JPS582202B2 - Satsuki Yuzai Oyobi Sono Seihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an insecticide characterized by containing a substituted acetate represented by the general formula (■) as an active ingredient, and a method for producing the same.

(In the formula, n represents an integer of 1 to 5, and R1 represents a hydrogen atom, a halogen atom, a methyl group, a methoxy group, a methylthio group, a trifluoromethyl group, a chloroethynyl group, or a methylenedioxy group.

R2 represents a lower alkyl group or an impropenyl group.

R3 represents a hydrogen atom or a cyano group, m represents an integer of 1 to 2, and R4 represents a hydrogen atom, a methyl group, or a halogen atom.

R5 represents a propargyl group, benzyl group, thenyl group, phenoxy group or phenylthio group.

) Currently used insecticides include organic phosphorus agents, carbamate compounds, and pyrethroid compounds, and among these groups, the present inventor has spent many years researching pyrethroid compounds.

While these insecticides have been extremely useful in household hygiene and agriculture, problems such as environmental contamination and food pollution have arisen, and it is desirable to have less toxicity, less residue in food, and better efficacy. It will be done.

Pyrethroid compounds are considered to be the most promising as a solution to this demand, but while conventional pyrethroid compounds have been sufficiently useful for household hygiene, it is difficult to develop them into agricultural applications, and this point has been kept in mind in this study. As a result of further extensive research, the inventors learned that the substituted acetate ester described in the present invention has an activity similar to that of pyrethroid compounds and has low toxicity to warm-blooded animals.

The present invention was completed based on the above findings.

The compound represented by the above formula (■) used as an active ingredient in the present invention can be prepared using the general formula (where n represents an integer of 1 to 5, R1 is a hydrogen atom,
Halogen atom, methyl group, methoxy group, methylthio group,
Indicates a trifluoromethyl group, chloroethynyl group, or methylenedioxy group.

R2 represents a lower alkyl group or an impropenyl group.

) or its reactive derivative represented by the general formula (■) (wherein, R3 is a hydrogen atom or a cyano group, and m is 1 to
R4 represents a hydrogen atom, a methyl group or a halogen atom.

R5 represents a propargyl group, benzyl group, thenyl group, phenoxy group or phenylthio group.

), and its halide or sulfoxylate.

Reactive derivatives of carboxylic acids include acid halides, acid anhydrides,
Examples include lower alkyl esters and alkali metal salts.

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

The reaction is carried out in a suitable solvent in the presence of an organic or inorganic base or acid as a deoxidizing agent or catalyst if necessary, and with heating if necessary.Representative examples of the compound represented by the above formula are shown, but of course the present invention It is not limited only to these.

The novel compound used as an active ingredient in the present invention is generally easily soluble in organic solvents.

Therefore, as insecticides for spraying, it can be used as emulsions, oils, powders, wettable powders, aerosols, etc. It can also be used as an insecticide for fumigation such as mosquito coils by mixing with wood flour or other suitable base materials. can.

Excellent effects can also be obtained when the active ingredient is dissolved in a suitable organic solvent and immersed in a mount, and the active ingredient is heated and evaporated using a suitable heating element to be used as a so-called electric mosquito repellent.

The compounds of the present invention will be explained in detail below by giving synthesis examples.

Synthesis Example 1 5.2 g of α-isopropyl-(3,4-methylenedioxyphenoxy)acetic acid chloride was added to 15 ml of dry benzene.
3-benzyl-α-cyanobenzyl alcohol 4. Add 5 g dissolved in 20 ml of dry benzene, and add 3 ml of dry pyridine as a condensation aid.
When added, crystals of pyridine hydrochloride precipitate.

After sealing the cap and leaving it overnight at room temperature, pyridine hydrochloride was filtered off, and the benzene solution was dried with sulfuric acid. The benzene was distilled off to obtain a viscous and transparent 3'-benzyl-α'-cyanobenzyl α-
8.1 g of isopropyl-(3,4-methylenedioxyphenoxy)acetate was obtained.

Synthesis Example 2 2.0 g of α-isopropyl-phenoxyacetic acid and 1.9 g of 3-phenoxybenzyl alcohol were mixed with 150 m of benzene.
1 and add 5 ml of concentrated sulfuric acid while stirring the solution vigorously.

Heat to reflux while stirring, and remove water produced by azeotropy using a dehydrating agent.

Benzene is replenished from time to time and the reaction is carried out for about 4 hours.

The reaction solution was then washed with an aqueous sodium bicarbonate solution and a saline solution, and then benzene was distilled off under reduced pressure to obtain 3.1 g of 3'-phenoxybenzyl α-isopropyl-(phenoxy)-acetate.

Synthesis Example 3 6.2 g of methyl ester of α-isopropenyl-(2,6-dimethyl-3,4-dichlorophenoxy)acetic acid and 4
- 2.9 g of propargyl benzyl alcohol was dissolved in 100 ml of dry toluene, 0.1 g of sodium hydride was added as a catalyst, and the mixture was heated and stirred.

The methanol distilled out by azeotroping with toluene is removed.

