CN113264924B

CN113264924B - Dioxane pyrimidine derivative and preparation method and application thereof

Info

Publication number: CN113264924B
Application number: CN202010093096.6A
Authority: CN
Inventors: 唐剑峰; 迟会伟; 赵士胜; 吴建挺; 徐龙祥
Original assignee: SHANDONG UNITED PESTICIDE INDUSTRY CO LTD
Current assignee: SHANDONG UNITED PESTICIDE INDUSTRY CO LTD
Priority date: 2020-02-14
Filing date: 2020-02-14
Publication date: 2022-11-08
Anticipated expiration: 2040-02-14
Also published as: CN113264924A

Abstract

The invention provides dioxane pyrimidine derivatives shown as a formula (I) as well as a preparation method and application thereof. The compound shows good activity to various pests and harmful mites in agriculture or other fields, particularly the introduced pentafluorothioether group can obviously improve the activity of the compound and shows excellent control effect to various pests/harmful mites. Moreover, the compounds can obtain good control effect at very low dosage, so the compounds can be used for preparing insecticide and acaricide. In addition, the compound has simple preparation steps and high product yield, thereby having good application prospect.

Description

Dioxane pyrimidine derivative and preparation method and application thereof

Technical Field

The invention belongs to the technical field of insecticides and acaricides, and particularly relates to a dioxane pyrimidine derivative and a preparation method and application thereof.

Background

In agricultural and horticultural crop production, damage caused by insect pests and mite pests is still very serious, and development of novel agricultural and horticultural chemicals, particularly insecticides and acaricides, is of great significance because the pests and the mites have resistance to existing chemicals. With the increase of the number of the working personnel of the old-aged farming, the development of a time-saving and labor-saving agricultural and horticultural medicament, in particular an insecticide and an acaricide, is necessary.

Patent document WO2013115391 discloses compounds of general formula of pyrimidines shown below and specific compounds (e.g. CK1 and CK 2), and the use of such compounds as pesticides.

However, the inventor finds that the control spectrum of the compound is narrow, the effect is slow, and the actual application effect is influenced. At low dosages, the biological activity of these compounds is not satisfactory in all cases. Therefore, it is desired to develop an insecticidal and/or acaricidal agent having more excellent properties.

Disclosure of Invention

In order to improve the problems, the invention provides a compound shown as a formula (I), a stereoisomer, a racemate, a tautomer, a nitrogen oxide or a pharmaceutically acceptable salt thereof,

r is the same or different and is independently selected from hydrogen, halogen, cyano, C _1-6 Alkyl, halo C _1-6 Alkyl radical, C _1-6 Alkoxy or halo C _1-6 An alkoxy group;

n is 0, 1,2, 3 or 4;

x is selected from oxygen or sulfur.

According to an embodiment of the invention, the compound of formula (I) has the following structure,

in the formulae (I-1), (I-2) and (I-3),

r is the same or different and is independently selected from hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl, trifluoromethyl, methoxy or trifluoromethoxy;

n is 0, 1,2, 3 or 4;

x is selected from oxygen or sulfur.

By way of example, the compounds of formula (I) are selected from the following compounds:

the invention also provides a preparation method of the compound shown in the formula (I), which comprises the following steps:

a) Reacting a compound shown in a formula (II-1) with a compound shown in a formula (III) to obtain a compound shown in a formula (I); alternatively, the first and second liquid crystal display panels may be,

b) Reacting a compound shown in a formula (VII) with a compound shown in a formula (VI) to obtain a compound shown in a formula (I);

wherein R, X, n have the definitions as described above and L is selected from a leaving group, such as Cl, br or I.

According to an embodiment of the present invention, the compound of formula (I) is prepared by the following method:

1) Preparing a compound shown in a formula (II) by reacting a compound shown in a formula (V-1) with propylene glycol, or preparing a compound shown in a formula (II-1) by reacting a compound shown in a formula (V) with propylene glycol;

2) The compound shown in the formula (I) is prepared by reacting the compound shown in the formula (II) with the compound shown in the formula (III), or the compound shown in the formula (I-1) is prepared by reacting the compound shown in the formula (II-1) with the compound shown in the formula (III), and then the compound shown in the formula (I) is prepared from the compound shown in the formula (I-1).

According to an embodiment of the invention, the reaction in step 1) may be carried out in the presence of a catalyst, such as p-toluenesulfonic acid.

According to an embodiment of the present invention, the reaction in step 1) may be carried out in a solvent; the solvent may be selected from one, two or more of aromatic hydrocarbon solvents, haloalkane solvents, nitrile solvents, ether solvents, ester solvents, for example, one, two or more selected from ethyl acetate, benzene, toluene, 1, 2-dichloroethane, acetonitrile, tetrahydrofuran or dioxane.

According to an embodiment of the present invention, the temperature of the reaction in step 1) may be 0 ℃ to the reflux temperature of the solvent used.

According to an embodiment of the present invention, the reaction in step 1) can be carried out by a method described in patent document CN104185628A or other similar methods.

According to an embodiment of the present invention, the reaction of the compound represented by the formula (II) with the compound represented by the formula (III) to prepare the compound represented by the formula (I) or the reaction of the compound represented by the formula (II-1) with the compound represented by the formula (III) to prepare the compound represented by the formula (I-1) in step 2) may be carried out in the presence of a base; the base may be selected from organic amines such as triethylamine, N-dimethylaminopyridine, etc., or sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, etc., alkali metal hydrides such as sodium hydride, potassium hydride, etc., alkali metal alkoxides such as potassium tert-butoxide, sodium ethoxide, sodium methoxide, etc., and alkyllithium such as methyllithium, N-butyllithium, etc., inorganic bases.

According to an embodiment of the present invention, in step 2), the molar amount of the base is 1 to 3 times the amount of the compound represented by formula (III).

According to an embodiment of the present invention, the reaction of the compound represented by formula (II) with the compound represented by formula (III) to prepare the compound represented by formula (I) in step 2), or the reaction of the compound represented by formula (II-1) with the compound represented by formula (III) to prepare the compound represented by formula (I-1) may be carried out in a solvent; the solvent may be selected from one, two or more of aromatic hydrocarbon solvents, haloalkane solvents, nitrile solvents, chain or cyclic ether solvents, amides, ketone solvents, and the like, for example, one, two or more selected from toluene, 1, 2-dichloroethane, acetonitrile, propionitrile, N-dimethylacetamide, N-dimethylformamide, diethyl ether, tetrahydrofuran, dioxane, acetone, butanone, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone.

According to an embodiment of the present invention, the temperature of the reaction of the compound represented by formula (II) with the compound represented by formula (III) to prepare the compound represented by formula (I) or the reaction of the compound represented by formula (II-1) with the compound represented by formula (III) to prepare the compound represented by formula (I-1) in step 2) may be 0 ℃ to the reflux temperature of the solvent used.

According to an embodiment of the present invention, in step 2), the reaction may be performed under an atmosphere of a gas inert to the reaction system, such as nitrogen, argon, or the like.

According to an embodiment of the present invention, in step 2), the compound represented by formula (I-1) is catalytically hydrogenated in an inert solvent in the presence of an organic base and a catalyst under a hydrogen atmosphere to prepare the compound represented by formula (I), and formic acid may also be used to generate hydrogen in the reaction system instead of the hydrogen atmosphere.

According to an embodiment of the present invention, the reaction of the compound represented by the formula (I-1) to prepare the compound represented by the formula (I) in the step 2) may be performed in the presence of a catalyst selected from at least one of tetrakis (triphenylphosphine) palladium, palladium on carbon, platinum, raney nickel, and the like.

According to an embodiment of the present invention, in the step 2), the compound represented by the formula (I-1) is reacted to prepare the compound represented by the formula (I) using the catalyst in an amount of about 0.0001 to 0.1 times by mole the compound represented by the formula (I-1).

According to an embodiment of the present invention, the reaction of the compound represented by formula (I-1) to prepare the compound represented by formula (I) in step 2) may be carried out in the presence of a phase transfer catalyst, such as a quaternary ammonium salt compound, e.g., tetrabutylammonium bromide, benzyltriethylammonium bromide, etc.

According to an embodiment of the present invention, in step 2), the reaction of the compound represented by formula (I-1) to prepare the compound represented by formula (I) may be carried out in the presence of a base selected from organic bases such as triethylamine, pyridine, sodium acetate, potassium acetate, etc., or inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, etc. The amount of the base to be used is usually about 0.5 to 5 molar times as large as that of the compound represented by the formula (I-1).

According to an embodiment of the present invention, in step 2), the solvent used in the reaction of the compound represented by formula (I-1) to prepare the compound represented by formula (I) may be selected from one, two or more of alcohols such as methanol, ethanol, etc., ethers such as tetrahydrofuran, dioxane, dimethoxyethane, etc., amides such as N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, etc., and water, etc.

