JPH06504046A - Pesticide compounds - 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] , I.A. This invention relates to a novel compound having pesticidal activity, a method for producing the same, and a method for producing the same. and its use in the control of pests. Than In particular, this invention relates to certain sulfur-containing heterocyclic compounds.

European Patent Publication No. 216625, European Patent Publication No. 216624 and European Patent Publication No. 30079 No. 7 discloses 2,6.7-)lithiabicyclo[2,2,2]octane. The main difference from the present invention lies in the type of substituent at the 1-position.

European Patent Publication No. 0294229, European Patent Publication No. 0294228 and European Patent Publication No. 037 No. 2816 contains a 1,3-dimethyl group with a fairly narrow range of alkyl substituents at the 5-position. A Chian pest control agent is disclosed.

A new group of compounds within the general scope of these prior disclosures may exhibit advantageous insecticidal activity, e.g. Combines insecticidal activity against flies and/or cockroaches with low toxicity to mammals. It has now been found that (or) it has with good stability.

Therefore, the present invention provides the following formula (■): (Here, n and no may be the same or different, respectively 0, l or is 2, R is hydrogen or methyl, R' is methyl, ethyl or cyclopropyl, R2 and R3 are the same may also be different, each being hydrogen or methyl, R" and R" are R1 is hydrogen or methyl and R1' is cyano , or R'' and R'' are bonded to form a group CHI S (0) (where -m is 0. 1 or 2)) The present invention provides a compound of

Preferably R is hydrogen.

When R1 and R'' combine to form a group cHts(o)-, R1 is ethyl Preferably, R2 and R3 are hydrogen.

m, n and no are preferably O.

When R'' is hydrogen or methyl and R1' is cyano, R', R'' and R Preferably all 3 are methyl.

One preferred group of compounds of formula (I) is the following formula (■): (Here, R, m, n and no are as described above, and R1 is preferably as described above. is ethyl).

A further preferred group of compounds of formula (I) is the following formula (■): (Here, R, R', R", R"%R", n and no are as above) belongs to.

The compound of formula (III) may exist as multiple stereoisomers. both to mixtures of and to the individual isomers themselves. Further, the present invention provides radiation of formula (I) Compounds labeled with functional labels, especially those in which one of the carbon atoms is CI4, and one or more carbon atoms It also includes hydrogen atoms in which the hydrogen atom is replaced with tritium.

Preferred compounds among the compounds of formula (I) include: ・1-(3,3-dimethylbutyl)-4-n-propyl-2,6゜7-trithia Bicyclo[2,2,21octane・1-(3,3-dimethylbutyl)-4-n- Propyl-2,6゜7-trithiabicyclo[2,2,2]]octane-2-oxy S 5-tert-butyl-2-cyano-2-(3,3-dimethylbutyl)-1,3-di Chian ・1-(3,3-dimethylbutyl)-4-ethyl-2,6,7-trithiabiscic B[2,2,2]octane.

The compound of formula (1) can be produced by the following method (i) or (it). Ru.

Method (i) is based on the following formula (IV): by the reaction of the anion obtained from the compound with an alkylating agent. preferred alkyl Examples of halogenating agents include halogenating agents, such as 3,3-dimethylbutyl iodide. Ru. The anion of the compound of formula (IV) is preferable in situ from the compound of formula ([V]). can be obtained appropriately. This reaction is carried out using an inert solvent, e.g. an ester such as tetrahydrofuran. temperature in the range -100 to 20°C, preferably in the range -80 to -20°C. This is preferably carried out in the presence of a strong base, such as butyllithium.

In formula (IV), R'' and R'' are combined to form a group CH, S (0), The compound is prepared as described in European Patent Publication No. 300,797. be able to.

A compound in which Rt' is cyano in formula (IV) has an alkali group instead of a nitrile group. It can be prepared by converting the corresponding compound containing a dehyde functional group. Wear. This conversion converts the aldehyde into O,N-bis(trifluoroacetyl)hydrohydride. This can be carried out by reacting with a suitable reagent such as xylamine. Ru. The aldehyde is prepared from a 2-unsubstituted dithiane by treating it with a strong base, e.g. By reacting with a formylating agent, e.g. dimethylformamide, in the presence of lithium. Manufactured by.

Process (if) is where it is desired to produce a compound of formula (n). This is a compound of the following formula (V) 2, (a) Compound tBucH* CHx X (where X is the activated carbon a Lewis acid, preferably an alkyl trichloride, with an acid group, such as a carboxylic acid halide. Reaction in the presence of trifluoride or boron trifluoride ether complex compound, or (b) conversion in the presence of a suitable acid, e.g. hydrogen chloride gas, with the compound tBuCH,CH2CN Depends on the reaction.

The reaction (a) is carried out under an inert atmosphere, e.g. nitrogen atmosphere, in an inert solvent, e.g. In halogenated hydrocarbons such as dichloromethane, non-polar parts, e.g. It is suitably carried out at a temperature in the range of 50°C, preferably -60°C.

The reaction (b) is carried out in an inert solvent, e.g. with aromatic hydrocarbons, chlorinated hydrocarbons or in ether, preferably toluene, dichloromethane or tetrahydrofuran, It is suitably carried out in the non-polar region, i.e. at a temperature in the range of -70 to 70°C, preferably at 0°C. be exposed.

The compound of formula (V) has the following formula (■): (wherein R is a CI-C4 alkylsulfonyl or arylsulfonyl group, e.g. is methanesulfonyl or p-toluenesulfonyl group) can be produced from the corresponding compound by the following method (a), (b) or (c). can.

Process (a) comprises the reaction of a compound of formula (l with sodium trithiocarbonate and subsequent by continuous acid hydrolysis and reduction of This reaction with sodium trithiocarbonate is , in a solvent, e.g. a zwitterionic aprotic solvent such as dimethylformamide, Non-polar part, e.g. temperature in the range 10-150°C, preferably in the range 20-130°C It can be carried out at a temperature of Acid hydrolysis is performed using dilute inorganic acids such as dilute sulfuric acid or using dilute hydrochloric acid in a non-polar region, for example at a temperature in the range of 0 to 100°C, preferably 20°C. It has been successfully performed at temperatures in the range ~30°C. Reduction of metal hydrides, e.g. In a non-reactive solvent, e.g. using a reducing agent such as lithium aluminum hydride, e.g. in an ether such as diethyl ether, in a non-polar region, e.g. in the range 0-100°C. It is successfully carried out at ambient temperatures, preferably in the range of 30-60°C.

