RU2076599C1 - Insecticide composition - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: insecticide composition has 0.5-25 wt.-% of compound of the formula ArCR′R²CH = CHCH₂D where: Ar - phenyl-group substituted with one or two halogen atoms, C₁-C₄-haloidalkyl, C₁-C₄-alkoxy, C₁-C₄-haloidalkoxy or methylenedioxy or naphthyl possibly substituted with halogen; R′ and R² together with carbon atom to which they linked form cyclopropyl or 2,2-dihalogencyclopropyl group; D - 3-phenoxyphenyl or 4-fluoro-3-phenoxyphenyl, special additions, the balance. Composition is used for plant protection. EFFECT: enhanced effectiveness of composition. 1 tbl

Description

 The invention relates to pesticides, in particular to insecticidal compositions based on new compounds.

 The inventors have identified drugs that, being effective in controlling a wide range of insects and other pests, are of particular interest in combating the infection of rice crops.

The invention provides an insecticidal composition based on new compounds of formula (I)
Ar-CR ¹ R ² -CH = CH-CH ² -D,
where Ar is phenyl substituted with one or two halogen atoms, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or methylenedioxy or naphthyl groups, optionally substituted with a halogen atom.

R ₁ and R ₂ together with the carbon atoms to which they are attached represent cyclopropyl, possibly substituted with two halogen atoms,
D-3-phenoxyphenyl or 4-fluoro-3-phenoxyphenyl.

Although in more preferred embodiments, preparative methods for the preparation of compounds (I) are such that the product does not contain a structural isomer of the formula
ArCR ₁ R ₂ CH ₂ CH CH-D (II)
some techniques may result in an isomer contaminated product.

 Although compound (I) should preferably be substantially free from the presence of compound (II), contamination of less than 10%, typically less than 1% of its amount in molar terms, may be allowed, the presence of more than 50% of compound II, is a rarity.

 When the compound of formula (I) is chiral, it naturally exists in various stereoisomeric forms. The present invention encompasses both mixtures of stereoisomers and individual stereoisomers.

где группы R¹, R² и R³ раскрыты в описании к патенту.UK Patent 2,120,664 A describes a group of aromatic alkane derivatives useful as insecticides against agricultural and garden pests, of the formula

where the groups R ¹ , R ² and R ^{3 are} disclosed in the description of the patent.

The vast majority of the compounds described in this application are such that R ¹ and R ² represent alkyl groups. Three examples of compounds are given in which R ¹ and R ^{2 are} joined to form a cycloalkyl group (cyclobutyl). These compounds were tested on grasshoppers of green rice leaf. The compounds of this invention differ from compounds CB 2120664A by the presence of an olefin group, which gives them improved insecticidal activity, as demonstrated by comparing the compounds A of the present invention and B corresponding to the claims.

 Compositions based on compounds of formula I can be used to control pests in the household, horticulture, agriculture and medicine, including veterinary medicine.

 The invention also encompasses a method for preparing a pesticidal composition, which comprises mixing a compound of formula (I) with an inert carrier or diluent, thereby giving the composition.

 Compositions can be presented in the form of dusts and granular solids, wettable powders, mosquito coils and other solid preparations, or in the form of emulsions, emulsifiable concentrates, sprays and aerosols and other liquid preparations after the addition of suitable solvents, diluents and surfactants.

 Compositions suitable for farming and horticulture requiring the active ingredient to have significant photostability are of particular interest, in particular compositions suitable for processing crops, such as rice, that are cultivated under environmental conditions that allow Compound I to be exposed to fish. It should be noted that the safety of fish in such applications is of paramount importance and suitable compositions should not contain fish toxic ingredients.

 The pesticidal compositions of the invention typically contain 0.001-25% by weight of a compound of formula (I), but the compositions may also contain higher concentrations of the active ingredient of formula (I), for example up to 95%, in compositions intended for sale as concentrates diluted by the end user before use.

 Compositions according to the invention may, depending on the intended use, include diluents such as hydrocarbon oils, for example xylene and other petroleum fractions, water, anionic, cationic and nonionic surfactants, antioxidants and other stabilizers, as well as perfumes and coloring agents. These inert ingredients can be of the type and proportions that are traditionally used in pesticidal compositions containing pyrethroid-like compounds.