According to an embodiment of the present invention, the reaction temperature of the compound represented by formula (I-1) to prepare the compound represented by formula (I) in step 2) may be 0 ℃ to the reflux temperature of the solvent used.

According to an embodiment of the present invention, the reaction of preparing the compound represented by formula (I) from the compound represented by formula (I-1) in step 2) is a reaction carried out under a hydrogen atmosphere, and the hydrogen pressure may be selected from a standard pressure to 10atm. When formic acid is used, the reaction is preferably carried out under an atmosphere inert to the reaction, such as nitrogen and/or argon.

According to an embodiment of the present invention, the reaction of the compound represented by the formula (I-1) to prepare the compound represented by the formula (I) in step 2) may be carried out by a method described in J.org.chem.,1955,20,225 or other similar methods.

According to an embodiment of the present invention, the compound represented by formula (II) used in step 2) may be prepared from the compound represented by formula (II-1) by the same procedure as the reaction conditions for preparing the compound represented by formula (I) from the compound represented by formula (I-1).

According to an embodiment of the present invention, the compound represented by formula (V-1) or formula (V) can be obtained by a method described in patent document WO2001017975, or can be obtained commercially.

The preparation of the compounds of the formula (I) and their starting materials here can be carried out, depending on the reaction conditions and the choice of starting materials which are suitable in each case, by replacing, for example, in a one-step reaction only one substituent by another substituent according to the invention or by replacing, in the same reaction step, a plurality of substituents by further substituents according to the invention.

If the individual compounds are not obtainable via the above routes, they can be prepared by derivatizing the other compounds or by routinely varying the synthetic routes described.

After completion of the reaction, the reaction mixture can be worked up in a customary manner, for example by mixing with water, separating the phases, recrystallization, distillation and, if appropriate, purification of the crude product by chromatography, for example on alumina or silica gel.

The pharmaceutically acceptable salts of the compounds of formula (I) of the present invention may be prepared by known methods. For example by suitable acid treatment to give an acid addition salt of a compound of formula (I). The preparation method comprises the following steps: the pharmaceutically acceptable salts of the compounds of formula (I) can be conveniently obtained by reacting the compounds of formula (I) with an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, trifluoroacetic acid, malic acid or citric acid in a solvent such as water, diethyl ether or toluene.

The above preparation process allows to obtain an isomeric mixture of the compound of formula (I), if it is desired to obtain the pure isomers, which can be separated by conventional methods such as crystallization or chromatography.

All reactions described above may conveniently be carried out at atmospheric pressure or the autogenous pressure of the particular reaction, unless otherwise indicated.

The present invention also provides a pesticidal composition, such as an insecticidal and/or acaricidal composition, comprising, as an active ingredient, one, two or more of a compound represented by formula (I), a stereoisomer, a racemate, a tautomer, a nitrogen oxide, or a pharmaceutically acceptable salt thereof.

According to an embodiment of the invention, the active ingredient is present in the composition in an amount of 0.1 to 99.9% by weight, such as 0.5 to 99%.

According to an embodiment of the invention, one, two or more agriculturally and/or forestry and/or hygienically acceptable carriers are also included in the composition.

According to an embodiment of the invention, the composition may be administered in the form of a formulation.

For example, the compounds of formula (I) as active ingredients are dissolved or dispersed in a carrier or formulated so as to be more easily dispersible for insecticidal and/or acaricidal use.

According to an embodiment of the invention, the formulation includes, but is not limited to, the following forms: granules, dispersible granules, wettable powder, oil suspension, water suspension, emulsion in water, aqueous solution, missible oil or microcapsules and the like.

According to embodiments of the invention, a liquid or solid carrier, and optionally a surfactant, may also be added to the composition.

The invention also provides application of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof as pesticides, such as insecticides and/or acaricides.

The invention also provides application of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof in preparation of pesticides, such as insecticides and/or acaricides.

The invention also provides a method for controlling pests and/or mites, which comprises applying an effective amount of at least one of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, nitrogen oxides and pharmaceutically acceptable salts thereof or applying the pesticide composition to a growth medium of the pests and/or the mites.

According to an embodiment of the invention, the effective amount is from 10 to 1000 grams per hectare, preferably from 20 to 500 grams per hectare.

The active substances according to the invention or the active substances to be used according to the invention are suitable, in view of good plant tolerance, favourable warm-blooded animal toxicity and good environmental compatibility, for protecting plants and plant organs, increasing harvest yields, improving the quality of the harvest and for controlling animal pests, mites and the like which occur, in particular, in agriculture, horticulture, animal husbandry, forestry, gardens and leisure facilities, in warehouse pest protection and material protection, and in the hygiene sector. They are preferably used as plant protection compositions. They are active against conventional sensitive and resistant species and against all or individual developmental stages.

The pests and mites include but are not limited to:

<xnotran> (Arthropoda), (Arachnida), , (Acarus spp.), (Aceriasheldoni), (Aculops spp.), (Aculus spp.), (Amblyomma spp.), (Amphitetranychusviennensis), (Argas spp.), (Boophilus spp.), (Brevipalpus spp.), bryobiagraminum, (Bryobiapraetiosa), (Centruroides spp.), (Chorioptes spp.), (Dermanyssusgallinae), (Dermatophagoidespteronyssinus), (Dermatophagoidesfarinae), (Dermacentor spp.), (Eotetranychus spp.), (Epitrimeruspyri), (Eutetranychus spp.), (Eriophyes spp.), glycyphagusdomesticus, (Halotydeusdestructor), (Hemitarsonemus spp.), (Hyalomma spp.), (Ixodes spp.), (Latrodectus spp.), (Loxosceles spp.), (Metatetranychus spp.), neutrombiculaautumnalis, nuphersa spp., (Oligonychus spp.), (Ornithodorus spp.), (Ornithonyssus spp.), (Panonychus spp.), (Phyllocoptrutaoleivora), (Polyphagotarsonemuslatus), (Psoroptes spp.), (Rhipicephalus spp.), (Rhizoglyphus spp.), </xnotran> Sarcoptes (Sarcoptes spp.), medrypanus (Scorpioomaurus), stereotarsonemus spp., steneotarsonemus muspinki, tarsonemus spp., tetranychus spp., amycorhus arguta (Thunbergus spp.), trombicula arvensis (Trombicularvillea freddugesi), vaejovis spp., dermanyssus dorsiflorus (Vasaslopsis);