Method (b) involves reacting the compound of formula (Vl) with potassium thiocyanate to form a A thiocyanate intermediate is obtained which is then subjected to alkaline hydrolysis and reduction to form Ru. The thiocyanation reaction is carried out in a non-reactive solvent, such as dimethylformamide. in a zwitterionic aprotic solvent at a high temperature, e.g. It is preferably carried out successfully at a temperature in the range of 120-170°C. alkali Hydrolysis is performed in an aqueous solvent system using an alkali hydroxide such as sodium hydroxide. Preferably in an aqueous solvent system containing a miscible solvent such as ethanol, the non-polar part, e.g. For example, it has been successfully carried out at a temperature of 0 to 70°C, preferably 20 to 30°C. Ru. Reduction is carried out using zinc (preferably zinc powder) and hydrochloric acid (preferably concentrated hydrochloric acid). in a hydrocarbon solvent such as toluene using a suitable reducing agent at a non-crystal temperature, preferably at high temperature. It is preferably carried out at a temperature in the range of 70°C to 120°C.

Method (c) involves reacting a compound of formula (V+) with sodium sulfide and sulfur to form a bicarbonate compound. (dithiolane) disulfide, which is then reduced with zinc and hydrochloric acid. and reduction to a compound of formula (Vl) by reaction with an agent.

The first reaction is carried out in an aprotic solvent, e.g. with a C9-C4 alkali such as ethanol. in a canol at a non-crystal temperature, such as a temperature in the range of 0°C to 100°C, preferably 60°C to It has been successfully performed at temperatures in the range of 85°C. For reduction, use zinc powder and concentrated hydrochloric acid. in a hydrocarbon solvent such as toluene at a non-crystal, preferably elevated temperature, e.g. It has been successfully carried out at temperatures ranging from 70°C to 120°C.

A compound in which one or more of m, n and no in formula (I) is other than O, It can be prepared by oxidizing the corresponding compound in a lower oxidation state.

This oxidation is typically carried out using halogenated hydrocarbons such as acetonitrile or chloroform. at a non-selective temperature, e.g. in the range 0-100°C, preferably 20°C, in an inert solvent such as It is carried out at a temperature in the range of -30<0>C. Examples of suitable oxidizing agents include Peracids such as lorperbenzoic acid may be mentioned. This oxidation of anhydrous sodium acetate successfully (carried out) in the presence of a buffer such that m is 2 and n and no are 0. Compounds in which m is 0 or 1 in formula (1) include permanganese potassium acid in a ketone, e.g. acetone, at a non-crystal temperature, e.g. -30°C. It can be produced at a temperature of ~100°C, preferably -10-30°C. Wear.

The compounds of formula (I) are suitable for use in arthropods, such as insects and acarina, broadworms, i.e. nematodes. and for use in controlling pests such as molluscs, e.g. slugs. Can be done. Accordingly, the present invention provides an effective amount of a compound of formula (I) for use in arthropods, trozoans, and other animals. and/or from administration to molluscs or to environments where they are susceptible. Provided is a method for controlling arthropods, pharypids and/or molluscs. In addition, the main The invention comprises administering to an animal or location an effective amount of a compound of formula (1). (including people) and (or) plants (including trees) and (or) stored products. Control and/or movement of arthropods, larvae and/or molluscs. Things (including people) and/or plants (including trees) and/or stored products methods for eradicating arthropods, broadworms and/or molluscs. Also provided. Furthermore, the present invention provides a method for controlling arthropods, pharypids and/or molluscs. for use in human and veterinary medicine, public health management, and agriculture. Compounds of formula (I) are provided.

The compounds of formula (I) can be used in fields, pastures, plantations, greenhouses, orchards and vineyard crops, It is particularly effective in protecting grasses, ornamental plants, and plantation and forest trees; Examples of these include grains (corn, wheat, rice, sorghum), Cotton, tobacco, vegetables and salad vegetables (legumes, oilseed crops, cucumbers, lettuce) , onions, tomatoes and peppercorns), field crops (e.g. potatoes, sugar beets, peanuts, soybeans, rapeseed), sugar cane, pasture crops and forage (e.g. corn, sorghum, alfalfa), farm crops (e.g. tea, coffee, cocoa, bananas) fruit, oil palm, coconut, rubber, spices), orchard crops (e.g. stone fruits, citrus fruits) oranges, kiwifruit, avocados, mangoes, olives, walnuts) and vineyards. Crops, ornamental plants, flowers in greenhouses, gardens, and parks? ! Trees, forests, farms and seedlings There is protection of trees (both deciduous and evergreen) in tree fields.

In addition, the compound of formula (I) can be used in wood (growing, felled, processed , those in storage and those used for construction) and wasps (e.g. Uroceras). erus) or beetles (e.g. 5 colytids, Brachys platypodid, lyctid, bostrich bostriehid, cerambycid, a It is also effective in protecting against attacks by anobiids.

Compounds of formula (I) may also be used in foods such as cereals, fruits, nuts, spices and tobacco. Stored products, whether intact, ground or formulated into products; It is also useful in protecting against attack by moths, beetles and mites. Also, save Stored animal products, such as leather, hair, wool and feathers (in their original form or processed) (e.g. carpets or textiles) are also protected from attack by moths and beetles. and stored meat and fish are also protected from attack by beetles, mites and flies. Ru.

Furthermore, the compound of general formula (1) is harmful to humans and livestock or is a vector of disease. arthropods, worms or molluscs, such as those mentioned above; For controlling insects, especially tick, mite, L/lice, chisels, midges, biting, noisy, flies and insects that cause fly disease Effective in controlling snails.

The compounds of formula (I) can be used as such or diluted in known manner for the above-mentioned purposes. It can be used by applying it in the form of a dipping agent, spray, atomization, etc. agents, lacquers, foams, dusts, powders, aqueous suspensions, pastes, gels. creams, shampoos, greases, flammable solids, vaporized mats, Flammable coils, poison baits, supplementary foods, hydrating powders, granules, aerosols, emulsifying concentrates, oil-based Suspensions, oil solutions, pressurized fills, impregnated products, bore-on formulations or well known to those skilled in the art. Other standard formulations include: Immersion concentrates are not applicable by themselves is diluted with water and the animal is immersed in an immersion bath containing the immersion cleaner. Spout Fog agents can be applied by hand or by spray laces or arches. can. Animals, soil, plants or surfaces to be treated should be treated with a liberally applied spray. It may also be saturated by applying a small amount or a very small amount of the spray to only the surface. It may be coated with Aqueous suspensions may be applied in the same manner as sprays or dips. I can do it. Powders can also be spread by dusters, and in the case of animals, they can be applied using a duster with holes. It can also be placed in a plastic bag and attached to a tree or scraping stick. Paste, shampoo Pours and greases can also be applied by hand and can also be applied using inert materials, e.g. For example, on the surface of a material where an animal may rub its body against the material and transfer it to the skin. It can also be sprayed. A bore-on formulation means that all or most of the liquid is on the animal. It is applied as a small volume liquid unit onto the back of the animal so that it is retained.

