkyl” used in compound words such as methyl, ethyl, linear or branched, such as n-propyl, isopropyl or different butyl isomers means an alkyl of the form. Alkoxy is methoxy, ethoxy, n-propyloxy and isopropyloxy. Alkenyl is vinyl, 1-propenyl, Straight-chain or branched alkenes such as 2-propenyl and different butenyl isomers means . Alkynyl includes ethynyl, 1-propynyl, 2-propynyl and straight or branched alkynes, such as butynyl isomers. Archi Ruthio means methylthio and ethylthio. Alkylsulfonyl and alkyl Ruamino is defined similarly to the previous example.

Halogen can be used alone or in compound words such as “haloalkyl” to include fluorine, means chlorine, oxaline or iodine. Furthermore, compound words such as “haloalkyl” , the alkyl may be the same or different, but some Alternatively, all of them can be replaced with halogen atoms.

Examples of haloalkyls include CH2CHF2, CF2CFs and CH2CHFC. ] is included.

The total number of carbon atoms in a substituent is defined by the prefix “C.-C,” where 1 and ] are from 1 to It is represented by the number 6). For example, C,-C,alkylsulfonyl is methylsulfonyl. represents from nyl to propylsulfonyl; C2 alcoquine is OCH2 CH. of and C3 alkoxy is OCHz CH2 CH3 and OCH CCHs )2; C2 alkylcarbonyl represents C(0)CHS; C, alkyl Carbonyl is C (0) CH, CH2 CH, and C (0) CH (CHs )2; and as a final example, C3 alkoxycarbonyl represents C(0)○CH 2CH, and C4 alkoxycarbonyl is C (0) CH2 CH2 Represents CHs and UC (0) CH (CHs)2.

Compounds of formula (1) in which R1 is a group other than hydrogen are as specifically shown in Scheme 1. can be prepared from analogous compounds of formula I in which R1 is equal to hydrogen.

In the formula: ■ is an alkylating agent, an acylating agent, or a sulfonylating agent.

Typical conditions are I(R1=H) in a suitable solvent in the presence of a proton acceptor. A combination of and an alkylating agent, acylating agent or sulfonylating agent represented by ■ Requires. The compound of formula ■ is typically present in equimolar amounts or in stoichiometric excess. and alkylation of alkyl halides and alkyl sulfonates, etc. Acylating agents such as acyl halides and acylic anhydrides and sulfonyl halides and sulfonating agents such as silane and sulfonic anhydrides. The proton accepting volume is Typically used in the range of 1 molar equivalent to 20 molar equivalents, and NaH and K Metal hydrides such as H, amide bases such as lithium diisopropylamide, pyridine and amine bases such as triethylamine, lithium carbonate, sodium carbonate, carbonate Inorganic carbonates such as cesium and cesium carbonate, sodium methoxide and potassium Metal alkoxides such as t-butoxide, and hydroxides such as NaOH and KOH is included. Typical solvents are dimethylformamide, N-methylpyrrolidone and polar aprotic solvents such as acetonitrile, diethyl ether and tetrahydrogen. Ethers such as dorofuran, as well as methanol, ethanol, propatool and water and other protic solvents. Typical reaction temperatures range from 0°C to the reflux temperature of the solvent. and reaction times range from 5 minutes to several days.

Compounds of formula I in which R1 is equal to H, as shown in Scheme 2, For the reaction of a compound of formula ■ with 2-chloroethylmethyl sulfide (IV) in the presence of It can be manufactured more easily.

H3 (wherein: Z=CHNO, or NN0z) The reaction shown in Scheme 2 typically in a polar aprotic solvent such as DMF in the presence of 1 equivalent of a base such as NaH, Between room temperature and 150°C, preferably at 100°C, equimolar amounts of the compound Requires mixing of compound ■. The product typically has its solvent removed and then including but not limited to chloroform, methylene chloride, methanol, ethanol ethyl acetate, triethylamine, saturated ammonium hydroxide aqueous solution or the like The color of Norica gel can be removed using a suitable solvent or solvent mixture, including a mixture of solvents. Extract by mucochromatography.

Alternatively, compounds of formula I where R1 equals H and Z equals CHNO, Produced by reacting diamine V with a compound of formula ■ as shown in scheme 3. can be built.

In the formula: X is a free radical such as SCH3, OCs R5 or halogen.

The reaction of Scheme 3 typically uses, but is not limited to, methanol, ethanol, from room temperature in polar solvents such as alcohol, acetonitrile, tetrahydrofuran or water. V and ■ (usually 1° 1-bis(methylthio)-2 at a temperature between the reflux temperature of the solvent - ditroethylene) is required. but not limited to those using proton acceptors such as , NaOH, sodium carbonate or triethylamine. can be done.