 In addition to these inactive ingredients, the compositions according to the invention may contain one or more additional active ingredients, which may be other pyrethroid type or other types of pesticidal compounds, and the composition may also include synergists, especially the type that is capable of synergizing with the activity of natural pyrethrin and peritroid-like insecticides. Synergists of this type include piperonyl butylate, tropital and seamex.

 The compounds of formula (I) can be used in such a way as to ensure the reduction of infection by pests or the prevention of infection, or both.

 The compounds in the compositions according to the invention can be used as insecticides or acaricides, for example, at home for spraying premises to control infection with house flies or other insects, in addition, they can be used to process crops or cereals during storage to combat infection by insects or other pests, then they can be used to spray growing crops, such as cotton, to control the infection by common pests, and they can ut also be used in human or veterinary medicine, for example, as a spray for cattle in order to prevent or combat infestation by insects or other pests.

 However, it should be noted that the compounds in the composition according to the invention are of particular interest for use in crops that are cultivated in environments in which fish are exposed to pesticides.

The invention is illustrated by the following examples:
the temperature is indicated in ^o C and the refractive indices n _D measured at 20 ^o C.

 Example 1. 1- (4-chlorophenyl) -1- (E-3 (phenoxyphenyl) prop-1-enyl) cyclopropane.

 A. 1- (4-Chlorophenyl) -1-cyclopropanomethanal (compound a).

A mixture of 1- (4-chlorophenyl) -1-cyclopropanomethanol (7 g), pyridinium dichromate (21.7 g) and dichloromethane (200 ml) was stirred overnight at room temperature. Petroleum ether (bp 40-60 ^° C., 200 ml) was added and stirring was continued for another 30 minutes. The mixture was filtered through a layer of zeolite and charcoal, and the solvent was distilled off under reduced pressure. The residue was dispersed at 0.3 mm Hg. and the main fraction, t.kip. 73-75 ^o C, consists of the target aldehyde, yield 5.2 g, n _D 1.5532.

 B. 1- (4-Chlorophenyl) -1- (2,2-dibromovinyl) cyclopropane (compound b).

Triphenylphosphine (17.4 g) was added to a stirred solution of dry carbon tetrabromide (11 g) in dry dichloromethane (200 ml) under a nitrogen atmosphere. After 15 minutes, 1- (4-chlorophenyl) -1-cyclopropanomethanal (3 g) dissolved in dichloromethane (10 ml) was added. The mixture is stirred for 2 hours at room temperature, poured into a saturated solution of ammonium chloride and extracted with petroleum ether (mp. 60-80 ^° C.) three times. The combined extracts were washed with water, dried and the solvent was distilled off under reduced pressure to obtain the target compound, yield 5.1 g, n _D 1.5976.

 C. 1- (4-Chlorophenyl) -1-ethynylcyclopropane (compound c).

To a stirred solution of 1- (4-chlorophenyl) -1- (2,2-dibromovinyl) cyclopropane (1 g) in dry ether (50 ml) under nitrogen atmosphere and cooled to -78 ^° C was added 1.6 M n- butyllithium (3.7 ml) for 15 minutes while maintaining the temperature below 60 ^° C. After stirring for another 5 minutes, 2N. aqueous hydrochloric acid (40 ml) and the mixture allow to warm to room temperature. The mixture was extracted with ether (three times), filtered, dried and the solvent was distilled off under reduced pressure to obtain the target compound, yield 0.5, n _D 1.5460.

 D. 1- (4-Chlorophenyl) -1- (E-3- (3-phenoxyphenyl) prop-1-enylcyclopropane (compound (I)).

To a stirred solution of 2-methyl-2-butene (0.5 ml) in dry ether (2 ml) in a nitrogen atmosphere at 0 ^° C. is added a borane methyl sulfide complex (1.15 ml of a 2M solution in ether) and the mixture is stirred for 1 h A solution of 1 (4-chlorophenyl) -1-ethynylcyclopropane (0.4 g) in ether (5 ml) was added in one portion, stirred for 10 minutes and then allowed to warm to room temperature for 1 hour. Then under reduced pressure ether is distilled off and the residue is dissolved in dry benzene (10 ml) and maintained in a nitrogen atmosphere.

