JPS6124591A - Methylenedioxybenzyl ether compound, its preparation and insecticidal effect promoting agent composed of said compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X and Y are H, lower alkyl or lower alkoxy; R is H or lower alkyl). EXAMPLE:3,4-Methylenedioxybenzyl furfuryl ether. USE:Agent for promoting insecticidal effect. PREPARATION:The objective compound can be prepared by reacting the alpha-substituted-3,4-methylenedioxybenzyl halide of formula II (X' is halogen) with furfuryl alcohol at an equivalent ratio of preferably 1:1-10, optionally in a solvent such as benzene, preferably in the presence of 1-5 equivalent of a dehydrohalogenation agent (e.g. pyridine, sodium hydroxide, 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 (11 [wherein, X and Y are the same or different and represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and R
represents a hydrogen atom or a lower alkyl group. ] 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.

It has been well known that sesamin and the like contained in sesame oil enhance the insecticidal efficacy of insecticides such as pyrethrin and allethrin. Sesamin and the like have little insecticidal efficacy by themselves, but when added to insecticides such as pyrethrin and allethrin, their efficacy is significantly enhanced. At present, 3゜4-methylenedioxy-6-propylbenzylbutyl diethylene glycol ether (hereinafter referred to as piperonyl butoxide) and N-(2-ethylhexyl)-bicyclo[2,2,1]but-5-ene ether hydrophthalic acid-2,8-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. 2'1-32 (1980). ] Under these circumstances, the present inventors have conducted intensive studies on enhancing the insecticidal efficacy of each insecticide, and have found that if the compound of the present invention is added to these insecticides and used, the insecticidal efficacy can be increased. The present inventors have discovered that scales can not only enhance insecticide resistance, but 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 optimum amount to be added may be determined 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-propargylfurfuryl dp, 1.-cis, trans-chrysanthemum acid ester).
, floparsulin (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-tetrahydrophthalimido)methyl d, l-cis.

trans-chrysanthemum acid ester), phenothrin (8-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
, l-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-chlorophenylacetate), telarethrin (2-methyl-4-oxo-3-(2-propenyl)-2 -cyclopenten-1-yl 2,2,3.3-tetramethylcyclopropanecarboxylic acid ester), d-empenthrine ((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-furarethrin ((S)-2-methyl-4-oxo-3-(2-propynyl)cyclobent-2-enyl (IR)-cis, trans-chrysanthemum acid ester) ), fenfluthrin (pentafluorobenzyl (IR,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid ester), cyfluthrin ((R,S), -4-fluoro -3-phenoxybenzyl (LR5')-cis, trans-8-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid ester), deltamethrin ((S)-α-cyano-3-phenoxy Benzyl (IR, l5)-3-(2,2-dibromovinyl) -
2,2-dimethylcyclopropanecarboxylic acid ester)
, fluparinate ((R5)-α-cyano-3-phenoxybenzyl 2-(2-chloro-α,α.

α-trifluoro-p-toluidino)-3-methylbutyric acid ester), cyhalothrin ((R5)-a-cyano-
3-phenoxybenzyl (IR5)-cis, trans-
3-(2-chloro-3,3゜3-toI7fluoroprop-1-enyl)-2,.

2-dimethylcyclopropanecarboxylic acid ester), terrarethrin ((S)-α-cyano-3-7,/-ji
z Henshi #, (IR, B S ) 2 e 2-dimethyl-3-(1,2,2,2-tetrabromoethylcyclopropanecarboxylic acid ester), (R5)-cyano-
6-phenoxy-2-pyridylmethyl (IR3)-cis, trans-8-(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, (R8)-〇-cyano 3-phenoxy Benzyl (S”)-2-(4-difluoromethoxyphenyl)-3-methylbutyric acid ester, (R5)-α-cyano-
3-phenoxybenzyl 2,2-dichloro-1-(4-
(ethoxyphenyl)-cyclopropane carboxylic acid ester, etc. Carbamate insecticides include, for example, BP
MC (2-5ec-butylphenyl N-methylcarbamate), MPMC (8,4-xylyl N-methylcarbamate), MTMC (m-tri/l/N-mef/
1/carbamate), PHC (2-isoprobogysyphenyl N-methylcarbamate), carbaryl (1-naphthyl N-methylcarbamate), etc.

The compound of the present invention has the general formula [1] [wherein X, Y and R are the same as above, and Xe represents a halogen atom]. ] Halogenated a
It can be produced by reacting a 4-methylenedioxybenzyl compound and furfuryl alcohol.

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

The amount of reagents provided for reaction 1 is halogenated α-substituted-8
, 4-methylenedioxybenzyl compound (111 equivalents), 1 to 10 equivalents of furfuryl alcohol, and 1 to 5 equivalents of the dehalogenating hydrogen agent.

The reaction temperature is from room temperature to about 100℃, and the reaction time is 0.5~
It takes about 40 hours.

Examples of the solvent 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, dimethylsulfoxide, and mixtures thereof.