Alternatively, compounds of formula ■ where R1 is H and Z is CHNOz can be prepared according to the scheme As shown in Scheme 4 using conditions similar to those described for reaction 3. By reacting diamine ■ with 2,2,2-trihalonitroethane of formula ■, can be manufactured by The reaction of Scheme 4 is typically limited to However, amines such as triethylamine and pyridine, Na2 CO3, Km C O3 and Na carbonates such as HC03, or LiOH, NaOH or KOH It is necessary to use 1 to 10 molar equivalents of a base such as a hydroxide such as Ru.

In the formula: L, Xt and X3 are halogens.

Compounds of formula I where R1 is H and Z is NNO, can be prepared by the method described in Scheme 3. Using exactly the same method as diamine ■, nitroguanidine ■ (where Y is Nl 2) or S-methyl-N-ditroisothiourea (wherein Y is SCH3) It can be produced by reacting with either R1 is H A method for preparing compounds of formula I where Z is NNO2 is shown in Scheme 5.

In the formula: Y=NH3 or SCH3゜ As shown in Scheme 6, the compound of formula (2) in which Z is CHN O2 has 1.2 -Can be produced by reacting noaminopropane ■ with a compound of formula ■ Wear. The conditions for carrying out these reactions are exactly similar to those described in Scheme 3. be.

Scheme 6 In the formula: X is a free radical such as SCH3 or QC6H.

The compound of formula 2 in which Z is NNO2 is the compound of formula I (R'=H , Z=NNCh) in exactly the same manner as described for the preparation of 1.2- It can be produced by reacting diaminopropane ■ with a compound of formula ■. Ru.

The production of diamine ■ is carried out using the two-step method shown in Scheme 7. Step 1 Stage 2 In step 1 of Scheme 7, 2-(methylthio)ethylamine (X) is potassium cyanide and acetaldehyde in the presence of 1 to 2 equivalents of acid in When processed together, aminonitrile XI is produced. Other cyanide salts and H CN can be used in the method. Halogenated salts and other acid salts of X It can be used in this method. Suitable solvents include, but are not limited to, meth Includes mixtures of alcohol, ethanol, impropatol and water as well as solvents.

Many alternative methods for the preparation of aminonitriles such as XI can be found in the literature. Ru. (For example, 5ynth, Co+emun, 1985.15.157 ;5ynthesis, 1979.127. ) In step 2 of Scheme 7, aminonitrile XI is reduced to produce diamine ■ to be accomplished. This reduction is carried out in an amount ranging from 0.75 molar equivalents to 3 molar equivalents of hydrogenated alkaline minium lithium in a solvent such as diethyl ether or THF from -10°C. This is most easily carried out by using a temperature in the range of the reflux temperature of the solvent. Can be done. Alternatively, the production of V by reduction of xl can be achieved using palladium on carbon. It can also be carried out using hydrogenation over a catalyst such as.

The following examples further illustrate the invention.

2-(methylthio)ethylamine 24.4g (0.27mol) and methanol At -10°C, add 294 L of HCI aqueous solution to 10 QmL of solution. Treatment was carried out by dropwise addition with cooling in a water bath for 15 minutes. The generated solution was 17.4 g (0.27 mol) of potassium cyanide and 150 mL of water at -10°C and then treated with 13 g of acetaldehyde (0.29 mole) at 5-10°C. ) was added. The resulting solution was stirred at room temperature for 6 hours and then diluted with saturated sodium bicarbonate. The solution was injected into a mixed solution of 300 mL of CH, C1, and an aqueous solution IL of 300 mL of CH. that water The organic layer was further extracted with two 200 mL portions of CH2Cl2, and the combined organic layers were saturated. Wash with 500 mL of NaHCO3 aqueous solution, dry with anhydrous Mg5Os, filter, and and concentrated to give 37.6 g (97%) of a pale yellow oil.

'HNMR (200MHz, CDC15) δ3. 78-3.　60(rn, IH), 3. 17-2. 97 (m, IH), 2. 94-2. 74 (m, LH), 2.71-2.62 (m, 2H), 2.12 (S, 3H) , 1.67 (brs, IH), 1.52 (dSJ=784mL, 0.0 84 mol) and (CHs CH2)! 0 (163 mL) and stir vigorously (mechanically). 6.04 g (0,042 mol) of the product from Step A was added to the solution 82 mL of (CHsCH2)zO was added dropwise to OoC. Generate The white heterogeneous mixture was stirred at 00C for 1 hour, at room temperature for 1 hour, then at 0C. A solution of 3.1 mL of HzO, 15% in 10 mL of Tetrahuman O’7 run, cooled to Carefully and sequentially add 3.1 mL of NaOH and 9.3 mL of H2O at 0 °C. It was inactivated by Dilute the resulting mixture with 155 mL of (CH3CH2)20. The mixture was diluted and stirred at room temperature overnight. Filter the resulting mixture and concentrate the filtrate to a dark yellow oil. 6.4 g was obtained. '　HNMR (200MHz.

CDCl5)62. 97-2. 45 (m, 7H), 2. 11 (S, 3H), 1.75 (br s, 3H), 1.05 (d.

J=6Hz, 3H).