coleoptera (Coleoptera) (beetle): leguminous species (Acanthoscelides spp.) (elephant), phaseolus vulgaris (Acanthoscelides obtectus) (common pisiform image), ceratophyllum album (Agrilus planipes) (Fraxinus variegatus) and Flammulina species (Agriotes spp.) (wireworm), anoplophora glabripennis (Asian longhorn longipedunculus), gothistle species (Anthonium spp.) (Arthobium family), gothistle (Anthonium grandis) (Cotton bollworm cocoon), apium mellea species (Aphidius spp.) (Aprionus spp.) (Anthonium spp.) (elephant), aconitum species (Apocynia spp.) (Holotrichia grub) black striped tortoise (atacinia pretzeriana), cryptogamic beet (atomys specularis) (small beet beetles), cucurbita species (autolophore spp.), weevil (bothrodes punctiformis) (beetroot weevil), pissodactyla species (weevil), pisiform (Bruchus pisorum) (pea weevil), cacoesia species (cacoes spp.), tetrastigma variegata (Callosobruchus maculatus) (southern cowpea weevil), mammalia maculans (carpophila hemiptera) (xerophycus diaboloides), testudina (Cassida witta), zena species (costatus spp.), ccorooma species (Ccorooma spp.) (Chloromonids), bulletia controversa (Cerotoma trifur cata) (Bulletia controversa), symphytum species (Ceratorchus spp.) (weevil), ccorooma spp.) (Chloromonas sp.) (Ccorooma spp.)) (Ccorooma spp.) (Ccorotoma), ccorooma spp. (Ccorotoma spp.) (Ccorolla), brassica alba boiss (deuteronchusassimilis) (cabbage weevil), brassica napus (brassica juncea) (cabbage weevil), chayote beetle (brassica juncea napi), flea beetle (Chaetocnema spp.) (trichomonas), colaspis (Colaspis spp.) (beetle), conoderus sclaris, conoderus stigmausses, plum weevil (Conotrachelus nennula), cotinus nitidis (greenbie), asparagus caterpillars (Crioceris aspalata), gibberella ferruginea (rusty grambellet), corynebacterium parvum (criclepialus turcz), corynebacterium parvum (criclepialus turcz) (turcz beetle), species of genus entocyclicus (nematode), species of genus elephant (cutsulio spp.) (elephant), species of genus ceramystus (cytrochela spp.) (grub) elephant trunk (Cylindrocpturus adspersus) (sunflower weevil), mango leaf-cutting elephant (Deporaus marginatus) (mango leaf-cutting weevil), dull ham (Dermestes ladanius) (ham leather), dull white abdomen (Dermestes maiches) (white abdomen dull), diabrotica sp (Diabrotica spp.) (leaf beetle), mexican bean beetle (Epilachna varivcsis) (Mexican bean beetle), worm trunk (rautinius cubae) (grass weevil), siberian white root neck weevils (Hyperbius palustris) (pangolin scales (pales weevil)), phyllopomorpha species (Hypera spp.) (weevil), alfalfa leaf weevil (Hypera pottica) (purple alfalfa weevil), hyperdoss species (Hyperdoss spp.) (Atlantic stem weevil (Hyperodes wevil)), coffee berry small sand (Hyperthenimus hampeici) (coffee berry beetle), teech small sand species (echinodermaphys spp.) (echinoderm) et al (engravers)), (echinoderm small sand (engraveris)), (acanthosis japonica) tobacco beetle (Lasioderma serricorn) (tobacco beetle), potato beetle (leptinotara decemlinea ta) (colorado potato beetle), liogenys fuscus, liogenys suturalis, lissorhoptrus oryzae (Lissorhoptrus oryzae), sildenus species (Lyctus spp.) (woodbetheus moths/sildenus beetles)), (woodenbottom moth/sildenus beetles)), (Lasioderma serricorn beetles) (Lasioderma serricorne beetles), and (lachnum serricorn beetles) and (lachnum serricorn beetles, lachnum japonicum, etc.) maecollaspira, megaselis species (megaselis spp.), corn beetles (melanotus communis), lounge beetles (Meligethes spp.), rape beetles (Meligethes aereus) (pollen beetles), pentacea chinensis (melotha) (common european beetles), obeea breve, horned beetles (obenfaris), coconut shell beetles (oricane beetles) (market beetles (merigler beetles)), corn beetles (oryzae chrysolepis (origans chrysopha), corn beetles (oryzamutual), corn beetles (millinervus), corn beetles (elephant beetles) (bugs beetles), corn beetles (elephant beetles) (common beetles spp.) (elephant beetles) (common beetles (elephant beetles), corn beetles (elephant beetles) and corn beetles (elephant beetles) (elephant beetles (elephant beetles) are included in the genus of the genus megasella, corn beetles (melos) and corn beetles (beetles) are included in the genus, black horn mud worm (Oulema melanopus) (orange foot mud worm), rice mud worm (Oulema oryzae), rhynchophylla rosea species (Pantomorus spp.), phyllopodium species (Phyllophaga spp.) (May/Juniperus chafer), phvlophaga cuyaban, phyllotreta spp. (Chrysomyiame spp.) (Chrysomyiame) Marble species (Phynchites spp.), japanese cuora (Popilia japonica) (Japanese chafer), oncorhynchus (Prostephans truncates) (Oncorhynchus gordonus (larger grain borer)), oncorhynchus (Rhizopertha dominica) (Lesser grainburer), root cuora (Rhizotrogus spp.) (European chafer)), rhynchosia species (Rhynchosia spp.) (weevil), silly species (Scolytus spp.) (woodchuck moth), shenophorus species (Shenophorus spp.) (elephant), pisum leaf elephant (Sinynana lincat) (pea leaf weevil), rice weevil species (Sinopophyllus spp.) (grain weevil), grain weevil (Sinopophyllus grandis) (millworm (graweevil)), rice weevil (Sitophilus oryzae) (rice weevil)), medicinal material (Stebium panum) (medicinal material beetle)), pseudograin species (Tribolium spp.) (facial weevil), red rice grain beetle (Tribolium castaneum) (red bud)) (Tribolium spp.) (facial weevil.), red rice grain beetle (red bud), tribolium affluens (conjugated flower beets), piebald bastard (Troogermamavarriabile) (bureau needles) and Zabrus tenbeioids.

Dermaptera (Dcrmaptcra) (earwigs).

From the order of the wing (Dictyoptera) (cockroach): german cockroach (blattaria germanica) (German cockroach)), blattaria orientalis (Blatta orientalis) (eastern cockroach), blattaria pencydonoides (parkinsonia pennyensis), periplaneta americana (perilanea americana) (americacoceckroach), blatta australis (periantha australiana) (Australia nckkroach), periplaneta brown (pcriparia) (brown cockroach), periplaneta smoke (Periplaneta fuliginosa) (black cockroach (cockowybron cockroach)), periplaneta green (sugarcane percoassus) (brown cockroach), and Periplaneta fuliginosa (cockroach) (cockroach (cockroach)), and Periplaneta fuliginosa (cockroach Blatta nigra) (cockroach Blatta nigricana (brown cockroach)).

Diptera (Diptera) (flies): aedes species (Aedes spp.) (mosquito), lucerne fly larvae (Agromyza frontella) (alfalfa blossom flies), agromyzis species ((Agromyza spp.) (leaf flies), bactrocera species (fruit flies), garlerthan fruit flies (anastrepa subspina) (garlerthan fruit flies), anopheles species (Anopheles spp.) (mosquito), bactrocera species (fruit flies), melon flies (Bactrocera flies) (melon flies), citrus fruit flies (Bactrocera dorsalis) (citrus fruit flies), trematopsis species (ceitis spp.) (fruit flies), medullosa (sea fly), sea fly larvae (sea fly). (deer fly), trypetid species (chrysopsis spp.) (cochlioma spp.) (blowfly larvae), mosquito species (contininia spp.) (24302mosquitoes), culex spp.) (mosquitos), leaf \24302 (Dasineura spp.) (24302mosquitoes), oil vegetable leaf (Dasineura brasica) (cabbage 24302mosquitoes), gerbil species (Delia spp.), gray fly (denlia turn) (root maggot), fruit fly species (Drosophila spp.) (vinegar fly), housefly species (Fannia spp.) (fanningus spp.) Botrytis cinerea (Fannia clavulis) (Botrytis cinerea), botrytis megacephala (Gasterophilus intestialis) (Pagets mammalis), gracillia persea, haematobia irutans (horn fly), musca melanogaster species (Hylemia spp.) (root maggot), dermomyia striata (Hyporoderma Lineatum) (common dermus grub), musca maculatus species (Liriomyza spp.) (leaf miner), musca brassicae (Liriomyza brasica) (Serpentis pellicus (serpen eleaf miner)), musca ovis (Mephalus ovis) (sheep tick), musca spp.) (Musca) and Musca (Musca domestica) (Musca family fly (Musca)), (autumn fly) housefly (vusca domestica) (house fly), sheep fly (oestermosvis) (sheep nose fly), european straw fly (Oscinella front) (Sweden straw fly), beet spring fly (Pegomyia beta) (spinach leaf miner), musca sp (P horbia spp.), carrot stem fly (Psila rosa sativa) (carrot rust fly)), cherry fruit fly (Rhagoletis cerasi), apple fruit fly (Rhagoletis pomonella) (apple worm (apple bug)), chinese red mud worm (Sitodiplis osmia) (orange wheat leaf fly (orange yellow fly), apple fruit fly (apple leaf fly (apple fly)), and apple fruit fly (apple leaf fly)) Stable flies (stock oxyscalcilins), horsefly (Tahanus spp.), and Aedes (Tipula spp.).

Hemiptera (Hemiptera) (stinkbug): <xnotran> (Acrosternum hilare) ( (green stink bug)), (Blissus leucopterus) ( (chinch bug)), (Calocoris norvegicus) ( (potato mirid)), (Cimex hemipterus) ( (tropical bed bug)), (Cimex lectularius) ( (bed hug)), daghertusfasciatus, dichelops furcatus, (Dysdercus suturellus) ( (cottonstainer)), edessa meditabunda, (Eurygaster maura) ( (cereal bug)), euschistus heros, (Euschistus servus) ( (brown stink bug)), (Helopeltis antonii), (Helopeltis theivora) (tea blight plantbug), (Lagynotomus spp.) (), (Leptocorisa oratorius), (Leptocorisa varicornis), (Lygus spp.) ( (plant bug)), (Lygushesperus) (western tarnished plant bug), (Maconellicoccus hirsutus), neurocolpus longirostris, (Nezara viridula) (southern green stink bug), (PhyLocoris spp.) (), (Phytocoris californicus), phytocoris relativus, piezodorus guildingi, (Poecilocapsus lineatus) (fourlined plant bug), </xnotran> Psallusvaccinicola, pseudophyta perseae, scaptocoristana, and Conus species (Triatoma spp.) (Blodsucngconense bug)/Nephocoris suturalis (kissing bug).

