JPS6124585A - Methylenedioxybenzyl ether compound, method for producing the same, and insecticidal efficacy enhancer comprising the compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is H, lower alkyl or lower alkynyl; n is 1-3). EXAMPLE:alpha-Isopropyl-3,4-methylenedioxybenzyl methoxyethyl ether. USE:Agent for promoting insecticidal effect. Effective also on vermin resistant to insecticides. PREPARATION:The objective compound can be prepared by reacting the alpha-isopropyl-3,4-methylenedioxybenzyl halide of formula II (X is halogen) with (poly) ethylene glycol monoether of formula III preferably at an equivalent ratio of 1:1 -10, optionally in a solvent, preferably in the presence of 1-5 equivalent of a dehydrohalogenation agent (e.g. pyridine, triethylamine, etc.) at room temperature -100 deg.C for 0.5-40hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [■] [wherein R represents a hydrogen atom, a lower alkyl group or a lower alkynyl group, and n represents 1.2 or 3]. ] methylenedioxybenzyl ether compound (
Hereinafter, it will be referred to as the compound of the present invention. ), its production method, and an insecticidal efficacy enhancer comprising the compound.

ゝ・, ”,,,,,＼ It is well known that sesamin, etc. contained in sesame oil enhances the insecticidal efficacy of insecticides such as pyrethrin and allethrin. However, when added to insecticides such as pyrethrin and allethrin, their efficacy is significantly enhanced.Currently, 3゜4-methylene dioxy, ci-6-propylbenzylbutyl diethylene glycol ether (hereinafter referred to as piperonyl butoxide) ) and N~(2-ethylhexyl)-bicyclo[2,2,1]but-5-ene anhydrophthalic acid-2,3-dicarboximide (MGK-264
), 4-(3゜4-methylenedioxyphenyl)-5-
Methyl-1,3-dioxane (safloxane) and the like are also known to exhibit a similar insecticidal effect.

However, the most widely used of these compounds, piperonyl butoxide, shows significant insecticidal efficacy enhancement effects against pyrethrins, but not so much against allethrins, and many of these compounds It does not necessarily show a sufficient enhancing effect on insecticides such as carbaryl.

Furthermore, in recent years, with the rapid increase in the use of various insecticides in various parts of the world, a reduction in the insecticidal efficacy of insecticides has become a problem due to the emergence of many insecticide-resistant insect pests. [Tadashi Miyata; “Agriculture and Horticulture” Vol. 53, No. 1, 17-
22 (1978), Kazuo Yasutomi; Plant Protection Vol. 34, No. 11, pp. 27-82 (1980). ] The present inventors
Under these circumstances, as a result of intensive studies on enhancing the insecticidal efficacy of various insecticides, it was found that if the compound of the present invention is added to these insecticides and used, the insecticidal efficacy can not only be enhanced; They discovered that scales can also control insecticide-resistant pests, and have completed the present invention.

When the compound of the present invention is added in an amount of 0.5 to 50 times (weight ratio) to a pyrethroid or carbamate insecticide, the insecticidal efficacy of the insecticide itself can be greatly enhanced, and it can also be used to improve insecticide resistance against insects. can also be controlled. The amount to be added may be determined to be an optimal amount within the above range depending on the type of insecticide, the type of pest to be controlled, the formulation form, etc.

Examples of pyrethroid insecticides whose insecticidal efficacy is enhanced by adding the compound of the present invention include pyrethrin and allethrin, as well as phenothrin (5-propargyl furfuryl d,]-cis, trans-chrysanthemum acid ester), phlopulsulin (2-methyl-5-propargyl-3-furylmethyl d,1-cis,trans-chrysanthemum acid ester),
Resmethrin (5-benzyl-3-furylmethyl d,l
-cis, trans-chrysanthemum acid ester), tetramethrin (
N-(3,4,5,6-tetrahydrophthalimide)
Methyl d,l-cis.

trans-chrysanthemum acid ester), phenothrin (3-phenoxybenzyl d, l-cis, trans-chrysanthemum acid ester)
, permethrin (3-phenoxybenzyl d,l-cis,trans-3-(2,2-dichlorovinyl)-2,2
-dimethylcyclopropanecarboxylic acid ester), cypermethrin (α-cyano-3-phenoxybenzyl d
, 1-cis, trans-3-(2,2-dichlorovinyl)-2', 2-dimethylcyclopropanecarboxylic acid ester), phenpropathrin (α-cyano-3-phenoxybenzyl 2.2, 3.3 -tetramethylcyclopropanecarboxylic acid ester), fenvalerate (α-cyano-3-phenoxybenzyl α-isopropyl-p-
chlorophenylacetic acid ester), terrarethrin (2-methyl-4-oxo-3-(2-flopenyl)-2-cyclopene, then-1-yl 2,2,3.3-tetramethylcyclopropanecarboxylic acid ester), d - empensuline ((R.

