Derivatives of simple ether, remedy for insect control and connection phenol

 

(57) Abstract:

Derivative of a simple ester of the General formula I, where R1- halogen; a is the group-CH(R2)-(CH)m-CH(R3)-N(R4)-C(= Y)-X-R5, -CH(R2)-(CH2)m-CH(R3)-W-C(= Y)-cyclo-C3H5, -CH(R2-(CH2)m-CH(R3)-CH2-CH(R2)-C5H5N(R2)n,

-CH(R2)-C6H6(R9)n,; R2, R3, R4Is h or methyl, R5- C1-4-alkyl; R6, R10, R11- H, C1-4-alkyl; R9- halogen or C1-4-alkyl; E is a residue of formula (a)-(C), R12is halogen or methyl; X, Y is oxygen or sulfur; W is NH; 1, m, n = 0-2, possess excellent suppressive effect against harmful insects and harmful mites. 3 C. and 8 C.p. f-crystals, 22 PL.

The invention relates to a derivative of a simple ester, application and intermediate compounds used for their production. More specifically, the present invention relates to a derivative of a simple ester, which have excellent suppressive action against harmful organisms, to means for combating harmful organisms containing them as active ingredients, and to the interim joint is developing compounds which have excellent suppressive action against harmful organisms. As a result, they found that the derivative of a simple ester of the General formula P-1, which is shown below, have excellent suppressive action against harmful organisms, from which was created the present invention. Thus, the present invention relates to derivatives of simple ether (hereinafter referred to as the present (s) compound (I)) General formula:

< / BR>
where R1is halogen;

A represents any of groups of the following General formula Q-1 - Q-11:

-CH(R2)-(CH2)m-CH(R3)-N(R4)-C(=Y)-X-R5(Q-1)

-CH(R2)-(CH2)m-CH(R3)-X-C(=Y)-N(R5R6(Q-2)

-CH(R2)-(CH2)m-CH(R3)-W-C(=Y)-cyclo-C3H5(Q-3)

-CH(R2)-(CH2)m-CH(R3)-CH(R7)-O-R8(Q-4)

-CH(R2)-(CH2)m-CH(R3)-CH2-B (Q-5)

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
R2, R3, R4and R7, independently, are hydrogen or stands;

R5and R8, independently, are C1-C4the alkyl (optionally substituted with halogen or methoxy), C3-C4
R6is a group represented by R5or hydrogen;

R9is halogen or C1-C4the alkyl (optionally substituted with halogen);

R10and R11independently are hydrogen, C1-C4-alkyl or C3-C4-alkenyl;

B is a group of the General formula:

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
or

< / BR>
E is a group of General formula

< / BR>
< / BR>
< / BR>
R12is halogen or stands, optionally substituted with halogen,

X and Y, independently, are oxygen or sulfur;

W is oxygen, sulfur or NH; and

l, m and n, independently, are an integer from 0 to 2; and the means for combating harmful organisms containing them as active ingredients.

The present invention also relates to a derivative of a phenol of General formula

< / BR>
where E is defined above, which is used as intermediate compounds used in obtaining the above derived simple ether.

These compounds possess excellent activity, such juvenile hormone, in particular against harmful insects, i.e., they have such function. For this reason, these compounds for the most part can serve as growth regulators, chemical sterilizers, ovicidal inhibitors or reproduction of obtaining significant regulated effects against various harmful insects, including those that have an increased resistance to existing insecticides, such as those that occur in agriculture, forestry and horticulture; such that infect stored stocks of cereals, and those that are harmful to health.

These derivatives represented by the above General formula P-1.

As the halogen represented by R1, R9and R12may be mentioned fluorine, chlorine, bromine or iodine.

As C1-C4-alkyl (optionally substituted by halogen or a methoxy group), represented by R5, R6and R8can be specified, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, fluorine-butyl, 2,2,2-triptorelin, 2-foretel, 2-chloroethyl, 2-bromacil, 2,2,3,3,3-pentafluoropropyl, methoxyethyl and 3-methoxypropyl.

As C1-C4-alkenyl (optionally substituted with halogen), presents R5, R

As C3-C4-quinil (optionally substituted with halogen), presents R5, R6and R8can be specified, for example, propargyl, 2-butynyl, 4,4,4-Cryptor-2-butenyl.

As C1-C4-alkyl (optionally substituted with halogen), presents R9can be specified, for example, methyl, ethyl, n-propyl, isopropyl, sec-butyl, isobutyl, tert-butyl, trifluoromethyl and 2,2,2-triptorelin.

As C1-C4the alkyl represented by R10and R11can be specified, for example, methyl, ethyl, propyl, 2-methylethyl, butyl, 2-methylpropyl, 1-methylpropyl or 1,1 - dimethylethyl.

As C3-C4-alkenyl represented by R10and R11can be specified, for example, allyl, 2-butenyl, 2-methylallyl or 1-methylallyl.

As methyl, optionally substituted with halogen, which is represented by R12can be specified, for example, methyl, deformity and trifluoromethyl.

In these compounds, the preferred position of Deputy CH2-E is p - or m-position relative to the A-O-, especially preferred is a p - position.

In these compounds E predpochtitelnei is the group in which n is 0.

And is preferably one of the groups represented by Q-1, Q-2, Q-3, Q-5 and Q-10, among which preferred is a group, where R2, R3and R4all are hydrogen and m is preferably 0. As a particularly preferred group A can be mentioned a group represented by Q-1. In preferable is a group of the General formula P-3.

When these compounds are asymmetric(in) atom(s) of carbon, whereas in the present invention included both their optically active isomer, (i.e., ( + ) - and (-)-form) having biological activity, and their mixtures in any ratio.

These compounds can be obtained, for example, by reacting a derivative of a phenol of General formula

< / BR>
where R1E and l are defined above, with a compound of General formula

A-L (P-5)

where A is defined above, and L is a halogen (e.g. chlorine, bromine, iodine), mesilate or tosyloxy, in the presence of a base.

This reaction is usually carried out in an inert organic solvent. As the solvent used, you can specify, for example, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; NITRILES, tailgate; alcohols, such as methanol, ethanol and n-propyl alcohol; ethers, such as diethyl ether, diisopropyl ether, 1,2-diethoxyethane, tetrahydrofuran and dioxane; polar solvents such as N,N-dimethylacetamide, dimethylsulfoxide, sulfolan and hexamethylphosphoric triamide; water; or mixtures thereof. In order to ensure a more peaceful course of the reaction, may be added to the phase transfer catalyst, for example, benzyltriethylammonium and Tetra-n-butylammonium.