Homoptera (Homoptera) (aphids, scale, whiteflies, leafhoppers): <xnotran> (Acrythosiphonpisum) ( (pea aphid)), (Adelges spp.) (adelg d s), (Aleurodes proletella) ( ), (Aleurodicus di sperses), (Aleurothrixus flccosus) ( (woolly whitefly)), (Aluacaspis spp.), amrasca bigutella bigutella, (Aphropho ra spp.) ( (leafhopper)), (Aonidiella aurantii) ( (California redscale)), (Aphis spp.) (), (Aphis gossypii) (cotton aphid), (Aphis pomi) (apple aphid), (Aulacorthitm solani) ( (foxgloveaphid)), (Bemisia spp.) (), (Bemisia argentifolii), (Bemisia tabaci) (sweetpotato whitefly), (Bemisiatabaci (Gennadius)), (Brachycolus noxius) ( (Russian aphid)), (Brachycorynclia asparagi) ( (asparagusaphid)), brevennia rehi, (Brevicoryne brassicae) ( ), (Ceroplastes spp.) (), (Ceroplastes rubens) (red wax scale), (Chionaspis spp.) (), </xnotran> Tolyphacida (Chromophalus spp.) (scale), cericerus pela (Coccusp.) (scale), pink apple aphid (Dysaphis plantaginea) (royy apple aphid), pectinopus viridis (Empoasca spp.) (leafhopper), aphis gossypii (Eriosoma lanigerum) (woolly apple aphid), blastus gossypii (Icerya mercasisi) (cottony custom apple aphid), and Blastus gossypii (Icerya mercasi) (cottony cushinus scale) mango yellow line leafhopper (Idioscopeus nitidus) (mango leaf hopper), laodelphax striatellus (small brown plant hopper), lepidosaphe species (Lepidosaphe spp.), long-tube aphid species (Macrosiphumum spp.), euphorbia superba (Macrosiphumae) (potato aphid (potatoaphid)), mylophagus avenae (Ma crosiphuguranium) (English grazing aphid (English grain aphid), engli mangium (Englich aphid)), (Laodelpha mangium, englich aphid, etc.) long-tube rose aphid (rose aphid), quadphilin eatus (purple alpine cicada), mahanarva frimbiola, amanopsis dirhodula (rose aphid), midi longeronis, myzus persicae (peach aphid), green peach aphid (green aphid) Nephotettix spp (cicada), nephotettix cinctipes (green leafhopper), nilaparvata lugens (brown planthopper), psyrifos chaff (parlatinia perganii) (chaff scale), psyrium nigrum (parlatioraziziphi) (ebony scale), the plant species Triplophora zeae (Peregrinus maidis) (corn delphacid), laoderma species (Philaenus spp.), lawsonia melanogaster (Lawsonia melanogaster), phylloceroides viticola (Phyllostachys vitiae) (graptophylloxera), lepidogrisella pyrenoidosa (Phyllosphaera) piceae (sperce bud), phyllophaera pythium species (Plasmococcus spp.), lepidogrisella species (Pseudococcus sp.sp.), beckia ananas (Psudococcus brvicpcs) (pine mcalyticus), phyllophora peltata (Quadrature ductus furnacalis) (Schizophyllus flavus), phyllophora chrysospora (Phyllophora flavus) Triplophora (Phyllophora flavus), phyllophora viridans (Phyllophysaloides), phyllophora chrysospora indica (Phomopsis flavus) and Phyllophysaloides (Phomopsis flavus), phyllophora solanacephalalis (Phosphaera) and (Triplophora flavedodes), phyllophysaloderma (Triplophora spp.), lepida spp), phyllophora flavedodes (Phosphaera) and (Triplophora flavedodes niloti, phyllophysaloides), phyllophora sp (Triploca) Lepida sp (Triplophora spp The genus Tocopaia (Unaspis spp.) (Lecanis), tocopperas acutus (Unaspis yanonensis) (Arrowhead scale), and Zulia entreriana.

Hymenoptera (Hymenoptera) (ants, wasps and bees): the present invention relates to a medicament for treating or preventing diseases of the species septoria (acromyrmex spp.), neobrella (athallia rosae), phyllopodium species (Atta spp.) (ieafcunting ants), nigripes species (Camponotus spp.) (carpenter ant)), melleophaga species (Diprion spp.) (wasp), formica species (Formica spp.) (ant), argentina (iridoxrema hum.) (arge), formica spp. (argente), formica spp. (Formica spp.) (argente), formica spp. (unilocum minutum) (solpelleback ant), formica species (neobreve spp.) (phyllopodium spp.) (poinset), formica spp. (wasp), and a (wasp), and to a new conifer species (phytoplanuginella (trichoderma spp.) (wasp (solvee spp.) (wasp.) (solomotus spp.) (soleno), and a wasp (solenon) (wasp.) (soleno (solenos (solenon.) (solenon).

Isoptera (Isoptera) (termites): <xnotran> (Coptotermes spp.), (Coptotermes curvignathus), (Coptotermes frenchii), (Coptotermesformosanus) (Formosan subterranean termite), (Cornitermes spp.) ( (nasute termite)), (Cryptotermes spp.) (), (Heterotermes spp.) ( (desert subterranean termite)), ((IIeterotermes aureus), (Kalotermes spp.) (), (Incistitermes spp.) (), (Macrotermes spp.) ( (fungusgrowing termite)), ((Marginitermes spp.) (), (Microcerotermes spp.) ( (harvester termite)), (Microtermesobesi), (Procornitermes spp.), (Reticulitermes spp.) ( ), reticulitermes banyulensis, (Reticulitermes grassei), (Re ticulite rmes f la vi pes) ( ), (Reticulitermes hageni), (Reticulitermes hesperus) ( ), (Reticulitermes santonensis), (Reticulitermes speratus), (Reticulitermes tibialis), (Reticulitermes virginicus), </xnotran> The genus Reticulitermes spp (Schedorrhiotomes spp.) and the genus archaebacteria spp (Zootermopsis spp.) (Pythium species).

