JPS6144871B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (In the formula, R represents an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or a haloalkenyl group.) and its optical and geometric isomers. , its production method, and an insecticide characterized by containing this compound as an active ingredient. Various types of alcohol components of chrysanthemum acid esters have been studied and put into practical use, but they are susceptible to oxidative decomposition by light, which has limited their use outdoors. Recently, research into acid components has become active, and a compound that is more stable to light than conventional pyrethroids by replacing the methyl group with a halogen atom has been discovered. However, when considering issues such as environmental pollution and chronic toxicity, compounds with structures similar to naturally occurring organic compounds, mainly consisting of carbon, hydrogen, oxygen, and nitrogen, are considered to be advantageous as future insecticidal ingredients. As a result of repeated research, the present inventor has found that the compound represented by the above formula () has an extremely excellent insecticidal effect as an insecticidal ingredient against various sanitary pests and agricultural and horticultural pests, and has extremely low toxicity to warm-blooded animals. We learned that it is much more stable against light than conventional pyrethroids. In this way, the compound represented by the above formula () overcomes the drawback of conventional pyrethroids such as being unstable to light, and is an excellent pest control composition that has a wide insecticidal spectrum and low toxicity. ) can be easily obtained at low cost. 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 (In the formula, R represents an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or a haloalkenyl group.) or a reactive derivative thereof and 5-benzyl-3- It can be prepared by reacting with furyl methyl alcohol or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts. Examples of reactive derivatives of alcohol include chloride. The reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base or acid as a deoxidizer or catalyst, and optionally with heating. Representative examples of the compound represented by the above formula () are as follows, but the present invention is of course not limited to these. (1) 5'-benzyl-3'-furylmethyl 2.2.
3-Trimethyl-3-methoxycyclopropanecarboxylate n ²⁰ _D 1.5428 (2) 5'-benzyl-3'-furylmethyl 2.2.
3-Trimethyl-3-ethoxycyclopropanecarboxylate n ²⁰ _D 1.5471 (3) 5'-benzyl-3'-furylmethyl 2.2.
3-Trimethyl-3-n-propoxycyclopropanecarboxylate n ²⁰ _D 1.5519 (4) 5'-benzyl-3'-furylmethyl 2.2.
3-trimethyl-3-(2-chloroethoxy)-
Cyclopropane carboxylate n ²⁰ _D 1.5588 (5) 5'-benzyl-3'-furylmethyl 2.2.
3-Trimethyl-3-isopropoxycyclopropanecarboxylate n ²⁰ _D 1.5492 (6) 5'-benzyl-3'-furylmethyl 2.2.
3-Trimethyl-3-n-butoxycyclopropanecarboxylate n ²⁰ _D 1.5584 (7) 5'-benzyl-3'-furylmethyl 2.2.
3-Trimethyl-3-isobutoxycyclopropanecarboxylate n ²⁰ _D 1.5571 (8) 5'-benzyl-3'-furylmethyl 2.2.
3-Trimethyl-3-(2,2-dichlorovinyloxy)-cyclopropanecarboxylate
n ²⁰ _D 1.5628 (9) 5'-benzyl-3'-furylmethyl 2.2.
3-Trimethyl-3-n-amyloxycyclopropanecarboxylate n ²⁰ _D 1.5686 (10) 5'-benzyl-3'-furylmethyl 2.2.
3-Trimethyl-3-(2,2-dichloroethoxy)-cyclopropanecarboxylate
n ²⁰ _D 1.5651 The compound of the present invention is a novel compound, is solid or liquid at room temperature, and is generally easily soluble in organic solvents. Therefore, it can be used as an insecticide for spraying in the form of 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 do. Also, when used as a so-called electric mosquito repellent by dissolving this active ingredient in an appropriate organic solvent and soaking it in a mount, or dissolving it in an appropriate solvent and heating and evaporating it with an appropriate heating element, it is as good as a mosquito coil. This shows the effect of The compound of the present invention is extremely stable to light compared to conventional pyrethroids and can be used as an agricultural and horticultural insecticide.
The stability can be further improved by adding an antioxidant such as 2,6-ditertiarybutyl-4-methylphenol (BHT) or 2,5-ditertiarybutylhydroquinone (DBHQ).
The compound of the present invention also includes N-octylbicycloheptenedicarboximide (trade name MGK-264),
Mixture of N-octylbicycloheptenedicarboximide and arylsulfonate (trade name)
The insecticidal effect can be further enhanced by adding a synergist such as MGK-5026), octachlorodipyrropuru ether, or piperonyl butoxide. The compounds of the present invention may also be used with other insecticides such as organic phosphorus agents such as sumithion, DDVP, diazinon, etc.
-Naphthyl-N-methylcarbamate, 3,4-
Carbamates such as dimethyl-N-methyl carbamate, conventional pyrethroid insecticides such as pyrethrin, allethrin, phthalthrin, flamethrin, and phenothrin, insecticides such as padan, galecron, and lannate, or acaricides, fungicides, and nematocides. agents, herbicides, plant growth regulators, fertilizers,
By mixing other agricultural chemicals, a multipurpose composition with excellent efficacy can be obtained, and labor savings and synergistic effects among the chemicals can be fully expected. Next, the insecticidal test results of the compounds of the present invention will be shown. Test Example 1 Insecticidal test by spraying 0.2% white light solution (A) of the 10 compounds of the present invention of the above compound examples, 0.2% and piperonyl butoxide 0.8
% white light solution (B), 0.1% white light solution of 0.1% and phthalthrin (C), and white light solution of 0.2% each of allethrin and phthalthrin. The effectiveness was calculated and the mortality rate after 24 hours was determined as follows.