As used grounds can be specified, for example, alkali metals such as sodium and potassium; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate; hydrides of alkali metals, for example, sodium hydride; alkoxides of metals such as ethoxide sodium and sodium methoxide; and organic bases, such as pyridine, triethylamine, N, N-dimethylaniline and 4-N,N-dimethylaminopyridine.

The reaction is usually carried out in a temperature range from 0oC to 200oC or the boiling point of the used solvent, preferably in the field from the 20oC to 120oC. the Time of reaction is soo 100 mol, preferably from 1 to 2 mol, of each of the compounds of General formula P-5 and the base 1 pray derivative of a phenol of General formula P-4.

After completion of the reaction, the reaction mixture after neutralization, if necessary, by addition of an aqueous solution of ammonium chloride, is subjected to the usual subsequent treatments such as extraction with an organic solvent, and concentrating with the release of these compounds. If necessary, purification can be accomplished by chromatography on silica gel or by recrystallization.

These compounds can be obtained in accordance with the following reaction scheme 1, 2, 3 or 4 (see the end of the description).

In the reaction schemes 1, 2, 3 and 4 R2, R3, R4, R5, R6, R7, R8X, Y, l, and m are defined above; Q1, Q2, Q3, Q4and Q5are halogen (e.g. chlorine, bromine, iodine); and T represents an alkali metal (e.g. sodium, potassium) salt of the Quaternary ammonium or NH2(R5R6.

In tables 1-13 presents some typical examples of these compounds of General formula

< / BR>
where E is any of the E1E2or E3listed below

< / BR>

< / BR>
where R1E and l are defined above, and R13is C1-C4the alkyl (e.g. methyl, ethyl) or phenyl, in the presence of a base.

As possible used grounds can be specified, for example, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as barium hydroxide; and carbonates of alkali metals such as potassium carbonate and sodium carbonate.

The reaction is usually conducted in a solvent. As a possible solvent used can be specified, for example, alcohols, such as methanol, ethanol, n-propyl alcohol, ethylene glycol and diethylene glycol; water; or mixtures thereof.

The reaction is usually carried out in a temperature range from 0oC to 200oC or the boiling point of the used solvent, preferably in the range of 20oC to 120oC. the Time of reaction is usually from 1 to 50 hours.

The amounts of reactants used in the reaction are preferably in the ratio from 1 to 2 mol of base to 1 mol of derived complex ester Vendee of ester of the phenol of General formula P-6 can be obtained, for example, by reacting a derivative of ester of the phenol of General formula

< / BR>
where R1, R13l and L are defined above, with a compound of General formula

E-H (R-8)

where E is defined above in the presence of a base.

This reaction is usually carried out in an inert organic solvent. As a solvent, which can be used can be specified, for example, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; NITRILES, such as acetonitrile, propionitrile and isobutyronitrile; ketones, such as acetone, methyl isobutyl ketone and methyl ethyl ketone; alcohols, such as methanol, ethanol and n-propyl alcohol; ethers, such as diethyl ether, diisopropyl ether, 1,2-diethoxyethane, tetrahydrofuran and dioxane; polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, sulfolan and hexamethylphosphorotriamide; or mixtures thereof.

As the substrate that can be used can be specified, for example, alkali metals such as sodium and potassium; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; carbonates of alkali metals such as sodium carbonate and carbonate Kali is>alkoxides, such as methoxide and ethoxide), such as ethoxide sodium and sodium methoxide; and organic bases such as pyridine, triethylamine, N,N-dimethylaniline and 4-N,N-dimethylaminopyridine.

The reaction is usually carried out in a temperature range from 0oC to 20oC or the boiling point of the used solvent, preferably in the range of 20oC to 120oC. the Time of reaction is usually from 1 to 50 hours.

The amounts of reactants used in the reaction, typically correspond to a ratio of from 1 to 10 mol, preferably 1 to 2 mol, of each of the compounds of General formula P-8 and grounds to 1 mol of derived complex ester of the phenol of General formula P-7.

In table 14, provided at the end of the description, shows some typical examples of the phenolic compounds of General formula P-3 [where E1E2and E3defined in table 1, and the numbering of the position of the substituent (R12)nis such, as shown in table 1].

These compounds possess excellent suppressive action against harmful organisms, for example, harmful insects and harmful mites, such as described below:

Harmful insects Hemiptera:

delphacidae (faced little brown (LaodelphaK striatellus); cycatki (Deltocephalidae) such as Cicada green rice (Nephotettix cincticeps), Cicada green rice (Nephotettix virescens), Cicada green rice (Niphotettix nigropictus), Cicada zigzag rice (Recilia dorsalis), Cicada green tea (Empoasca onukii); and Cicada grape (Arboridia apicalis); aphids (Aphididae) such as cotton aphid (Aphis gossypii) and peach aphid (Myzus persicae); bugs-the defenders (Heteroptera: Pentatomidae); whiteflies (Aleyrodidae), such as whiteflies batata (Bemisia tabaci) and the greenhouse whitefly (Tpialeurodes vaporariorum); scale insects (Coccidae); bugs-lace (Tingidae), listblock (Psyllidae). and so on

Harmful insects Lepidoptera:

butterflies-the liquidation (Pyralidae), such as Ognevka stem (Chilo suppressalis), rice moth (Gnaphalocrocis medinalis) and Ognevka barn South (Plodia interpunctella); moths (Noctuidae), such as scoop ordinary (Spodoptera litura), "marching" rice worms (Spodoptera exigua) and "marching" cabbage worms (Mamestra brassicae), butterflies white and yellow (Pieridae), such as normal mermaid (Pieris rapae crucivora); leafroller (Tortri-cidae), such as Adoxophyes spp., Carposinidae; moth-minelayers the miner (Gracillariidae); Gelechiidae; wananchi (Lymantriidae); Plusidae; Agrotis spp. such as the noctuid moth Agrotis segetum and scoop Upsilon (Agrotis ipsilon); Heliothis spp. ; mol cabbage or a scoop of cabbage (Plutella xylostella); a mole or mole skin coat (Tinea pellionela); mol furniture (Tineola bisselliela) and the eniorhynchus; Aedes spp.; such as Aedes aeqypti and Aedes albopiotus; Anopheles spp., such as Anophelinae sinensis; deruny (Chironomidae), house flies (Musidae), such as the fly room (Musa domestica) and house fly (Muscina stabulans); Calliphoridae; Sarcophagidae; Anthomycidae, such as the fly room small (Fannia canicularis), the larva of a fly germ (Hylemya platura) and fly maggot onion (Hylemya antique), Midge (Cecidomyiidae); fruit flies (Tephritidae), sand Martin (Ephydridae); Drosophila (Drosophilidae); baboonery (Psychodidae); Simuliidae; Tabanidae; jagalchi autumn (Stomoxyidae); and so on