5) -1-ethynyl-2-methyl-2-pentenyl (I
R)-cis, trans-chrysanthemum acid ester), d-cyphenothrin ((R,S)-α-cyano-3-phenoxybenzyl (IR)-cis.

(trans-chrysanthemum acid ester), (S)-d-prarethrin ((S) = 2-methyl-4-oxo-3-(2-propynyl)cyclobent-2-enyl (IR)-cis, acid ester), fenfluthrin (pentafluorobenzyl (IR,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid ester), cyfluthrin ((R,5)-4- Fluoro-3-phenoxybenzyl (IR3)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid ester), deltamethrin ((S)-α-cyano-3-phenoxy Benzyl(IR,3S)-3-(2,2-dibromovinyl)-2
, 2-dimethylcyclopropanecarboxylic acid ester),
Fluparinate ((R3)-α-cyano-3-phenoxybenzyl 2-(2-chloro-α,α.

α-trifluoro-1)-toluidino)-8-methylbutyric acid ester), cyhalothrin ((R5)-α-cyano-3-phenoxybenzyl (IR5)-cis, trans-3-(2-chloro-3,3゜3-trifluoroprop-1-enyl)-2゜2-dimethylcyclopropanecarboxylic acid ester), tetramethrin C(S)-α-cyano-3-phenoxybenzyl (IR, 3S) -2,2
-dimethyl-8-(1',2,2,2-tetrabromoethylcyclopropanecarboxylic acid ester), (R5)-
Cyano-6-phenoxy-2-pyridylmethyl (IR8
)-cis, trans-3-(2,2-dichlorovinyl)
-2,2-dimethylcyclopropanecarboxylic acid ester, 2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether, 2-(4-ethoxyphenyl)-2-methyl-5-(3- phenoxyphenyl)pentane, (R5)-α-cyano-3-phenoxybenzyl (S )-2-(4-difluoromethoxyphenyl)-8-methylbutyrate, (R8)-α-cyano-3-phenoxy benzyl 2,2-dichloro-1-
(4-ethoxyphenyl)-cyclopropanecarboxylic acid ester, etc. Carbamate insecticides include, for example, BPMC (2-5ec-butylphenyl N-methylcarbamate), MPMC (8,4-xylyl N-methylcarbamate), etc. ), MTMC(m-)lyl N-notylcarhamate), P)iC(2-isopropoxyphenyl N
-methyl carbamate), carbaryl (1-naphthyl N
- Methyl carbamate, etc.

The compound of the present invention has the general formula (1) [wherein, X represents a halogen atom]. ] with the halogenated α-isopropyl-8゜4-methylenedioxybenzyl and the general formula (Il1) H(-OCH,CH,,→-
ORC1) [wherein R and n are the same as above.

It can be produced by reacting with (poly)ethylene glycol monoether shown in ].

The reaction is carried out in a solvent or without a solvent, preferably in the presence of a dehydrohalogenating agent.

Reagent A to be used in the reaction is (poly)ethylene glycol monoether (1 equivalent) per equivalent of halogenated α-isopropyl-8,4-methylenedioxybenzyl [1].
) 1 to 10 JIL, dehalogenation and hydrogenation agents 1 to 5.

The reaction temperature is from room temperature to about 100C, and the reaction time is 0.5~
It is about the same as 40 o'clock.

Solvents include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as dioxane and tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxy V, or mixtures thereof. be.

Dehydrohalogenating agents include organic bases such as pyridine, triethylamine, N,N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, etc. There are alkali metal alkoxides, etc.

After the reaction is completed, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, distillation, recrystallization, etc.

Next, production examples of the compounds of the present invention will be described.

Production Example Add 11f of sodium hydroxide to Methyl Cellosolve 87N, heat to 60-65°C, and after the sodium hydroxide has dissolved, 52g of α-isopropyl-8,4-methylenedioxybenzyl chloride is added dropwise over 1 hour. did. After further stirring at the same temperature for 2 hours, excess methyl cellosolve was distilled off under reduced pressure, and 100 g of water was added.

After hydration with acetic acid, extraction with benzene, washing with water, distilling off the benzene, and distilling under reduced pressure, α-isopropyl-8,4
-methylenedioxybenzylmethoxyethyl ether 2
I got 9f.

bp, 110~LL IC10,2arHg d:
: 1.0904no1.6085 Some of the compounds of the present invention that can be produced by such a production method are listed in Table 1.

