JPS5846481B2 - Pest control composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides compounds of the following general formula [I
The present invention relates to a pest control composition containing the substituted acetate represented by the following as an active ingredient, and a method for producing the same.

[In the formula, R1, R2, and R3 are the same or different and represent a hydrogen atom, a lower alkyl group, an alkenyl group, or a halogen atom, and X represents the general formula (If), (III) or (
IV) (In the formula, R4 is an allyl group, a propargyl group, a benzyl group, a thenyl group, a furylmethyl group, a phenoxydyl group, or a phenylthio group, and R3 is a hydrogen atom, a methyl group, a trifluoromethyl group, or a halogen atom, and R4 This also includes the case where R5 and R5 are bonded at the terminal to form a trimethylene chain or a tetramethylene chain.

R6 is a hydrogen atom, an ethynyl group or a nitrile group, n is an integer of 1 to 2, A is an oxygen atom, an ionic atom or -C
H=CH- group, R7 is a phthalimide group, thiophthalimide group, di- or tetrahydrophthalimide group, or dialkylmaleimide group, R8 is an allyl group, propargyl group, benzyl group, or alkagenyl group, R9 is a hydrogen atom or a methyl group. represent.

) represents a group represented by

Y represents a lower linear or branched alkyl group.

] Since the discovery of BHC and DDT, the development of basic pesticides such as phosphoric acid, carbamates, and pyrethroids has been remarkable, and they have flourished to the point where there is a strong correlation between the amount of pesticides used and crop yields. The pre-accumulation and pre-chronic conditions are considered problematic, and on the other hand, they have even encouraged the development of various resistant pests.

Therefore, it is most desirable that the substance has low toxicity, leaves little residue, decomposes quickly, and is incorporated into the ecosystem and rendered non-toxic.

In particular, it does not contain heavy metal atoms or halogen atoms, and contains carbon, hydrogen,
Oxygen-based compounds are considered to be advantageous as pesticides.

Possible active groups of existing insecticides
These active groups include organic phosphorus, carbamate, chrysanthemum ester, and organic chlorine, but engineers in the five industries know the advantages and disadvantages of each of these active groups and selectively select only the advantages from these derivatives. Currently, efforts are being made to discover new insecticides by synthesizing derivatives that leave behind.

The inventors of the present invention believe that each of the above-mentioned active groups basically has a certain range of properties as an insecticide, and that it is difficult to go beyond that range and eliminate the drawbacks. While actively searching for an active group having a new skeleton, we discovered a substituted acetate represented by the above general formula [1].

The compounds of the present invention have a very wide range of various advantages,
Its selectivity is strong, and depending on the compound, it is possible to create a structure that retains only its advantages as an agricultural chemical.

Traditionally, esters considered to be insecticidal groups, such as phosphoric acid esters and chrysanthemum esters JV, are thought to have a basic structure that is active on phosphoric acid and cyclopropanecarboxylic acid, respectively, with a double bond of S ( O) is an essential structure, and in the case of chrysanthemum acid, a three-membered ring is an essential structure, each of which acts as a core, and its activity waxes and wanes depending on changes in its surroundings.

The ester of the compound of the present invention represented by the general formula (1) is considered to have an important active basic skeleton on the acid side, and its essential structure is one hydrogen at the α-position carbon of the ester group and an appropriate substituent (1),
It is realized by having a substituted or unsubstituted ethynyl group, while the alcohol side has the above general formula (If), (
III, ], (IV, as shown in l, is an alcohol moiety of the ester group conventionally well known as pyrethroid insecticides, and can be esterified with the acid shown in the general formula [■] described later in the present invention) We have discovered a compound that has strong insecticidal efficacy and specific strong selectivity.

However, the order of activity in esters of existing alcohols with existing acids cannot be directly applied to the evaluation of the efficacy of the esters of the present invention, and exhibits completely different effects.

Therefore, esters resulting from a combination of the acid of the present invention and existing excellent alcohols do not necessarily exhibit excellent activity.