Harmful insects Coleoptera:

flea dlinnoyu, for example, leaf-corneil (Diabrotica virgifera and Diabrotica undecimpunctata; scarabs (Scarabaeidae) such as Anomala cuprea and Anomala rufocuprea; weevils (Curculionidae), for example, the maize weevil (Sitophilus zeamais), rice weevil water (Lissorphoptrus oryzophilus) and bean weevil (Calosohruchys chinensis), chernotsky (Tenebrionidae), for example, the larva of the yellow meal worm (Tenebrio molitor) and khruschak chestnut (Tribolium castaneum); leaf beetles (Shrysomelidae), for example, beetle blaska striped (Phyllotreta striolata) and leaf (Aulacophora femoralis); grinders bread (Anobiidae); Epilachna spp., for example, the ladybug dvadtsativosmiletny (Epilachna vigintioctopunctata); Lyctidae; Kabushiki (Bostrychidae), Longhorn beetles (Cerambycidae), etc.

Harmful insects Dictyoptera:

the red cockroach (Blatella germanica), Periplaneta fuliginosa, the American cockroach (Peroplaneta amer
Thrips palmi, tea thrips (Scirtothrips dorsalis), trips wheat (Thrips hawaiiensis), etc.

Harmful insects Hymenoptera:

ants (Formicidae); these sawflies (Tenthredinidae), such as cabbage Sawfly (Athalia rossae japonensis), etc.

Harmful insects Orthoptera:

the mole crickets (Gryllotalpidae), these grasshoppers (Acrididae), etc.

Harmful insects Aphaniptera;

PUREX processes irritans, etc.

Harmful insects Anoplura:

Pediculus humanus capitis, Phthirus pubis, etc.

Harmful insects Isoptera:

Reticulitermes speratus, termite Coptoternes formosanus, etc.

The spider mites (Tetranychidae):

clasic Carmine spider (Tetranychus cinnabarinus), clasic spider bimaculated (Tetranyohus urticae), clasic spider Kanzowa (Tetranychus kasawai), clasic red citrus (Panonychus citri), clasic red fruit (Panonychus ulmi), etc.

Ticks (Ixodidae):

Boophilus microphus etc.

Scabies mites, Dermatophagoides, Ornithonyssus etc.

If these compounds are used in combination with other insecticides and/or acaricides, the inhibitory effect achieved by the present compounds, can find practical application to many different places when used against a wider variety of harmful insects.

When used as active ingredients for pest control these connections, although they may be used as such without adding any other ingredients usually used in the form of formulations, such as oil sprayers, emulsifiable concentrates, wettable powders, flowable concentrates for aqueous suspensions or aqueous amulti chemically-reactive type or fumigants in the form of a porous ceramic plate; LLV funds or poisoned bait by mixing with solid carriers, liquid carriers, gaseous carriers or lures and, if necessary, adding a surfactant and other additives used in the composition.

These drugs contain these compounds as active ingredients, usually in amounts of from 0.001% to 95% by weight.

As the solid carrier used for the preparation, can be specified, for example, fine powders or granules of clay materials (e.g. kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, Fubasami clay (Fubasami), acid clay), various types of talc, ceramics, other inorganic minerals (e.g. sericite, quartz, sulfur, active carbon, calcium carbonate, hydrated silica), chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride). As a liquid medium can be specified, for example, water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methyl ethyl ketone), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, methylnaphthalene), alifaticheskii the tat), the NITRILES (e.g. acetonitrile, isobutyronitrile), ethers (e.g. diisopropyl ether, dioxane), acid amides (e.g. N,N-dimethylformamide, N,N-dimethylacetamide), halogenated hydrocarbons (e.g. dichloromethane, trichloromethane, carbon tetrachloride, dimethyl sulfoxide, vegetable oils (e.g. soybean oil, cotton oil). As the gaseous carrier or propellant can be specified, for example, flue gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether and carbon dioxide.

As surface-active substances can be specified, for example, alkyl sulphates, alkyl sulphonates, alkylarylsulphonates, alkylsilane ethers and their polyoxyethylene derivatives, esters of polyethylene glycol, esters of polyhydric alcohols and alcohol derivatives of sugar.

As additives for use in the composition can be specified, for example, locking agents or dispersing agents, for example, casein, gelatin, polysaccharides (e.g. starch powder, gum Arabic, cellulose derivatives, alginic acid), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (e.g. polyvinyl alcohol, polyvinylpyrrolidone, on the BHT (2,6-di-tert-butyl-4-METHYLPHENOL), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or their esters.

As the main product for fumigants samosgorayuschey type can be specified, for example, tools, burning with heat, such as a nitrate salt, a nitrite salt, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose and wood powder; stimulants thermolysis, such as salts of alkali metals, salts of alkaline earth metals, dichromate and chromates; substances that produce oxygen, for example, potassium nitrate; means to support combustion, such as melamine and wheat starch; fillers, such as diatomaceous earth; and a binder such as synthetic paste.

As the main product for fumigants chemical reaction type can be specified, for example, exothermic agents, for example, sulfides, polysulfides, hydrosulfide and hydrates of salts of alkali metals and calcium oxide; catalysts, such as carbon materials, iron carbide and activated clay; organic foaming agents such as azodicarbonamide, benzosulfimide, dinitrophenylhydrazone.

As the main product for poison baits can be specified, for example, components of lures, such as powder, grain, vegetable oil, sugar and crystalline cellulose; antioxidants such as dibutylester and nordihydroguaiaretic acid; preservatives such as dehydroacetic acid; a means of preventing an error in feeding, such as powder, red pepper, and tools with alluring scents, for example, the smell of cheese and the smell of onions.

Compositions, such as liquid concentrates (for aqueous suspensions or aqueous emulsions) are obtained usually by suspension 1 - 75% of the compound in water containing 0.5 - 15% dispersant, about 0.1 - 10% suspendida agents (for example, protective colloids or compounds, which impart thixotropy) and 0 - 10% of appropriate additives such as antifoams, corrosion-resistant tools, stabilizers, substances that enhance wettability, tools that enhance permeability, antifreeze agents, antifungal agents, anti-smoke agent). To obtain oil suspensions instead of water you can use different oils in which these compounds are essentially insoluble. As a protective colloid can e substances, giving thixotropy can be specified, for example, bentonite, aluminumagnesium, xanthan gum and polyacrylic acid.

