JPS60100541A - Hydrocarbon compound, its preparation, insecticide and acaricide comprising it as active ingredient - Google Patents

Abstract

NEW MATERIAL:A hydrocarbon compound shown by the formula I (R1 is halogen, lower alkyl, lower alkoxyl, or lower haloalkoxyl; R2 and R3 are methyl or R2 and R3 are linked to form ethylene; R4 is H, or F; R5 is H, or halogen). USE:An insecticide and an acaricide. Having extremely high effect, showing excellent effects on insect pests having resistance to organic phosphorus agent and carbamate agent, being relatively inexpensive. PREPARATION:A carbonyl group of a compound [e.g., 2-methyl-2-(4-ethoxyphenyl)-5-(3-anilinophenyl)-3-pentane] shown by the formula II is reduced, a carbonyl group of a compound shown by the formula III is reduced, or a compound shown {e.g., 1-(4-ethoxyphenyl)-1-[3-(3-bromo-4-fluorophenyl)propyl]cyclopropane} shown by the formula IV is reacted with a compound shown by the formula Vin the presence of a salt and copper or a copper compound, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel hydrocarbon compound represented by the following general formula (1), a method for producing the same, and an insecticide or acaricide containing the compound as an active ingredient.

[In the formula, l? 1 represents a halogen atom, lower alkyl group, lower alkoxyl group, or lower haloalkoxyl group)
, R2 and R3 each represent a methyl group, or R2
and R3 combine to represent an ethylene group. R4 represents a hydrogen atom or a fluorine atom, and R5 represents a hydrogen atom or a halogen atom. ] As a result of repeated research for the purpose of developing a compound having excellent insecticidal and acaricidal activity, the present inventors found that the above general formula (1
) The compound of the present invention represented by 1. It has extremely high insecticidal and acaricidal efficacy and is fast-acting. 2. It is also highly effective against pests that are resistant to organic phosphorus agents or carbamate agents.

8. Can be manufactured relatively inexpensively.

The present invention was completed based on the discovery that the present invention has the following characteristics.

Specific pest insects for which the compounds of the present invention are particularly effective include Hemiptera such as planthoppers, leafhoppers, aphids, and stink bugs; Lepidoptera such as diamondback moths, Japanese mealybugs, and armyworms; and Diptera such as Culex mosquitoes and houseflies. , the German cockroach and other orders of the order Ophthalmia, Coleoptera, and Orthoptera, and spider mites include the red-throated spider mite, the orange spider mite, and the like.

The compound of the present invention can be produced, for example, by the following method.

<Production method (A)> General formula 1) [In the formula, R1, R2, R3, R, and R5 have the same meanings as above]. ] The carbonyl group of the compound represented by is converted into hydrazone by adding hydrazine and water in an inert solvent such as diethylene glycol or triethylene glycol under a nitrogen atmosphere, and then adding a base such as potassium hydroxide or sodium hydroxide. Add and heat at 180℃ to 220℃ for 2 hours to 2 hours.
The so-called Wolf-Kishner reduction (which continues heating for days)
J. Chem. Soc., 4202 (1958)
*J.

Amer, Chem, Soc, 86.2909 (19
64)) to convert into a methylene group, a compound represented by general formula (1) is obtained.

In this method, examples of the compound represented by the general formula (1) used as a raw material include the following compounds.

2-Methyl-2-(4-ethoxyphenyl)-5-(8
-anilinophenyl)-8-pentanone2-methyl-2-(4-ethoxyphenyl)-5-(8
-anilino-4-fluorophenyl)-8-pentanone1-(4-ethoxyphenyl)-t-(a-(8-anilinophenyl)-1-propanoylcocyclopropano(4-ethoxyphenyl)-1 -(8-(3-anilino-4-fluorophenyl)-!-propanoyl]cyclopropane 2-methyl-2-(4-chlorophenyl)-5-(8-
Anilino-4-fluorophenyl)-8-pentanone (Production method (B)) General formula (I) [In the formula, R+ e Rz -Rs I R4r'yot'
艮 means the same thing as above. ] By replacing the carbonyl group of the compound represented by formula with a methylene group in the same manner as in the production method (A), a compound represented by general formula CI) is obtained.

In this method, examples of the compound represented by the general formula (1) used as a raw material include the following compounds.