Furthermore, depending on the compatibility of the combination of the acid of the present invention with various alcohols, advantages such as fast-acting, permeability, transferability to the plant body, residual effect, lethal effect, metamorphosis-disturbing property, sterility, and ability to suppress egg production can be freely obtained. It is thought that it is possible to make this possible.

In addition, regarding the spectrum of its insecticidal efficacy, the unique combination of acid and alcohol of the present invention is selected for Coleoptera, Lepidoptera, Diptera, Orthoptera, Hemiptera, Homoptera, Acari, etc. It shows selective, non-selective efficacy.

It is also expected to be useful against pests such as nematodes.

Furthermore, since it differs from the basic structure of existing insecticides, it is of course effective against resistant insect pests, and its toxicity is generally low, as shown in the examples.

To produce the substituted acetate ester represented by the general formula (1), use the general formula (V) [wherein s R1y R2J R3 and Y represent the same meanings as above.

] or its reactive derivative and the general formula % formula % ( ) [wherein, X represents the same meaning as above.

] or its halide or sulfoxylate.

The term "reactive derivatives of acids" as used herein refers to acid halides, acid anhydrides, esters with low-boiling alcohols, or alkali metal salts, silver salts, or salts of organic tertiary bases of acids.

Furthermore, the substituted acetate ester represented by the general formula CI) has optical isomers derived from the α-1 carbon, but it goes without saying that all of these esters are included in the present invention.

To explain in more detail the method for synthesizing the substituted acetate compound represented by the general formula (1), the reaction between an acid and an alcohol is carried out under suitable dehydration conditions, for example, at room temperature or in a suitable inert solvent with dicyclohexylcarbodiimide. This is achieved by reacting at a warm temperature.

When an acid halide is used as the reactive derivative, it is reacted with the alcohol using an organic tertiary base such as pyridine or triethylamine as a deoxidizing agent to obtain the desired ester in sufficient yield at room temperature.

Any acid halide may be used within the scope of the present invention, but acid chloride is usually used.

Although the presence of a solvent is not indispensable during the reaction, its use is desirable in order to allow the reaction to proceed smoothly, and an inert solvent such as benzene, toluene or petroleum benzine is usually used.

When esters of the aforementioned acids with low-boiling alcohols (e.g. methanol, ethanol, etc.) are used as reactive derivatives, they are treated in the presence of a suitable organic base catalyst, preferably an alkali metal alkoxide or sodium hydride of the corresponding low-boiling alcohol. The desired ester can be obtained in good yield by carrying out a heating reaction with the alcohol in an inert solvent such as toluene and removing the generated low-boiling alcohol from the reaction system using a rectification column.

Alternatively, when an acid anhydride is used as the reactive derivative, no reaction aid is particularly required, and the purpose can be achieved with the alcohol at room temperature.

At this time, heating and the presence of a solvent such as toluene or xylene are convenient for the reaction to proceed smoothly, but both are not essential.

When using halides or sulfoxylates of the alcohols, the acids are used as alkali metal salts, silver salts or salts of organic tertiary bases, which are formed by adding base and acid simultaneously to form during the reaction. It's okay.

During the reaction, the presence of a solvent such as benzene, acetone, dimethylformamide, etc. is desirable, and the reaction is preferably carried out by heating to the boiling point of the solvent or lower.

Chlorine and bromine atoms are often used as halogen atoms.

The method for producing the ester of the present invention will be explained in more detail with reference to Examples below.

Example 1 (Production example of 5-benzyl-3-furylmethyl 3/4/-dimethyl-2'-ethyl-3'-pentenoate) 1.90 g of 5-benzyl-3-furfuryl alcohol (0 , 01 mol) and pyridine 1.
58 g (0.02 mol) of 3,4-dimethyl-2-ethyl-3-pentenoyl chloride was dissolved in this solution while cooling with ice water. It was added dropwise over about 30 minutes.

After the dropwise addition was completed, the reaction was completed by stirring at room temperature for 3 hours.

The reaction solution was separated into 50 g of ice water to separate the benzene layer, and the aqueous layer was extracted twice with 20M benzene.