Table 1 General formula %Formula % (When the compound of the present invention is added to the above-mentioned insecticide and used as an insecticidal efficacy enhancer, the solid carrier, liquid carrier, gaseous carrier, and surfactant are usually used for the preparation. Mixed with adjuvants, oils, emulsions, wettable powders, granules, aerosols, incense sticks, smoking agents,
It is formulated into a powder, etc. to which attractants such as baits preferred by pests are added.

Solid carriers include clays (e.g., kaolin, bentonite, acid clay, pyrophyllite, sericite), talcs, fine particles such as inorganic minerals (e.g., hydrated silicon dioxide, pumice, diatomaceous earth, sulfur powder, activated carbon), etc. There is a powder or powdery substance. Liquid carriers include alcohols (e.g. methyl alcohol, ethyl alcohol), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, kerosene), esters, nitriles, acid amides (e.g. methylformamide, dimethylacetamide), halogenated hydrocarbons kind (
For example, dichloroethane, trichloroethylene, carbon tetrachloride), etc.

Gaseous carriers include liquefied petroleum gas, dimethyl ether, lower hydrocarbons (eg, butane, propane), and the like.

Surfactants include alkyl sulfates, alkyl sulfonates, a) lekylaryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, and the like. Formulation auxiliaries, such as fixing agents and dispersing agents, include casein, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, lignin sulfonic acid, bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc., and stabilizers. Examples include acidic isopropyl phosphate, tricresyl phosphate, tall oil, epoxidized moieties, various surfactants, and various fatty acids or esters thereof.

Next, formulation examples will be described. The compounds of the present invention are indicated by the compound numbers in Table 1, and parts are parts by weight.

Formulation example 1 97.7 parts of oil are thoroughly mixed to obtain an oil solution.

Formulation Example 2 Tetramethrin 0.035 parts, resmethrin 0.015 parts
0.15 parts of the compound of the present invention (2), 2 parts of xylene, and 97.8 parts of deodorized kerosene are thoroughly mixed to obtain an oil solution.

Formulation Example 3 1.5 parts of resmethrin, 1.5 parts of the compound of the present invention (1), 6 parts of xylene, and 6 parts of deodorized kerosene are mixed and filled into an aerosol container, and 85 parts of propellant (liquefied petroleum gas) is added through the valve part. is filled under pressure to obtain an aerosol.

Formulation Example 4 Phenothrin O, a part, resmethrin 0.2 part, piperonyl butoxide 0.5 part, present compound (1) 0
．． 5 parts, deodorized kerosene 12.5 parts and emulsifier Atmos 30
Mix 1 part of nioleic acid monoglyceride (main component), add 50 parts of pure water to emulsify, and fill this into an aerosol container with 35 parts of a 3:1 mixture of deodorized butane and deodorized propane to obtain a water-based aerosol. .

Formulation Example 5 Dissolve 0.3 parts of fenvalerate and 1.5 parts of the compound of the present invention (1) or (2>) in 20 parts of acetone, add 98.2 parts of 300 Metsstarck, and stir and mix thoroughly with a crusher. Acetone is evaporated from the powder to obtain a powder.

Formulation Example 6 5 parts of phenothrin, 20 parts of the compound of the present invention (4), 15 parts of emulsifier Tsurpol 8005X (main component: polyoxyethylene alkyl phenyl ether), and 60 parts of xylene
Mix well to obtain an emulsion.

Formulation Example 7 5 parts of resmethrin, compounds of the present invention (1), (2), X1
5 parts of xylene and 55 parts of xylene are thoroughly mixed to obtain an emulsion.

Formulation Example 8 Walamesurinfu. 5 parts, 2.5 parts of resmethrin, 40 parts of the compound of the present invention (2), and the emulsifier Tsurpol 50290.
(Main component: polyoxyethylene alkylphenyl ether) 2.5 parts were mixed well, and 300 Metsstarck 47
Add 5 parts and thoroughly mix with a crusher to obtain a wettable powder.

Formulation Example 9 Tetramethrin 0.4 part and the compound of the present invention (1) or (
2) Dissolve 1.2 parts in 20 parts of methanol, mix well with 98.4 parts of incense stick carrier (a mixture of tab flour, lees flour, and wood flour in a ratio of 3:5:1). After evaporating the methanol, add 150 parts of water, mix thoroughly, and mold and dry to obtain an incense stick.

Formulation Example 10 0.2 g of resmethrin and 0.8 g of the compound of the present invention (1)
Dissolve in an appropriate amount of chloroform, 3.50×1.5α,
The fibers were adsorbed onto a 0.3-thick silk filter paper and heated using an electric heating plate to obtain a fumigated insecticidal composition.

These preparations are effective against sanitary pests such as flies, mosquitoes, and cockroaches, as well as fruit tree pests such as cabbage butterflies, armyworms, diamondback moths, and goats, canola pests, plant-parasitic mites, and grain storage pests such as brown elephant and mealybug moth. It can be used to control not only insecticide-sensitive pests but also insecticide-resistant pests. It can also be used in combination with other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc.