After cooling, the toluene layer was separated by pouring it into cold water, and the toluene was distilled off under reduced pressure to obtain a viscous and transparent 4'-propargylbenzyl α-isopropenyl (2,6-dimethyl-3,4-dichlorophenyl). 7.6 g of (enoxy)acetate were obtained.

Synthesis Example 4 6.2 g of sodium salt of α-isopropyl-(2-fluoro-4-trifluoromethylphenoxy)acetic acid and 3-
5.9 g of phenylthio-5-chloro-α-cyanobenzyl chloride was dissolved in 50 ml of benzene, and the mixture was heated under reflux for 3 hours.
After reacting for an hour in a nitrogen stream, the reaction solution was cooled and the precipitated common salt was filtered off. After thoroughly washing with brine and drying with salt water, benzene was distilled off under reduced pressure and 3'-phenylthio 9.6 g of -5'-chloro-α-cyanobenzyl α-isopropyl-(2-fluoro-4-trifluoromethylphenoxy)acetate was obtained.

Synthesis Example 5 4.1 g of α-inpropyl-(4-methylphenoxy)acetic anhydride and 3-phenokyl-4-fluoro-α-cyanobenzyl alcohol2. 4 g dry pyridine 5
The solution was dissolved in 0 ml and stirred at room temperature overnight.

The next day, the reaction solution was poured into ice water and extracted with ether.
After thoroughly washing the ether solution with aqueous sodium bicarbonate and brine, drying with sodium chloride solution and distilling off the ether under reduced pressure, 3'-phenoxy-
3.8 g of 4'-fluoro-α-cyanobenzyl α-isopropyl-(4-methylphenoxy)acetate was obtained.

Next, the compounds shown in the table below were obtained in the same manner as in Synthesis Examples 1 to 5.

In the table, a, b, c, d, and e in the esterification method column have the following meanings.

a: Esterification method using acid chloride b: Dehydration esterification method of acid and alcohol using concentrated sulfuric acid in an inert solvent c: Esterification method by transesterification using sodium hydride or an alkali metal alkoxide as a catalyst in an inert solvent Method d: Esterification of an acid with a salt of an alkali metal, silver or organic tertiary base and a halide of an alcohol.Method e: Esterification with an acid anhydride.The compounds are indicated by the numbers of the above compound examples.

In addition, the substituted acetate of the present invention is added to N-octylbisylbutene dicarboximide (trade name: MGK-26).
4) When a synergist such as a mixture of N-octylbicycloheptene dicarboximide and alkylaryl sulfonate (trade name MGK-5026), octachlorodipropyl ether, piperonyl butoxide is added, the The insecticidal efficacy can be further increased.

Further, by using two or more of the compounds of the present invention in combination, it is possible to express a more excellent control effect, and other insecticides such as organic phosphorus agents such as sumithion, DDVP, diazinon, salithion, surecide, and 1-naphthyl. - Carbamate agents such as N-methylcarbamate, 3,4-dimethylphenyl-N-methylcarbamate, 2-isopropoxyphenyl-N-methylcarbamate, pyrethrin, allethrin, phthalthrin, resmethrin, flamethrin, phenothrin, permethrin, Cyclopropane carboxylic acid ester agents such as Embererate, phenolics such as 2,6-ditertiary butyl-4-methylphenol (BHT), 2,6-ditertiary butylphenol, phenyl-α-naphthylamine, phenyl-β-naphthylamine Amine-based antioxidants such as Padan, Galecron, Rannate, etc., insecticides, acaricides, fungicides, nematicides, herbicides,
By mixing plant growth regulators, 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 insecticidal test results of the compounds of the present invention will be shown.

Test Example 1 An emulsion was prepared by blending 30% each of the compounds (1) to (12) of the present invention, 50% xylene, and 20% Solpol SM-200 (registered trademark of Toho Chemical).

These emulsions and a 300-fold diluted solution of 1-naphthyl-N-methylcarbamate 30% emulsion in water as a control commercial drug were sprayed on rice plants planted in pots at 10 ml/pot.
We covered it with a wire mesh cylinder and released 10 leafhoppers into it, and after one day we observed whether they were alive or dead.
The mortality rate was over 0%.

Test Example 2 A 2.5% white lamp solution of each of the compounds of the present invention was prepared, and the relative effectiveness was calculated from the falling and supine rate using house flies according to the Nagasawa spray drop method, and the results were as follows.

The sample drug number is the same as that of the active ingredient example above.

Test Example 3 Regarding the compound of the present invention, 0.2% white lamp solution (A), 0.
2% and piperonyl butoxide 0.8% white lamp solution (
B), white light solution of 0.1% and phthalthrin 0.1% (
C) was tested in the same manner as Test Example 2.

Test Example 4 A mosquito coil containing 0.5% of the insecticidal ingredient was prepared and tested for its effectiveness in making adult Culex mosquitoes fall and roll over.

This experiment was conducted according to the method of Nagasawa and Katsuta, Vol. 16 (1951), p. 176, and the relative effectiveness of the incense sticks was calculated as follows.