The benzene layers were combined and washed with 5% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution, and saturated brine in this order.

The pale yellow oil obtained by distilling off benzene under reduced pressure was purified by flowing down a column of 100 g of silica gel using benzene-n-hexane (1:3) as a developing solvent.

2.74 g of the desired ester (84.0% of the theoretical yield based on the carboxylic acid chloride used) was obtained as a colorless oil.

n231.5417 Example 2 (Production example of 5-benzyl-3-furylmethyl 2'-(2゜2-dichlorovinyl)-isovalerate) 2-(2,2-dichlorovinyl)-isovalerate 9.85
．． (0.05 mol) and 5-benzyl-3-furylmethanol 9.41. 16.51. @(0.08 mol)
of dicyclohexylcarbodiimide was added and the mixture was left sealed overnight.

The next day, the reaction was completed by heating under reflux for 4 hours, and after cooling, the precipitated dicyclohexyl urea was removed.

The viscous oil obtained by concentrating the filtrate was purified by flowing down a 500 g silica gel column (developing solvent, chloroform ditetrachloride = 3:1) to obtain the desired ester i.
o, sg (58.0% of the theoretical yield for the carboxylic acid used).
7%) as a colorless viscous oil.

npi・01.5364 Example 3 (4,5-7”t'ramethylene-2-chenylmethyl-
Production example of 2'-isopropyl-4'-methyl 3'-pentenoate) 5.89 g (0.02 mol) of 2-isopropyl-4-methyl-3-pentenoic acid anhydride and 4°5-tetramethylene- 2-chenylmethanol 1.68.9 (0
,01 mol) in 50 ru of dry pyridine,
The mixture was stirred overnight at room temperature.

The next day, the reaction solution was poured into 100 g of ice water, and 20 m of ether was added.
1 was used for extraction three times.

Combine the ether layers and add 5% sodium hydroxide aqueous solution 301f.
lI! The mixture was extracted twice to remove by-product carboxylic acid.

The ether layer was further washed with 10% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution, and saturated brine, and then dried over anhydrous sodium sulfate.

Removal of ether under reduced pressure gave crude ester 3.24.

Using benzene-n-hexane (1:3) as a developing solvent,
8 g of the desired ester ts (61.5% of the theoretical yield based on the carboxylic anhydride used) was obtained by flowing down a column of 90.9 silica gel.

n n21-5170 Example 4 (3-benzylbenzyl 2'-isoprobyl-4'
Production example of methyl-3'-pentenoate) 50rILl
of dimethylformamide at 3.92. ! i? (0,01
5 mol) of 3-benzylbenzyl bromide and 1.5 mol of 2-isopropyl-4-methyl-3-pentenoic acid.
6F (0.01 mol) and triethylamine 2.02 g (
0.02 mol) and stirred overnight at room temperature.

The reaction solution was poured into 50 g of ice water and extracted three times with 3011 L of ether.

The ether layers were combined, washed successively with 5% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution, and saturated brine, and then dried using anhydrous sodium sulfate.

The crude ester obtained by distilling off the ether under reduced pressure was
The desired ester 2.43F was purified by flowing down a column of 0 g silica gel (developing medium, benzene-n-hexane (1:3)) as a colorless oil (relative to the carboxylic acid used). 72.4% of theoretical yield).

n221.5465 The compounds shown in the table below were obtained in the same manner as in Examples 1 to 4.

The substituted acetate compound represented by the general formula CI) of the present invention exhibits excellent insecticidal activity and is expected to have a repellent action against mites or a synergistic action with other biologically active compounds, and is useful in agriculture, horticulture, forestry, It can be provided widely and inexpensively as a composition for sanitary purposes and for controlling stored grain pests and mites.

In practice, when using these compounds, suitable solvents, fillers, diluents, activators, dispersants, surfactants, wetting agents,
By blending appropriate amounts of one or more of pressurizing agents, emulsifiers, and food attractants, emulsions, irrigation agents, powders, granules, fine granules, powder granules, liniments, oils, aerosols, mosquito coils, Used in smoke agents, heated smoke agents, electric mosquito repellents, baits, etc.

