JPH03115203A - Insecticide and acaricide containing 2-arylpropyl ether derivative - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (Ar is phenyl, phenoxy, lower cycloalkyloxy, lower alkoxy lower alkoxy, lower alkoxy lower alkylthio, lower haloalkoxycarbonyl or phenyl replaced with tetrahydrofuryloxy). EXAMPLE:3 Phenoxybenzyl 2-[4-(cyclohexyloxy)phenyl]-2-methylpropyl ether. USE:An insecticide and an acaricide, having low toxicity to human, animals, fishes, excellent immediate effects, residual effects and flushing effects and effective for controlling sanitary insect pests such as flies and cockroaches, agricultural insect pests such as leafhopper, cabbage armyworms and diamond moth, louse, acarid, etc. PREPARATION:A compound shown by formula II {one of A and B is halogen and the other is O-M [M is H, alkaline (earth) metal or both A and B are OH} is reacted with a compound shown by formula III to readily give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a low toxicity insecticide and acaricide containing a novel 2-arylpropyl ether derivative.

More specifically, the present invention relates to the general formula (1) (wherein Ar is a phenyl group, a phenoxy group, a lower cycloalkyloxy group, a lower alkoxy lower alkoxy group, a lower alkoxy lower alkylthio group, a lower haloalkoxycarbonyl group, or a tetrahydrofuryl group). This invention relates to an insecticide and acaricide characterized by containing a 2-arylpropyl ether derivative represented by (representing a phenyl group substituted with an oxy group).

Pesticides have played an extremely important role in improving agricultural productivity, and the appearance of synthetic organic pesticides has completely changed the food situation for humankind, bringing great benefits in terms of preventing infectious diseases transmitted by insects.

However, the use of organochlorine insecticides DDT and BIIC is limited because they remain in the environment for a long time after use, and these have been replaced by organophosphorus insecticides and carbamate insecticides. Although they are widely used, problems have arisen in the resistance of various insect pests to these insecticides.

In addition, difficult-to-control pests are appearing in some areas, and it is expected that problems such as drug-resistant pests will continue to spread and become more serious in the future.

To this day, as humans seek to continue to provide sufficient food for the foundation of their civilization and for further development in the future, the emergence of drugs with better insecticidal activity has been urgently needed. There is.

In recent years, synthetic pyrethroid insecticides have been in the spotlight against this background. It has excellent insecticidal power and is highly effective against pests resistant to organic phosphorus agents or carbamate agents, and is characterized by relatively low toxicity to humans and livestock. However, the fatal drawback of this synthetic pyrethroid insecticide is that it is extremely toxic to fish, which limits its range of use. Furthermore, they are more expensive than conventionally developed insecticides.

The agricultural chemicals that will be developed in the future must be able to overcome the drawbacks mentioned above. In other words, it is desirable that it be highly safe, leave no residue, decompose quickly and do not pollute the environment, be highly active against the current problem of drug-resistant and difficult-to-control pests, and be manufactured at low cost. It is.

The present inventors have devoted themselves to research and development of insecticidal and acaricidal agents that meet the above conditions, and have found that 2-phenylpropyl ether derivatives and thioether derivatives have high insecticidal and acaricidal activity, are fast-acting and It has been found that this compound has excellent residual efficacy, has low toxicity not only to humans and livestock, but also to fish, and can be put to practical use at a relatively low cost.

After further exploration of this group of compounds and research on their insecticidal properties, the combination of two types of alcohol residues led to the discovery that
Excellent pest insect with selective and non-selective effects on Lepidoptera, Orthoptera, Hemiptera, Termite, Diptera, Acari, etc., has a wide insecticidal spectrum, and has extremely low toxicity to humans and livestock. It has been found that it can be used as a pesticidal composition. In addition, many of them were found to have low toxicity to fish, leading to the completion of the present invention.

The compound of the present invention has an active structure different from that of conventional pesticides,
In addition to sanitary pests such as flies, mosquitoes, and cockroaches, it is highly effective against agricultural pests such as planthoppers, leafhoppers, armyworms, diamondback moths, leafhoppers, aphids, caterpillars, and spider mites, especially against leafhoppers. It is also extremely effective in controlling stored grain pests such as , Japanese bollworm moth, and brown elephant, animal parasitic lice, and mites, and is also effective against other pests.