2.6 g (0,018 mol) of product of step B, 2,2-bis-(methylthio) -1-nitroethylene 2.9g (0,018 mol) and absolute ethanol 13m A solution of L was heated at reflux for 5 hours, cooled to room temperature 4 hours, and concentrated to a brown oil. 4.8 g of a solid substance was obtained. 40:1:0.1 CHz C12: CHs CH 20H: 48%N) (40) Soybean Chromatography - 18g of yellow oil was obtained and solidified when left standing. did. (m, p, 60-62'C) Grind the solid with 1-talobutane An off-white solid was obtained which melted at 66-68'C. ’　HNMR(2 00MHz, CDC] s) 68.63 (br s, LH), 6.53 (s , LH), 4.21-4.03 (m, IH), 3.90 (t, IH), 3. 40-3.28 (m, 3H), 2.78-2.58 (m, 2H), 2.1 6 (S, 3H), 1.36 (d, 3H).

Example 1, 2.6 g (0,018 mol) of the product of Step B, S-methino N-ni A solution of 2.4 g of troisothiourea and 18 mL of absolute ethanol was mixed at reflux temperature. Heated for 8 hours. The resulting mixture was cooled to room temperature and concentrated to give 3.5 g of a brown oil. Obtained. 40:1:0.1 CH2Cl1CH3C) 120H: 48%NH By flash chromatography of the oil on silica gel using ,OH 1.25 g of pale yellow oil was obtained. ’　HNMR(200MHzSCDCl -g) δ8.08 (br s, IF (), 4. 18-4. 00 (m , IH), 3.92 (t, IH), 3.78 (dd, IH), 3.42- 3.24 (m, 2H), 2.84-2.60 (m, 2H), 2.17 (S , 3H), 1.37 (d, -3H).

By the general methods described herein or obvious variations thereof, Table 1.2 and the Compounds of Dex Table A can be prepared.

In Table 1.2 and Index Table A, the following abbreviations were used: Me -C H3n-Bu　TCH2)3CH3Et　”CH2CH31-Bu　-c H2co(CH3)2 difference Table 1 Table 2 Formulation/Usage The compounds of the present invention generally comprise a liquid or solid diluent or an organic solvent. may be utilized in formulations with commercially appropriate carriers. Therefore, the arthropodicide of the present invention The composition comprises an effective amount of the compound of formula (1) and (a) a surfactant, (b) an organic solvent. , and (C) at least one solid or liquid diluent. It consists of one type. Useful formulations can be prepared in conventional manner. that dust, granules, feed, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable This includes functional concentrates, dry flow agents, and others. Sprayable formulations are diluted with a suitable solvent Use by spraying from approximately 1 liter to several hundred liters per hectare. can do. Fortified compositions are primarily used as intermediates for further formulations. It will be done. The formulation specifically comprises 1 active ingredient plus a surfactant and/or diluent. An effective amount of the active ingredient within the approximate range below, such as 0.00 weight percent. will contain diluents and surfactants.

weight percent Active ingredient, diluent, surfactant 6L Moisturizing Powder 25-90 0-74 1-10 Oil Suspension, Emulsion, Solution 5- 50 40-95 0-15 (including emulsifiable concentrate) Dust 1-25 70-99 0-5 Granules, bait and 0.01-99 5-9 9.99 0-IE Beret Reinforced Composition 90-99 0-10 0-2 Typical solid diluent is Watkin s, et al, , Handbook of In5ecticideD ust Diluents and Carriers, 2nd Ed,, Dorland Books, Caldwell, mew Jersey. Wettable powders contain more absorbent diluents, And thicker diluents are preferred for dust. Typical liquid diluents and solvents are Marsden, 5olvents Guide, 2nd Ed, I terscience, New York, 1X50 It is described in. Solubility below 0.1% is preferred for suspension concentrates: solution concentrates is preferably stable against phase separation at 0°C.

Eagle cCutcheon’s Detergents and Emulsif iers^nnual, A11ured Publ.

Corp, Ridgewood, New Jersey, and 5is ely and Wood, Encyclooedia of 5 surface Active Agents, Chemical Publ, Co,, Inc., New York, 1X6j It Surfactants and recommended uses are summarized in the table. All formulations are foamy and cakey May contain small amounts of additives to inhibit corrosion, corrosion, microbial growth, etc. Wear. Preferably, the ingredients are approved by the United States Environmental Protection Agency or similar government agency of the country in which they are used. It should be approved for the intended use by the government.

Methods for preparing these compositions are well known. The solution simply mixes the ingredients Manufactured by The finely divided solid composition is mixed and usually (or hammer milled) Or produced by grinding with a liquid energy mill. Water-dispersed granules are fine Can be produced by agglomerating fine powder compositions: for example, Cros set at, Pe5ticide Formulations.

Washington, D.C., 1988, pp. 251-259. Illuminated Ll. Suspensions 1 are prepared by wet milling: e.g. U.S. Pat. See No. 60.084. Granules and pellets are produced in preformed granular containers. The active substance can be prepared by spraying or by agglomeration methods. Bro wning.