In order to make it clearer that the composition provided by the present invention is excellent, an experimental example of the effect will be shown next.

Experimental Example 1 An emulsion is prepared by blending 25% of each of the compounds (1) to (21) of the present invention, 50% of Kijirole, and 25% of Tsurpol 5M-200 (registered trademark of Toho Chemical).

Among the above formulations, (1), (2), ell
, dilute a9 with water to 10 ppm, and add 3
A group of 30 Culex mosquito larvae were placed in a 200 ml glass beaker, and after being left for one day, the survival or death was examined.

Experimental Example 2 Compound of the present invention (+), (5), αB, (20
1 was dissolved in acetone and coated on the bottom of a waist-high glass petri dish with a diameter of 14 (14772) at a concentration of 1 g (a i )/rrl.

German cockroach adult 1 after the acetone has completely vaporized
0 animals were released, and after 24 hours of contact, survival and death were investigated.

As is clear from the above experimental examples, since the compound of the present invention exhibits excellent biological activity, the composition of the present invention can be used for planthoppers, leafhoppers, armyworms, etc.
Agricultural pests, such as the diamondback moth, nocturnal moth, cabbage butterfly, and chestnut beetle, or forest pests, or forest pests are extremely useful for controlling sanitary pests such as heat worms, sharks, flies, and cockroaches, grain storage pests such as the black elephant, mites, and the like.

It is particularly excellent in that it can be freely used for crops before harvesting, home gardening, greenhouse cultivation, food-related packaging materials, etc. because it has low toxicity and is harmless when stored.

In preparing the composition of the present invention, it is possible to achieve better control effects by combining two or more of the compounds of the present invention, and other insecticides such as DDT,
BHC, organic chlorine agents such as methoxychlor, Sumithion (registered trademark of Sumitomo Chemical), DDVP, diazinon,
Fenthion, Cyanox (registered trademark name of Sumitomo Chemical)
organic phosphors such as 1-naphthyl-N-methylcarbamate, 3.4-dimethylphenyl N-methylcarbamate, 3.5-dimethylphenyl IN-7 carbamate, pyrethrin, allethrin neopinamine (Sumitomo Chemical (registered trademark name), Kryslon (registered trademark name of Sumitomo Chemical) and their respective geometric isomers, optically active forms, or other known cyclopropane carboxylic acid ester agents, and piperonyl butoxide, which is a synergist for Solera, Sulfoxide, safroxane, S-421, etc., terephthalic acid, isophthalic acid, BHT when used as a heat fumigant, phenol derivatives as stabilizers, bis-phenol derivatives, phenyl-α-naphthylamine, phenyl-β-naphthylamine, Arylamines such as condensates of phenetidine and acetone, other insecticides such as Padan and Galefron, acaricides, fungicides,
By mixing nemicides, herbicides, fertilizers, and other agricultural chemicals, a multipurpose composition with excellent efficacy can be obtained, and labor savings and synergistic effects among the drugs can be fully expected.

Next, the preparation and effects of the composition of the present invention will be explained using formulation examples and examples, but the scope of the present invention is not limited by the tb Rinto examples.

Formulation Example 1 Compounds of the present invention (1), (2), (4), (
13), (16), (20 parts each of 191, 10 parts each of Sumithion (same as above), 10 parts of Tsurupol 5M-200 (same as above), Kijirol 6
By adding 0 part of the emulsions and stirring and dissolving them thoroughly, each emulsion is obtained.

Formulation example 2 Compounds of the present invention (2), (4), (5), CI
! 2 parts of each of I), 1 part of 3.4-dimethylphenyl N-methyl car/cumate and 2 parts of piperonyl butoxide were added to each of them, dissolved in 20 parts of acetone, and 300 mesh diatoms ± 95 parts were added. After thorough stirring and mixing in a crusher, the acetone is evaporated and steamed to obtain each powder.