The compositions thus obtained, is used as such, or after dilution with water or etc., They can be used when mixing or no mixing with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feed, etc.

When these compounds are used as tools for pest control in agriculture, the rate of application is usually from 0.001 to 500 g, preferably from 0.1 g to 500 g/10 ar (1000 m2). Formulations such as emulsifiable concentrates, wettable powders and flowable concentrates are usually used after dilution with water to a concentration of application is from 0.0001 to 1000 ppm. Formulations such as granules and dusty used as such without dilution. When these compounds are used as a means for combating harmful organisms to prevent epidemics, their mixtures, such as emulsifiable concentrates, wettable powders and flowable consecutive, such as oil sprayers, aerosols, fumigants, ULV tools and poison baits are used as such.

All these application quantity and concentration of the coating can vary depending on the type of composition, time of application, place of application, method of application, kind of harmful organisms, such as insects, harmful mites and ticks, severity and other conditions, and they can be increased or decreased without limitation with respect to the above-mentioned range.

Examples

The present invention is further illustrated by the following examples of the preparation, examples of compositions and examples of tests; however, the present invention is not limited to these examples. The following examples of the preparation of these compounds.

An example of obtaining 1.

4-(1-Pyrazolyl)METHYLPHENOL [obtained in the following way: a mixture of pyrazole (351 mg), 4-acetoxybenzoic (1 g), anhydrous potassium carbonate (1.30 grams) and anhydrous N, N-dimethylformamide (30 ml) was heated at 100oC and stirring for 3 hours. Then the reaction mixture was poured into ice saturated aqueous solution of ammonium chloride (200 ml) which was extracted twice ethylacetate magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in ethanol (20 ml) to which was added a 5N aqueous solution of sodium hydroxide (1,03 ml) and the mixture was stirred at room temperature overnight. Then to the reaction mixture were added water (10 ml) and concentrated under reduced pressure to remove most of the ethanol. The residue was poured into ice mixture of acetic acid (310 mg) and water (100 ml) and was extracted twice with ethyl acetate (50 ml). The organic layers were combined, washed with a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure] was dissolved in anhydrous N,N-dimethylformamide (20 ml), was added methyl ether 2 - chloroethylamino acid (710 mg) and potassium carbonate (1,43 g) and the mixture was heated at 60oC under stirring for 6 hours. Then the reaction mixture was poured into ice saturated aqueous solution of ammonium chloride (100 ml), and was twice extracted with ethyl acetate (50 ml). The organic layers were combined, washed with a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel to obtain 128 mg of methyl ester of 2- [4- (1-pyrazolyl)methylphenoxy] this is of 2.

To a mixture of potassium carbonate (435 mg), 2-chloro-4-(2-2H-1,2,3-triazolyl) METHYLPHENOL (300 mg) and anhydrous N,N-dimethylformamide (30 ml) was added dropwise anhydrous N,N-dimethylformamide solution (2 ml) of methyl ester of 2-chloroethylamino acid (216 mg) at room temperature and stirring. Then this mixture was heated at 60oC under stirring for 6 hours and poured into ice saturated aqueous solution of ammonium chloride, which was extracted with ethyl acetate. The organic layer was washed with water and then a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel and received 329 mg methyl ester 2-[2-chloro-4-(1-pyrazolyl)methylphenoxy]-ethylcarbamate acid (compound 7). Yield 74%.

Example for the preparation of 3.

4-(1-Pyrazolyl)METHYLPHENOL [obtained by the method described in square brackets in the example of obtaining 1] was dissolved in anhydrous N,N-dimethylformamide (20 ml) to which was added ethyl ester 2-chloroethylamino acid (782 mg) and potassium carbonate (1,43 g) and the mixture was heated at 60oC when was stirred for 6 hours. Then the reaction mixture was poured into chilled LDO the definition layers were mixed, washed with a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel to obtain 149 mg of ethyl ester of 2-[4-(1-pyrazolyl)methylphenoxy] ethylcarbamate acid (compound 1). Yield of 11% (per 4-acetoxybenzoic).

Example 4.

2-Chloro-4-(1-pyrazolyl)METHYLPHENOL [obtained in the following way: a mixture of pyrazole (275 mg), 4-acetoxy-3-chlorobenzylamino (1 g), anhydrous potassium carbonate (1,11 g) and anhydrous N,N-dimethylformamide (30 ml) was heated at 100oC under stirring for 3 hours. Then the reaction mixture was poured into ice saturated aqueous solution of ammonium chloride (200 ml), which was twice extracted with 50 ml ethyl acetate. The organic layers were combined, washed with a saturated solution of sodium chloride (50 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in ethanol (20 ml) to which was added a 5N aqueous solution of sodium chloride (0,97 ml) and the mixture was stirred at room temperature overnight. Then to the reaction mixture were added water (10 ml) and concentrated under reduced pressure to Udaloy was twice extracted with 50 ml ethyl acetate. The organic layers were combined, washed with a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure] was dissolved in anhydrous N, N-dimethylformamide (20 ml) to which was added ethyl ester 2-chloroethylamino acid (613 mg) and potassium carbonate (1.23 g), and the mixture was heated at 60oC and stirring for 6 hours. Then the reaction mixture was poured into ice saturated aqueous solution of ammonium chloride (100 ml), which was twice extracted with ethyl acetate (50 ml). The organic layers were combined, washed with a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel and received 189 mg ethyl ester 2-[2-chloro-4-(1-pyrazolyl)methylphenoxy]ethylcarbamate acid (compound 2). Exit 14% (on the basis of 4-acetoxy-3-chlorobenzylamino).

Example of getting a 5.

To a mixture of potassium carbonate (298 mg), 2-chloro-4-(1-pyrazolyl)METHYLPHENOL (300 mg) and anhydrous N,N-dimethylformamide (200 ml) was added dropwise anhydrous N, N-dimethylformamide solution (2 ml) of 4-chlorobenzylchloride (232 mg) at room temperature and stirring. Then this blend of Peor ammonium chloride and was extracted with ethyl acetate. The organic layer was washed with water and then a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel with getting 454 mg of 2-chloro-1-(4-chlorobenzoyloxy)-4-(1-pyrazolyl)methylbenzene (compound 4). Yield 95%.