Furthermore, the compound of the present invention has excellent fast-acting properties and residual effectiveness, and also has a flushing effect. The compound of the present invention not only knocks down and kills pests, but also has repellent properties and has the effect of repelling pests from hosts.
It has the great advantage of not causing any phytotoxicity to Solanaceae plants, such as fenvalerate, which is a representative synthetic pyrethroid. In addition, it has low toxicity to mammals. Some of the compounds of the present invention are also highly safe for fish, and are not only suitable for exterminating pests in rice fields, but also for exterminating aquatic pests such as mosquitoes and mite larvae. Alternatively, it can be used to exterminate pests by spraying by aircraft over a wide area dotted with lakes, marshes, ponds, rivers, etc., without the risk of killing the fish that live there.

Therefore, the insecticides and acaricides containing the compounds of the present invention can be applied in a very wide range of situations, including against agricultural and horticultural pests.

They are highly active as insecticides and acaricides for grain storage pests, sanitary pests, house pests, forest pests, and some aquatic pests, and are extremely safe and can be put to practical use in various formulations at low cost.

The 2-arylpropyl ether derivative represented by the general formula (1) according to the present invention is a new compound.
The phenyl group represented by is a phenyl group which may be optionally substituted with the same or different substituents shown below. Examples of the substituent include phenyl, phenoxy, cycloalkyloxy, alkoxyalkoxy, alkoxyalkylthio, haloalkoxycarbonyl, and tetrahydrofuryloxy groups.

Specific examples of the aryl group are shown below, but are not limited to the examples. That is, 4-cyclopentyloxyphenyl group, 4-biphenyl group, 4-phenoxyphenyl group, 4-cyclohexyloxyphenyl group, 4-methoxymethoxyphenyl group, 4-ethoxymethoxyphenyl group, 4-(1-ethoxyethoxy ) Phenyl, L%,
'l-(]-methoxyethoxy)phenyl group, 4-(
2-ethoxyethoxy)phenyl group, 4-(2゜2.
2. -trifluoroethoxycarbonyl)phenyl group,
Examples include 4-methoxymethylthiophenyl group, 4-(tetrahydro-3-furyloxy)phenyl group, and 4-ethoxymethylthiophenyl group.

Next, the method for producing the compound of the present invention will be described in detail as follows.

The compound represented by the general formula (II) is converted into a compound represented by the general formula (m)C
H.

[In the formula, Ar represents the above-mentioned meaning, one of the groups A and B represents a halogen atom, and the other group represents an OM group (in the formula, M is a hydrogen atom or an alkali or alkaline earth atom) The 2-arylpropyl ether derivative represented by the general formula (1) can be easily produced by reacting it with a compound represented by the following formula (representing a metal atom) or both representing a hydroxyl group].

That is, when the alcohol of the general formula [■] [in the formula, the group A represents an O-H group] is reacted with the halide of the general formula [■] [in the formula, the group B represents a halogen atom], The desired 2-arylpropyl ether derivative can be obtained by carrying out one reaction at room temperature to heating in a suitable solvent in the presence of a base as a deoxidizing agent. The bases mentioned here refer to alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal hydrides, alkali metal alcolades, alkali metal oxides, alkali metal carbonates, sodium amide, triethylamine, etc., and also deoxidizing agents. Silver oxide can also be used as a metal. In addition, water can be used as a solvent,
Aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, and petroleum benzene;
Halogenated hydrocarbons such as chloroform and dichloromethane, non-prone polar solvents such as dimethylformamide and dimethyl sulfoxide, lower alcohols such as methanol and ethanol, diisopropyl ether, diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, Ethers such as dioxane, nitriles such as acetonitrile and propionitrile, ketones such as acetone and diisopropyl ketone, etc. can be used. Further, by using a phase transfer catalyst such as tetra-n-butylammonium bromide or triethylbenzylammonium bromide as a catalyst, the 2-arylpropyl ether derivative having the l'-like structure can be obtained in good yield.

General formula [■] In the c formula, the group A represents an O-M group (in the formula, M is not a hydrogen atom)] and the general formula [■] [In the formula, the group B represents a halogen atom] When reacting with a halide in [case], a 2-arylpropyl ether derivative can be obtained by carrying out one reaction in the above-mentioned solvent at room temperature to heating. If the reactivity is poor, it is also suitable to add a catalytic amount of potassium iodide, copper iodide, etc.