Lepidoptera (Lepidoptera) (moths and butterflies): <xnotran> Achoea janata, (Adoxophyes spp.), (Adoxophyes orana), (Agrotis spp.) (), ((Agrotis ipsilon) ( ), (Alabama argillacea) ( (cottonleaf worm)), amorbia cuneana, amyelosi transitella (navel orange worm), anacamptodes defectaria, (Anarsia lineatella) (peach twig borer), (Anomis sabulijera) (jute looper), (Anticarsiag emmatalis) (velvetbean caterpillar), (Archips argyrospila) (fruit tree leafroller), (Archips rosana) (rose leafroller), (Argyrotaenia spp.) (tortricid moths), (Argyrotaenia citrana) ( (orange tortrix)), autographa gamma, bonagota cranaodcs, (Borbocinnara) (rice leaffolder), (Buccula trix thurberiella) (cottonleafperforator), (Caloptilia spp.) ( ), capua reticulana, (Carposina niponensis) ( (peach fruit moth)), (Chilo spp.), (Chlumetia transversa) (mango shoot borer), (Choristoneurarosaceana) (oblique banded leaf roller), (Chrysodeixis spp.), (Cnaphalocerus medinalis) ( (grass leafroller)), </xnotran> Pieris spp (Colias spp.), lypocladia litura (Conpomorpha crameriella), codling moth (Cossus) (codling moth), cnaphalocrocis medinalis (crambe spp.) (Sod webworks), prunus funestus (Cydia funebrana) (plum fruit moth (plurfruit forth)), prunus molesta (Cydia molesta) (oriental fruit moth)), prunus nutshell (pea moth), plumbum xylostella (Cydia pomonella) (codling moth)), darna diducta, diaphania (stem moth) (ste borre)), borer species (Diatraea spp.) (stem borer (talk borer)), diatraea saccharalis (sumarcane borer), diatraea grandiflora (sutraea grandiflora) (suthwesterweer), diamond-impregnated Diamond species (Earias spp.) (Helicoverpa armigera), elaeagna exanthera (Earias insulata) (Egyptianbollworm), diamond emeraldii (Earias vitta) (Rough northern bollworm), edwardia emeraldii (Earias vitta). Corn seedling borer (Elasmopalstus lignosellus) (messenger corn kernel borer), light brown apple moth (Epiphysia punctata na) (light brown apple moth), pink egg borer species (Ephestia spp.) (pink egg borer), pink egg borer (Ephestia calutella) (mond moth), tobacco pink egg borer (Ephestia lutella) (tobacco leaf borer (tobacac moth)), mediterrata kuehella (Ephestia kuehneella) (Mediterranean flower moth), epiecetes species (epiecetes spp.), noctuid (epiotecan corporation), scoliota indica (eroiota thrax) (bananas skipper), lucilia tenuifolia (eupocetiella mangifera) (grape berry moth)), prototheca incisa (Euxoa auricularis) (armychur), cutworm species (feldia spp.) (cutworm), hornworm species (gordonia spp.) (stem worm), grapholitha molesta (grapholitta molesta) (peach (apricot) fruit core worm (oriental fruit moth)), fringed moth (helentta indica (bean leaf moth (leaf moth)), and cyanea species (helminth leaf moth) (cabbage leaf moth (leaf moth)). Cotton bollworm (Helicoverpa armigera) (cotton bollworm), oriental fruit moth (Helicoverpa zea) (corn borer ridge (borer/bollworm)), species of fruit moth (Heliothis spp.) (night moth), oriental tobacco budworm (Heliothis virescens) (tobacco budworm), cabbage moth (Hellula undaria) (caageweb work), species of genus of Indian (Indian belching.) (root borer), tomato spotted moth (kefir lycopersicella) (tomato stem worm), solanum white borer (Leucinododes (Indian bombycis) (egg plant), spiculella (Leucoptera nutans), species of genus of spinifera (Leptospira), and species of fine (lithrosporiella, grape leaf roller (Lobesia fortana) (grape fruit moth), loxagrotis species (Loxagrotissp.), spodoptera exigua (Spodoptera exigua), douglas-Hayata (Loxagrotis albicostata) (western bean crop), gypsy moth (Lymantria dispar) (gypsy moth), peach fruit moth (Lymantria kelella) (apple leaf moth (apple leaf), oil palm bag moth (Mahasena corbeti) (oil palm bat), anoplophora sp (Malacospos spp.) (ten caterpillar), cabbage looper (Mamestra brassiccus) (cabbage armyworm), pod borer (Maruca testulalis) (bean wild borer), bag moth (metal planta) (knot worm), mythimna unipunctata (tree armyworm), neonectarines (small tomato borer (tomato leaf), yellow rice borer (Npinula pyralis) (rice leaf borer), rice stem borer (apple leaf borer) (apple leaf moth), rice stem borer (apple leaf borer)). European corn borer (Ostrinianubilis) (European corn borer), oxydia vesulia, pantoea armoricana (Pandemiscarana) common grape leaf roller (common currant roller), plumbum rubra (Pandemia hepes) (brown apple roller), african damantula (Papilio demodula), henry moth (Pectinophora gossypiella) (red bell bollworm (pink bollworm)), spodoptera species (Peridroma spp.) (root cutting insect), phlebia versicolor (Peridrora savoides) (variegated cutworm), coffee leaf miner (Perileria cofiguana) (Hithi coffee flower bud), phthalria punctatus (Phthalria punctifera) (Phlebia punctifera), phlebia punctifera (Phormidis) and Periploca punctifera (Phoenii), periploca punctatus (Phormidis) Henria punctifera (Henry), hayata officinalis (Phononia punctifera) and Periploca punctifera (Phormidis) as well as a species (Periploca punctifera), the species Trichoplusia (Phyllotrichum sporum.) (leaf miner), pieris rapae (Pieris ra pae) (exotic cabbage caterpillar (imported cabbagageum)), trichoplusia (Platyphenona scabra), pythium insidiosum (Pythagorean indica) (Indian mealy moth), plutella xylostella (Plutella xylostella) (diamondback moth), vitis vinifera (Polyporus virosa) (grapevine berry moth) (grapple berry moth), phyllostachys aurantia (Prays endoceps), olea europaea (Prussian olive mole) (olive moth), comydia species (Pseudaea spp.) (Spodoptera nocturna), pseudaulia (Spodoptera frugiperda), spodoptera frugiperda (Spodoptera frugii) (Plutella xylostella), spodoptera melanosporus (Scirpus androgens) (Scirpus nipula flava), spodoptera litura (Raphiguas (Raphigua) and Spodoptera (Scirpus nipula) are Anthriscus species (Sesamia spp.) (stemborer), spodoptera oryzae (Sesamia infensens) (pink rice stem borer), sesamia pinicola (Sesamia agroides), spodoptera littoralis (Setora agnoides), spodoptera cuprina (Setora nitens), spodoptera littoralis (Sitotroga cerealis) (Antomomonas grandis molh), spodoptera viticola (Spargyroptera pilifera), spodoptera griseifolia (Spodoptera exigua) (Spodoptera corpulentum), spodoptera frugiperda (Spodoptera spongia), spodoptera trichoptera flavescens (Spodoptera), spodoptera trichoptera (southern armyworm), spodoptera lita (Thermopsis), spodoptera litura (Synechoides) and Spodoptera (Spodoptera) species (Spodoptera) including Spodoptera litura), spodoptera litura (Spodoptera) and Spodoptera litura (Spodoptera), thermoidia gemmatalis, chlamydia armyworms (Teneola bisseliella) (webbingcles moth), trichoplusia ni (cab looper), tetranychus tomatidae (Tutsabsoluta), phlomis nidulans species (Yponomeuta spp.), dryopsis coffee (Zeuzacoffeae) (red branchborer), zeuzera pyrina (Lepidogra litura) and Spodoptera litura (Spodoptera litura).

Mallophaga ((Mallophaga) feather louse (chewing lice)): ovine feather louse (Bovicola ovis) (sheet biting louse), turkey short horn feather louse (chicken feather louse), and chicken feather louse (Menopon gallina) (common henhouse).

Orthoptera (Orthoptera) (grasshopper, locust and cricket): longhorned grasshopper (grasshopper horns) (Mormon cricket), mole cricket (Gryllotalpidae), locusta migratoria (Locusta migratoria), grasshopper species (Melanoplus spp.) (grasshopper), podophyllum longhorn (microcentrumretrierve) (angular winged katydia), ptophylla species (Pterophylla spp.) (grasshopper), stolocusta chinensis (scleroderma reedirective) (scuddella furtypata) (forktail bush), and stenotropha auricularia (vanilloides).

Phthiraptera (Phthiraptera) (sucking lice): the blood sucking lice species (haematoponus spp.) (cattle and pig lice), sheep jaw lice (linogluchus ovilus) (sheep lice), head lice (pediluus humanus capitis) (body lice), human body lice (pediluus humanus) (body lice) and crab lice (Pthirus pubis) (crab lice louse).

Siphonaptera (daphnaptera) (fleas): ctenocephalides canis (dog flea), ctenocephalides felis (cat flea) and human flea (Pulex irutans) (human flea).

Thysanoptera (thrips): cithrips tabaci (Frankliniella fusca) (tobaco third), frankliniella occidentalis (Frankliniella occidentalis) (western flower third), frankliniella shultzei (Frankliniella williamsii) (maize third), frankliniella viridis (IIeliophidia) (greenhouses third), riphiproxithromus cruentatus, scirpus spp (Scirothrix spp), platycodon grandiflorum (Scirothrix third) (citrus third), camellia marianum (Scirothrix darussis) (yellows third), taeniothrix thips, taeniothianthus spp (Thinophora crisps), and Threshonia species (Thripp).

From the tassel tail (Thysanura) (bristletail): chlamydomonas species (Lepisma spp.) (silverfish) and locusta species (Thermobia spp.) (locusta spp.).

From the order of Acarina (Acarina) (mites (mite) and cicadas (tick)): <xnotran> (Acarapsis woodi) ( (tracheal mite of honeybee)), (Acarus spp.) ( ), (Acarus siro) ( (grain mite)), (Aceria mangiferae) (mango bud mite), (Aculops spp.), (Aculops lycopersici) (tomato russetmite), aculops pelekasi, (Aculus pelekassi), (Aculusschlechtendali) ( (apple rust mite)), (Amblyomma amcricanum) (lone star tick), (Boophilus spp.) (), (Brevipal pusobovatus) (privet mite), (Brevipalpus phoenicis) (red and black flatmite), (Demodex spp.) (mange mites), (Dermacentorspp.) ( ), (Dermacentor variabilis) (american dog tick), (Dermatophagoidespteronyssinus) (house dust mite), (Eotetranycus spp.), (Eotetranychus carpini) ( (yellow spider mite)), (Epitimerus spp.), (Eriophyes spp.), (; odes spp.) (), ((Metatetranycus spp.), (Notoedres cati), </xnotran> Pediobolus species (Oligonychus spp.), demodex coffeensis (Oligonychus cofee), demodex wintergreen (Oligonychus iliciformis (southern mite), demodex gemiformis species (Panychus spp.), demodex citrinopileatus (Panychus cirri) (citrus red mite), demodex apple (Panychus ulmi) (European red mite), demodex citri (Phylloptuta oleurovora) (citrus red mite), demodex laterosologylus (lateral polyphagotarsonemus) (guangmus mite (bronmite)), (Phyllocercosmophorus purpura) (citrus red mite, paeonia lateral polyphylla (Polytarsonemus) (Polyglea mite (bronmite)), (Phyllo) red blood rhipicephalus (rhipicephalus anguineus) (brown dog tick), rhizomorph species (rhizomorphyphus spp.) (root mite (bulb mite)), sarcoptes scabies (Sarcoptes scabies) (itch mite), crocodile crown gall mite (tetragonophys perseaus), tetranychus species (Tetranychus spp.), tetranychus urticae (Tetranychus urticae) (two-spotted spider mite (twospotted spider mite)) and Varroa destructor (Varroa destructor) (bee mite).