Example of getting a 6.

To a mixture of potassium carbonate (387 mg), 2-chloro-4-(2-pyridone-1-yl)METHYLPHENOL (300 mg) and anhydrous N,N-dimethylformamide (200 ml) at room temperature and stirring was added dropwise anhydrous N,N-dimethylformamide solution (2 ml) ethyl ester 2-chloroethylamino acid (212 mg). This mixture was stirred at 60oC for 6 hours and poured into ice saturated aqueous solution of ammonium chloride, which was extracted with ethyl acetate. The organic layer was washed with water and then a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel with getting 303 mg of ethyl ester 2-[2-chloro-4-(2-pyridone-1-yl)methylphenoxy]ethylcarbamate acid (compound 34). Yield 68%.

Example of getting a 7.

To a mixture of potassium carbonate (211 mg), 4-(5-chloro-2-p and was added dropwise anhydrous N,N-dimethylformamide solution (2 ml) of 2-chloro-5-(chloromethyl)pyridine (206 mg). Then this mixture was mixed at the same temperature for 12 hours and poured into ice saturated aqueous solution of ammonium chloride, which was extracted with ethyl acetate. The organic layer was washed with water and then a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel with getting 397 mg of 1-[-(2-chloropyridin-5-yl)metiloksi] -4-[(5-chloro-2-pyridine-1-yl)methyl] benzene (compound 29). Yield 87%.

Example receipt 8.

To a mixture of anhydrous N,N-dimethylformamide (5 ml) and sodium hydride (60% oil dispersion) (62 mg) was added pyrazole (100 mg) and the mixture was stirred for 30 minutes. Then was added dropwise anhydrous N,N-dimethylformamide solution (5 ml) of 3-[4- (1-pyrazolyl)methylphenoxy]propylamino (obtained in reference example get 1, described below) (434 mg) and the mixture was stirred at room temperature for 5 hours. Then the reaction mixture was diluted with ethyl acetate (50 ml), washed twice with a saturated aqueous solution of ammonium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting oil was subjected to column chromatog the color masla. Yield 82%.

Example of receipt 9.

To a mixture of 2-[4-(1-pyrazolyl)methylphenoxy] ethylamine (obtained in reference example getting 2, described below) (300 mg), triethylamine (210 mg) and anhydrous toluene (20 ml) under stirring and ice cooling was added dropwise an anhydrous toluene solution (2 ml) cyclopropanecarbonitrile (159 mg). Then the mixture was stirred at a temperature of from 0oC to 10oC for 1 hour and poured into ice saturated aqueous solution of ammonium chloride, which was extracted with ethyl acetate. The organic layer was washed with water and then a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel to obtain 100 mg of N-{2-C4-(1-pyrazolyl)methylphenoxy] ethyl} -cyclopropanecarboxamide (compound 14). The output 25%.

Example 10.

To a mixture of 2-[4-(1-pyrazolyl)methylphenoxy]ethanol obtained in reference example for the preparation of 3, described below) (500 mg), triethylamine (255 mg) and dry toluene (20 ml) was added dropwise an anhydrous toluene solution (1 ml) utilizationof (179 mg). Then the mixture was stirred at room temperature over 87 mg of ethyl ester of 2-[4-(1-pyrazolyl)-methylphenoxy] ethylcarbamate acid (compound 37). Exit 13%.

An example of obtaining 11.

A mixture of 4-(1-pyrazolyl)METHYLPHENOL [obtained in the same manner as that described in square brackets in the example of obtaining 1] (2 g), glycidol (936 mg) in dry xylene (10 ml) and a catalytic amount of Tetramethylammonium was stirred at 60oC for 6 hours. Then the reaction mixture was subjected to chromatography on silica gel with getting 941 mg of 2-hydroxy-3-[4-(1-pyrazolyl)methylphenoxy]propanol.

A mixture of 2-hydroxy-3-[4-(1-pyrazolyl)methylphenoxy]propanol (941 mg), propionic aldehyde (308 mg), dry toluene (20 ml) and catalytic amount of p-toluenesulfonic acid was heated under reflux with stirring for 4 hours. Then the reaction mixture was poured into ice 5% aqueous solution of acid sodium carbonate (100 ml), then was extracted twice with ethyl acetate (50 ml). The organic layers were combined, washed with a saturated solution of sodium chloride, dried with anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel with getting 723 mg of 4-[4-(1-pyrazolyl)methylphenoxy]methyl-2-ethyl-1,3-dioxane (compound 38). Exit 66% (based on 2-hydroxy-3-[4-(1-pyrazolyl)MetLife who by their numbers and physical properties (through the definition of each substituent of compounds of General formula P-1).

The following examples of the preparation of intermediate compounds of General formula P-2.

Example obtain the intermediate compound 1. Getting 2-chloro-4-(1-pyrazolyl)METHYLPHENOL.

(1) preparation of 2-chloro-4-were-2,2-dimethylpropanoate. To a mixture of 2-chloro-4-METHYLPHENOL (100 g), triethylamine (92,3 g) and anhydrous tetrahydrofuran (1 l) at a temperature of 5oC to 10oC and stirring for 1 hour was added dropwise trimethylacetyl chloride (93.0 g). Then after stirring at the same temperature for 3 hours the reaction mixture was poured into a mixture of ice water, which was extracted with diethyl ether. The organic layer is washed with 3% aqueous hydrochloric acid solution and then with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The oil obtained was distilled under reduced pressure and was received was 155.3 g of 2-chloro-4-were-2,2-dimethylpropanoate in the form of a colorless transparent liquid. The yield of 97.7%.

So Kip. 113-8oC/5 mm RT.article nD21,81,4949.

(2) Obtaining 4-methyl bromide-2-chlorophenyl-2,2-dimethylpropanoate.

To a mixture of 2-chloro-4-were-2,2-dimethylpropanoate (50.0 g), anhydrous sodium carbonate (23,8 g) and carbon tetrachloride (500 hours) was added dropwise bromine (35.2 g). When the control reaction (red color of bromine disappeared) if necessary, add a very small amount of benzoyl peroxide, and the stirring continued until the reaction is completed.

After completion of the reaction, the reaction mixture was cooled to 10oC, and undissolved products were removed by filtration with suction, and then concentrated under reduced pressure obtaining of 68.7 g of 4-methyl bromide-2-chlorophenyl-2,2-dimethylpropanoate in the form of a pale yellow solid product. The apparent output of 101.7%. The solid product was recrystallized from a solvent mixture of hexane and toluene to obtain white crystals.