In another flask, tetrakis (triphenylphosphine) palladium (0) (0.1 g) was stirred under nitrogen in dry benzene (10 ml) and a solution of 3-phenoxybenzyl bromide (0.6 g) in dry benzene (10 ml) was added over 10 min. ) To this mixture was added the previously prepared reagent, followed by the addition of a 2M aqueous solution of sodium hydroxide (2.3 ml), and the mixture was refluxed for 2 hours. After cooling, a 3M aqueous solution of sodium hydroxide (1 ml) was added, followed by 30% H ₂ O ₂ (1 ml). After the termination of the exothermic reaction, the reaction mixture was stirred at room temperature for 30 minutes, poured into water, and then extracted with ether (three times). The combined extracts were washed with water, dried and the solvent was distilled off under reduced pressure. The product was isolated by flash chromatography on silica gel eluting with pure petroleum ether (mp. 40-60 ^° C.) to give 0.41 g of the final product. n _D 1.5988.

Examples 2-11 The following aldehydes are prepared according to the procedure for Example 1 (A):
d. 1- (3,4-Dimethylenedioxyphenyl) -1-cyclopropanomethanal, n _D 1.5545.

e. 1- (4-Ethoxyphenyl) -2,2-difluoro-1-cyclopropanomethanal, n _D 1.5063.

 The precursor of compound (e) is prepared as follows.

 1- (4-Ethoxyphenyl) -2,2-difluorocyclopropane-1-methanol.

To 1.0 g of lithium aluminum hydride in 120 ml of dry ether at room temperature, 5.4 g (0.02 mol) of ethyl 1- (4-ethoxyphenyl) -2,2-difluorocyclopropane-1-carboxylate in 20 ml of ether are added dropwise. The reaction mixture was stirred for 1 hour, after which 1.0 ml of water, 1.0 ml of 15% NaOH were added, followed by 3.0 ml of water. The solid precipitate was filtered off, washed with ether, and the combined extracts were dried and concentrated under reduced pressure to obtain a colorless oil (4.2 g): n _D 1.5129.

 1- (4-Ethoxyphenyl) -1-cyclopropanomethanal (compound f) is prepared as follows.

 1-cyano-1- (4-ethoxyphenyl) cyclopropane.

 To 7.5 ml (0.012 mol) of 1.7 M n-butyllithium in hexane, 10 ml of anhydrous tetrahydrofuran was rapidly added at room temperature under a nitrogen atmosphere, followed by a solution of 4-ethoxyphenyl-acetonitrile (0.8 g, 0.005 mol) in 4 ml of tetrahydrofuran for 5 minutes The reaction mixture was stirred with a magnetic stirrer for 1 h, and then 0.50 g (0.005 mol) of 1,2-dichloroethane in 10 ml of tetrahydrofuran were treated for 40 min (slow addition is very important). After 16 hours, the mixture was hydrolyzed by adding 10 ml of 3 N HCl, then taken up in ether, washed with water, sodium bicarbonate, water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. Yield: 0.64 g of a viscous semi-crystalline substance in the form of an oil.

 1- (4-Ethoxyphenyl) -1-cyclopropane-methanal (compound f).

To 0.625 g (0.0033M) of 1-cyano-1- (4-ethoxyphenyl) cyclopropane in dry benzene (25 ml) and dry heptane (10 ml) at 0 ^° C. in a nitrogen atmosphere, diisobutylaluminum hydride was added dropwise through a hypodermic syringe into hexane (3.4 ml of T solution, 0.0033 mol). The mixture was stirred for 3 hours at 0 ^° C., then allowed to warm to room temperature, poured into saturated ammonium chloride and ice and acidified with diluted H ₂ SO ₄ and then extracted with ether. The ether layer was washed with saturated sodium bicarbonate, saturated sodium chloride and dried. The solvent was distilled off under reduced pressure, and the aldehyde was purified by column chromatography on florisil with petroleum ether (mp. 60-80 ^° C.) as an eluent. Yield: 0.42 g (n _D : 5342).