Halide of general formula [■] [where group A represents a halogen atom] and general formula [■] [where group B is a 0-M group (
In the case where M represents the above-mentioned meaning), the reaction can be carried out in the same manner as described above. In particular, the general formula [■] [wherein the group A
represents a halogen atom] and the general formula [■
When reacting the alcohol of formula c, where group B represents an 0-H group, in the presence of an aprotic polar solvent, preferably dimethyl sulfoxide or sulfolane, and in the presence of a base as a deoxidizing agent, The desired 2-arylpropyl ether derivative can be obtained in good yield by reacting under heating.

When the alcohol of the general formula [■] [in the formula, the group A is a hydroxyl group] is reacted with the alcohol of the general formula [■] [in the formula, the group B is a hydroxyl group], a catalyst is present. A 2-arylpropyl ether derivative can be obtained by performing a dehydration reaction below. Sulfuric acid as a catalyst,
Acid catalysts such as hydrochloric acid, aromatic sulfonic acids and sulfonic acid chlorides, boron trifluoride, aluminum chloride, etc. can be used. Iodine, solid acid catalysts (alumina-titanium oxide, etc.), dimethyl sulfoxide, alumina, sulfamide, ion exchange resins, etc. can also be used as dehydration catalysts. If necessary, it is preferable to carry out the reaction in an inert solvent such as benzene or toluene that is azeotropic with water while removing produced water under reflux.

In addition, the alcohol of the general formula [■] [where the group A represents a hydroxyl group] is dissolved in the presence of a dehydrating agent, and if necessary in the presence of a catalyst. A 2-arylpropyl ether derivative can also be obtained by reacting with an alcohol [in case of a group]. The dehydrating agent is preferably, for example, N,N=substituted carbodiimide, especially N,N-dicyclohexylcarbodiimide, and the catalyst is, for example, cuprous chloride. The reaction is carried out in the presence of a suitable inert solvent or diluent at room temperature or under heat. Suitable solvents or diluents include, for example, ethers such as l,2-jethoxyethane, dioxane, and tetrahydrofuran, aprotic polar solvents such as dimethylformamide, hexamethylphosphonic acid triamide, and dimethyl sulfoxide, acetone, methyl ethyl ketone, and cyclohexanone. Examples include ketones.

In addition, as a method for producing 2-arylpropyl ether derivatives, metal alcoholades or sulfonic acid esters of alcohols of general formula [■] [in the formula, group A represents a hydroxyl group] and general formula [■] [in the formula , when the group B is a hydroxyl group], a method for reacting the alcohol of the general formula [■] [where the group A is a hydroxyl group] with the alcohol of the general formula [■] [where the group B is When the alcohol is a hydroxyl group, there are methods of reacting the alcohol with a metal alcoholade or a sulfonic acid ester, but these methods are disadvantageous in terms of yield.

Is the starting material represented by general formula (II) known?
Or produced by methods similar to known methods described in the literature. That is, the alcohol represented by the general formula [■] [where JJA represents a hydroxyl group] is, for example, the corresponding arylacetonitrile A ".CH,.
It is obtained by alkylating CN [Ar represents the above-mentioned meaning] with an alkyl halide, then hydrolyzing the obtained nitrile to convert it into the corresponding carboxylic acid, and reducing the carboxylic acid.

Alternatively, a halide obtained by adding methallyl halide to an aryl (when group A represents a halogen atom in general formula (II)) is converted into an alcohol.

An example manufacturing route is shown diagrammatically below.

in toluene CH.

50% Na OH or KOI + Phase Transfer Catalyst References Roczniki Chem, + 39(9), 1
223 (1965) (Pal) (Chemical
Abstract (1966)) 6 64° 12595° [In formula [■], group A is a halogen atom] References Chem, Ber, 94. 2609(
1961) f:VI) (1) Mg (
II) (Group A=○H)-> (2)0□ (3) +1”30 References J, Am, Chem, Soc,, 65
．． 14.69 (1943) References Chem, Ber
,, 94. 2609 (1961) [■] [Group A = OH] is synthesized by the following route (3).

In addition, the alcohol of the general formula [■] [where the group A is a hydroxyl group] is Helvetica Chimi
ca Acta, 54.868 (1971).

The metal alcoholade of the general formula [■] [where the group A represents an O-M group and 1M is not a hydrogen atom] is prepared by a conventional method.
For example, it can be easily obtained by reacting a total hydride such as sodium hydride with an alcohol of general formula [■] [where group A represents an OM group and 1M is a hydrogen atom]. I can do it.