So pl. 63,3oC.

(3) Obtain 2-chloro-4-(1-pyrazolyl)were-2,2-dimethylpropanoate.

A mixture of pyrazole (15.3 g), sodium hydride (60%, 8,99 g) and anhydrous N, N-dimethylformamide (200 ml) was stirred at a temperature of from 60oC to 70oC in nitrogen atmosphere for 2 hours. After the evolution of hydrogen ceased, the mixture was cooled to 10oC. To this mixture at room temperature and stirring for 1 hour was added dropwise anhydrous N,N-dimethylformamide solution (300 ml) of 4-methyl bromide-2-chlorophenyl-2,2-dimethylpropanoate (68 g) and the mixture was stirred with ethyl acetate. The organic layer was washed with a saturated aqueous solution of ammonium chloride and then with a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography on silica gel to obtain 39.5 g of 2-chloro-4-(1-pyrazolyl)were-2,2-dimethylpropanoate in the form of a colorless oil. An output of 60%. nD21,81,5461.

(4) to Obtain 2-chloro-4-(1-pyrazolyl)METHYLPHENOL.

A mixture of 2-chloro-4-(1-pyrazolyl)were-2,2-dimethylpropanoate (20,0 g), 20% aqueous sodium hydroxide solution (50 ml) and ethanol (300 ml) was heated under reflux for 5 hours. Then the reaction mixture, to which was added water, concentrated under reduced pressure, and have established a pH of 6.0 using concentrated hydrochloric acid. The mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography on silica gel with receipt of 11.5 g of 2-chloro-4-(1-pyrazolyl)METHYLPHENOL in the form of white crystals. Output 80,7%. So pl. 152,9oC.

Example obtain the intermediate compound 2.

Getting 2-chloro-4-(2-2H-1,2,3-the ptx2">

A mixture of 2H-1,2,3-triazole (of 2.26 g), sodium hydride (60%, 1.31 g) and anhydrous N,N-dimethylformamide (100 ml) was stirred at a temperature of from 60 to 70oC in nitrogen atmosphere for 2 hours. After the evolution of hydrogen ceased, the mixture was cooled to 10oC. To this mixture at room temperature and stirring for 1 hour was added dropwise anhydrous N, N-dimethylformamide (150 ml) solution of 4-methyl bromide-2-chlorophenyl-2,2-dimethylpropanoate (10 g) and the mixture was stirred at 80oC for 1 hour. After cooling, the reaction mixture was poured into ice water, then extracted with ethyl acetate. The organic layer was washed with a saturated aqueous solution of ammonium chloride and then with a saturated solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography on silica gel to obtain 2-chloro-4-(2-2H-1,2,3-triazolyl)were-2,2-dimethylpropanoate.

(2) Obtain 2-chloro-4-(2-2H-1,2,3-triazolyl)METHYLPHENOL.

A mixture of 2-chloro-4-(2-2H-1,2,3-triazolyl)were-2,2-dimethylpropanoate (3 g), 20% aqueous sodium hydroxide solution (10 ml) and ethanol (60 ml) was heated under reflux for 5 hours. Then the reaction smesovany hydrochloric acid. The mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography on silica gel to obtain 2-chloro-4-(2-2H-1,2,3-triazolylmethyl)phenol. In accordance with the same method it is possible to obtain 4-(1-pyrazolyl)METHYLPHENOL, 4-(2-2H-1,2,3-triazolyl)METHYLPHENOL, 2-methyl-4-(2-2H-1,2,3-triazolyl)METHYLPHENOL and 2-methyl-4-(1-pyrazolyl)METHYLPHENOL.

Example obtain the intermediate compound 3.

(1) preparation of 2-chloro-4-(2-pyridone-1-yl)were-2,2-dimethylpropanoate.

A mixture of 2-pyridone (3.11 g) of sodium hydride (60%, 1,31) g and anhydrous N, N-dimethylformamide (100 ml) was stirred at a temperature of from 60oC to 70oC in nitrogen atmosphere for 2 hours. After the evolution of hydrogen ceased, the mixture was cooled to 10oC. To this mixture at room temperature and stirring for 1 hour was added dropwise anhydrous N,N-dimethylformamide (150 ml) solution of 4-methyl bromide-2-chlorophenyl-2,2-dimethylpropanoate (10 g) and the mixture was stirred at 80oC for 1 hour. After cooling, the reaction mixture was poured into water and was extracted with ethyl acetate. The organic layer was washed the major magnesium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography on silica gel with receipt of 7.60 g of 2-chloro-4-(2-pyridone-1-yl)were-2,2-dimethylpropanoate in the form of white crystals. The yield was 73%. So pl. 145, 2mmoC.

(2) Obtain 2-chloro-4-(2-pyridone-1-yl)METHYLPHENOL.

A mixture of 2-chloro-4-(2-pyridone-1-yl)were-2,2-dimethylpropanoate (7.6 g), 20% aqueous sodium hydroxide solution (19 ml) and ethanol (200 ml) was heated under reflux for 5 hours. Then the reaction mixture to which was added water, concentrated under reduced pressure, and have established a pH of 6.0 using concentrated hydrochloric acid. The mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography on silica gel to obtain 3.98 g of 2-chloro-4-(2-pyridone-1-yl)METHYLPHENOL in the form of white crystals. Yield 71%. So pl. of 193.5oC.

Examples get the source compounds used in the examples get 8 and 9 will be described respectively in the following reference production examples 1 and 2.

Reference example get 1.

To a mixture of 4-(1-pyrazolyl)METHYLPHENOL (5 g), 1,3-dibromopropane (11,59 g) and water is), and heated under reflux for 30 minutes. Then the reaction mixture was heated under reflux with stirring for one hour, cooled to room temperature and was extracted with diethyl ether (300 ml). The organic layer is washed with 5N aqueous solution of sodium hydroxide and then with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to chromatography on silica gel with 3-[4-(1-pyrazolyl) methylphenoxy] propyl bromide (4,76 g) as white crystals. Yield 56%. So pl. 42 - 47oC.

Reference example getting 2.