Next, test examples will show that the compounds of the present invention can be used as insecticidal efficacy enhancers. In addition, the compound of the present invention is
It is indicated by the compound number in Table 1.

Piperonyl butoxide was also used for comparison.

Test Example 1 Add 5 times the amount (by weight) of the compound of the present invention or piperonyl butoxide to flamethrin, permethrin, fenvalerate, or carbaryl, dilute this with acetone to a predetermined concentration, and inject a small amount onto the thoracic dorsal plate of an adult house fly using a microsyringe. dripped.

The house flies tested were insecticide-sensitive and insecticide-resistant. After 24 hours, the animal was examined for viability and the 50% lethal dose (LDso (μg/@)) was determined.

The results are shown in Table 2.

Table 2 Test Example 2 A filter paper of the same size was placed on the bottom of a polyethylene cup with a diameter of 5.5 strokes, and a 2500-fold water dilution of an emulsion containing the compound of the present invention or piperonyl butoxide according to Formulation Example 7 (resmethrin 20 ppm) was added. equivalent) 0.7g? was dropped onto the filter paper, and 30 g Iq/of sucrose was added to the cup as bait.

Ten female adult house flies were released into the container, the lid was placed on the container, and 48 hours later, their viability was determined and the mortality rate (%) was determined (2 repetitions). Note that the house fly used as the test sample was the same as in Test Example 1.

The results are shown in Table 3.

Table 3 Test Example 3 (70011) 10 adult female Culiae mosquitoes were released into a glass container (corresponding to the compound of the present invention according to Formulation Example 1 or an oil solution containing piperonyl butoxide (phenothrin 5001) 1)m). 0.5 ysl of was sprayed into a glass chamber/<n for 10 minutes. During this time, the number of knockdown insects was checked at regular intervals, and the 50% knockdown time (KT5o (minutes)) was determined. 24 more
After a certain period of time, whether the animals were alive or dead was checked and the mortality rate (%) was determined. The results are shown in Table 4.

Table 4 Test Example 4 A 1000-fold water dilution of an emulsion containing the compound of the present invention or piperonyl butoxide according to Formulation Example 6 (phenothrin 5
01) I) equivalent to m) per 2 cups on a turntable to 180 tel plastic cups of rice one month after sowing.t) 15gf? Spread. After air-drying, cover with a wire mesh cage and place insecticide-resistant leafhopper adults 15.
The head was released, and 24 hours later, the animal was examined to see if it was alive or dead, and the mortality rate was determined (2 repetitions). Furthermore, adults appeared in the same manner 3 and 7 days after spraying, and their survival and death were examined 24 hours after each application, and the mortality rate (
%) was determined (2 replicates). The results are shown in Table 5.

Table 5 * Comparison and control l-naphthyl N-methylcarbame) 50
2000 times water dilution of 96 hydrating powder (equivalent to 250 ppm) **Comparison vs.
1')I)m equivalent) Test Example 5 According to Formulation Example 6, 4 times the amount (weight ratio) of the compound of the present invention C) or piperonyl butoxide was added to fenvalerate or permethrin to form an emulsion, and these were diluted with 500 times water. diluent (fenvalerate or permethrin 11001) (corresponding to I)). This has a diameter of 6
Cabbage leaves cut into circles of α were soaked for 1 minute, air-dried, then transferred to a plastic petri dish, and insecticide-resistant diamondback moths were grown for 2 minutes.
0 animals were released, and 48 hours later, their survival was examined and the mortality rate was determined (2 repetitions).

The results are shown in Table 6.

Table 6 * Comparison control S-methyl N-(methylcarbamoyloxy)thioacedemidate 45% hydrating powder diluted 1000 times with water (equivalent to 450p1 m)

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a hydrogen atom, a lower alkyl group, or a lower alkynyl group, and n is 1, 2 or 3
represents. ] A methylenedioxybenzyl ether compound represented by 2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents a halogen atom. ] Halogenated α-isopropyl-3,4-methylenedioxybenzyl represented by the general formula H-(OCH_2CH_2)-_nOR [wherein R represents a hydrogen atom, a lower alkyl group or a lower alkynyl group, and n is 1 , represents 2 or 3. ] There are general formulas ▲ numerical formulas, chemical formulas, tables, etc. that are characterized by reacting with (poly)ethylene glycol monoether shown by ▼ [In the formula, R and n are the same as above. ] A method for producing a methylenedioxybenzyl ether compound. 3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents a hydrogen atom, a lower alkyl group, or a lower alkynyl group, and n represents 1, 2, or 3. ] An insecticidal efficacy enhancer comprising a methylenedioxybenzyl ether compound represented by the following.