Nematoda (nematodes): the species Aphelenchoides spp (bud and leaf and pine wood nematodes), the species Trichinella (Belnolalimus spp.), the species Stcing nemates, the species Cyclotella spp (Criconema spp.), the species Dirofilaria immitis (dog heartworm), the species Ditylenchus spp (Ditylenchus spp.) (Stem and bulb nematodes), the species Heterodera spp (Cyst nemates), the species Heterodera zeae (Heterodia cystnemorpha) (corn stunnemode), the species Hirschnella spp (Rosemophila spp.) (Romenhades) the species neozontalgia (endoplasmius spp.) (surface nematodes), meloidogyne species (Meloidogyne spp.) (root-knot nematodes), meloidogyne incognita (root-knot nematodes), glochidion coioides (onchoca volvulus) (hook-tail work), pralylenus spp.) (rot nematodes), perforators species (root-knot nematodes) (piercing nematodes) and helicobactor (rotilenus reniformis) (kit-shaped nematodes).

General class (general classes of insects): white pine worm (Scutigerella immacula).

Owing to their positive properties, the compounds of the formula (I) can be used advantageously for protecting crops, domestic animals and livestock animals of agricultural and horticultural importance, as well as the environment customary for humans, against pests and/or mites.

The amount of the compound of formula (I) to be used to obtain the desired effect will vary depending on various factors such as the compound used, the crop to be protected, the type of pest, the extent of infection, the climatic conditions, the method of application and the dosage form employed.

The ingredients of the dosage forms or compositions described herein are selected in accordance with the physical properties of the active ingredient, the mode of application and environmental factors such as soil type, moisture and temperature.

Useful dosage forms include solutions such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspensions), and the like, which may optionally be viscous jellies. Useful dosage forms also include solids such as powders, granules, tablets, pills, films, and the like, which may be water-dispersible ("wettable") or water-soluble. The effective components can be microencapsulated and made into suspension or solid dosage form; in addition, the whole dosage form of the effective components can be encapsulated. The capsule can control or delay the release of the effective components. Sprayable formulations can be diluted in a suitable medium using spray volumes of about one to several hundred liters per hectare. The high concentration composition is mainly used as an intermediate for further processing.

Typical solid Diluents are described in Watkins et al, handbook of Instrument Dual ingredients and Cariers, 2nd Ed., dorland Books, caldwell, new Jersey. Typical liquid diluents are described in Marsden, solventsguide,2nd Ed., interscience, new York, 1950. McCutcheon's Detergents and Emulsifiers annular, allured pub. Corp., ridgewood, new Jersey, and Sisely and Wood, encyclopedia of Surface Active Agents, chemical Publ. Co., inc., new York,1964, list surfactants and recommended applications. All formulations may contain small amounts of additives to reduce foaming, coalescence, corrosion, microbial growth, etc., or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, sulfonated dialkyl succinates, alkyl sulfates, alkyl benzene sulfonates, organosilanes, N-dialkyl taurates, lignosulfonates, aldehyde condensates for naphthalenesulfonates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite, kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium bicarbonate, sodium sulfate, liquid diluents include, for example, water, N-dimethylformamide, dimethyl sulfone, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, olive oil, castor oil, linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and cocoa oil, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, dodecanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the components. Powders and fines can be prepared by mixing and typically by grinding in a hammer mill or liquid energy mill, typically by wet milling; see, for example, U.S. Pat. No. 3060,084, granules and pellets are prepared by spraying the active substance onto freshly prepared granular carriers or by granulation techniques. See Browning, "Agglomeration", chemical Engineering, december 4, 1967, pp147-48, perry s Chemical Engineering, handbook,4TH Ed., mcGraw-Hill, new York,1963, pages 8-57and following, and WO 91/13546. Preparation of pellets as described in U.S.4172714, water dispersible and water soluble granules as described in U.S.4144050, U.S.3920442 and DE 3246493 to prepare tablets as described in US 5180587, U.S.5232701 and U.S. 5208030. The films may be prepared by the methods described in GB2095558 and u.s.3299566.

For more information on processing see U.S.3,235,361, col.6, line 16960. Quadrature. Chol.7, line 19and EXAmplies 10-41; U.S.3,309,192, col.5, line 43through col.7, line 62and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167and169-182; U.S.2,891,855, col.3, line 66through col.5, line 17and amplifiers 1-4; klingman, weed Control as a Science, john Wiley and Sons, inc., new York 1961, pp 81-96; and Hance et al, weed Control Handbook,8th Ed., blackwell Scientific Publications, oxford,1989.

Herein, for certain applications of the compositions, for example in agriculture, one, two or more other fungicides, insecticides, acaricides, herbicides, plant growth regulators or fertilizers and the like can be added to the insecticidal and/or acaricidal compositions according to the invention, whereby additional advantages and effects can be produced.

Advantageous effects

The compound of formula (I) shows good activity to various pests and mites in agriculture or other fields. Furthermore, these compounds can be used for the preparation of insecticides and/or acaricides because of their excellent control effect at very low doses.

The inventor of the application finds that the introduction of a pentafluorothioether group into the compound in the formula (I) has a large influence on the activity of the compound, and the biological activity is remarkably improved. Therefore, the compound shows excellent control effect on various pests/mites such as aphids, brown planthoppers, frankliniella occidentalis, tetranychus cinnabarinus and the like.

In addition, the compound provided by the invention has the advantages of simple preparation steps and high yield, and therefore, the compound has a good application prospect.

Terms and definitions

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs. All patents, patent applications, and publications cited herein are incorporated by reference in their entirety unless otherwise indicated. If there are multiple definitions of terms herein, the definition in this section controls.

It is understood that reference may be made to this document (including Carey and Sundberg "ADVANCED ORGANIC CHEMISTRY 4 ^TH The definition of standardized chemical terms is found in ed, vols.a (2000) and B (2001), plenum Press, new York). Unless otherwise indicated, conventional methods within the skill of the art are employed, such as mass spectrometry, NMR, IR and UV/Vis spectroscopy, and pharmacological methods. Unless a specific definition is set forth, the terminology used herein in the pertinent description of analytical chemistry, organic synthetic chemistry, and pharmaceutical and medicinal chemistry is known in the art. Standard techniques can be used in chemical synthesis, chemical analysis, pharmaceutical preparation, formulation and delivery, and treatment of patients. For example, the reaction and purification can be carried out using the manufacturer's instructions for use of the kit, or in a manner known in the art or as described herein. The techniques and methods described above can generally be practiced according to conventional methods well known in the art, as described in various general and more specific documents referred to and discussed in this specification. In the present specification, groups and substituents thereof may be selected by one skilled in the art to provide stable moieties and compounds. When a substituent is described by a general formula written from left to right, the substituent also includes chemically equivalent substituents obtained when a formula is written from right to left, as long as it complies with the valence rules. For example, CH ₂ O is equivalent to OCH ₂ The substitution position may be bonded with an oxygen atom or a carbon atom of a methylene group.

The term "C _1-6 Alkyl is understood to mean having from 1 to 6 carbon atomsA straight or branched chain saturated monovalent hydrocarbon group. For example methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl.

The above term "alkyl", e.g. "C _1-6 The definition of alkyl "applies equally to compounds containing" C _1-6 Other terms for alkyl ", e.g. the term" halo C _1-6 Alkyl group and C _1-6 Alkoxy group "," halogeno C _1-6 Alkoxy "and the like.

The term "halogen" is understood to mean fluorine, chlorine, bromine or iodine.