(1) To a mixture of 4-(1-pyrazolyl)METHYLPHENOL (15 g), 32,35 g 1,2-dibromethane and water (150 ml) under stirring was added dropwise an aqueous solution of sodium hydroxide (4,13 g) dissolved in water (30 ml), and heated under reflux for 30 minutes. Then the reaction mixture was heated under reflux with stirring for one hour, cooled to room temperature and was extracted with diethyl ether (300 ml). The organic layer is washed with 5N aqueous solution of sodium hydroxide and then with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. in the form of white crystals. Yield 47%. So pl. 63 - 65oC.

(2) a Mixture of 2-[4-(1-pyrazolyl)methylphenoxy]ethylbromide (5.0 g), phthalimide potassium (3,95 g) and dry dimethyl sulfoxide (50 ml) was heated at 60oC and stirring for 15 hours. Then the reaction mixture was poured into ice water and was extracted with ethyl acetate. The organic layer was washed with water and then a saturated solution of sodium chloride, dried over magnesium sulfate and concentrated under reduced pressure. The crystalline residue was recrystallized from a solvent mixture consisting of ethyl acetate, toluene and ethanol, obtaining 3.0 g N-{2-[4-(1-pyrazolyl)methylphenoxy]ethyl}phthalimide in the form of white crystals. Yield 49%. So pl. 142 - 145oC.

(3) a Mixture of N-{2-[4-(1-pyrazolyl)methylphenoxy]ethyl]phthalimide (2,79 g), hydrazine hydrate (0,47 g) and methanol was heated under reflux with stirring for 1 hour. Then the reaction mixture to which was added methylene chloride (200 ml), concentrated under reduced pressure to remove most of the methanol. The organic layer is washed with 2n sodium hydroxide, dried over anhydrous sodium sulfate and concentrated under reduced pressure to get 1,69 g of 2-[4-(1 - pyrazolyl)methylphenoxy]ethylamine as a colorless memoro in example 10.

Reference example preparation of 3.

Getting 2-[4-(1-pyrazolyl)methylphenoxy]ethanol.

A mixture of 4-(1-pyrazolyl)METHYLPHENOL (60 g), ethylchloride (54,9 g), potassium carbonate (95,1 g) and anhydrous dimethylformamide (500 ml) was heated at 50oC and stirring for 5 hours and then cooled to room temperature. The reaction mixture was poured into water (1 l) and was extracted twice with ethyl acetate (200 ml). The organic layers were combined, washed with water, saturated aqueous ammonium chloride and then with saturated sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain crude ethyl-4-(1-pyrazolyl)methylphenoxyacetic in the form of butter.

To anhydrous tetrahydrofuranate (500 ml) suspension of lithium aluminum hydride (38 g) at -78oC and stirring for 30 minutes was added dropwise a solution of the above crude ethyl-4-(1-pyrazolyl)methylphenoxyacetic dissolved in anhydrous tetrahydrofuran (100 ml). The mixture was stirred at the same temperature for 1 hour and then at -20oC for a further 2 hours. The reaction mixture was again cooled to -78oC, and then at the same temperature was added dropwise water (38 ml), 15% aqueous solution g is that sodium (200 g) and the mixture was stirred at room temperature for 2 hours. Then the reaction mixture was filtered through celite and the filtrate was concentrated under reduced pressure. The residue was subjected to chromatography on silica gel with receipt of 64.5 g of 2-[4-(1-pyrazolyl)methylphenoxy]ethanol as white crystals. Yield 86% (based on 4-(1-pyrazolyl)METHYLPHENOL). So pl. 56 - 58oC.

Here are examples of compositions for means of combating harmful organisms containing these compounds as active ingredients, in which "parts" are given in mass units, and these connections are marked with the numbers that are given in tables 15 to 18.

Sample preparation 1.

Emulsifiable concentrates.

Ten parts of each of the present compounds 1 to 39 was dissolved in 35 parts of xylene and 35 parts of dimethylformamide, to which was added 14 parts steelfinish of polyoxyethylene ether and 6 parts chalcedonianscelebrate and the mixture is well stirred to give 10% emulsifiable concentrate of each compound,

Example of preparation 2.

Wettable powders.

Twenty parts of each of the present compounds 1 to 39 was added to a mixture consisting of 4 parts of acrylourethane, 2 parts salicylaldiminato, 20 parts encodes ivali using an electric mixer, getting a 20% wettable powder of each compound.

Sample preparation 3.

Granules.

To 5 parts of each of the present compounds 1 to 39 were added 5 parts of fine powder of synthetic hydrated silicon oxide, 5 parts nitrilotriacetate, 30 parts of bentonite and 55 parts of clay and the mixture well stirred. Then to this mixture was added an appropriate amount of water and the mixture was further stirred, granulated in a granulator and air-dried to obtain 5-percentage of granules each connection.

Sample preparation 4.

Dusty.

One part of each of the present compounds 1 to 39 was dissolved in an appropriate amount of acetone, to which was added 5 parts of fine powder of synthetic hydrated silicon oxide, 0.3 part of PAP and 93,7 part of the clay and the mixture was stirred with an electric stirrer. After removal of the acetone by evaporation got 1% dust each connection.

Sample preparation 5.

Aqueous suspension.

Twenty parts of each of the present compounds 1 to 39 and 1.5 parts of trioleate sorbitan mixed from 28.5 parts of an aqueous solution containing 2 parts by palmost sand mill, added 40 parts of an aqueous solution containing 0.05 part of xanthan resin and 0.1 part of aluminumagnesium, and then 10 parts of propylene glycol. The mixture was stirred and received a 20% aqueous suspension of each connection.

Sample preparation 6.

Oil sprayers.

First, 5 parts of xylene and 5 parts of trichloroethane was dissolved 0.1 part of each of the present compounds 1 to 39. Then the solution was mixed from 89.9 parts of deodorized kerosene was obtained with 0.1% oil sprayer each connection.

Example of preparation 7.

Oil aerosols.

First for dissolution was mixed with 0.1 part of each of the present compounds 1 -39, 0.2 parts of tetramethrin, 0.1 part of d - phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene. The solution was placed in an aerosol container, which is then supplied valve. Under high pressure through the valve downloaded 30 parts of propellant (liquefied petroleum gas), it was obtained an oil spray of each compound.

Sample preparation 8.

Water sprays.

First for dissolution was mixed with 0.2 part of each of the present compounds 1 to 39, 0.2 part of d-allethrin, 0,2 name, registered firm Atlas Chemical Co. (Atlas Chemical Co. )] . Mix together with 50 parts of pure water were placed in an aerosol container, which was supplied with the valve. Under high pressure through this valve was loaded with 40 parts of a propellant (liquefied petroleum gas), it was obtained an aqueous aerosol of each compound.