2-Methyl-2-(4-ethoxyphenyl)-6-(8
-anilinophenyl)-6-pentanone2-methyl-2-(4-ethoxyphenyl)-5-(8
-anilino-4-fluorophenyl )-5-pentanone 1-(4-ethoxyphenyl)-1-(8-(8-anilinophenyl)-8-propanoylfucyclopropane 1-(4-ethoxyphenyl)- 1-(8-(8-anilino-4-fluorophenyl)-3-propanoylfucyclopropane 2-methyl-2-(4-chlorophenyl)-5-(8-
Anilino-4-fluorophenyl)-5-pentanone production method (C)> General formula (IV) [In the formula, RH represents a lower alkyl group or a lower alkoxyl group, and R,, R3 and R4 have the same meanings as above. represents. ] A compound represented by the general formula (V) [In the formula, R5 represents the same meaning as above. ] in an inert solvent (e.g. dimethylformamide, dimethylacetamide, pyridine, etc.), a base (e.g. potassium carbonate, soda carbonate, etc.) and copper or a copper compound (
For example, by reacting in the presence of copper chloride, copper powder, etc., at 120°C to 150°C in a nitrogen stream for 10 to 60 hours, the same meaning as in general formula (vI) is expressed. ] A compound represented by the following is obtained.

<Manufacturing method (D)> A compound represented by the general formula (ff) and the general formula ([) [wherein, R5 has the same meaning as above]. ] in an inert solvent (e.g. dimethylformamide, dimethylacetamide, pyridine, etc.) with a base (
For example, potassium carbonate, soda carbonate, etc.) and copper or a copper compound (for example, cuprous chloride, copper powder, etc.) are reacted at 120°C to 150°C for 10 to 60 hours in a nitrogen stream, and then water or The compound represented by the general formula (vl) is obtained by deacetylation in alcohol in the presence of a base (eg, caustic potash, caustic soda, etc.) or an acid (eg, hydrochloric acid, sulfuric acid, etc.).

Examples of the compound represented by the above general formula ([V) that serves as a raw material in the above production methods (C) and (D) include the following compounds.

2-Methyl-2-(4-ethoxyphenyl)-5-(8
-bromo-4-fluorophenyl)pentane 1-(4-ethoxyphenyl)-1-(8-(8-bromo-4-fluorophenyl)propyl]cyclopropane 2-methyl-2-(4-ethoxyphenyl)- 5-(8
-bromophenyl)pentane 1-(4-ethoxyphenyl)-1-(8-(8-bromophenyl)propylfucyclopropane 2-methyl-2-(4-methylphenyl)-5-(8-
bromophenyl)pentane 2-methyl-2-(4-methylphenyl)-5-(8-
Bromo-4-fluorophenyl)pentane 2-methyl-2-(4-methoxyphenyl)-5-(8
-Bromo-4-fluorophenyl) penkune 1-(4-methoxyphenyl)-1-(8-(8-bromo-4-fluorophenyl)propylfucyclopropane Also, as a compound represented by general formula (V), Examples of the compound represented by the general formula (■) include aniline, p-chloroaniline, and p-fluoroaniline, and examples of the compound represented by the general formula (■) include acetanilide, p-chloroacetanilide, and p-fluoroacetanilide.

In addition, in the above manufacturing methods (A), (B), (C) and (11), general formulas (1), (I) and (IV
) can be produced, for example, by the route shown below.

■° Compound represented by general formula (1) ■-1 ■ Compound represented by general formula (1) 4 ■ Compound represented by general formula (1v) ■-2 4 [In the formula, R has 1 to 4 carbon atoms] 2 represents an alkyl group, R□,
R; , R, , R3, R4 and R5 have the same meanings as above. Furthermore, examples of the compounds of the present invention produced based on the above production method are shown in the table below, but of course the compounds of the present invention are not limited to these examples.

The compounds of the present invention will be explained in more detail with reference to Examples below.

Example 1 Production of compound (4) by production method (A) 1-(p-ethoxyphenyl)-i-(a-(m-anilinophenyl)
- Add 0.471 hydrazine hydrate to 1.2y of t-oxopropylcocyclopropane, add 80vtl to diethylene glycol I-, and heat to 80°C to loo°C. Then processed potassium hydroxide 0.479 2'00
The reaction was carried out at ~210°C for 5 hours.

Cool the reaction solution to room temperature, add water and ether to separate the liquid,
The aqueous layer was extracted twice with ether, the ether layers were combined and washed twice with saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography. 0.58f of the desired product was obtained as a pale yellow oil.