These aldehydes are converted to the corresponding dibromovinyl compounds according to the procedure for Example 1 (B) in to obtain:
Compound
(e) 1- (2,2-Dibromovinyl) -1- (4-ethoxyphenyl) cyclopropane, n _D 1.5976,
(h) 1- (2,2-Dibromovinyl) -1- (3,4-methylenedioxyphenyl) cyclopropane, n _D 1.5970.

(i) 1- (2,2-Dibromovinyl) -1- (4-ethoxyphenyl) -2,2-difluorocyclopropane, n _D 1.5433.

The following acetylenes are prepared according to the procedure for Example 1 (C):
Compound
(j) 1- (4-Ethoxyphenyl) -1-ethylcyclopropane, n _D 1.5325.

(k) 1- (3,4-Methylenedioxyphenyl) -1-ethynylcyclopropane, n _D 1.5569.

(cc) 1- (4-Ethoxyphenyl) -1-ethynyl-2,2-difluorocyclopropane, n _D 1.5170.

The following olefins are prepared according to the procedure for Example 1 (D):
Compound
2.1- (4-Chlorophenyl) -1- (E-3- (4-fluoro-3-phenoxyphenyl) prop-1-enyl) cyclopropane, n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{D}}$ 1.5805.

3.1- (4-Ethoxyphenyl) -1- (E-3-phenoxyphenyl) prop-1-enyl) cyclo-propane, n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{D}}$ 1.5837.

4.1- (4-Ethoxyphenyl) -1- (E-3- (4-fluoro-3-phenoxyphenyl) prop-1-enyl) cyclopropane, n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{D}}$ 1.5799.

5.1- (3-, 4-methylenedioxyphenyl) -1- (E-3- (3-phenoxyphenyl) prop-1-enyl) cyclopropane, n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{D}}$ 1.5969.

6. 1- (3,4-Methylenedioxyphenyl) -1- (E-3- (4-fluoro-3-phenoxyphenyl) prop-1- (E) -enyl) cyclopropane, n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{D}}$ 1.5886.

7. 1- (4-Ethoxyphenyl) -1- (E-3- (3-phenoxyphenyl) prop-1-enyl-2,2-difluorocyclopropane, n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{D}}$ 1.5763.

8. 1- (4-Ethoxyphenyl) -1- (E-3- (4-fluoro-3-phenoxyphenyl) prop-1-enyl) -2,2-difluorocyclopropane, n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{D}}$ 1.5689.

 To obtain compounds 7 and 8, the procedure of Example 1 (D) was modified by reducing the contact time of the reaction mixture with alkaline hydrogen peroxide to 5 minutes.

 Example 9. A. (A- (4-Chlorophenyl) -1- (E-3- (3-phenoxyphenyl) prop-1-en-3-enyl) cyclopropane (compound m).

A mixture of 1- (4-chlorophenyl) -1-cyclopropane-methanal (1.80 g 0.01 M) 3-phenoxy-acetophenone (2.12 g, 0.01 M) and 3.0 g potassium hydroxide in 25 ml ethanol was stirred for 2 hours at room temperature. The reaction mixture was poured into 200 ml of water and extracted with ether. The ether extract was washed with water, dried and the solvent was distilled off under reduced pressure to obtain 4.1 g of crude 1- (4-chlorophenyl) -1- (E-3- (3-phenoxyphenyl) prop-1-en-3-onyl) cyclopropane which is purified by column chromatography on 100 g of chlorisil (eluent: petroleum ether (b.p. 60-80 ^° C.) and ethyl acetate: 9/1) to obtain 3.04 g of pure product. n _D 1.5943.

 B. 1- (4-Chlorophenyl) -1- (E-3- (3-phenoxyphenyl) prop-1-enyl) cyclopropane and 1- (4-chlorophenyl) -1- (E-3- (3- phenoxyphenyl) prop-2-enyl) cyclopropane.