The compounds of formula (I) can be used as formulations ready for use on animals, plants or surfaces. or can be manufactured as a formulation requiring dilution before use, but both types The formulation comprises a compound of formula (I) in intimate admixture with one or more carriers or diluents. Contain as a substance. The carrier may be liquid, solid or gaseous; , and may also consist of mixtures of these substances, and the compound of formula (I) Concentrations from 0.025 to 99% (w/v) depending on whether further dilution is required can exist.

Dusts, powders and granules and other solid formulations may contain compounds of formula (I). Powdered solid inert carriers, such as suitable clay, kaolin, bentonite, Attapulgite, adsorbent carbon black, talc, mica, chalk, gypsum, phosphoric acid Tricalcium, powdered cork, magnesium silicate, vegetable carrier, starch and Contained as an intimate mixture with diatoms, etc. Such solid formulations generally have the formula ( A solid diluent is impregnated with a solution of the compound of I) in a volatile solvent, and the solvent is removed. evaporate and, if desired, grind the product to obtain a powder; It is manufactured by granulating, solidifying or encapsulating.

The propellant for the compound of formula (1) can be prepared in an organic solvent (e.g. as listed below). solutions, or emulsifying concentrates (also called water-miscible oils) (this is for immersion purposes) Aqueous emulsions prepared on the farm (which can also be used for immersion cleaners) or a spray cleaning agent). Such concentrates contain active ingredients in organic solvents and and with or without one or more emulsifiers. solvent can be present in a wide range, but in an amount of 0-90% (W/V) of the composition. Preferably, it is present. These solvents include, for example, kerosene, ketones, alcohols, You can choose from sylene, aromatic naphtha and other solvents well known to compounders. Wear. The concentration of emulsifier can vary within a wide range, but in the range of 5-25% (W/V) It is preferable to have one. The emulsifier is preferably a polyoxygen of an alkylphenol. Non-containing polyoxyethylene derivatives of alkylene esters and hexite anhydrides Ionic surfactants, sodium lauryl sulfate, sulfate esters of aliphatic alcohols, etc. ether, sodium and potassium salts of alkylaryl sulfodiic acids, alkyls It is an anionic surfactant containing sodium and potassium salts of sulfosuccinic acid. Yang Examples of ionic emulsifiers include benzalkonium chloride and quaternary ammonium ether. Contains sulfates, etc.

Examples of amphoteric emulsifiers include carboxymethylated imidacillin oleate and alkaline emulsifiers. Examples include kyldimethylbetaine.

Evaporative mats are usually made of a cotton and cellulose mixture made of a board approximately 35 x 22 x 3 mm in size. The active ingredient dissolved in an organic solvent and optionally oxidized From those treated with concentrates up to 0.3 m12 containing inhibitors, dyes and fragrances. Become. The pesticide is vaporized using a heat source such as an electrically operated mat heater.

Combustible solids are usually formed by mixing wood flour or a binder with the active ingredient and shaping. It consists of a rod-shaped body (normally coiled). Dyes and fungicides may also be added.

Wettable powders include an inert solid carrier, one or more surfactants, and optionally stabilizers. and/or contains an antioxidant.

Emulsifying concentrates contain emulsifiers and often organic solvents such as kerosene, ketones, Alcohol, xylene, aromatic naphtha and other solvents well known in the art. Contains agents.

Wettable powders and emulsifying concentrates usually contain 5-95% by weight of active ingredient and are used before being diluted with e.g. water.

Lacquering agents dissolve the active ingredient in an organic solvent together with a resin and optionally a plasticizer. The solution consists of

Immersion cleaners can not only be prepared from emulsifying concentrates but also have formula (I) Wettable powders, soaps made by intimately mixing a compound with a dispersant and one or more surfactants It can also be prepared from dipping liquids and aqueous suspensions.

Aqueous suspensions of a compound of formula (I) may be prepared in combination with suspending agents, stabilizers or other agents. It may be suspended in water. Suspensions or solutions may not be applied by themselves. It can also be applied in known manner in diluted form.

Greases (or ointments) include vegetable oils, synthetic fatty acid esters, wool fat and soft paste. It can be manufactured from an inert substrate such as ruffin. The compound of formula (I) is Preference is given to homogeneous dispersion by means of mixtures in the form of solutions or suspensions. Also, The ointment base can be made by diluting an emulsifiable concentrate with an ointment base.

In addition, pastes and shampoos may be prepared by using a suitable base material such as a compound of formula (1). Semi-solid that can exist homogeneously dispersed in soft or liquid paraffin formulation or a non-greasy base with glycerin, mucilage or suitable soap. It is made based on. Greases, shampoos and pastes are usually These are applied without dilution to the appropriate amount required for processing. of the compound of formula (I).

Aerosol sprays combine the active ingredient with an aerosol propellant as well as a co-solvent (e.g. as simply dissolved in halogenated alkanes and the solvents mentioned above). can be manufactured.

A bore-on formulation is a compound of formula (1) dissolved or suspended in a liquid medium. It can be manufactured as In addition, avian and mammalian hosts may contain compounds of formula (I). By having a plastic article impregnated with and appropriately shaped, It can also protect against ectoparasitic mites. Such items may impregnated collars, tags, bands, sheets and and strips. Preferably the plastic material is polyvinyl chloride (PVC) It is.

Once the compound of formula (I) is applied to animals, homes or outdoor areas, the selected chemical may vary depending on the compound, the time interval between treatments, the nature of the formulation, and the presence or absence of infestation. However, generally 0.001 to 20.0% (w/v), preferably 0.01 to 1% (w/v) 0% of the compound should be present in the applied formulation. of compounds onto animals The amount of deposition depends on the method of application, the size of the animal, the concentration of the compound in the applied formulation, and the formulation. Although it varies depending on the factors used to dilute it and the properties of the formulation, it is generally 0.0 0.001% to 0.5% (W/w), with the exception of bore-on formulations. Such undiluted formulations generally contain from 0.1 to 20.0%, preferably from 0.1 to 20.0%. It is deposited at a concentration in the range of 10%. The amount of compound that should be applied to the stored product is generally It is in the range of 0.1 to 20 ppm. Space spray is 0 per treatment space. ．． 001 to 1 mg to give an average initial concentration of the compound of formula (I). I can do it.

Compounds of formula (I) are also useful for protecting and treating plant species. in this case contains an effective amount of active ingredient as an insecticide, acaricide, nematocide or molluscicide. Applicable. The amount applied depends on the selected compound, type of formulation, mode of application, plant species, and planting. Varies depending on density, presence of infestation, and other similar factors, but generally Suitable application rates for crops range from 0.001 to 3 kg/ha, preferably is 0. It ranges from 1 to 1 kg/ha. A typical agricultural formulation is A compound of formula (I) in the range 0.0001% to 50% by weight, preferably 0.1% Contains ~15% by weight of compound of formula (1).