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 Furfuryl alcohol 196N and sodium hydroxide 2
Add 1 g of chloride 8,4
-Methylenedioxybenzyl 869 was added dropwise over 1 hour. After further stirring at the same temperature for 2 hours, the mixture was allowed to cool, and excess sodium hydroxide was neutralized with acetic acid. Excess furfuryl alcohol was distilled off under reduced pressure, and 800 ml of toluene was added. The precipitated salt was filtered off, toluene was distilled off, and the mixture was distilled under reduced pressure to obtain 68 g of 8° 4-methylenedioxybenzylfurfuryl ether.

bp, 125-180℃10. lmHg d 1.28
68no1.5589 Some of the compounds of the present invention that can be produced by such a production method are listed in Table 1.

Table 1 Compounds When the compound of the present invention is added to the above insecticide and used as an insecticidal efficacy enhancer, the solid carrier, liquid carrier, gaseous carrier, and surfactant are usually mixed with the formulation adjuvant. oils, emulsions, hydrating agents, 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 (eg, dichloroethane, trichloroethylene, carbon tetrachloride), and the like.

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

Surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl 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. Stabilizers include isopropyl acid phosphate, tricresyl phosphate, tall oil , epoxidation part,
There are various surfactants, various fatty acids or their derivatives, etc.

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.

or! 0.25 parts, xylene 2 parts and white kerosene 97.
Mix 7 parts well to obtain an oil solution.

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

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 0.3 parts, resmethrin 02 parts, piperonyl butoxide 05 parts, the compound of the present invention (40.5 parts,
Mix 12.5 parts of deodorized kerosene and 1 part of emulsifier Atmos 300 (main component nioleic acid monoglyceride), and add 5 parts of pure water.
0 parts to emulsify, and fill 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 03 parts of fenvalerate and the compound of the present invention (1) or (
2) Dissolve 1.5 parts in 20 parts of acetone, add 98.2 parts of 300 Metsstarck, mix thoroughly with a shaker, and then evaporate the acetone 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 3005-X (main component: polyoxyethylene alkylphenyl ether), and 6 parts of xylene
Mix 0 parts thoroughly 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 7977927.5 parts, resmethrin 2.5 parts, the compound of the present invention (2) 40 parts, and emulsifier Trupol 50290
(Main component: polyoxyethylene alkylphenyl ether)2. ．． Mix 5 parts well and add 300 Metsstarck 4
Add 7.5 parts and thoroughly mix with a shaker 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 tuff flour, lees flour, and wood flour in the ratio of 3:5:1), and then mix well. 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 y of the compound of the present invention (1)
Dissolve in an appropriate amount of chloro f4/l/m, 3.5mX1
．． 5(7), adsorbed on a filter paper with a thickness of Q and 3 yxm to obtain a fumigated insecticidal composition using an electric heating plate and heated fibers.

These preparations kill insects such as sanitary pests such as flies, mosquitoes, and cockroaches, fruit tree pests such as cabbage butterflies, armyworms, diamondback moths, and noctuid moths, plant-parasitic mites, and grain storage pests such as the brown elephant and the 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 (LD5G (μg/i)) was determined. The results are shown in Table 2.

Table 2 Test Example 2 A filter paper of the same size was placed at the bottom of a polyethylene cup with a diameter of 5.5 cM, and a 250θ water diluted solution (Resmethrin 201) I of an emulsion containing the compound of the present invention or piperonyl butoxide according to Formulation Example 7 was placed on the bottom of a polyethylene cup with a diameter of 5.5 cM. )0.7m7
was dropped onto the filter paper, and 30Q sucrose was added to the cup as bait.

Ten female adult house flies were released into the container, and the container was covered with a lid. After 48 hours, the survival 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 Ten adult female Culiae mosquitoes were released into a glass chamber of 70 (W), and the compound of the present invention according to Formulation Example 1 or an oil solution containing piperonyl butoxide (phenothrin 5
0.5 ml of the solution (equivalent to ooppm) was sprayed into the glass chamber over a period of 10 minutes. During this period, the number of knockdown insects was checked at regular intervals to determine the 50% knockdown time (KT5 (1 minute)).Furthermore, after 24 hours, the survival rate was determined to determine the mortality rate (%). It is 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
．． 1) 15s+ was applied per 2 cups on a turntable to rice plants one month after sowing, which were planted in 180 goblin stick cups. After air-drying, it was covered with a wire mesh cage and 15 adult insecticide-resistant leafhoppers were released. After 24 hours, their survival was determined 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 spraying, and the mortality rate (%
) was determined (2 iterations). The results are shown in Table 5.

Table 5 *Comparison 1-Naphthyl N-methylcarbamate 50
% hydrating agent diluted 2000 times with water (250I)I)m equivalent)

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X and Y are the same or different and represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and R is Represents a hydrogen atom or a lower alkyl group. ] A methylenedioxybenzyl ether compound represented by 2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X and Y are the same or different and represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and X' represents a halogen atom. ] A general formula characterized by reacting a halogenated α-substituted-3,4-methylenedioxybenzyl compound and furfuryl alcohol ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X , Y and R are the same as above. ] A method for producing a methylenedioxybenzyl ether compound shown by 3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X and Y are the same or different and represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and R is a hydrogen atom or a lower alkyl group. represents. ] An insecticidal efficacy enhancer comprising a methylenedioxybenzyl ether compound represented by the following.