Example 2 Synthesis of compound (1) by production method (C) 2-methyl-2
-(4-ethoxyphenyl)-5-(8-bromo-4-
2.2 f of (fluorophenyl)pentane are dissolved in 50 #l of dry dimethylformamide. This has 0.9 potassium carbonate
6N, 0.65f of aniline, and 0.8f of cuprous chloride were added, and the mixture was heated to 140-150°C under a nitrogen stream for 86 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into ice water, and extracted with ethyl acetate. The aqueous layer was extracted once with ethyl acetate, the ethyl acetate layers were combined, washed twice with saturated brine, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography. , object 0.
Obtained 81F.

When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, it is usually used as a solid carrier, liquid carrier, gaseous carrier, or other formulation aids (such as surfactants, dispersants, etc.).
Wetting agents, stabilizers, etc.) to produce various preparations such as emulsions, wettable powders, powders, granules, oils, aerosols, heated fumes (mosquito coils, electric mosquito repellents, etc.), fogging, etc. Use as a fumigant, non-heated fumigant, poison bait, etc.

The active ingredient content during their manufacture is o, oi ~95%.

Solid carriers include fine powders or powders such as clays (e.g. kaolin, bentonite, acid clay, pyrophyllite, sericite), talcs, and other inorganic minerals (e.g. hydrated silicon dioxide, pumice, diatomaceous earth, sulfur powder, activated carbon). Examples include things like this.

Liquid carriers include alcohols (e.g. methyl alcohol, ethyl alcohol), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. ethyl ether, dioxane, Celsolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene). ,
xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. kerosene, kerosene), esters, nitriles, acid amides (e.g. dimethylpolamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene, Examples include carbon chloride).

In addition, as surfactants, alkyl sulfate esters,
Examples include alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, and polyhydric alcohol esters.

Furthermore, usable fixing agents and dispersants include casein, gelatin, starch powder, CMC, and PAP (
(isopropyl phosphate), TCP (tricresyl phosphate), tall oil, epoxidized parts, various dish surfactants, various fatty acids or their esters, etc.

Examples of formulations are shown below.

Formulation Example 1 By dissolving 0.2 parts of each of the compounds (1) to (4) of the present invention in white kerosene to make a total of 100 parts, each oil solution is obtained.

Formulation Example 2 10 parts each of the compounds (i) to (4) of the present invention, and
15 parts of an emulsifier (Turupol ao 05X (registered trademark of Toho Chemical)) and 75 parts of xylene are added to each, and these are thoroughly stirred and mixed to obtain each emulsion.

Formulation Example 3 Compound of the present invention (B) 0.2 parts, tetramethrin 0.2
1 part, 7 parts of xylene, and 82.6 parts of deodorized kerosene were mixed and dissolved.
After filling the aerosol container and attaching the valve part,
An aerosol is obtained by filling 60 parts of a propellant (liquefied petroleum gas) under pressure through the valve portion.

Add 0.3 g of ester chrysanthemum acid ester and add 20 m of methanol.
Mosquito coil carrier (tab powder: lees powder: wood flour: 8:1)
99.41 (mixed at a ratio of 6:1) and stirred evenly.
After evaporating the methanol, add 150 seconds of water and mix well. The mixture is molded and dried to obtain a mosquito coil.

Formulation Example 5 10 parts of fenitrothion was added to 20 parts each of the compounds (1) to (4) of the present invention, and an emulsifier (Tsurpol 5029-0
(Toho Chemical registered trademark)) were thoroughly mixed, 65 parts of 800 mesh diatomaceous earth were added, and the mixture was thoroughly stirred and mixed in a crusher to obtain each wettable powder.

Formulation Example 6 2 parts of naphthyl-N-methyl carbamate was added to 1 part of each of the compounds (1) to (4) of the present invention, dissolved in a suitable amount of acetone, 97 parts of 800 mesh Kruk was added, and the mixture was crushed in a shaker. After thorough stirring and mixing, the acetone is removed by evaporation to obtain each powder.

Formulation Example 7 To 5 parts each of the compounds (1) to (4) of the present invention, 5 parts of Toyolignin CT (trademark name of Toyobo Registration Department) and 90 parts of GSM Clay (registered trade name of Sieglite Co., Ltd.) were added, and the mixture was placed in a vacuum cleaner. Stir thoroughly to mix.

Next, 10% of water is added to the mixture, and the mixture is stirred and mixed, granulated using a granulator, and dried through ventilation to obtain each granule.

The compound of the present invention can be widely used as an agricultural and horticultural insecticide and acaricide in rice fields, fields, orchards, tea gardens, mulberry gardens, lawns, pastures, forests, etc., and can also be used as an insecticide and acaricide for epidemic prevention. can.

Next, test examples will be used to demonstrate that the compounds of the present invention are useful as active ingredients for insecticides and acaricides.

The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used as comparative controls are indicated by the following compound symbols.