The term "halo C _1-6 Alkyl is understood to mean straight-chain or branched alkyl radicals in which the hydrogen atoms are partially or completely replaced by halogen atoms, e.g. -CF ₃ 。

The term "halo C _1-6 Alkoxy "is to be understood as meaning that the hydrogen atoms of the alkyl radical of the alkoxy radical may be partially or completely replaced by halogen atoms, such as ClCH ₂ CH ₂ O-。

The term "pharmaceutically acceptable salt" as used herein refers to salts that retain the biological effectiveness of the free acid and free base of the specified compound and that are not biologically or otherwise undesirable. The compounds of the present application also include pharmaceutically acceptable salts, such as nitrates, hydrochlorides, sulfates, phosphates, or the like. Pharmaceutically acceptable salts refer to the form in which the base group in the parent compound is converted to a salt. Pharmaceutically acceptable salts include, but are not limited to, inorganic or organic acid salts of base groups such as amine (amino) groups. Pharmaceutically acceptable salts of the present application can be synthesized from the parent compound by reacting a basic group in the parent compound with 1-4 equivalents of an acid in a solvent system. Suitable salts are listed in Remingtong's Pharmaceutical sciences, 17 ^th ed., mack Publishing Company, easton, pa.,1985, p.1418 and Journal of Pharmaceutical Science,66,2 (1977), for example, hydrochloride.

"stereoisomers" as used herein refers to isomers resulting from the different arrangement of atoms in a molecule in space. The compounds of formula (I) contain asymmetric or chiral centers and, therefore, exist in different stereoisomeric forms. All stereostructures and mixtures of formula (I) are as such, including racemic mixtures, as part of the present application. Diastereomeric mixtures can be separated into the individual diastereomers, based on their different physicochemical properties, by well-known means, e.g., resolution of the enantiomers can be converted into the diastereomers by reaction with a suitable optically active substance (e.g., a chiral alcohol or Mosher's moylchloride), which can be separated and converted (e.g., hydrolyzed) into the corresponding individual isomers. Some of the compounds of formula (I) may be atropisomers (e.g., substituted aryl) are also part of this application. Enantiomers can also be separated using a chiral chromatography column. The compounds of formula (I) may exist in different tautomeric forms, which forms are included within the scope of the present application. For example, compounds in the form of keto-enols and imine-enamines.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

The following chromatographic conditions were used for the LC-MS detection analysis in the examples below:

a chromatographic column: agilent ZORBAX SB-C18 mm x 4.6mm,5 μm (i.d);

detection wavelength: 254nm; flow rate: 0.8mL/min; column temperature: 30 ℃;

gradient elution conditions:

time (min)	Methanol (%)	0.1 aqueous formic acid solution (% by volume)
			0.00	50	50
5.00	50	50
			10.00	90	10
20.00	90	10

Synthetic examples

Example 1: preparation of 4- ((5- (1, 3-dioxane-2-yl) pyrimidin-4-yloxy) methyl) phenylpentafluorosulfide (Compound 1)

The first step of reaction: preparation of 4, 6-dichloro-5- (1, 3-dioxan-2-yl) pyrimidine: 17.9g (0.1 mol) of 4, 6-dichloropyrimidine-5-carbaldehyde were dissolved in 100mL of toluene at room temperature, and the mixture was stirred. To the above mixture were added 1.75g (0.01 mol) of p-toluenesulfonic acid and 15.2g (0.2 mol) of propylene glycol, respectively. Heated to reflux for 1 hour. After the heating was stopped, the mixture was concentrated under reduced pressure, and 50mL of ethyl acetate was added to the residue, which was washed with a saturated aqueous sodium bicarbonate solution (20 mL) and a saturated brine (30 mL), respectively. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. And (5) purifying by column chromatography to obtain 20.2g of a product with the yield of 86%.

LC-MS[M+H] ⁺ ＝235.01、[M+Na] ⁺ ＝256.99、[M+K] ⁺ ＝272.96。

The second step of reaction: preparation of 4-chloro-5- (1, 3-dioxane-2-yl) pyrimidine: 11.8g (0.05 mol) of 4, 6-dichloro-5- (1, 3-dioxan-2-yl) pyrimidine, 8.5g (0.1 mol) of sodium ethoxide and 4.6g of palladium on carbon were dissolved in 150mL of ethanol, respectively, at room temperature. And reacting for 6 hours under a hydrogen atmosphere. The mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. To the concentrate was added 10mL of a saturated aqueous sodium bicarbonate solution. Ethyl acetate (3 × 20ml) was extracted. The organic layer was washed with water (20 mL) and saturated brine (20 mL), and dried over anhydrous magnesium sulfate. The solvent is removed under reduced pressure, and the product is obtained by column chromatography with the yield of 4.1g and 40 percent.

LC-MS[M+H] ⁺ ＝201.05、[M+Na] ⁺ ＝223.03、[M+K] ⁺ ＝239。

The third step of reaction: preparation of 4- ((5- (1, 3-dioxan-2-yl) pyrimidin-4-yloxy) methyl) phenylpentafluorosulfide: 0.44g (0.011 mol) of sodium hydride was dissolved in 10mL of N, N-dimethylformamide at 0 ℃. To the mixture was added 2.34g (0.01 mol) of 4- (hydroxymethyl) phenylpentafluorosulfide in portions, the temperature being kept below 5 ℃. Then, 1.85g (0.009 mol) of 4-chloro-5- (1, 3-dioxan-2-yl) pyrimidine was added to the mixture and reacted at room temperature for 4 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate (3 × 20ml). The organic layers were combined, washed with water (20 mL) and saturated brine (20 mL), and dried over anhydrous magnesium sulfate. The solvent is removed under reduced pressure, and the product is obtained by column chromatography, wherein the yield is 2.7g and 75 percent.

LC-MS[M+H] ⁺ ＝399.08、[M+Na] ⁺ ＝421.06、[M+K] ⁺ ＝437.03。

¹ HNMR (400 MHz, solvent (CD) ₃ ) ₂ SO)δ(ppm):2.06(2H,m),3.96(2H,t),4.16(2H,m),

5.61(2H,s),5.80(1H,s),7.68(2H,d),7.94(2H,d),8.62(1H,s),8.80(1H,s)。

Example 2: preparation of 3- ((5- (1, 3-dioxan-2-yl) pyrimidin-4-yloxy) methyl) phenylpentafluorosulfide (Compound 23)

0.44g (0.011 mol) of sodium hydride was dissolved in 10mL of N, N-dimethylformamide at 0 ℃. To the mixture was added 2.34g (0.01 mol) of 3- (hydroxymethyl) phenylpentafluorosulfide in portions, the temperature being kept below 5 ℃. Then, 1.85g (0.009 mol) of 4-chloro-5- (1, 3-dioxan-2-yl) pyrimidine was added to the mixture and reacted at room temperature for 4 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate (3 × 20ml). The organic layers were combined, washed with water (20 mL) and saturated brine (20 mL), and dried over anhydrous magnesium sulfate. Decompression desolventizing, column chromatography to obtain 2.5g of product with 70% yield.

LC-MS[M+H] ⁺ ＝399.08、[M+Na] ⁺ ＝421.06、[M+K] ⁺ ＝437.03。

¹ HNMR (400 MHz, solvent (CD) ₃ ) ₂ SO)δ(ppm):2.07(2H,m),3.96(2H,t),4.16(2H,m),5.62(2H,s),5.80(1H,s),7.72(2H,d),7.78(1H,d),7.84(1H,d),8.61(1H,s),8.80(1H,s)。

Example 3: preparation of 3- ((5- (1, 3-dioxan-2-yl) pyrimidin-4-yloxy) methyl) -5-fluorophenylpentafluorosulfide (Compound 27)

0.44g (0.011 mol) of sodium hydride was dissolved in 10mL of N, N-dimethylformamide at 0 ℃. To the mixture was added 2.56g (0.01 mol) of 3-fluoro-5- (hydroxymethyl) phenylpentafluorosulfide in portions, the temperature being kept below 5 ℃. Then, 1.85g (0.009 mol) of 4-chloro-5- (1, 3-dioxane-2-yl) pyrimidine was added to the mixture and reacted at room temperature for 4 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate (3 × 20ml). The organic layers were combined, washed with water (20 mL) and saturated brine (20 mL), and dried over anhydrous magnesium sulfate. The solvent is removed under reduced pressure, and the product is obtained by column chromatography, wherein the yield is 2.46g and 65 percent.

LC-MS[M+H] ⁺ ＝417.07、[M+Na] ⁺ ＝439.05、[M+K] ⁺ ＝455.02。

¹ HNMR (400 MHz, solvent (CD) ₃ ) ₂ SO)δ(ppm):2.07(2H,m),3.96(2H,t),4.16(2H,m),5.62(2H,s),5.80(1H,s),7.32(1H,d),7.46(1H,d),7.64(1H,d),8.62(1H,s),8.81(1H,s)。

The present invention also synthesizes the compounds in the following tables, with reference to the methods in the above examples, and the results of their characterization are shown in the following tables:

formulation examples

In the following examples, all percentages are by weight and all dosage forms are prepared using conventional methods.