The alcohol of the general formula [■] [where group B is a hydroxyl group] is known as an alcohol component of synthetic pyrethroids.

Next, the method for producing the 2-arylpropyl ether derivative of the present invention will be described in more detail with reference to synthesis examples.

Reference synthesis example 1. (Etherification method A) Synthesis of 3-phenoxybenzyl 2-[4-(cyclohexyloxy)phenyl]-2-methylpropyl ether.
0% jon on) 0.50g, then 2-C
A solution of 2.5 g of 4-(cyclohexyloxy)phenyl-2-methylpropyl alcohol/10 mQ acetonitrile was added dropwise at 50°C.

After heating under reflux for 30 minutes, 3-phenoxybenzyl bromide 2. The mixture was added dropwise between 50 to 50°C, and the mixture was further heated under reflux for 1 hour. After cooling to room temperature, it was poured into water and extracted with toluene.

The toluene extract was washed with saturated saline and dried.

The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography on 100 g of silica gel (developing solvent: toluene-hexane (1: )) to obtain the desired ether (yield: 78%). Ta.

n'D.・J. , 55] 6 Elemental analysis value: C2S■z40i C H Calculated value (%) 80,89 7.96
Measured value (%)' 8]. 13 7.78 Reference synthesis example 2. (Etherification method B) Synthesis of 3-phenoxybenzyl 2-(4-phenoxyphenyl)-2-methylpropyl ether Toluene 2
Sodium hydride (60% in oil) 0m12
, 2.42 g of 2-(4-phenoxyphenyl)-2-methylpropyl alcohol was added and heated under reflux.
g/25% DMF-toluene lOmQ solution was added dropwise over 15 minutes.

Stirring was continued for 10 minutes, and then a toluene solution of 3.9 g/Ion (l) of 3-phenoxybenzyl bromide was added dropwise over 20 minutes. After heating under reflux for 1 hour, the mixture was cooled to room temperature and drained into water.Toluene The toluene extract was washed with water and then dried.

The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography on 120 g of silica gel (developing solvent: toluene-hexane (1:1)) to obtain the desired ether (yield 79%). .

np”’1.5930 Elemental analysis value: C2, H□. 0.

C H Calculated value (%) 82.05 6.65
Measured value (%) 82.22 6.47
Reference synthesis example 3. (Etherification method C) 3-phenoxybenzyl 2-[4-ethoxymethoxy)phenyl]-2-methylpropyl 50% sodium hydroxide 30 g, 2-(4-(ethoxymethoxy)phenyl]-2-methylpropyl alcohol 4 .5g, 3-phenoxybenzyl chloride 4.4g
and 1.0 g of tetrabutylammonium bromide were added, and the mixture was heated under reflux at 80° C. for 1 hour. After cooling to room temperature, water was added, extracted with toluene, and washed with water.

After drying the toluene extract, the toluene was distilled off under reduced pressure, and the resulting crude ether was subjected to column chromatography on 160 g of silica gel (developing solvent: 1-luene-hexane).
1:1)) to purify the desired ether (yield: 8
1%).

n♂0・'1.5330 Elemental content value: C26H,. 0°CH Calculated value (%) 76.82 7.44 Measured value (%) 76.58 7.63 Reference synthesis example 4. (Etherification method D) Synthesis of 3-phenoxybenzyl 2-(4-(cyclopentyloxy)phenyl-2-methylpropyl ether 2-(4-(cyclopentyloxy)phenyl)-2
-A mixture of 4.7 g of methylpropyl alcohol, 4.4 g of 3-phenoxybenzyl chloride, 1.0 g of h-ethylbenzylammonium bromide, and 20ε of 50% sodium hydroxide was stirred at 50°C for 2 hours.

After adding water and benzene and shaking well, the mixture was separated. The benzene layer was washed with water and dried. The crude ether obtained by distilling off benzene under reduced pressure was subjected to column chromatography on 160 g of silica gel (developing solvent: toluene-hexane (1:
1)) to obtain the desired ether (yield 85%).
) was obtained.

rl♂'・J, 5753 1225, 1110° 3.31 (211, s), 4.36 (211, s), 4
．． 62 (111, m), 6.6-7.3 (138, m)
.