Test Example 1 2 ml of a 200-fold dilution (equivalent to 500 ppm) of the emulsion of the compound of the present invention obtained in Formulation Example 2 with water was added to 1
Soaked in 8N artificial bait for Spodoptera japonica, diameter f
Place in a lag polyethylene cup. Ten 8th instar Spodoptera larvae were released into the larvae, and 6 days later, their survival and death were examined (2 repetitions).

Test Example 2 A 2,00@ dilution solution (equivalent to 600 ppm) of an emulsion of the compound of the present invention below with water (equivalent to 600 ppm) 1 m/
The mixture was soaked into artificial feed bf for snailfish prepared in a polyethylene cup with a diameter of 5.5 aI. Ten 10-day-old nymphs were released into the larvae, and 8 days later, the survival and death of the larvae was examined (2 repetitions). The results are shown in the table below.

Test Example 8 Compounds of the present invention (1) (8) and a control compound were diluted with acetone to a predetermined concentration, and 10 male adult cockroaches
Apply topically to the ventral thorax of the head.

After treatment, the animals were kept together with food and water in a polyethylene cup, and 8 days later, they were examined to see if they were alive or dead, and the LD5° value (50% lethal dose) was determined.・(3 repetitions) Test Example 4 7 days after sowing, -
10 adult female spider mites per leaf, 2
Store in a constant temperature room at 5℃. After 6 days, a chemical solution prepared by diluting the following emulsion of the present compound and control compound according to Formulation Example 2 with water to 500 ppm of active ingredient was sprayed on a turntable at 1 ONt per pot, and at the same time 2 ml of the same wave was applied.
Irrigate the soil. After 8 days, the number of spider mites on each appendage was counted.

The effectiveness criteria are And so. The results are shown in the table below.

Claims (1)

[Scope of Claims] (1) General formula [wherein Ro represents a halogen atom, a lower alkyl group, a lower alkoxyl group, or a lower haloalkoxyl group,
4 and Tori each represent a methyl group, or R3 and Tori combine to represent an ethylene group. Ryo represents a hydrogen atom or a fluorine atom, and a lump represents a hydrogen atom or a halogen atom. ] A hydrocarbon compound represented by (2) General formula [wherein R1 represents a halogen atom, a lower alkyl group, a lower alkoxyl group, or a lower haloalkoxyl group,
Bird and R8 each represent a methyl group, or R2 and R3 combine to represent an ethylene group. A tow represents a hydrogen atom or a fluorine atom, and an island represents a hydrogen atom or a halogen atom. [In the formula, R1*1%-Rs-R4 and circles have the same meanings as above. ] A method for producing a hydrocarbon compound shown in [In the formula, R1 represents a halogen atom, a lower alkyl group, a lower alkoxyl group, or a lower haloalkoxyl group,
R1 and Rs each represent a methyl group, or R2 and R3 combine to represent an ethylene group. A circle represents a hydrogen atom or a fluorine atom, and R5 represents a hydrogen atom or a halogen atom. [In the formula, R1-Rs-Rs-R4 and bird represent the same meanings as above. ] A method for producing a hydrocarbon compound shown in (4) General formula [wherein R1 represents a lower alkyl group or a lower alkoxyl group, R2 and R3 each represent a methyl group,
Alternatively, R2 and R3 combine to represent an ethylene group, and R4 represents a hydrogen atom or a fluorine atom. ] A compound represented by the general formula [wherein R5 represents a hydrogen atom and tξ represents a halogen atom]. [In the formula, R; , R, , R3, R4 and R5 have the same meanings as above] . ] A method for producing a hydrocarbon compound shown in (5) General formula [In the formula, RQ represents a lower alkyl group or a lower alkoxyl group, R8 and R3 each represent a methyl group, or R2 and R3 combine to represent an ethylene group, and R4 represents a hydrogen atom or Represents a fluorine atom. ] The compound represented by the general formula and the compound represented by the general formula are reacted with a base or in the presence of a copper compound, and then deacetylated. , R, , R, , R4 and R5 have the same meanings as above. ] A method for producing a hydrocarbon compound represented by ゛. (6) General formula [wherein R1 represents a halogen atom, a lower alkyl group, a lower alkoxyl group, or a lower haloalkoxyl group,
R2 and R11 each represent a methyl group, or R2 and R3 combine to represent an ethylene group. R4 represents a hydrogen atom or a fluorine atom, and R5 represents a hydrogen atom or a halogen atom. ] An insecticide and acaricide characterized by containing a hydrocarbon compound represented by the following as an active ingredient.