Example 4:

in this example, the compound obtained in the above example is used to prepare a wettable powder, specifically, the wettable powder is prepared from the following raw materials in proportion:

compound 1.0%, dodecylphenol polyethoxy glycol ether 2.0%, sodium lignosulfonate 4.0%, sodium aluminosilicate 6.0%, and montmorillonite (calcined) 23.0%.

Example 5:

in this example, granules were prepared using the compounds obtained in the above examples, specifically using the following raw materials:

the compound is 23.0 percent, the other components are sodium dodecyl sulfate 2 percent, calcium lignosulfonate 6 percent, potassium chloride 10 percent, polydimethylsiloxane 1 percent and soluble starch to be 100 percent.

Example 6:

in this example, the compound obtained in the above example is used to prepare an extruded pellet, specifically using the following raw material composition:

25.0 percent of compound, 10.0 percent of anhydrous calcium sulfate, 5.0 percent of crude calcium lignosulfonate, 1.0 percent of alkyl sodium naphthalene sulfonate and 59.0 percent of calcium/magnesium bentonite.

Example 7:

in this example, the compound obtained in the above example is used to prepare emulsifiable concentrate, and specifically, the emulsifiable concentrate is prepared by using the following raw material compositions:

compound 34.0%, solvent 150%, PEG400 5%, rhodacal 70/B3%, rhodameen RAM/77%.

Example 8:

in this example, the compound obtained in the above example is used to prepare an aqueous suspension, specifically using the following raw materials in proportion:

compound 39.0%, POE polystyrene phenyl ether sulfate 5.0%, xanthan gum 0.5%, polyethylene glycol 5%, triethanolamine 1%, sorbitol 0.5%, and water to 100.0%.

Determination of biological Activity

Example 9:

1. determination of insecticidal Activity

In this example, several insects were tested for insecticidal activity using the compounds prepared in the above examples.

And (3) testing the insecticidal activity: the test method is as follows, a test solution with a desired concentration is prepared by dissolving a test compound sample in a suitable solvent (the kind of solvent is acetone, methanol, DMSO, etc., and is selected according to its dissolving ability for the sample). The test cell consisted of a small open container containing 12-15 day old radish plants. The test plants were preimpregnated by placing 30 to 40 pests on a leaf cut from the cultivated plant on one leaf of the test plant (leaf cutting method). As the leaves dehydrate, the pests move on the test plants. After the preliminary dip-dyeing, the soil of the test cell was covered with a layer of sand.

The test method is as follows: the test was repeated three times, and after spraying the prepared test compound solution, each test unit was allowed to dry for 1 hour, and then a black mesh cap was placed on top. The test cells were kept in a growth chamber at 25 ℃ and 70% relative humidity for 6 days. Insect mortality was then visually assessed for each test unit.

(1) Test results for the control of myzus persicae by exemplary example Compounds

At a dose of 600ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 1. 2, 3, 5, 14, 19, 22, 23, 27, 28, 34, 39, 40, 41;

at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to the green peach aphids comprise: 1. 2, 3, 5, 14, 19, 22, 23, 34, 39, 40, 41;

at a dose of 50ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 1. 2, 3, 5, 19, 22, 23, 34, 39, 40.

(2) Test results for the control of Aphis gossypii by exemplary example Compounds

At a dose of 600ppm, the compounds with the fatality rate to cotton aphid of more than 80 percent comprise: 1. 2, 3, 5, 14, 19, 22, 23, 27, 28, 34, 39, 40, 41;

at a dose of 100ppm, the compounds with the lethality rate of more than 80% to cotton aphid comprise: 1. 2, 3, 5, 14, 19, 22, 23, 34, 39, 40, 41;

at a dose of 50ppm, the compounds with the fatality rate to cotton aphid of more than 80 percent comprise: 1. 2, 3, 5, 19, 22, 23, 34, 39, 40.

(3) Test results for controlling frankliniella occidentalis by exemplary example Compounds

At a dose of 600ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1. 2, 3, 5, 14, 19, 22, 23, 27, 28, 34, 39, 40, 41;

at a dose of 100ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1. 2, 3, 5, 14, 19, 22, 23, 27, 28, 34, 39, 40, 41;

at a dose of 50ppm, the compounds with the fatality rate of over 80 percent to frankliniella occidentalis have the following characteristics: 1. 2, 3, 5, 14, 19, 22, 23, 34, 39.

(4) Test results for the control of Nilaparvata lugens by exemplary example Compounds

At a dose of 600ppm, the compounds with the mortality rate of more than 80 percent to prodenia litura comprise: 1. 2, 3, 5, 14, 19, 22, 23, 27, 28, 34, 39, 40, 41;

at a dose of 100ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 1. 2, 3, 5, 14, 19, 22, 23, 27, 28, 34, 39, 40, 41;

at a dose of 50ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 1. 2, 3, 5, 19, 22, 23, 34, 39, 40, 41.

2. Acaricidal Activity assay

In this example, several mite-killing activity tests were carried out using the compounds prepared in the above examples.

The test method is as follows: a sample of a compound to be tested is dissolved in a suitable solvent (the kind of the solvent is acetone, methanol, DMSO, and the like, and is selected according to the dissolving capacity of the solvent on the sample), and an aqueous solution of tween 80 with a mass fraction of 0.1% is used to prepare a solution to be tested with a required concentration. The double-sided adhesive tape is cut into 2-3 cm long, the double-sided adhesive tape is attached to one end of a microscope slide, paper pieces on the adhesive tape are removed by tweezers, female adult mites which are consistent in size, bright in body color and lively in action are selected by a zero-number brush pen, the backs of the female adult mites are adhered to the double-sided adhesive tape (not to adhere to mite feet, mite whiskers and mouth parts), 2 lines of the double-sided adhesive tape are adhered to each piece, and 15-20 heads of the double-sided adhesive tape are adhered to each line.

The test method is as follows: the test is repeated for 4 times, and after the test is placed in an incubator for 2 hours at the temperature (25 +/-1) DEG C, the relative humidity of 85% and the photoperiod of L: D = (16) h, dead or inactive individuals are removed by binocular observation, and the number of the repeated insects in each time is ensured to be more than 30. Soaking one end of the glass sheet with the mites into the liquid medicine, slightly shaking for 5s, taking out, and quickly sucking off the mites and the redundant liquid medicine around the mites with absorbent paper. And (4) placing the mites in the incubator, checking the result by using binoculars after 24 hours, lightly touching the mite bodies by using a writing brush, taking the mites with enough immobility as death, and calculating the lethality. The mortality rate was calculated as follows:

the following results were obtained for the Tetranychus cinnabarinus part:

at a dose of 600ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1. 2, 3, 5, 14, 19, 22, 23, 27, 28, 34, 39, 40, 41;

at a dose of 100ppm, the compounds with a mortality rate of more than 80 percent on tetranychus cinnabarinus comprise: 1. 2, 3, 19, 22, 23, 34, 39.

3. Test results for exemplary example compounds and control agents

This example uses comparative activity tests of some of the compounds of the invention with reference drugs (control drugs CK1 and CK2 were prepared by themselves according to the method described in patent document WO2013115391, see background art for the structures of CK1 and CK 2). The results of the tests are given in the following table.

In addition to the compounds listed in the above table, other exemplary compounds of the present invention have better control activity against pests, mites than the control agents. Therefore, the compound shown as the formula (I) shows good activity to various pests and mites in the agricultural field.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims

1. A compound represented by the formula (I), or a pharmaceutically acceptable salt thereof,

(I)

wherein the compound shown in the formula (I) is selected from the following compounds:

。

2. a process for preparing a compound according to claim 1, comprising the steps of:

b) Reacting a compound shown as a formula (VII) with a compound shown as a formula (VI) to obtain a compound shown as a formula (I);

wherein R, X, n have the definitions as defined in claim 1 and L is selected from a leaving group Cl, br or I.

3. A pesticidal composition comprising, as an active ingredient, one, two or more of the compounds of claim 1, or pharmaceutically acceptable salts thereof.

4. The pesticide composition as set forth in claim 3, wherein the active ingredient is contained in the pesticide composition in an amount of 0.1 to 99.9% by weight.

5. The pesticide composition as set forth in claim 4, further comprising one, two or more kinds of agriculturally and/or forestry and/or hygienically acceptable carriers.

6. The pesticidal composition according to claim 5, which is applied in the form of a formulation which is a granule, a wettable powder, an oil suspension, an aqueous emulsion, a water agent, an emulsifiable concentrate or a microcapsule.

7. The pesticide composition as set forth in claim 6, wherein a surfactant is further added to the pesticide composition.

8. Use of one, two or more of the compounds of claim 1, or pharmaceutically acceptable salts thereof, in the preparation of a pesticide; the pesticide is an insecticide and/or acaricide.