Sample preparation 9.

Spiral from mosquitoes.

To 0.3 g of each of the present compounds 1 to 39 were added 0.3 g of allethrin and the mixture was dissolved in 20 ml of acetone. The solution is evenly mixed with with 99.4 g of a carrier for spiral from mosquitoes (obtained by mixing the powder Taboo, pyrethrum powder and wood flour at a ratio of 4:3:3), and was added 120 ml of water. The mixture was well mixed, molded and dried, thus obtaining the spiral from mosquitoes from each connection.

Sample preparation 10.

Electric mats from mosquitoes.

To 0.4 g of each of these compounds 1-39, 0.4 g of d-allethrin and 0.4 g of paperbacked was added to dissolve acetone in an amount such that the total volume was equal to 10 ml of This solution in the amount of 0.5 ml is uniformly impregnated basis for electric mats from mosquitoes (obtained by pressing a fibrous mixture of chlorine is tons of mosquitoes from each connection.

Example of preparation 11.

Compositions, heat with the formation of smoke.

First, the appropriate amount of acetone was dissolved 100 mg of each of these compounds 1-39, and then the solution was saturated porous ceramic plate size 4.0 cm x 4.0 cm and a thickness of 1.2 cm, while receiving preheat the fumigant from each connection.

Sample preparation 12.

Poisoned bait.

First, 0.5 ml of acetone was dissolved 10 mg of each of the present compounds 1 to 39, this solution was added to 5 g of the solid powder bait for animals (solid food powder feed CE-2, trade name, registered company Japan Clea Co., Ltd (Japan Kli Co., Co., Ltd.)), and uniformly mixed. Then after removal of the acetone by air drying was received 0.5% of poisoned bait each connection.

The following examples of tests show that these compounds are suitable as active ingredients to combat harmful organisms in these examples, the present compounds represented by numbers, which are given in tables 15 to 18.

Example test 1.

Activity against larvae of delfiniti brown ricinine, obtained in accordance with example 1 drug, was diluted with water to a prescribed concentration and sprayed seedlings of rice grown in plastic cups with a consumption rate of 20 ml/2 vessel. After air drying for ten larvae of delfiniti brown rice (Nilaparvata lugens) freely taken out in each Cup. After 10 days using the following equation 1 was determined by the ratio of inhibition of hatching:

The results are shown in table 19.

Example of test 2.

Activity against larvae of delphacidae brown rice, inhibiting metamorphosis (heavy processing).

Emulsifiable concentrate of the test compound obtained according to example 1 drug, was diluted with water to a prescribed concentration and placed in a polyethylene Cup with a volume of 650 ml After the Cup was covered with a lid having a hole, the rice seedlings grown in a polyethylene Cup with a volume of 30 ml, was placed in the hole so that the bottom was flooded with a chemical solution. Two days after treatment in the Cup freely taken out ten larvae of delphacidae brown rice (Nilaparvata Lugens). After 10 days using the above equation 1 tx2">

Activity against mosquito ordinary, inhibiting hatching.

Emulsifiable concentrate of the test compound obtained according to example 1 drug, diluted with water, and 0.7 ml of this dilution was added to 100 ml of ion-exchange water (concentration of active ingredient 3,5 frequent. per million). It easily put twenty larvae of ordinary mosquito (Culex pipiens pallens) last age stage and taken out for 8 days, giving them the bait. Using the above equation 1 was determined by the ratio of inhibition of hatching. The results are shown in table 21.

Example test 4.

Testing of insecticides against cotton aphid (Aphis gossypii).

Emulsifiable concentrate of the test compound obtained according to example 1 drug, was diluted with water to a prescribed concentration and poured on the part located close to the roots of cucumbers grown in plastic cups, with a consumption rate of 100 cm3/vessel. 3 days after spraying on the leaves freely taken out five adult aphids. 14 days after free removal using the following equation 2 was determined reference value:

Kered treatment untreated group; Cai- the number of insects during observations in the untreated group; Tb- the number of insects before the treatment in the experimental group; and Tai- the number of insects at the time of observation in the experimental group. The results are shown in table 22.

Industrial applicability.

In accordance with the present invention proposed new derivatives of simple ether having an excellent inhibitory effect against harmful organisms. These simple derivatives of ether are used as active ingredients of pest control.

1. Derivative of a simple ester of the General formula

< / BR>
where R1is halogen;

A represents any of the groups having the following formulas Q-1 - Q-11:

-CH(R2)-(CH2)m-CH(R3)-N(R4)-C(=Y)-X-R5(Q-1)

-CH(R2)-(CH2)m-CH(R3)-W-C(=Y)-cyclo-C3H5(Q-3)

-CH(R2)-(CH2)m-CH(R3)-CH2-B (Q-5)

< / BR>
< / BR>
R2, R3and R4, independently, are hydrogen or stands;

R5is1- C4-alkyl;

R6is a group represented by R5or hydrogen;

hydrogen, WITH1- C4-alkyl;

In is a group of General formula

E is a group of General formula

< / BR>
< / BR>
< / BR>
R12is halogen or stands;

X and Y, independently, are oxygen or sulfur;

W is NH; and

l, m and n, independently, are an integer from 0 to 2.

2. Derivatives of simple ether under item 1, where E is a group of General formula

< / BR>
where R12and n are defined above.

3. Derivatives of simple broadcast on p. 2, where n is equal to 0.

4. Derivatives of simple ether under item 1, where a is a group represented by Q-1, Q-3 or Q-5.

5. Derived simple ether under item 1, where a is a group represented by Q-1, Q-3 or Q-5 or R2, R3and R4are hydrogen; and m is 0.

6. Derived simple ether under item 1, which represents a methyl ester-2-[4-(1-pyrazolyl)methylphenoxy]ethylcarbamate acid.

7. Derived simple ether under item 1, representing 1-{3-[4-(1-pyrazolyl)methylphenoxy]propyl}pyrazole.

8. Derived simple ether under item 1, N represents-{2-[4-(1-pyrazolyl)methylphenoxy]ethyl}cyclopropanecarboxylic.

9. Derived simple ether under item 1, representing soboli, including the active ingredient is a derivative of a simple broadcast, media and other additives, characterized in that as a derived simple ether it contains a connection on p. 1 in an effective amount.

11. The connection of the phenol of General formula

< / BR>
where E is a group of the General formula:

< / BR>
where R12is halogen or stands, and n is an integer from 0 to 2.

 

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