Elemental analysis value: Czsl13zO:+ CH Calculated value (%) 80.73 7.74 Measured value (%) 80.55 7.89 Reference synthesis example 5. (Etherification method E) Synthesis of 3-phenoxybenzyl 2-(4-phenylphenyl)-2-methylpropyl ether 9.98 g of 4-phenylneophyl chloride, 9.67 g of 3-phenoxybenzyl alcohol, 45% sodium hydroxide 3
．． 9 g and 48 g of dimethyl sulfoxide were heated and stirred at 140° C. for 3 hours. 45% sodium hydroxide 1.8g
was added, and the reaction was continued at the same temperature for an additional 4 hours. The reaction solution was poured into water, extracted with benzene, and the benzene extract was washed with water and then dried. The crude ether obtained by distilling off benzene under reduced pressure was subjected to column chromatography on 400 g of silica gel (developing solvent: toluene-hexane (1:1).
)) to obtain the desired ether (yield 82% vs. consumed 4-phenylneophyl chloride).

no"' l -6066 Elemental analysis value: C2, H□60□ CI+ Calculated value (%) 85.26 6.91 Measured value (%) 85.44 6.79 Regarding typical compounds of the present invention The notation is as shown in Table 1.

A typical method for producing the starting material [[] will be explained below using reference examples.

Reference example 1゜2-(4-(cyclopentyloxy)phenyl]-2-
Synthesis of methylpropyl alcohol Synthesis was performed according to the following sequence.

(1) A mixture of 10 g of 4-(cyclopentyloxy)acetonitrile, 20 g of potassium hydroxide, 20 g of water, and 2 g of triethylbenzylammonium bromide was
While maintaining the temperature at 0°C to 90°C, 7 g of methyl iodide was added dropwise over 1 hour. Next, 10 g of potassium hydroxide and 2 g of triethylbenzylammonium bromide were added, and at the same temperature, 7 g of methyl iodide was added dropwise over 2 hours.

After cooling to room temperature, extraction was performed with toluene.

11.0 g of crude α,α-dimethyl 4-(cyclopentyloxy)acetonitrile was obtained from the toluene layer.

(2) α,α-dimethyl compound synthesized by (+) 11.0
A mixture of 80 g of diethylene glycol, 20 g of water, and 20 g of potassium hydroxide was stirred at 130°C to 150°C for 6 hours.

After cooling to room temperature, water and toluene were added and stirred. After standing still, the aqueous layer was separated. This was acidified with concentrated hydrochloric acid, and then extracted with ether. The ether extracted solution was washed with water and then dried. Ether was distilled off under reduced pressure to give 2-[4
8.5 g of -(cyclopentyloxy)phenyl]-2-methylpropionic acid was obtained.

Melting point = 108-110°C Elemental analysis value: C0, +1□. 03 CH Calculated value (%) 72,55 8.12 Measured value (%) 72.48 8.08 (3
) 2.5 g of lithium aluminum hydride was added to 30 mQ of dry tetrahydrofuran, and while heating and refluxing, a solution of 8.0 g of 2-(4-(cyclopentyloxy)phenyl-2-methylpropionic acid synthesized in (2))/20 companies of dry tetrahydrofuran was added. was added dropwise over 1 hour. After further heating under reflux for 1 hour, ethyl acetate and water were added in that order under water cooling to decompose excess lithium aluminum hydride. Next, extraction was performed with toluene. The obtained toluene solution was washed with water, After drying, the solvent was distilled off under reduced pressure to obtain 6.5 g of the desired 2-(4-(cyclopentyloxy)phenyl-2-methylpropyl alcohol).

Elemental analysis value: C1, +1220□ CH Calculated value (%) 76.88 9.46 Measured value (%) 76.76 9.38 Reference example 2゜2-(4-(cyclopentyloxy)phenyl2-
Methylpropyl alcohol was then synthesized according to the following sequence.

(1) 2,4-bis(
Add 8.0 g of 4-hydroxyphenyl)-4-methyl-2-pentene, 8.0 g of potassium hydroxide and 8.0 g of water, and add cyclopentyl bromide at 105-110°C.
++Q was added dropwise over 1 hour, and the mixture was kept at the same temperature for 1 hour. After cooling to room temperature, it was drained into water and extracted with toluene.

After washing the toluene extract with water and drying, the solvent was distilled off under reduced pressure to obtain 12.8 gt% of the target 2,4-bis[4-(cyclopentyloxy)phenyl-4-methyl-2-pentene.
is.