”＾gglomeration-1Chemical Engineering , December 4.1967, pages 14V and following, Perry’s Chemical En gineer's Handbook, 4th Ed, @.

McGrav-Hill, New York, 1963. pages 8 to 57 and following, and International Publication No. 91/1354 Please refer to pamphlet No. 6. Pellet is US Patent No. 4,172,714 It can be manufactured as described in the specification. Water-dispersible granules and water-soluble granules are No. 3,246,493. Wear.

Further information regarding preparation techniques can be found in U.S. Pat. No. 3,235,361, no. 7111 from column 6, line 16! , line 19 and Example 10 to Example 41, U.S. Pat. Specification No. 3,309,192, column 5, line 43 to column 7, line 62 and implementation Example 8.12.15.39.41.52.53.58.132.138-140. 162-164.166.167 and 169-182; U.S. Patent No. 2.891. No. 855 specification, column 3, line 66 to column 5, line 17 and Example 1-4: Kli ngman, Weed Control as aScience, Joh n WiLey and 5ons, Inc., New York, 1 961. pp, 81-96; ce et all, Weed Control Handbook, 8th Ed, Blackwell 5 scientific@Pu See bl1cations, Oxford, 1989.

In the examples below all parts are by weight. Compound number is index This is shown in Table A.

Compound 1 20% oil-soluble sulfonates and Mixture of polyquine ethylene ether 10% Isophorone 70% The ingredients are mixed and stirred with mild warming to promote dissolution.

Fine screen filtration during packaging to ensure that insoluble foreign matter in the product is removed Implement.

Sodium alkylnaphthalene sulfonate 2% Sodium lignin sulfonate 2% Synthetic amorphous silica 3% The active ingredient is mixed with the inert material in a blender. After grinding in a hammer mill , remix the ingredients and sieve through a 50 mesh screen.

Wettable powder of Example B 10% Pyrophyllite (powder) 90% The wettable powder and pyrophyllite diluent are thoroughly mixed and then packaged. made The product is suitable for use as dust.

montmorillonite granules (Low volatile substance, O', 7110.30mm; tJ, S, S, No, 25-50 sieve) Dissolve 98% of the above active ingredient in a volatile solvent such as acetone and double coat. Spray the montmorillonite granules in a sieve. The acetone is then added Evaporate by heat. The granules are then allowed to cool and packaged.

Wettable powder of Example B 15% Plaster 69% Potassium sulfate 16% The ingredients are mixed in a rotary mixer and sprayed with water to complete the granulation. Big The material of the part is the target Q, 1mm to 0.42mm (U, S.

S, No. 18 to 40 sieves), take out the granules, dry them, Then sift it. Crush large-sized materials and sample again in the desired area. Manufacture materials for is. These granules contain 4.5% active ingredient.

Compound 1 25% N-methylpyrrolidone 75% Mixing and stirring the ingredients produces a solution suitable for direct small volume use.

Compound 2 40.0% Polyacrylic acid thickener 0.3% Dodecyclophenol polyethylene glycol ether 0.5% disodium phosphate Rium 1.0% Sodium phosphate 0.　5%- Polyvinyl alcohol 1.0% Water 56.7% When the above ingredients are mixed and ground in a sand mill, substantially all of them are less than 5 microns. produces particles of size.

Calcium ligninsulfonate 12% Sodium ligninsulfonate 3% Mix the ingredients and moisten with approximately 20% water. Shape the mixture into a cylinder with a diameter of 1 mm. Extrusion, which is crushed into pieces approximately 1 mm to 10 mm long. this are dried and used as described in Example 1.

Preformed granules from Example H 98% Compound 1 is dissolved in acetone and sprayed onto the preformed granules in a mixer.

The acetone is evaporated by heating. Then, the granules are left to cool and used as bait granules. Compound 1 3.0% polyethoxylated nonylphenol and Sodium dodecylbenzenesulfonate 9.0% crushed corn cob 8 8.0% The mixture of the above-mentioned chemical compound and surfactant is dissolved in a suitable solvent such as acetone and ground. Spray on the corn cob. The granules are then dried and wrap it.