【table】

[Table] Test Example 2 Insecticidal test by fumigation Mosquito coils containing 0.5% of the insecticidal ingredient were made and tested for their effectiveness in making Culex mosquito adults fall and fall upside down. This experiment was published in Insect Control Science Volume 16 (1951).
The relative effectiveness of the incense stick was calculated according to the method of Nagasawa, Katsuta et al., p. 176, and the results were as follows. The sample drug number is the same as that of the active ingredient example above.

[Table] Test Example 3 Insecticidal test using microdropping method.
An acetone solution with a predetermined concentration was added in twice the amount and applied to the thoracic dorsal plate of adult house flies using a microsyringe, and the relative insecticidal power against allethrin and the synergistic effect with piperonyl butoxide were determined from the mortality rate after 24 hours. The effects were investigated and are as follows.

[Table] Examples of the present invention are shown below. The compound names are the same as those in the active ingredient examples above. Example 1 5.1 g of 2,2,3-trimethyl-3-(2,2-dichlorovinyloxy)-cyclopropanecarboxylic acid chloride was dissolved in 15 ml of dry benzene, and 5-benzyl-3-furylmethyl alcohol was added to the solution.
Add 3.8 g dissolved in 20 ml of dry benzene, and then add 3 ml of dry pyridine as a condensation aid to precipitate crystals of pyridine hydrochloride. After sealing the cap and leaving it overnight at room temperature, the crystals of pyridine hydrochloride were separated, the benzene solution was dried with sulfuric acid, and the benzene was distilled off under reduced pressure to obtain 5'-benzyl-3'-furylmethyl 2,2,3-. 7.2 g of trimethyl-3-(2,2-dichlorovinyloxy)-cyclopropanecarboxylate was obtained. Example 2 4.2 g of 2,2,3-trimethyl-3-n-butoxycyclopropanecarboxylic acid and 5-benzyl-
3.8 g of 3-furyl methyl alcohol to 150 g of benzene
ml and add 5 ml of concentrated sulfuric acid while stirring the solution vigorously.
Add. Heat to reflux while stirring and remove water produced by azeotropy using a dehydrating agent. Benzene was replenished from time to time and the reaction was carried out for about 4 hours. The reaction solution was then washed with aqueous sodium bicarbonate and brine, and the benzene was distilled off under reduced pressure.
5'-benzyl-3'-furylmethyl 2,2,3-
6.8 g of trimethyl-3-n-butoxycyclopropanecarboxylate was obtained. Example 3 3.9 g of sodium salt of 2,2,3-trimethyl-3-ethoxycyclopropanecarboxylic acid and 5-
4.1 g of benzyl-3-furyl methyl chloride was dissolved in 50 ml of benzene and reacted under reflux in a nitrogen stream for 3 hours. The reaction solution was cooled and the precipitated salt was separated. After thorough washing with brine, sulfate was added. 5′-benzyl-
3'-furylmethyl 2,2,3-trimethyl-3
-Ethoxycyclopropane carboxylate 6.3
I got g. Example 4 Methyl ester of 2,2,3-trimethyl-3-n-propoxycyclopropanecarboxylic acid 4.3
g and 5-benzyl-3-furylmethyl alcohol
Heat 3.8g to 150℃. When the temperature reaches 150°C, add 0.25 g of sodium and start distilling off methanol. When the distillation of methanol has stopped, 0.25 g of sodium is further added and the above operation is repeated while keeping the temperature around 150°C until the theoretical amount of methanol is obtained. The mixture was then cooled and dissolved in ether, and the ether solution was washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over nitric acid, and the ether was distilled off under reduced pressure.
5'-benzyl-3'-furylmethyl 2,2,3-
6.6 g of trimethyl-3-n-propoxycyclopropanecarboxylate was obtained. Example 5 4.3 g of 2,2,3-trimethyl-3-chloroethoxycyclopropanecarboxylic acid anhydride and 3.8 g of 5-benzyl-3-furyl methyl alcohol were mixed, and 8 g of 98% sulfuric acid was gradually added while stirring. 80〜
After reacting at 100°C for 3 hours, it was dissolved in ether, and the ether solution was thoroughly washed with aqueous sodium bicarbonate and brine, dried over nitric acid, and the ether was distilled off under reduced pressure to give 5'-benzyl-3'-furylmethyl 2. - 5.9 g of 2,3-trimethyl-3-chloroethoxycyclopropanecarboxylate was obtained. Reference example 1 White kerosene was added to 0.2 parts of the present compound (1) and the whole