(2) 12.8g of 2.4-bis[4-
(cyclopentyloxy)phenyl-4-methyl-2
- Pentene was dissolved in 150 mQ of acetone and 50 g of potassium permanganate was added at 30°C. 1 at 30℃
After stirring for 0 hours, 20 mQ of ethyl alcohol was added dropwise under cooling to decompose excess potassium permanganate. After continuing to stir for 1 hour, the produced manganese dioxide was filtered and thoroughly washed with water and acetone. Acetone was distilled off under reduced pressure, acidified with dilute hydrochloric acid, and extracted with toluene. A dilute aqueous sodium hydroxide solution was added to the obtained toluene solution, and after shaking well, the aqueous layer was separated. The resulting aqueous solution was then acidified with concentrated hydrochloric acid, extracted with toluene, washed with water, and dried. Toluene was distilled off under reduced pressure to obtain 6.8 g of the desired 2-[4-(cyclopentyloxy)phenyl]-2-methylpropionic acid.

(3) Process according to Reference Example 1 (3) to obtain the desired 2-[4-
(Cyclopentyloxy)phenyl-2-methylpropyl alcohol was obtained.

Other 2-aryl-2-methylpropyl alcohols were synthesized by the methods of Reference Examples 1 and 2 or by known methods.

When actually applying the compound of the present invention, it can be used alone without adding other ingredients, but in order to make it easier to use as a pesticidal agent, it can be formulated with a carrier and diluted as necessary. It is generally applied as follows. No special conditions are required for formulating the compound of the present invention.

Emulsions,
Prepared into any dosage form such as wettable powders, powders, granules, fine granules, oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.), fumes such as Folaking, non-heated fumigants, poison baits, etc. I can do it,
These can be used for various purposes depending on their purpose.

Furthermore, by combining two or more of these compounds of the present invention, it is possible to exhibit superior insecticidal and acaricidal activity, and also to use other physiologically active substances.

For example, allethrin, N-(chrysansemoylmethyl)-
3,4,5,6-titrahydrophthalimide, 5-
Benzyl-3-furylmethyl chrysanthemate, 3-phenoxybenzyl chrysanthemate, 5-propargylfurfuryl chrysanthemate, other known cyclopropane carboxylic acid esters, 3-phenoxybenzyl 2,
2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylate, 3-phenoxy-
α-cyanobenzyl 2,2-dimethyl-3-(2,2
-dichlorovinyl)-cyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl 2.2
-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-1-carboxylate, 3-phenoxy-
Synthetic pyrethroids such as α-cyanobenzyl α-isopropyl-4-chlorophenylacetate and their various isomers or pyrethrum extract, o,o-diethyl-o-(3-oxo-2-phenyl-2H-pyridazine-6- yl) phosphorothioate (Mitsui Toatsu Chemical registered trademark Offnac), o,o-dimethyl-α-(2,2-dichlorovinyl)-phosphate (DDVP), o,o-
Dimethyl-α-(3-methyl-4-nitrophenyl)phosphorothioate, diazinon, o,o-dimethyl-
o-4-cyanophenyl phosphorothioate, 0.0-
Dimethyl-5-(α-(ethoxycarbonyl)benzyl)phosphorodithioate, 2-methoxy-411-1,
3,2-benzodioxaphosphorine-2-sulfide,
Organophosphorus insecticides such as 0-ethyl-〇-4-cyanophenylphenylphosphonothioate, l-naphthyl-N
-Methyl carbamate (NAC), m-tolyl-N-
Methyl carbamate (MTMC), 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-dimethylcarbamate (pyrimer), 3.4-dimethylphenyl N-methylcarbamate, 2-impropoxyphenyl N-methylcarbamate, etc. By mixing with carbamate insecticides, other insecticides, acaricides or fungicides, nematicides, herbicides, plant growth regulators, fertilizers, BT agents, konchu hormone agents, other agricultural chemicals, etc. Furthermore, multipurpose compositions with excellent efficacy can be created, and synergistic effects can also be expected.

Further, for example, α-(2-(2-butoxyethoxy)ethoxy)-4,5-methylenedioxy-2-propyltoluene (piperonyl butoxide), 1,2-methylenedioxy-4-(2- (Octylsulfinyl)propyltrunzene (sulfoxide), 4-(3,4-methylenedioxyphenyl)-5-methyl-1,3-dioxane (safloxane), N-(2-ethylhexyl)-
Bicyclo(21211) but-5-ene-2,3-dicarboximide (MGK-264), octachlorodipropyl ether (s-421).

Its potency can also be increased several times by adding known synergists for pyrethroids, such as impolnyl thiocyanoacetate (Garnite).