The compounds of the invention can be used in growing agricultural crops 1. Storage crops, forests, greenhouse crops, Foliage plants, nursery crops, stored foods and textile products, livestock, household, and public and animals are a wide range of leaf-feeding, fruit-feeding, and seed-feeding pests. Water-based and soil-dwelling arthropods (including insects, mites and nematodes) that serve as feed. It shows activity for (words). Experts in the field believe that all compounds You will appreciate that they are not necessarily equally effective against pests. However, the book All compounds of the invention contain eggs, larvae and adults of the order Lepidoptera. ; Larva of the order CoLeoptera that feeds on eggs, leaves, fruits, roots, and seeds. and adults] of the order Hemiptera and Homoptera. Eggs, immatures and adults; eggs, larvae, nymphs and adults of the order Acari, hymenoptera Orders (Thysanoptera), Orders (Orthoptera) and Orders Hymenoptera Adult and immature insects of (Dermaptera): eggs of Diptera , immature worms and adults: and adult and immature worms of Nematoda (Nematoda). Shows activity against pests including. Compounds of the invention also specifically include Hymenoptera (H ymenoptera), Isoptera, Ph. thiraptera), Acari (Siphonoptera), Cockroaches ( Blattari), Thysanaura and Buscobutellae (P scoptera) pests belonging to the arachnid family (Arachnida): and It is also active against Ilelminthes. This compound is particularly suitable for Abrochi Chikara Undesim Punctata Hwarji [Southern Corn Red Rootworm] ] (Diabrotica ), Masculosteles fasciphrons [Aster leaf hopper] (Ma scrosteles fascifrons), boll weevil [boll weevil] le lyville] (Tetnomus grandis), spider mite (Tet ranychus urticae), Spodoptera f. rugiperda), Aphis fabae (black bean aphid) (Aphis fabae), tobacco moth (■eliothis viresc) ens), Rissorhobuturus oryzophilus and Rice Water Rye Bill) (Lissorhoptrus oryzophilus), Oure Oulema oryzae (rice leaf beetle), hemlock Terra frucifuela [White Packed Plant Hopper] (Sogate lla furcifera), black leafhopper (Nephotettix) cincticeps), brown planthopper (Nilaparvata lug) ens), Laodelphax 5triatellus , Chil.

5 uppressalis), rice leaf beetle (Cnaphalocrosis) Medinalis), Scotinophala lulida [Blankreis Sudzink] bag) (Scotinophalalurida), Raginotomus erotica Ngatos [rice tink bag] (Lagynotomus elonga) tus), Leptocorisa chinenns [rice bag] (Leptocori sa chinensis), Fretos Bunchgel [Slender Rice Buck] C1etus puntiger), and Nezara birizula [Southern Active against green stinkbag) (Nezara viridula) It is gender. For a more detailed description of pests, see WO 90/10623 pamphlet. Please refer to pamphlet No. 9010 O673.

The compounds of the invention may also be used as one or more insecticides, antifungals, nematicides, fungicides, Acaricides, biochemicals (sea+iochemicals), repellents, attractants , mixed with pheromones, appetite stimulants or other biologically active compounds. Multi-component pesticides can be produced that provide a broader range of agricultural protection.

Examples of other agricultural protection agents with which the compounds of the invention can be formulated include: Monocrotofufos, carbofuran, tetrachlorvinphos, malathion, barati -Methyl, methomyl, chloromethrin, diazinon, deltamethrin, Xamil, Fuenvalerate, Esfenvalerate, Permethrin, Prof Enofos, sulprofos, triflumuron, diflubenzuron, methoprene, but Profezin, thiodicarb, acephate, azinphos-methyl, chlorpyrifo dimethoate, honphos, isofenphos, methidathion, methamidophos, fosmenot, phosfamidon, fosalon, pirimicarb, phorate, terbufos , trichlorfon, metquinchlor, bifuentrin, bifuenate, nfurto Phosphorus, Fuenbropathrin, Fluparinate, Flucitrinate, Tricumetri Insecticides such as carpendazim, thiuram, and rotinone, metaldehyde, and rotinone. Syn, maneb, taloloneb, benomyl, nomoxanil, fenbropine, fe Impropimorph, triadimefon, captan, thiophanate methyl, thiabene dazole, fosethyl-^1, chlorothalonil, chlorane, metalaxyl, carbonate Butafor, iprodione, oxanxyl, vinclozolin, Kasugamycin, Myclobutanil, Tebuconazole, Difenoconazole, Daniconazole, Flu Quinconazole, Penconazole, Propiconazole, Unicon Seal, Flute Liafor, Prochloraz, Birifenox, Fuenarimol, Triazimenor dichlobutrazol, cotperoxychloride, furalaxyl, forbec Antifungal agents such as silane and flusilazole: aldquincarb, fenamifos and phos Anti-nematode drugs such as chetan; oxytetracycline, streptomycin and trisalts Antibacterial agents such as basic copper sulfate, binapacryl, oxiraoxix, chlorobenzi rate, dicofol, genochlor, cyhexatin, hexythiazox, a mitlers, propargite and fenbutatine A tick dewormer such as Bacillus thuringiensis (Bacillus thuringiensis) ringiensis) and bacculovirus, etc. There are many biological products.

In some cases, other drugs may be used that have a similar range of animal control effects but a different mode of action. Combinations with arthropodicides may be particularly beneficial for treatment of resistance.

The present invention further provides for the extermination of arthropod and nematode pests that reside in leaves and soil, and for agricultural products and animals. a method for protecting property and human health, the method comprising one or more more than one compound of formula I, or a set containing at least one such compound The product should be protected in effective amounts in pest environments, including infested agricultural and non-agricultural areas. or directly to the pest to be exterminated. Preferred administration The method involves applying the compound by means of a spraying device to the pests that are infested or need to be protected. in the environment, in leaves, animals, humans or their surroundings, in the soil or animals, in plant parts, It is spraying. Alternatively, foliar administration of granular formulations of these compounds It can be administered or incorporated into the soil or rice field. Direct spray and residual spray Fog, atmospheric spray, systemic ingestion, bait, ear tags, explosives, propellants, fumigants, aerosols, Other methods of administration may also be utilized, including, and many others. these The compounds can be put into the food that arthropods eat or otherwise be eaten by arthropods. If so, they can be incorporated into traps and other devices to entice people to come into contact with those compounds. Ru.