Obtain 0.2% oil solution as 100 parts. Reference Example 2 White kerosene is added to 0.2 parts of the compound of the present invention (2) and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil solution. Reference Example 3 To 20 parts of the compound of the present invention (4), 10 parts of Solpol SM-200 (registered trademark of Toho Chemical) and 70 parts of xylol were added and mixed and dissolved with stirring to obtain a 20% emulsion. Reference Example 4 0.4 parts of the present compound (5), 0.1 part of resmethrin, and 1.5 parts of octachlorodipropyl ether were added to purified lamp liquid.
After dissolving in 28 parts and filling it into an aerosol container and attaching a valve part, 70 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol. Reference Example 5 0.5 g of the present compound (6) and 0.5 g of BHT were added to 99.0 g of a base material for mosquito coils such as pyrethrum extract powder, wood flour, starch powder, etc.
A mosquito coil is obtained by a known method. Reference Example 6 0.4 g of the compound (7) of the present invention and 1.0 g of MGK-5026 are uniformly mixed into 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method. Reference Example 7 3 parts of the compound (8) of the present invention and 97 parts of clay were thoroughly ground and mixed to obtain a 3% powder. Reference example 8 40 parts of the present compound (9), 35 parts of diatomaceous earth, 20 parts of clay
1 part, 3 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder. Test Example 4 5 to 5 on a surface where a large number of green peach aphids appeared
A 1000-fold dilution with water of each of the emulsions containing the compounds (3), (4), (7), and (9) of the present invention obtained in Reference Example 3 was applied to a radish field at the 6-leaf stage. Scattered per 100/count. Two days later, the parasitism rate was investigated and found that the density had decreased to less than 1/10 of the pre-spraying density in each plot. Test Example 5 One day before applying the insecticidal active ingredient to potted fava beans, one tree was infested with approximately 200 aphids. Among the hydrating agents obtained by Reference Example 8
A 4000-fold dilution of solutions (2), (6), and (9) was sprayed onto leaves infested with insects using a compressed air spray method at a rate of 10 ml/pot, and the degree of damage was observed two days later. As a result, no increase in the degree of damage was observed in any of the cases. Test Example 6 Compound of the present invention among the emulsions obtained in Reference Example 3
Fresh leaves were immersed in the 2000-fold diluted solutions of (1), (4), (8), and (10) for about 5 seconds, and after the solution dried, they were placed in a shear dish and 10 healthy armyworm larvae were released. .
The test insects were released twice, once on the day of soaking the fresh leaves, and once 5 days later, and the mortality rate after 24 hours was determined.

[Table] Test Example 7 (2), (5), (8) and (9) obtained by Reference Example 7
Spread each of the powders uniformly at a rate of 2 g/m ² on the bottom of a waist-high glass shear dish with a diameter of 14 cm, and apply butter to the wall leaving 1 cm of the bottom. Adult German catroaches were released into the container in groups of 10, and if they were left in contact for 30 minutes and the cockroaches were transferred to a new container, more than 80% of the cockroaches could be killed three days later, even with a powder.

Claims (1)

[Claims] 1. General formula (In the formula, R represents an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group or haloalkenyl group having 1 to 3 carbon atoms.) Cyclopropane carboxylic acid ester derivatives and their optical and geometric isomers. 2 General formula (In the formula, R represents an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group or haloalkenyl group having 1 to 3 carbon atoms.) Cyclopropanecarboxylic acid or its reactive derivative represented by 5-benzyl - General formula characterized by reacting with 3-furyl methyl alcohol or its reactive derivative (Here, R represents the same meaning as above.) A method for producing a cyclopropane carboxylic acid ester derivative. 3 General formula (In the formula, R represents an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or a haloalkenyl group.) Insecticide. 4. The insecticide according to claim 3, which contains a pyrethroid synergist as an adjuvant.