The compound of the present invention has high stability against light, heat, oxidation, etc., but if necessary, antioxidants or ultraviolet absorbers, such as phenol derivatives such as BIT and BHA, bis-phenol derivatives, and phenyl-α - naphthylamine,
By adding an appropriate amount of arylamines such as phenyl-β-naphthylamine, a condensate of phenetidine and acetone, or benzophenone compounds as a stabilizing side,
A composition with more stable effects can be obtained.

The insecticide and acaricide of the compound of the present invention contains the compound at a concentration of 0.000
1-99% by weight, preferably 0.001-50% by weight
Contain.

Next, some examples of formulations in which the compound of the present invention is used as an insecticide or acaricide will be shown, but the present invention is not limited to these. All "1 part" indicates parts by weight.

Formulation Example 1 20 parts of the compounds of the present invention compounds listed in Table 1, compound numbers 1 to 10 (the same applies hereinafter), 20 parts of Tsurupol SM-100 (Toho Chemical 5xLG brand name), and 60 parts of Kijirol were stirred and mixed to make an emulsion. shall be.

Formulation Example 2 1 part of the compound of the present invention is dissolved in 8210 parts of acetic acid, 99 parts of clay for powders are added, and the acetone is evaporated to form a powder.

Formulation Example 3: Add 5 parts of surfactant to 20 parts of the compound of the present invention, and
After the dH combination, 5 parts of Kane 91 Fu was added, and the mixture was stirred and mixed in a Raikai machine to form a wettable powder.

Formulation Example 4: Add 2 parts of meta-tolyl N methyl carbamate to 0.2 parts of the compound of the present invention, and further add 0.2 parts of PAP (registered trademark of Nihon Kagaku Kogyo, physical property improver) and dissolve in 10 parts of acetone. Then, add 97.6 parts of clay for powder, stir and mix in a laikai, and evaporate the acetone to form a powder.

Formulation Example 5: Add 2 parts of Offnac (registered trade name of Mitsui Toatsu Chemicals) to 0.2 parts of the compound of the present invention, further add 0.2 parts of PAP (mentioned above), dissolve in 8210 parts of acetic acid, and prepare powder preparation. 97 clay
．． Add 6 parts and stir and mix in a laikai vessel, and evaporate the acetone to obtain a powder.

Formulation Example 6゜0.5 part of piperonyl butoxide to 0.1 part of the compound of the present invention
If you add 1 part to 100 parts and dissolve it in white kerosene, you will get an oil solution.

Formulation Example 7゜5 parts of Tsurupol 5M-200 (mentioned above) were added to 0.5 parts of the compound of the present invention and 5 parts of Offnac (mentioned above), and Kijirol 8
When dissolved in 9.5 parts, it becomes an emulsion.

Formulation Example 8 Compound of the present invention, 0.4 parts, piperonyl butoxide 0.
Mix and dissolve 2 parts, 6 parts of Kijiroll, and 17.6 parts of a deodorizing lamp, fill it into an aerosol container, attach the valve part, and then spray the propellant (6h gas of oxide stone) through the valve part.
If 84 parts are filled under pressure, it becomes an aerosol.

Formulation Example 9: When 0.05 g of the compound of the present invention is dissolved in an appropriate amount of chloroform and evenly adsorbed onto the surface of asbestos of 2.5 cm x 5 cm and 3 mm thick, a hot plate heating fiber fumigation insecticidal composition is obtained. becomes.

Formulation Example io.

The compound of the present invention 0° was dissolved in 20 mQ of methanol, and 99.5 parts of a carrier for incense sticks (mixed tab flour: lees flour: wood flour in a ratio of 3:5:1) was uniformly stirred and mixed. After evaporating the methanol, add 150 mQ of water, mix well, mold and dry to make mosquito coils.

Formulation Example 11゜1 part of the compound of the present invention, 3 parts of Offnac (mentioned above), 7 parts of Cerogen
Granules are obtained by mixing 2 parts of A (trade name of Daiichi Kogyo Seiyaku) and 2 parts of Sunextract (Yamaba Kokusaku Pulp Product) with 92 parts of clay, adding water, granulating the mixture, and sizing to the optimum particle size.

When applying the compound of the present invention, the amount of the active ingredient is generally 300g-1g per 10 ares, preferably 1g.
00g to 2g, more preferably 20g to 5g.