Powders, greases, pastes and aerosol formulations are usually prepared as described above. applied in a random manner, the compound of formula (I) is present in the applied formulation at 0.001 It can be used at a concentration of ~20% (W/v).

The compound of formula (1) is a common house fly (Musca domestica). estica)). Furthermore, in formula (I) Several species of compounds have activity against other arthropods. of these arthropods In example 1, Myzus persicae, Tetra Tetranychus urticae, Plutella Xylostella (Plutella xylostella), Curex (Cu lex) species, Tribolium castanelum eum), Sitophilus granar ius), Periplaneta ameri cana) and Blattella germanica a) is mentioned. Compounds of formula (I) are therefore suitable for arthropods, such as insects and Environments where mites are pests, such as agriculture, animal husbandry, public health management, and domestic environments. It is useful for controlling these arthropods in plants.

Examples of insect pests include Coleoptera (e.g. Anobium, Ceuthorrhynchus, Rhynchophorus chophorus), Cosmopolites, Lysolo Butrus (Li5sorhoptrus), Meligethes ), Hypothenemusl, Hylesinus us), Acal ymma, Lema, Cyriodes (Psylliodes), Levutinotarsa (1, ept, 1notarsa) l, Gonocephalum, Agriotes otes), Dermolepida, Heteronicus ()le teronychus), Phaedon, Triporium T) olium), Sitophilus, Diabrotica (D iabrotica), Anthonomus or Anthrena (Anthrenus species), Lepidoptera (e.g. Ephesti a), Mamestra, Earias, Pecti Nophora (Pectinophora), Ostrinia (Ostrinia), Trichoplusia, Pieris, Laphygma, Agrotis, Amanas (Amathes), Wiseana (Wiseana), Trypo (Trypo) rysa), Diatraea, Sporganothis anthis), Cydia, Archips, Plutella, Chilo, Heliot his), Subodoptera (5podoptera) or Tineol (Tineol) a) species), Diptera (e.g. Musca, Aedes, Anno Anopheles, Culex, Gl ossina), Simulium, Stomoxiz moxys), Haematobia, Tabanas anus), hydrotaea (J), Lucilia (Lucilia) l, Chrysol!1ia, Callitroga a), Dermatobia, Gasterophilus (Ga5t) erophi 1us), Hypoderma, Hiremiia (H ylemyia), Atherigona, Chlorobus (Ch lolops), Phytomyza, Cera titis), Liriomyza and Melophagus Phthiraptera (Phthiraptera), e.g. Damalina species, as well as members of the order Lepidoptera, e.g. Linognathus and Haematopinus species), Hemiptera (e.g. Aphis, 13Hisia), Pholodon, Aeneolamia , Empoasca, Parkinsie lla), Pyrilla, Aonidiella ), Coccus, Pseudococcus us), Helopeltis, Lygus, De Dy5dercus, Oxycarenus , Nezara, Aleurodes, Toria Triatoma, Psilla, Myzus ), Megoura, Phylloxera, Aplinis (Adelyes), Niloparvata (Ni1oparvata), Nephrotetix or Cimex species), Orthoptera (e.g. Locusta, Gryllus), Cystocerca (5chistocerca or Acheta spp.) , Hymenoptera (e.g. Blattel la, Peri planeta) or Blatta species), Hymenoptera (e.g. (Athalia), Cephus, App (Atta), Tsure 5olenopsis or Monomorium species), Isoptera (e.g. Odontotermes and Rechi) Reticuliter+nes species), Microptera (e.g. Ctenocephalides or Pulex sp. ), Cynoptera (e.g. Lepisma spp.), Hymenoptera (e.g. Porphyra spp.) Forficula spp.), Chalyptera (e.g. Peri psocus species) as well as Hymenoptera (e.g. Thrips t. abaci)).

Examples of mite pests include ticks, such as Boophilus ), Ornithodorus, Ribicephalus (Rh ipicephalus) @, Amblyomma genus, Hea Hyalomma FIX, Ixodes spp., Hemafu Genus Haemaphysalis, Dermace genus Ntor, genus Anocentor, Mite and +? F [insect (manges), such as Acarus, Tetranicus tranychus), Psoroptes, Notedones (No. toednes), Cyrabtera (5arcoptes), Sorelgates (Ps. orergates), Chorioptes, Yutron Eutrombicula, Demodex ([)Hodex), Ba Panonychus, Bryobia, Elio Er1ophyes, Blaniulus, Poly Polyphagotarsonemus, Skachigere Scutigerella and Oniscus species are mentioned. It will be done.

Directly attack plants and trees important in agriculture, forestry, and horticulture, or attack by spreading bacterial, viral, mycoplasma or fungal diseases; Examples of nematodes that attack root-knot nematodes [e.g. yne) species (e.g. Meloidogyne incognita ncognita))], cystic nematodes [e.g. Globodera ra) species (e.g. Globodera rostoensis tochiensis), Heterodera species (e.g. Heterodera avenae), Radfuo Radophulus species (e.g. Radopulus similis) holussimilis))], focal nematodes [e.g. Pratylenchus species (e.g. Pr atylenchus pratensis)), Belonorhymus (Bel onolaimus species (e.g. Belonolaimus gracilis) aimus gracilis), Teijin class (Tylenchulu) s) species (e.g. Tylenchulus semibenetrans) semipenetrans), rotidine class (Rotylenchul) us) species (e.g. Rotylenchulu s reniformis)), Rotylenchus species (e.g. Rotylenchus robustus) us) ), Helicotylenchus species (e.g. Helicotylenchus m. ulticinctus), Hemicycliophora ora) species (e.g. Hemicycliophora gracilis) hora gracilis), Criconemoides s) species (e.g. Criconemoides 5 1mllis)), Trichodorus species (e.g. Trichodorus primitiveus ], dagger nematodes [e.g. Xiphinema species (e.g. Xiphinema diversicauda tum)), Longidorus species (e.g. Longidorus Longidorus elongatus), Hobrola Hoplolaimus species (e.g. Hoplolaimus coronasis (H opolaimus coronatus), Anohelenkoides (Ap helenchoides) species (e.g. Anoelenchoides risemaboshi (A phelenchoides ritzema-bosi), Anoellenchoides Aphelenchoides besseyi)], stem bulb Nematodes [e.g. Ditylenchus species (e.g. Ditylenchus ・Ditylenchus dipsaci)].