The sample drug number is the same as that of the active ingredient example above.

From the above test examples, it is clear that the compounds of the present invention have excellent biological activity, and in cases where isomers exist, even more excellent effects can be exhibited if the optical isomers are resolved.

Based on these facts, the insecticide of the present invention is effective for controlling agricultural pests such as leafhoppers, planthoppers, cutworms, fall armyworms, diamondback moths, nocturnal moths, cabbage beetles, leaf beetles, aphids, and scale insects, grain storage pests such as brown elephants, and mites. extremely useful.

Also, like pyrethroid insecticides, it has low toxicity, so it is an excellent compound that can be used for crops before harvesting, home gardening, food, etc.

The preparation and effects of the insecticide of the present invention will be explained below with reference to examples, but the scope of the present invention is of course not limited to the following examples.

Example 1 Compounds of the present invention (1), (3), (6), (9) and (
11), 20 parts of Solpol SM-200 (same as above), and 60 parts of xylene were added to obtain each emulsion.

A 1000-fold diluted solution of each of the above emulsions was sprayed at 150 liters/10 a on a radish field infested with green peach aphid.

In a survey two days later, the density in each area was below 1/10 of the pre-spraying density.
It was decreasing.

Example 2 0.2 parts each of the compounds (2), (4), (8) and (11) of the present invention, 0.4 parts of phthalthrin, 1.0 part of octachlorodipropyl ether, and 0.1 parts of BHT.
1 part is dissolved in 28.3 parts of refined kerosene and filled into an aerosol container, a valve part is attached, and 70 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol.

When the above aerosol was sprayed on the surface of a 15 x 20 cm plywood board for 5 seconds and adult German cockroaches were brought into contact with it for 1 hour, more than 80% of the German cockroaches could be killed after 2 days.

Example 3 0.5 g each of the compounds (1), (4), (7) and (12) of the present invention, and 1.0 MGK-5026 each
and 98.5 g of a mosquito coil base material such as pyrethrum oil extract powder, wood flour, or starch powder to obtain a mosquito coil by a known method.

Example 4 0.1 g of each of the compounds (3), (5), (9) and (10) of the present invention, 0.05 g of biperonyl butoxide and 0.03 g of BHT were dissolved in acetone, and l
．． It was evenly adsorbed onto a 5 x 2.4 cm fiberboard and air-dried to obtain an electric mosquito repellent mat.

Example 5 10 parts each of the compounds (1), (3), (6) and (10) of the present invention, 20 parts of 1-naphthyl-N-methylcarbamate were added to each, and each was treated with Solpol SM-200.
5 parts (same as above) were thoroughly mixed, 65 parts of 300 mesh talc were added, and the mixture was thoroughly stirred and mixed in a grinder to obtain each wettable powder.

Example 6 Compounds of the present invention (2), (4), (5), (8) and (
Add white kerosene to 0.1 part of each of 12) and dissolve, making the total 100 parts to obtain each oil agent.

Example 7 5 parts of water were added to 5 parts each of the compounds of the present invention (4), (5), (9), and (11), 5 parts of sodium lignin sulfonate, and 85 parts of Fubasamiclay, and the mixture was thoroughly kneaded and granulated. Shape with a machine and dry to obtain granules.

Example 8 2 parts of 3,4-dimethylphenyl-N-methylcarbamate was added to 1 part each of the compounds (1), (3), (7), and (10) of the present invention, and the mixture was dissolved in 20 parts of acetone. hand,
After adding 97 parts of 300 mesh clay and thoroughly stirring and mixing in a crusher, the acetone is removed by evaporation to obtain each powder.

Claims (1)

[Claims] 1 General formula (I) (where n represents an integer of 1 to 5, R1 is a hydrogen atom, a halogen atom, a methyl group, a methoxy group, a methylthio group, a trifluoromethyl group, a chloroethynyl group) , or a methylenedioxy group. R2 represents a lower alkyl group or an isopropenyl group. R3 is a hydrogen atom or a cyano group, m is an integer of 1 to 2, and R4 is a hydrogen atom, a methyl group, or a halogen atom. R5 represents a propargyl group, a benzyl group, a thenyl group, a phenoxy group, or a phenylthio group.) An insecticide characterized by containing a novel substituted acetate ester as an active ingredient. 2. An insecticide characterized by containing a novel substituted acetate represented by the general formula (I) according to claim 1 and a synergist for pyrenuloids as active ingredients. 3 The following general formula (■) (where n represents an integer of 1 to 5, R1 is a hydrogen atom, a halogen atom, a methyl group, a methoxy group, a methylthio group, a trifluoromethyl group, a chloroethynyl group, or a methylenedioxy group) R2 represents a lower alkyl group or isipropenyl group. ~
R4 represents a hydrogen atom, a methyl group or a halogen atom. R5 represents a propargyl group, benzyl group, thenyl group, phenoxy group or phenylthio group. ) and the halide or sulfoxylate of Part 1 to obtain a novel substituted acetate ester represented by the general formula (■) according to claim 1. Method of manufacturing the agent.