 To 1.87 g (0.005 M) of 1- (4-chlorophenyl) -1- (E-3- (3-phenoxyphenyl) -1-prop-1-en-3-onyl) cyclopropane in 30 ml of ethanol was added 0, 28 g (0.0075 mol, 1.5 mol-eq) of sodium borohydride and the mixture was stirred for 3 hours at room temperature. Water (20 ml) was then added, followed by diluted HC (25 ml) and the mixture was taken up in ether (150 ml). The ether layer is washed with sodium bicarbonate (twice), water (three times) and dried. The solvent was distilled off under reduced pressure to obtain a crude intermediate alcohol (1.88 g).

Alcohol (1.88 g, 0.005 mol) and triethylsilane (0.87 g, 0.0075 mol, 1.5 mol equiv) in 50 ml of dry dichloromethane are cooled using an acetone / dry carbon dioxide bath under nitrogen atmosphere. Dropwise addition of boron trifluoride etherate (0.77 g, 0.0055 mol) gives a solution which is stirred until thin-layer chromatography shows that the alcohol is no longer present, and then quenched by the addition of approximately 15 ml of aqueous sodium bicarbonate. The cooling bath is removed and the solution is allowed to warm to room temperature with vigorous stirring. The mixture was transferred to a separatory funnel, ether (100 ml) was added, and all this was washed with bicarbonate (50 ml) and water (twice). Draining and distilling off the solvents gives an oil. Purification by column chromatography on florisil using petroleum ether (mp. 60-80 ^° C.) as an eluent gives 1.02 g of an oil, which is a 3: 8 mixture of two olefins. They are separated using petroleum ether (bp. 40-60 ^o C) as an eluent by thin layer chromatography on silica gel, and the plate is shown three times. 1- (4-Chlorophenyl) -1- (E-3- (3-phenoxyphenyl) prop-1-enyl) cyclopropane (n _D : 1.5988: yield 0.18 g rf 0.36) compound I) and 1- (4-chlorophenyl) -1- (E-3- (3-phenoxyphenyl) prop-2-enyl) cyclopropane (n _D : 1.5686: yield 0.53 g rf 0.4) are colorless viscous oils.

 Example 10. A. 1- (4-Chlorophenyl) -1- (1-hydroxypropan-2-enyl) cyclopropane (compound n).

To a stirred solution of 1- (4-chlorophenyl) -1-cyclopropanomethanol (1.8 g) in dry tetrahydrofuran (60 ml) at 78 ^° C was added 1M vinyl magnesium bromide (12 ml) in tetrahydrofuran over 10 minutes. The mixture was then allowed to warm to -20 ^° C. and saturated aqueous ammonium chloride (30 ml) was added. The mixture was concentrated under reduced pressure and extracted with ether (x3). The combined extracts were dried and the solvent was distilled off under reduced pressure to obtain the desired compound 3 g, n _D 1.5523.

 B. 1- (4-Chlorophenyl) -1- (E-3-bromoprop-1-enyl) cyclopropane (compound O).

To a stirred solution of 1- (4-chlorophenyl) -1- (1-hydroxy-prop-2-enyl) cyclopropane (2 g) in petroleum ether (mp. 60-80 ^° C 100 ml) was added 48% aqueous hydrobromic acid (30 ml) while maintaining the temperature between -20 ^° C. and -10 ^° C. After 30 minutes, water (100 ml) was added and the mixture was extracted with petroleum ether (mp. 60-80 ^° C. three times). The combined extracts were washed with water, saturated sodium bicarbonate, dried and the solvent was distilled off under reduced pressure to obtain the desired compound, 2.8 g, n _D 1.5678.