Direct attacks on plants and trees important for agriculture, forestry and horticulture, or Attack by spreading bacterial, viral, mycoplasma or fungal diseases Pests of molluscs that are harmful include slugs, such as Derocera s) species (e.g. Deroceras reticulatum) ulatum) (gray field slug), Arion (detail), Mirasi Milax species, land snails such as Helix species and aquatic snails. Snails include, for example, the species Planorbis. human Examples of molluscan pests that are vectors of livestock diseases include Bulinas inus) species, Physopsis species, butanorbis (Pla norbis species and θ Oricomelania species. It will be done.

The compounds of the present invention may also include one or more other pesticidal active ingredients ( e.g. pyrethroids, carbamates and organophosphates) and/or inducers. Can be used in combination with attractants, repellents, bactericides, fungicides, nematicides, anthelmintics, etc. . Additionally, the activity of the compounds of the invention may be affected by synergists or potency enhancers, such as piperonyl. Oxygen such as butoxide or propyl 2-propynylphenylphosphonate a synergist of the Dase inhibitor system, a second compound within the scope of the invention or the pyrethroid system. It is known that it can be enhanced by adding pesticides. won. When an oxidase inhibitor synergist is present in the formulations of the present invention, the synergistic The ratio of side to compound of formula (I) ranges from 25:1 to 1:25, e.g. approximately lO:1 Will.

As a stabilizer to prevent possible chemical decomposition of the compounds of the invention, , for example, antioxidants such as tocopherols, butylated hydroxyanisole and butylated hydroxytoluene), scavengers (e.g. epichlorohydrin) and organic or inorganic bases (e.g., which can act as basic stabilizers and scavengers). trialkylamines such as triethylamine).

The following examples illustrate preferred aspects of the invention in a non-limiting manner. all temperatures is the temperature in degrees Celsius.

"Knock down."

1-(3,3-dimethylbutyl-4-n-propyl-2,6,7-trithiabisi Chlorine 2.2.2 Offline (i) 2-hydroxymethyl-2-n-propylphen Lopan-1,3-diol (European Patent Publication No. 216.624) 28.0 g in 200 mI2 of dry pyridine at 0°C under nitrogen atmosphere. 74.0 g of methanesulfonyl chloride was added dropwise over 30 minutes. Pour this mixture into the chamber Warmed it to warm. After stirring for 18 hours, the mixture was poured into 200 mβ of water and Extracted twice with 00 mQ each of chloroform. 100% chloroform extract Washed twice with +t+42 portions of water, dried over anhydrous magnesium sulfate, and dried under vacuum. Evaporation gave a brown solid. Dry this with diethyl ether 200rnJZ 2-Hydroxymethyl-2-n-propylpropane-1,3-di 70.0 g of alltri(methanesulfonate) was obtained as a white solid. melting point 10 3-106℃.

(ii) 2-hydroxymethyl-2-n-propylpropane-1,3-diode (methanesulfonic acid)) in 100 mβ of dimethylformamide. Sodium trithiocarbonate ("di Journal of Org anic Chemistry) J Vol. 33 (1968), p. 1275 18.0 g was added. This mixture was heated to reflux (130°C) for 4 hours. ) and then cooled to room temperature. After stirring for a further 18 hours, 50 mI dilute sulfuric acid 2 was slowly added over 30 minutes. This mixture was extracted with chloroform. Lottery The extract was dried over anhydrous magnesium sulfate and evaporated under vacuum to give a brown liquid. Ta. Add 200 mβ of hexane and wash the mixture 3 times with 50 mg each of water. did. Dry over anhydrous magnesium sulfate and evaporate to give 6.8 g of an amber oil. I got it. 6.4 g of the crude oil was dissolved in 10 mβ of diethyl ether and 100ml of ethyl ether! , contains 3.0g of lithium aluminum hydride. into the suspended suspension at a rate sufficient to maintain reflux. Addition completed Afterwards, the mixture was stirred for another hour and then 3 mff of water was carefully added. . 3 mρ of dilute sulfuric acid was added followed by 3 mI2 of water. Filter this mixture and The solid matter was washed with 50 m2 of diethyl ether, and the filtrate was combined with anhydrous sodium sulfate. 2-mercaptomethyl-2-n-propylene 5.3 g of lupropane-1,3-dithiol was obtained as a pale yellow oil.

(iff) 2-mercaptomethyl-2-n-propylpropane-1,3-dithi Amberlyst (Ai berlyst) 15 J 1. 120 mj of dry toluene containing Og The mixture was refluxed with stirring in 2C. The mixture was cooled and filtered. Filter the filtrate under vacuum Evaporate and chromatograph the residue on alumina (eluent: dichloromethane). The mixture was purified by a mixture of hexane and hexane in a ratio of 1:10). 4-n-propyl- 3.1 g of 2,6,7-)lithiabicyclo[2,2,2]octane as a colorless solid Obtained by doing. Melting point: 139°C.

(iv) 3,3-dimethylbutan-1-ol (Aldrich ) and 1 equivalent of methanesulfonyl chloride as outlined in step (i). 3,3-dimethylbutyl methanesulfonate was prepared using the method.

(V) 13.6 g of 3,3-dimethylbutyl methanesulfonate and sodium iodide A mixture of 50 g of butanone in 175 mβ was heated to reflux with stirring for 1 hour. It flowed. The solvent was then removed under vacuum and the residue partitioned between diethyl ether and water. Arranged. The organic phase was separated, washed with water and brine, then washed with anhydrous magnesium sulfate. Dry. The solvent was removed under reduced pressure to give 10.7 g of 3,3-dimethylbutyl iodide. was obtained as a yellow liquid.

(vi) 4-n-propyl-2,6,7-trithiabicyclo[2,2,2]oc 2.2g of tan, dried tetrahydro straw 2f 5 Add 1.0% of n-butyllithium to the stirred solution. Drop 6M hexane solution 8, Omβ I put it down. The resulting solution was stirred at -70°C for 45 minutes, and 3,3-dimethyl iodide was added. Lubutil 2. 72 g was added. The reaction mixture was heated at -70°C for 2 hours. The mixture was stirred for a while, warmed to 20°C, and stirred at 20°C for 18 hours. Add water carefully. and the aqueous mixture was extracted with diethyl ether. Wash the ether extract with water , dried over anhydrous magnesium sulfate and evaporated under vacuum. Remove the residue using silica chromatography (eluent was a mixture of dichloromethane and hexane in a ratio of 1:10). It was purified by compound). 1-(3,3-dimethylbutyl)-4-n-propyl -2,6,7-trithiabicyclo[2,2,2]octane 2.0g as a colorless solid obtained as.

Using a similar method, 1-(3,3-dimethylbutyl)-4-ethyl-2,6, 7-Trithiabicyclo[2,2,2]octane was produced.