Next, the compound of the present invention has excellent insecticidal and acaricidal effects,
In order to clarify that it has low toxicity to warm-blooded animals and relatively low toxicity to fish, test examples are shown below.

Sample 2 20 parts of the compound of the present invention and Tsurupol 5M-200
(Toho Chemical registered trademark) 60 parts of Kijirole were added to 20 parts of the mixture, and the mixture was thoroughly stirred and mixed. Dilute the emulsion with distilled water to each test concentration.

Fish toxicity test is performed by dissolving the raw material of the test compound in acetone.
% solution and add the specified amount to water.

For toxicity tests on mice, the drug substance is dissolved or suspended in corn oil.

As control compounds, comparative compounds (a) to (i) shown below were used for testing in the same manner as for the compound of the present invention.

(a) (Publicly known Japan Information
ation Na33.13 (+977)) (c) Pyrethrin (d) Offnac (supra) (e) MTMG (supra) (f) Methomyl (S-methyl N-(methylcarbamoyloxy)thioacetamidate) (g ) DDVP (supra) (h) Ortolan (O,S-dimethyl N-acetylphosphoramidothiol note) (i) Permethrin [3-phenoxybenzyl 2,2-
Dimethyl-3-(2,2-diglolobinyl)-cyclopropane-1-carboxylate] Test side 1. Effects on Spodoptera trifoliata Emulsions of each test compound prepared according to Preparation Example 1 were mixed at 100 and 20%.
Prepare to pp+na degree. 10 sweet potato leaves for each solution
After being immersed for a second and air-dried, it was placed in a plastic cup with a diameter of 10 cm, and second instar larvae of Spodoptera were released and left in a constant temperature room at 25°C. 24 hours after treatment, the number of live and dead insects was investigated, and the mortality rate was calculated. The results are shown in Table 2 as the average value of three consecutive tests.

The test compounds are indicated by compound numbers in Table 1 above.

(The same applies hereinafter) Table 2 Test Example 2. Effect on resistant black leafhopper and susceptible black leafhopper Young paddy rice seedlings (2 to 3 leaves) were cultivated in pots with a diameter of 5c + a, and 100 and 20 ppma solutions of each test chemical prepared in the same manner as in Test Example 1 were applied to a sprayer. 32Q each
/Pot treated. After air-drying, the seedlings were covered with a wire mesh cylinder, and 10 adult female insects of resistant leafhopper (originated in intercultivation) and susceptible leafhopper (produced in Chigasaki) were released into each pot, and left in a glass greenhouse for 6 treatments to determine whether the insects were alive or dead after 24 hours. The number of deaths was investigated and the mortality rate was calculated. The results are shown in Table 3 as the average value of three runs.

Table 3 Test Example 3 Effect on adult two-spotted spider mites Ten adult two-spotted spider mites were placed on water-soaked absorbent cotton (2cm x 2c+n) with leaf disks of green bean leaves punched out with cork polar (diameter 15 mm). A chemical solution of each test drug having a concentration of 1,100 pp was applied to the sample at 3 mp using a spray tower.

After the treatment, it was left standing in a constant temperature room at 25°C, and the number of living and dead insects was investigated 24 hours after the treatment to determine the adult killing rate. The results are shown in Table 4 as the average value of three series.

Table 4 Test Example 4゜Fish Toxicity Fill a water hinoki with a width of 60 cm, a length of 30 cm, and a height of 40 cm+++, release 10 carp fish of the same size, approximately 5 CI11 in body length, and allow them to acclimate. 10.1 in concentration, O,
It was added at a concentration of 1Ppm, and after 48 hours, the number of living and dead fish was examined to see the effect on the fish. The results are shown in Table 5.

Table 5 Example 5 of a drug concentration test in which half of the test subjects died within 48 hours
．． Toxicity test A predetermined amount of drug dissolved or suspended in corn oil (0.2 mQ/10 g body weight) was orally administered to male mice (body weight 19-23 g), and the number of deaths was investigated after 7 days to determine the effect on the mice. . The results are shown in Table 6.

Table 6

Claims (1)

[Claims] (1) General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Ar is a phenyl group, phenoxy group, lower cycloalkyloxy group, lower alkoxy lower alkoxy group,
Lower alkoxy represents a phenyl group substituted with a lower alkylthio group, a lower haloalkoxycarbonyl group, or a tetrahydrofuryloxy group. ) An insecticide and acaricide characterized by containing a 2-arylpropyl ether derivative represented by the following as an active ingredient.