 C. 1- (4-Chlorophenyl) -1- (E-3- (3-phenoxyphenyl) prop-1-enyl) cyclopropane.

Grignard reagent is prepared at 20 ^o C by reacting 3-phenoxyphenyl bromide (0.3 g) and dry magnesium chips (0.26 g) in dry ether (4 ml) and cooled to 78 ^o C. Add copper bromide (I) (0, 03 g) followed by the addition of a solution of 1- (4-chlorophenyl) -1- (E-3-bromoprop-1-enyl) cyclopropane (0.28 g) in dry tetrahydrofuran (4 ml) over 3 minutes. The mixture was stirred at -78 ^° C for 5 minutes and then allowed to warm to room temperature for 15 hours. A saturated aqueous solution of ammonium chloride (10 ml) was added and the mixture was extracted with ether (x3), washed with water, dried and the solvent was distilled off at reduced pressure. The residue was purified by thin layer chromatography using petroleum ether (mp. 60-80 ^° C.) as an eluent. Yield 0.3 g.

 Following the procedures of the examples given, other compounds of the invention are prepared.

Pesticidal activity was evaluated for housefly (H. F) and horseradish leaf-eating babanuha (mustard beetle M.V.) using the following methods: Housefly (Musca domestica)
Female flies are treated in the thoracic region with a drop (1 μl) of an insecticide dissolved in acetone. For the test, duplicate samples of 15 flies are used for each dosage rate, and for each compound, the test is carried out for six dosages. After treatment, the flies were kept at a temperature of 20 ^° ± 1 ^° C and mortality was determined 24 and 48 hours after treatment. LD ₅₀ values are calculated in fly insecticide microprograms, and relative toxicity is calculated by the reciprocal of LD ₅₀ (see Sawicli et al. Bulletin of the World Health Orhanization 35, 893 (1966) and Sawicki et al. Entomologia and Exp Appli 10, 253 (1967).

 Mustard beetle horseradish leaf beetle babanuha (Phaedon coclkearial Fab.).

 Acetone solutions of the test compound are applied vertically to adult horseradish leaf beetles using a microdroplet carrier. Treated insects are kept for 48 hours, after which mortality is assessed. For each dosage, duplicate samples of 40-50 horseradish leaf beetles were used and 5 dosage levels were used for each compound.

Indicators LD ₅₀ and the relative strength of the action calculated in the same way as in the case of house flies.

 For both types of insects, the relative strength of the action is calculated by comparison with 5-benzyl-3-furylmethyl (1R) -transchrysanthemate (Bioresmetrin), which is one of the most toxic chrysanthemum acid esters known to affect flies of domestic animals and horseradish leaf beetle, and its toxicity in 24 times higher than that of allethrin for housefly, and 65 times higher than that of allethrin for horseradish leaf beetle.

 Results.

 The relative strength of action in relation to house flies (N.F.) and mustard beetle (M.V.) (bioresmetrin 100) is indicated in the table in columns HF and MB, respectively.

Compounds of formula ArCR ₁ R ₂ CH = CHCH ₂ D wherein A 3 is phenoxyphenyl, B 4-fluoro-3-phenoxyphenyl.

 Examples of compositions.

 Example 1. Emulsifiable concentrate, wt.

Active ingredient (compound of the invention) 1.5
Non-ionic emulsifier 25.0
Xylene 73.4
Antioxidant 0.1
Example 2. Wettable powder, wt.

Active ingredient (compound of the invention) 25.0
Attapulgite 69.5
Sodium isopropylbenzenesulfonate 0.5
Condensed Naphthalenesulfonic Acid Sodium Salt 2.5
Antioxidant 2.5
Example 3. Dust, wt.

Active ingredient (compound of the invention) 0.5
Antioxidant 0.1
Talc 99.0 (

Claims (1)

An insecticidal composition comprising the active ingredient a diphenyl ether derivative and target additives, characterized in that it contains a compound of the general formula as a diphenyl ether derivative
ArCR ₁ R ₂ CH CHCH ₂ D
where Ar is a phenyl group substituted with one or two halogen atoms, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or methylenedioxy groups, or naphthyl optionally substituted with a halogen atom;
R ₁ and R ₂ together with the carbon atom to which they are attached form a cyclopropyl or 2,2-dihalocyclopropyl group;
D 3-phenoxyphenyl or 4-fluoro-3-phenoxyphenyl,
and the ArCR ₁ R ₂ group and CH ₂ D form a trans configuration with respect to the double bond in the following ingredients, wt. Active ingredient 0.5 25.0
Targeted Supplements Rest

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