Although the compounds of the invention can be used in their pure state, very often one or more of these compounds and suitable carriers, diluents, and surfactants and possibly in combination with bait, depending on the intended end use. will be administered. Preferred methods of administration include aqueous dispersions or involves spraying refined oil solutions.

Spray oil, spray oil concentrate, spreading sticker-1 adjuvant, and synergistic agent and other Combination with solvents such as piperonyl butoxide often increases the potency of the compound. Ru.

The dosage required for effective extermination depends on the species of arthropod to be exterminated, the life cycle of the pest, its age, Size, location, time of year, crops or animals infested, eating habits, mating habits, surroundings It will depend on factors such as humidity, temperature, etc. Generally speaking, per hectare approximately Dosage rates of 0.01 kg to 2 kg of active ingredient are suitable for agricultural ecosystems under normal circumstances. 0.001 kg/hectare, which is sufficient to provide effective large-scale control of pests. A small amount of 8 kg/ha may be sufficient, or a large amount of 8 kg/ha may be required. There may be times. For non-agricultural use, the effective usage amount is approximately 1.0 mg. It may be in the range of 50mg/sqm from O, 1mg/sqm. A small amount of Torr may be sufficient or a large amount of 150 mg/sq. may be necessary.

The following tests demonstrate the control efficacy of compounds of formula I against specific pests: Please refer to Index Table A for details of the compounds. However, the present invention The pesticidal effects shown by the compounds are not limited to these species.

Compounds not included were either not screened or had a mortality rate of less than 80%. It was.

Compound Z R' m, p, 'C I CHNO2H66-68 2NN02H oil 3 CHNO2CHzCHCHz oil 4 NNO2C(0)CH3 oil Compound number 'HNMR data 1 32 6.41 (s, IH), 5.94-5.75 (m, IH), 5, 35-5. 18 (m, 2H), 4. 08-3. 78 (m, 5H) , 3.43 (dt, IH), 3.12 (dd.

LH), 2.83-2.58 (m, 2H), 2.14 (s, 3H), 1.35 (d, 3H).

4' 4.01 (dd, LH) 3.84-3.78 (m, LH), 3, 7 4-3. 65 (m, IH), 3.38 (dd, LH), 3.27 (dd d, LH), 2.78-2.60 (m, 2H), 2. 51 (s, 3H ), 2.17 (S, 3H), 1.29 (d, 3H).

1Spectra were obtained in CDCl3 unless otherwise indicated.

S=-duplex, d=duplex, t=triple, m=multiple.

Spectrum obtained at 2200MHz.

"Spectrum obtained at 400MHz.

Test A The fall armyworm test device consists of 12 containers. It was a tray made of styrene. The container contains filter paper moistened with water and approximately 8 square cm of lima bean leaves were added. 15-20 Spooptera 8 ounces (230 ml) of third molt intermediate instar larvae of P. frugiperda I put it in a plastic cup. A solution of each test compound ((75: 25) Acetone: distilled water solvent) was sprayed onto the tray and cup. Spraying is the Ray and cup directly at 30 ps ig (207 kPa) per knee car A flat fan spraying at a rate of 15 pounds of active ingredient (approximately 0.55 kg/ha) This was carried out by passing under the pressure nozzle on a conveyor belt.

The insects were then transferred to the tray (one larva per container). cover the tray , kept at a relative humidity of 27° 0150% for 48 hours, and then placed with lima bean leaves. Measurements were performed on 12 containers. Among the test compounds, the following compounds are 80 % or higher mortality rate. 1゜Test B Southern corn rootworm m) each containing one 1 inch square soybean-wheat malt feed A device consisting of a plastic cup containing 30 ml of water was prepared.