In the following steps (vii), (viii) and (ix), 2-mercaptomethyl An improved synthesis of -2-n-propylpropane-1,3-dithiol is described.

(vii) 2-hydroxymethyl-2-n-propylpropane-1,3-diode Dry 300g of Lutri (methane sulfonate) with 2000ml of dimethylformamide. 900 g of potassium thiocyanate was added to the stirred suspension in ff. Ta. The stirred mixture was kept at 140°C for 16 hours. Cool this mixture and dimethyl Partially distilled formamide (still rad temperature 50℃/15mmHg) approximately The volume was reduced to 1/3. Cool the residue and add 2000 mβ of water and 2000 m of toluene. ff was added. The mixture was stirred vigorously and the 0 layer was separated. Add more water layer 　oo.

Extracted three times with mβ of toluene. Combine the toluene extracts and add water and brine. Washed and dried over anhydrous magnesium sulfate. The solvent was removed under vacuum. 2-n -Propyl-2-thiocyanatomethyl-1,3-dithiocyanatopropane 140 ．． 0 g was obtained as a brown oil.

(viii) 2-n-propyl-2-thiocyanatomethyl-1゜3-dithio Dissolve 20g of cyanatopropane in 100mβ of toluene and add 800mβ of water. added. The aqueous mixture was stirred and 20 g of sodium hydroxide was added. this mixture was refluxed for 8 hours. This mixture was left overnight, the toluene layer was separated, and anhydrous sulfuric acid solution was added. dried with magnesium.

The solvent was removed under vacuum. 4-Mercaptomethyl-4-n-propyl-1,2- 17.0 g of dithiolane was obtained as a brown oil.

(Lx) 4-mercaptomethyl-4-n-propyl-1,2-dithiolane 36 ．． A solution containing 0 g in 200 ml of toluene was vigorously stirred. zinc powder Add 60g of hydrochloric acid solution (a solution of concentrated hydrochloric acid and water at a ratio of 1:1) to 1000mβ of nitrogen. It was added over a period of 3 hours under a simple flow. This mixture was refluxed for 3 hours. Cool this mixture. The mixture was cooled and extracted with 500ml of toluene. The toluene layer was treated with anhydrous magnesium sulfate. Dry and remove solvent under vacuum. 2-Mercaptomethyl-2-n-propyl 36.0 g of propane-1,3-dithiol was obtained as a pale yellow oil.

Steps (x) and (xi) include 1-(3,3-dimethylbutyl)-4-n-propylene. Alternative route to pill-2,6,7-trithiabicyclo[2゜2.2]octane I will post it.

(X) Dry hydrogen chloride gas flow in 100rr+j2 of dry toluene at 0°C. It lasted about 5 minutes. 2-mercaptomethyl-2-n-propylpropane-1, Add a solution of 1.8 g of 3-dithiol in 20 rnJ2 of dry toluene and then immediately added 4,4-dimethylvaleronitrile (G-M-White Size). (G, M, Whitesides), J・P-Sevenea (J, P , 5evenair) and R.W. Goetz, “The Journal of American Chemical Society f the American Chemical 5ociety) J, No. 89 (1967), p. 1135) in 20 mj2 of dry toluene. The containing solution was added. Hydrogen chloride gas was added to this stirred solution at 0°C for 1 hour. The time passed. This mixture was kept at 0°C for 3 days. Pour this mixture into water and The mixture was extracted with toluene. Wash the toluene extract with water and add anhydrous magnesium sulfate. dried in a humidifier. The solvent was removed under vacuum. Wash the solids with methanol and empty Air dried. 1-(3,3-dimethylbutyl)-4-n-propyl-2,6, 0.7 g of 7-trithiabicyclo[2,2,2]octane was obtained as a colorless solid. It was.

(xi) 0.57 g of aluminum chloride is contained in 10 ml of dichloromethane. 2-Mercaptomethyl was added to the stirred suspension at -70°C under a nitrogen atmosphere. -2-n-propylpropane-1,3-dithiol 0.84 g in dichloromethane A solution contained in 5mβ was added. After 5 minutes, 4,4-dimethylpene chloride Tanoil (G-M Whitesides, J-P Sevenea and R-W Gett, “Journal of the American Chemical Society” Volume 89 (196 7 years), p. 1135) 0.7 g was contained in dichloromethane l Omj2. The solution was added dropwise over 20 minutes. The reaction mixture was warmed to -20°C over 2 hours. . The reaction mixture was allowed to warm to 20°C overnight. diethyl ether 100ml 2 was added and the mixture was extracted with additional diethyl ether. Aete The combined extracts were washed with water, dried over anhydrous magnesium sulfate, and dried under vacuum. Evaporated. Recrystallized from acetone to give 1-(3,3-dimethylbutyl)-4- Colorless n-propyl-2,6,7-1-lithiabicyclo[2,2,2]octane Obtained as a solid.

In the following steps (xii), (xiii) and (xiv), 2-mercaptomethyme A further improved synthesis of 2-propane-1,3-dithiol is described.

(xii) 51 kg of p-toluenesulfonyl chloride was added to pyridine in a 410 β reactor. 60I2 and stirred the solution, keeping the internal temperature at 40-45℃. 2-Hydroxymethyl-2-n-propylpropane- in pyridine 30ρ 12 kg of 1,3-diol was added over 2 hours. After the addition is complete, this The mixture was cooled to 20°C and stirred at 20°C overnight. Add this mixture to 5 to 10 ℃ and then diluted with hydrochloric acid solution (concentrated hydrochloric acid 9 0I2 and water (90I2) were added over 60 minutes. After stirring for 30 minutes, this The batch was centrifuged. The wet solids were then slurried again with 120I2 water. , and centrifuged again. The solids are further washed with water until neutral and then moistened. It was dried under vacuum at 40°C until the content was less than 1%. colorless 2-hydro Roxymethyl-2-n-propylpropane-1゜3-dioltri(p-toluene) sulfonate) 47.0 kg was obtained. Melting point: 170-171°C.

(10.5 kg of sulfur and 150 kg of ethanol in a reactor of xiii1410A) 21.6 kg of sodium sulfide trihydrate was added to the stirred suspension in 42. Added. 2-Hydroxymethyl-2-n-propylpropane-1,3-diode After adding 25 kg of p-toluenesulfonate, the mixture was The mixture was warmed up and refluxed. After refluxing for 6 hours, the mixture was cooled to 20-25°C. Then 120C of water was added. Then add 80 ml of toluene and quickly stir this mixture. Stir for <15 minutes. - After installing the device at night, the 4102 with the lower water layer installed next to it. Transferred into reactor. This aqueous layer was extracted twice with 8012 parts of toluene, then water The layer was discarded. Combine the toluene extracts in a 410 il reactor and add 50 liters of Extracted 3 times with 1 cup of water.