Formulation Example 3 An oil solution is obtained by dissolving 0.5 part of the compound (2) of the present invention in white kerosene to make the total 100 parts.

Formulation Example 4 Add 10 parts each of 1-naphthyl-N-methylcarbamate to 10 parts each of the compounds of the present invention (2J, (4), (16)), and mix well with 5 parts each of Tsurpol 5M-200 (same as above). Then, add 75 parts of 300 Metsstark and stir and mix thoroughly in a crusher to obtain an irrigation agent.

Formulation Example 5 Compound (2) of the present invention 0.3. ! Allethrin 0. to li'.
Add 3g, dissolve in 20ml of methanol, and prepare a carrier for mosquito coils (mixing tab powder: lees powder: wood flour in the ratio of 3:5:1).
99.4. ! After uniformly stirring and mixing with ir and evaporating methanol, 150 mA of water is added, and the mixture is sufficiently kneaded and molded and dried to obtain a mosquito coil.

Example 5 Rice was grown 45 days after sowing in 1/50,000 Wagnerbot, and each emulsion obtained by Formulation Example 1 and each irrigation agent obtained by Formulation Example 4 were 400 times more concentrated with water. Spray the diluted solution at a rate of 10 ml/pot.

If you cover it with a cylindrical wire mesh and release about 30 adult black leafhoppers into it, after one day, 8
It was possible to kill more than 0% of leafhoppers.

Example 6 Each powder obtained according to Formulation Example 2 was prepared with a diameter of 14C1r.
Spread butter uniformly at a rate of 2 g/rrt on the bottom of a L-sized glass petri dish, and apply butter to the wall, leaving about 1crIL on the bottom.

When adult German cockroaches were released into the container in groups of 10 and left in contact for 30 minutes and the cockroaches were transferred to a new container, more than 80% of the cockroaches could be killed by either powder after three days.

Example 7 Approximately 5 Culex Culex adults were placed in a 70c11L cubic glass box.
If you release 0 mosquito coils and ignite both ends of the mosquito coil Ig obtained according to Formulation Example 5, place it in the center E of the bottom of the glass box.
After minutes, more than 80% of the mosquitoes could be turned upside down.

Example 8 Compound (2) of the present invention and piperonyl butoxide were each added in an amount 5 times the amount of the active ingredient, made into an acetone solution with a predetermined concentration, and applied to adult houseflies using a microinjector. I saw a synergistic effect.

As a result, the above-mentioned compounds of the present invention exhibited stronger insecticidal activity when piperonyl butoxide was added than when they were used alone.

Of course, piperonyl butoxide has no insecticidal effect on its own.

Claims (1)

[Scope of Claims] 1 General formula [wherein R1y R2 and R3 are the same or different and represent a hydrogen atom, a lower alkyl group, an alkenyl group or a halogen atom. X is a general formula (s where R4 is an allyl group, a propargyl group, a benzyl group, a thenyl group, a furylmethyl group, a phenoxydyl group, or a phenylthio group, and R5 is a hydrogen atom, a methyl group, a trifluoromethyl group, or a halogen atom, It also includes a case where R4 and R5 are bonded at the terminal to form a trimethylene chain or a tetramethylene chain. R6 is a hydrogen atom, an ethynyl group, or a nitrile group, n is an integer of 1 to 2, and A is an oxygen atom. , Iov atom or -C
H=CH- group, R7 is a phthalimide group, thiophthalimide group, di- or tetrahydrophthalimide group, or dialkylmaleimide group, R8 is an allyl group, propargyl group, benzyl group, or alkagenyl group, Ro is a hydrogen atom or a methyl group. represent. ) represents a group represented by Y represents a lower linear or branched alkyl group. ] A pest control composition comprising a substituted acetate ester represented by the following as an active ingredient. 2 General Formula [In the formula, R1, R2, R3 and Y each have the same meaning as stated in Claim 1. ] or its reactive derivative represented by the general formula [wherein, X has the same meaning as stated in claim 1]. ], or a halide or sulfoxylate thereof, to obtain a substituted acetate ester represented by the general formula set forth in claim 1. Law.