The test device sprays individual solutions of test compounds as described in Test A. did. After the spray in the cup dries, 5 Siaprotic Undenmupunk Tata Khwarji [Southern Corn Rootworm] (Diabrotic un decimpunctata howardi) at the intermediate stage of the second molt. -I put it in a cup. The cup was then covered and kept at 27°C for 48 hours at 50% relative The animals were kept at humidity, and then mortality was measured. Among the compounds tested, the following compounds After 48 hours, the specimen showed a mortality rate of over 80% = 1.2, Aster Leaf Hopper -(＾5ter　1eafhopper) test equipment 1 inch (＾5ter　1eafhopper) Plant in a layer of sterile soil 2.5 cm (2.5 cm) thick and 1/2 inch (1.25 cm) sand. A series of 12 oz (3 50ml) cup. The test equipment contains each of the compounds listed below. solution was sprayed as described in Test A. Auto topsoil spray liquid dried After that, 10 to 15 Macrostelles fasciphrons [Aster Leafhopper] Adults of Macrosteles fascifrons were placed in the ventilation lid. I sucked it up and put it into each cup that came with it. Place the cups at 27°C for 48 hours, Mortality measurements were taken after keeping at 0% relative humidity. Among the compounds tested, The compound showed a mortality rate of over 80%: 1.2.4°5 bollworms A series of adult Anthonomus grandis Placed in each 9-ounce (260 ml) cup. below the test equipment. Individual solutions of the compounds listed below were sprayed as described in Test A. next Each cup was covered with a vented lid and kept at 27°C and 50% relative humidity for 48 hours. The mortality rate was measured. Among the compounds tested, the following compounds caused a mortality rate of over 80%. Shown=1.2°Test E blank bean aphid (black bean aphid) leaves 10 to 15 Aphis fabae of all ages each. Aphis fabae) and spread it on the underside of their leaves. sprayed upward as described in Test A. Then the leaves were mixed with 4 ml of Aphids falling from leaves in a 3/8 inch diameter vial containing a sugar solution. I covered it with a clear plastic 1 oz cup to prevent it from escaping. the Mortality was measured after keeping the test apparatus at 27°C and 50% relative humidity for 48 hours. Ta. Among the test compounds, the following compounds showed a mortality rate of 80% or more = 1.2.3° Test F Solution against green leafhopper nymphs Systemically active test compounds are added directly to 10 mL of distilled water and completely dissolved. This transformation Inject the compound solution into a conical test device. Next, add a sponge plate with notches. to plant three rice seedlings into the device. Sponge plate the root system of the seedling in the compound solution The plant can be completely immersed, while the parts of the plant that are exposed to the atmosphere are soaked in the solution. isolated above. The sponge also allows test nymphs to accidentally come into contact with the test solution. Prevent touching. From 7 mm between the surface of the compound solution and the bottom of the sponge plate The 10 mm space prevents accidental penetration of the compound into the sponge. combination The concentration of test compound in the solution is 1100 pp. Rice seedlings are kept at 27℃, relative The compound is allowed to absorb from the solution for 24 hours in a growth chamber maintained at 65% humidity.

8 to 10 leafhoppers (Nephotettix cinctic) eps) at the intermediate stage of the third molt are transferred to the test apparatus using an aspirator. spread Store the device under similar temperature and humidity conditions as described above. 24 and 48 hours of infestation Afterwards, the number of live and dead nymphs is determined. Insects that cannot walk are classified as dead. . Among the test compounds, the following compounds showed a mortality rate of over 80% within 48 hours after infestation. =1.2゜ test G All solutions against brown planthopper nymphs The physically active brown planthopper (Nilaparvata lugens) was tested. The systemic activity of the solution against leafhopper nymphs, except that it is a species of A method similar to that used is used. Among the test compounds, the following compounds are prevalent48 Showed a mortality rate of 80% or more after hours = 1.2゜Test H Contact activity against nymphs of green leafhopper Leaf stage 1. Three rice plants (Ory zastiva) seedlings in 1/2 ounce (1 ounce) of Kumiai Brown artificial soil. 4 mL) into a plastic cup. Then add 7mL of distilled water to the cup. Add to. Test compounds are prepared by first dissolving the compound in acetone and then final testing. It is produced by adding water so that the compound concentration is 75:25 (acetone:water). Next Four plastic cups were sprayed, each cup serving as a repeat test. Place it on the rotating plate of the fog chamber. 2.0k using an air fine atomizing nozzle in those cups. Spray 5 Q mL of compound solution at a pressure of g/cm2 for 45 seconds. The rotating plate is 45 75 revolutions during a spray time of seconds. After spraying the compound solution, dry for about 2 hours. Store in a vented container. After drying, the cups were placed in a conical test device. Then cover the soil surface with 2 mm to 3 mm of quartz sand. 8 to 10 blacktip sharks Intermediate stage of third molt of leafhopper (Nephotettix cincticeps) Instar nymphs are transferred to the test apparatus using a suction device. Test equipment at 27℃, relative Store at 65% humidity. Live and dead nymphs were measured 24 and 48 hours after infestation. Set. Nymphs that cannot walk are classified as dead. Among the test compounds, the following compounds are 1 The brown planthopper showed a mortality rate of over 80% after 48 hours at 100pp. Contact active leaf sta on nymphs of N. planthopper ge)1. Three rice (Oryzastiva) seedlings with a height of about 10 cm were grown in Step 5. 1 1/2 oz (14 mL) plastic container containing Kumiai Brown artificial soil Transplant to stick cup. Then add 7 ml of distilled water to the cup. Tess For test compounds, first dissolve the compound in acetone and then make the final test compound concentration 75: 25 (acetone:water) by adding water. Then each car Place four plastic cups on the rotating plate in the spray chamber to serve as repeat tests. put. A pressure of 2.0 kg/cm2 was applied to those cups using an air fine atomizing nozzle. Spray 50 mL of the compound solution for 45 seconds. The rotating plate is sprayed during a 45 second spray period. 75 rotations. After spraying the compound solution, store it in a vented container for approximately 2 hours to dry. do. After drying, place the cups in a conical test device and cover the soil surface with 2 Cover with quartz sand of mm to 3 mm. 8 to 10 brown planthoppers (Nilap) arvata lugens) was tested using a suction device. transfer to the target device. The test device is stored at 27° C. and 65% relative humidity. 24 hours of spread Live and dead nymphs are measured during and after 48 hours. Nymphs that cannot walk are considered dead. Similar. The following compounds in the test compound are 80% or more after 48 hours at 1100pp Test J, which showed a mortality rate of =1.2°, was described in British Patent No. 1,483.633 Comprehensive in the book and specifically in WO 91/17659 Compound 1 for the normethyl derivative published as Compound 14 (page 96) This is a comparison. Although each compound was tested under similar conditions, a direct comparison Didn't test.