Toluene 12042 was then distilled by vacuum distillation (55-60°C 7140 mbar). was removed from the organic layer. The remaining bis(4-propyl-1,2-dithiolane-4 -ylmethyl) disulfide solution was used without further purification.

(xiv) bis(4-propyl-1,2-dithiolane- in 1.2fi toluene) 1.2 kg of 4-ylmethyl) disulfide (from the previous step) was placed in a nitrogen atmosphere. Zinc powder was added under vigorous stirring. Heat this mixture to 85°C and gently Concentrated hydrochloric acid at 3.1° C. was added dropwise over 3 to 4 hours while maintaining a gentle reflux. The addition Once complete, the reaction mixture was stirred at 90°C for 1-2 hours. After cooling, The reaction mixture was filtered to remove residual zinc. The organic layer was washed twice with water and then evaporated. Toluene was removed under air. 2-Mercaptomethyl-2-n-propylpropane -1,3-dithiol was obtained as a pale yellow oil in quantitative yield.

Steps (XV) and (xvi) include an alternative route to 4゜4-dimethylvaleronitrile. Describe.

(xv) 1547 g of 3,3-dimethyl-1-butene in a catalytic amount (0.5 g or less) To the cooled (below 40°C) and stirred AIBN was added 3.7 g of hydrogen bromide. It took 5 hours to blow. The amber reaction mixture was then cooled and then left overnight. Ta. 600 mρ of water was added and the mixture was stirred for 15 minutes. Separate the layers and separate the organic The layer was washed twice with 600 ml of water, then 60 ml of saturated sodium bicarbonate solution. Stirred with 0rnJ2 for 15 minutes. Separate the layers and add the organic layer to 600 mβ of water and salt. Wash with 500 mβ of water and add 2,580 g of 1-promu-3,3-dimethylbutane. Obtained as a mostly colorless liquid.

(xvi) In a stirred solution containing 456 g of sodium cyanide in water IQ, , under a blanket of nitrogen, 210 g of tetrabutylphosphonium bromide, toluene 1.512 g and 1023 g of l-bromo-3,3-dimethylbutane were added. stirring Heat the stirred emulsion to 50°C, then carefully heat to 85-88°C. (exotherm from 50°C to 63°C). 1 reactor after heating to this temperature for 6.5 hours. The mixture was cooled and stirred overnight. The organic layer was washed three times with 700 mJ of water each time, and Washed twice with 2M sodium hydroxide solution of 00mβ each, 500rr+! ! ,figure 4,4-dimethylvalero 1952 g of an amber toluene solution of nitrile was obtained. by distillation under atmospheric pressure Toluene was removed and the product was distilled under reduced pressure (boiling point 80-82°C/15mmHg ) to obtain 4,4-dimethylvaleronitrile (75% yield).

Outside 1 l-3,3-dimethylbutyl-4-n-propyl-2,6,7-to-1thiabisic B 2.2.2 Octane-2-oxide L-(3,3-dimethylbutyl)-4 -n-propyl-2,6゜7-trithiabicyclo[2,2,2]octane 0.6 g, 0.45 g of 3-chloroperbenzoic acid (Aldrich, purity 80-90%) and and 0.8 g of anhydrous sodium acetate were contained in 30 mj2 of anhydrous acetonitrile. The mixture was stirred at 20°C for 24 hours. Remove the solvent under vacuum and dissolve the residue in water. and ethyl acetate. Separate the amorphous layers and add sodium bicarbonate solution and Washed with brine and then dried over anhydrous magnesium sulfate. Remove solvent under vacuum The residue was chromatographed on silica (eluent: hexane and ethyl acetate). 1-(3,3-dimethylbutyl)-4-n- Propyl-2゜6,7-)-lithiabicyclo[2,2,2]]octane-2- 023 g of oxide was obtained as a colorless solid.

5-t-butyl-2-cyano-2-3,3-dimethylbutyl-1,3-dithiane (i) 5-t-butyl-1,3-dithiane (EL Eliel (E, L, E Liel et al., “Journal of the American Chemical Society,” Volume 98 (1976), page 3583) 5g of tetrahydrofu 17.75 mL of a 1.6 M n-butyllithium solution in hexane at ℃ was added. After stirring for an additional hour, the mixture was transferred by syringe to −1 It was added dropwise into 10 mβ of raw dimethylformamide cooled to 0°C. this mixture Stir at -10°C for 1 hour and then store at 0°C overnight. This reaction mixture The mixture was then poured into 100 mβ of ice water and extracted with hexane. Medium the aqueous layer with dilute hydrochloric acid. and then extracted again with diethyl ether. Ether extract in anhydrous sulfuric acid mug Dry over nesium and then evaporate under vacuum to obtain 3.1 g of white solid residue. Ta. The 5-t-butyl-2-formyl-1,3-dithiane thus obtained is The part existed as a dimer.

(it) 5-t-butyl-2-formyl-1,3-dithiane Ig under nitrogen atmosphere was heated to melt and then cooled. The viscous oil thus obtained was mixed with pyridine. The mixture was taken out into 100 mj2 of dry benzene containing 0.78 g of carbon.

0, N-bis(trifluoroacetyl)hydroxylamine (J-H-bome J. H. Pomeroy et al., “Journal of American Chemical Society, Vol. 81 (1959), p. 6340) 1.1 g and the resulting mixture was heated to reflux for 2 hours. After cooling, ether and water was added and the organic layer was separated. The aqueous layer is further extracted with fresh ether and then organically extracted. The liquids were combined and dried over anhydrous magnesium sulfate, then evaporated under vacuum. A yellow solid was obtained, which was purified by column chromatography on silica. Manufactured. 5-t by gradient elution using a hexane/dichloromethane mixture. -Butyl-2-cyano-1,3-dithiane 0.38 g was obtained as a white solid. Ta.

(iii) Add 0.5 g of 5-t-butyl-2-cyano-1,3-dithiane to tetra A solution contained in 15 mβ of hydrofuran was cooled to −50° C. under a nitrogen atmosphere. Ta. Add 2.0 mA of 1.6M n-butyllithium solution in hexane to obtain When 1.6 g of 3,3-dimethylbutyl iodide was added to the resulting mixture, -40 It was kept at ℃ for 2 hours. The reaction mixture was warmed to room temperature and allowed to stand overnight. Ethyl ether and water were added. Separate the organic layer and extract the aqueous layer with fresh ether. I put it out. The combined organic extracts were dried over anhydrous magnesium sulfate and evaporated under vacuum. I let it emanate. The residue was subjected to column chromatography using silica (eluent was ethyl acetate). and hexane (a mixture of 26% and 100% hexane). recrystallized from hexane 5-t-butyl-2-cyano-2-(3,3-dimethylbutyl)-1,3- 0.33 g of dithiane was obtained as a white solid.