test J Table 3 shows the observed activities of Compound 1 of the present invention and the normethyl derivative (Compound A). I'm comparing. The compounds were tested as described above, except that the dosage rate was 2.5 ppm. Although tested individually under the conditions described in Test H and Test I, no direct comparisons were made. I didn't.

Compound 1 Compound A Table 3 (%observed mortality rate) Species Compound 1 Compound A Black leafhopper Contact activity for (green 1 eafhopper) 100 59 agony 8! ! Shimoto Oyagyu Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE) , 0A (BF, BJ, CF, CGHU, JP, KP, KR, KZ, LK, MG, MN, MW, No, NZ, PL, RO, RU, SD, SK, UA, US, VN

Claims (8)

[Claims] 1. Formula I: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ During the ceremony: R1 is H, CH2CN, C1-C4 alkyl, C1-C4 haloalkyl, formi C2-C4 alkylcarbonyl, C2-C3 alkoxycarbonyl, C2- C4 alkoxyalkyl, C3-C6 dialkoxyalkyl, C1-C3 alkoxy xy, C1-C3 alkylsulfonyl, C2-C4 alkenyl, C2-C4 al quinyl, C1-C4 alkylamino, C2-C4 dialkylamino or optionally is benzyl substituted with R2; R2 is halogen, C1-C2 alkyl , C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 haloalkoxy, NO2 or CN. ri; and Z is CHNO2 or NNO2; compounds and agriculturally suitable salts thereof. 2. In the formula, R1 is H, C1-C4 alkyl, formyl, CH3S(O)2 or C The compound according to claim 1, which is H3C(O). 3. 3. A compound according to claim 2, wherein Z is CHNO2. 4. 3. A compound according to claim 2, wherein Z is NNO2. 5.5-Methyl-1-[2-(methylthio)ethyl]-2-(nitromethylene) - The compound according to claim 3, which is an imidazolidine. 6.5-Methyl-1-[2-(methylthio)ethyl]-N-nitro-2-imida 5. The compound according to claim 4, which is a zolidine imine. 7. Formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼I During the ceremony: R1 is H, CH2CN, C1-C4 alkyl, C1-C4 haloalkyl, formi C2-C4 alkylcarbonyl, C2-C3 alkoxycarbonyl, C2- C4 alkoxyalkyl, C3-C6 dialkoxyalkyl, C1-C3 alkoxy xy, C1-C3 alkylsulfonyl, C2-C4 alkenyl, C2-C4 al quinyl, C1-C4 alkylamino, C2-C4 dialkylamino or optionally is benzyl substituted with R2; R2 is halogen, C1-C2 alkyl , C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 haloalkoxy, NO2 or CN. ri; and Z is CHNO2 or NNO2 an effective amount of a compound of (a) a surfactant, (b) an organic solvent, and (c) less than and at least one solid or liquid diluent. Composition for foot animals. 8. A method for controlling arthropod and nematode pests that reside in leaves and soil, and that area, protected area or directly to said pest in an effective amount of Formula I (Formula I is ▲There are mathematical formulas, chemical formulas, tables, etc.▼I During the ceremony, R1 is H, CH2CN, C1-C4 alkyl, C1-C4 haloalkyl, formi C2-C4 alkylcarbonyl, C2-C3 alkoxycarbonyl, C2- C4 alkoxyalkyl, C3-C6 dialkoxyalkyl, C1-C3 alkoxy xy, C1-C3 alkylsulfonyl, C2-C4 alkenyl, C2-C4 al quinyl, C1-C4 alkylamino, C2-C4 dialkylamino or optionally is benzyl substituted with R2; R2 is halogen, C1-C2 alkyl , C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 haloalkoxy, NO2 or CN. ri; and Z is CHNO2 or NNO2) or an effective amount of a compound of formula I or an agriculturally suitable salt thereof; an agriculturally suitable salt, (a) a surfactant, (b) an organic solvent, and (c) at least one an arthropod killer comprising at least one solid or liquid diluent of seeds; A method comprising administering a composition for use in a product.