! 11 dishes j1 The following examples illustrate in a non-limiting manner the pesticidal activity of compounds of formula (I). .

11 stars 1 Compounds of the invention were tested as follows. That is, the compound is dissolved in acetone. (5%), then water and 5ynperonic (ratio 94 ．． 5% to 0.5%) to make an aqueous emulsion.This solution was then used to make an aqueous emulsion. The following insects were treated using

Musca domestica: Each end with gauze Twenty female muscae were placed in a covered cardboard tube. locked up like this Insects were sprayed with a solution containing the compound, and mortality was determined after 48 hours at 25°C. Examined.

Compounds 1.2.3 and 4 were active at less than 200 ppm.

Lutella xylostella Plutella x 1ostella Lutella larvae were placed on circular pieces of leaves and sprayed with a solution containing the compound. 25 Mortality was determined after 2 days at °C.

Compounds 1 and 4 were active at less than 11,000 pp. Placed on a circular piece of rapeseed leaves. After 24 hours, the solution containing the compound was poured into a circular piece. Sprayed. Mortality was determined after 2 days at 20°C.

Compounds 1 and 3 were active below 11000 pp.

Compound 4 was active at less than 200 ppm.

Diabrotic Power Undecim Bankata Diabroticaundecia + unctata Filter paper and food were sprayed with the test solution and then 10 second instar larvae were placed on them. I set it. Mortality was determined after 48 hours.

Compounds 1, 2.3 and 4 were active at less than 11000 pp.

1 tan 1 tan 1 The activity of the compounds of the invention against male Belybutaneta americana was tested under anesthesia. This was demonstrated by topically applying a butanone solution of the test compound to the test insects. 6 Mortality was determined after 1 day.

Compounds 1, 3 and 4 were active at less than 50 μg per insect.

The activity of the compounds of the invention against female Musca tomestica (WRL species) was tested. This was demonstrated by topical application of a butanone solution of the test compound to insects. 48 o'clock Mortality rates were examined afterwards.

Compounds 1.2.3 and 4 were active at less than 1 μg per insect.

Against male Blattella gera + anica The activity of the compounds of the invention can be determined by dissolving the test compounds in butanone in anesthetized test insects. Proven by applying the liquid topically. Mortality was determined after 6 days.

Compounds 1.2.3 and 4 were active at less than 1 μg per cockroach. Ta.

Go to mouse Compounds 1 and 2 were administered to mice at an oral dose of 200 mg/kg in D'MSO. It was non-toxic to

Deroceras and Ar1on's Nameku 2 30 Deloceras and Arions were exposed to 3 pieces of paper to be treated in the blood of a veterinarian with an outlet. did. Mortality was determined after 72 hours.

Compound 1 was active at less than 6% per 2crrr.

international search report 11th Symphony Orchestra ^-,,,-1, PCT/GB 91102239 International Investigation Report

Claims (18)

[Claims] 1. The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) {Here, n and n' are 0, respectively. 1 or 2, R is hydrogen or methyl; R1 is methyl, ethyl or cyclopropyl, R2 and R3 are the same may also be different, each being hydrogen or methyl, Ra and Rb are hydrogen or methyl, and Rb is cyano; Or Ra and Rb combine to form a group CH2S(O)m (where m is 0, 1 or 2) is formed} compound. 2. 2. A compound according to claim 1, wherein R is hydrogen. 3. Ra and Rb combine to form a group CH2S(O)m and R1 is ethyl. The compound according to claim 1 or 2, wherein 4. 4. A compound according to claim 3, wherein R2 and R3 are hydrogen. 5. 4. A compound according to claim 3, wherein m, n and n' are 0. 6. Claim 1 or 2, wherein Ra is hydrogen or methyl and Rb is cyano Compound according to item 2. 7. 7. A compound according to claim 6, wherein R1, R2 and R3 are all methyl. 8.・1-(3.3-dimethylbutyl)-4-n-propyl-2.6.7-tri Thiabicyclo[2.2.2]octane 1-(3.3-dimethylbutyl)-4- n-propyl-2.6.7-trithiabicyclo[2,2.2]octane-2-o oxido ・5-t-butyl-2-cyano-2-(3,3-dimethylbutyl)-1,3-di Chian as well as ・1-(3,3-dimethylbutyl)-4-ethyl-2.6.7-trithiabiscic A compound according to claim 1 selected from b[2.2.2]octane. 9. The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) {Here, n and n' are 0, respectively. 1 or 2, R is hydrogen or methyl; R1 is methyl, ethyl or cyclopropyl, R2 and R3 are the same may also be different, each being hydrogen or methyl, Ra and Rb are hydrogen or methyl, and Rb is cyano; Or Ra and Rb combine to form a group CH2S(0)m (where m is 0, 1 or 2) is formed} A method for producing a compound, comprising: (j) The following formula (IV): ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Anions and amines obtained from the compound (IV) Reaction with rkylating agent or (ii) When Ra and Rb combine to form a group CH2S(O)m, the following formula ( V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼The compound of (V) and (a) Compound tBuCH2CH2X (where X is an activated carboxylic acid group) reaction with ) in the presence of a Lewis acid Or (b) Reaction with compound tBuCH2CH2CN in the presence of a suitable acid The method described above. 10. One or more compounds of formula (I) according to any one of claims 1 to 8 A pesticidal composition comprising in admixture with a carrier or diluent. 11. The compound according to claim 10, which additionally contains a synergist or a drug efficacy enhancer. Pesticide composition. 12. One or more pest control active ingredients, attractants, repellents, bactericides, fungicides and The harmful substance according to claim 10 or 11, which additionally contains an anthelmintic and/or anthelmintic. Biocidal composition. 13. An effective amount of the compound according to any one of claims 1 to 8 is administered to arthropods, worms, etc. consisting of application to insects or molluscs or to environments where they are susceptible , arthropod, helminth or mollusc pest control method. 14. An effective amount of a compound of formula (I) according to any of claims 1 to 8 is administered to A method of controlling pests on plants, which consists in applying them to plants. 15. storing an effective amount of a compound of formula (I) according to any of claims 1 to 8; A method for controlling pest build-up on stored products, comprising applying them to stored products. . 16. An effective amount of a compound of formula (I) according to any of claims 1 to 8 is administered to an animal. A method of controlling pests on animals, which consists in applying them to objects. 17. Claim 1 for use in controlling pests on animals A compound of formula (I) according to any one of items 1 to 8. 18. Use of a compound of formula (I) according to claim 17, wherein the animal is a human.