JPS6193175A - Cyclopropanecarboxylic acid ester derivative, preparation of cyclopropanecarboxylic acid ester derivative, and insecticide containing cyclopropanecarboxylic acid ester derivative - Google Patents

Abstract

NEW MATERIAL:The cyclopropanecarboxylic acid ester derivative of formula I (R is 1-5C alkyl, 1-3C haloalkyl, or haloalkenyl) and its optical and geometrical isomer. EXAMPLE:5'-Benzyl-3'-furylmethyl 2,2,3-trimethyl-3-methoxycyclopropanecarboxy late. USE:Insecticide having broad insecticidal spectrum and low toxicity. PREPARATION:The cyclopropanecarboxylic acid ester derivative of formula I can be prepared by reacting the cyclopropanecarboxylic acid of formula II or its reactive derivative with 5-benzyl-3-furylmethyl alcohol or its reactive derivative.

Description

Detailed Description of the Invention The present invention provides novel cyclopropanes represented by the general formula (wherein R represents an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or a haloalknyl group). The present invention relates to a carboxylic acid ester ts conductor, its optical and geometric isomers, a method for producing the same, 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 due to light, which has limited their use outdoors. Recently, research on acid components has become active, and a compound that is more stable to light than conventional pyrethroi F 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 inventor has found the above formula (
While the compound shown in I) has an extremely excellent insecticidal effect on various sanitary pests and agricultural and horticultural pests as an insecticidal ingredient, it has extremely low toxicity to warm-blooded animals and is highly resistant to light compared to conventional pyrethroids. I knew it was stable. In this way, the compound represented by the above formula (I) overcomes the drawback of conventional pyrethroids that they are unstable to light,
It is an excellent pest control composition that has a wide insecticidal spectrum and low toxicity, and the cyclopropanecarboxylic acid constituting the above formula (I) can be easily obtained at low cost. The present invention was completed based on the above findings. The compound represented by the above formula (I) used as an active ingredient in the present invention can be prepared according to the general method for producing esters (in the formula, R is an alkyl group having 1 to 5 carbon atoms or Fi having 1 to 3 carbon atoms). (representing a haloalkyl group or a haloalknyl group) or a reactive derivative thereof; and 5
-benzyl-3-furyl methyl alcohol or a reactive derivative thereof.

Examples of reactive derivatives of carboxylic acids include acid halides,
Examples include acid anhydrides, lower alkyl esters, and alkali metal salts. An example of a reactive derivative of alcohol is talolide. 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 CI) are as follows, but the present invention is of course not limited to these.

5'-Benzyl-3'-furylmethyl 2,2.3-
) Dimethyl-3-methoxycyclopropane hydroxylate
n ” 1.54285'-benzyl-3'-
7lylmethyl 2,2.3-) dimethyl-3-ethoxycyclopropane hydroxylate
n 20 1.547
15'-benzyl-3'-7lylmethyl 2,2.3-
Triphthyl-3-n-proboxylate 92-propane triphoxylate n20
1.55195'-benzyl-3'-furylmethyl 2
,2,3-)limethyl-3-(2-chloroethoxy)-
Cyclopropane carboxylate n20
1.55885'-benzyl-3'-furylmethyl 2
,2,3-trimethyl-3-isoproboxycyclopropane hydroxylate n v
1-54925'-benzyl-3'-furylmethyl
2,2.3-)dimethyl-3-n-butoxycyclopropanecarboxylate
n 201.55845'-benzi-3'-furylmethyl 2,2.3-) samethyl-3-inptoxycyclopropane lupoxylate
n 201.55715'-benzyl-3'-
Furylmethyl 2,2.3-trimethyl-3-(2,
2-Dichlorovinyloxy)-cyclopropanecarboxylate n201.56285'-benzyl-3
'-Furylmethyl 2,2.3-)dimethyl-3-n
-Amyloxycyclopropane lupoxylate
n 1.56865'-benzyl-3'-furylmethyl 2,2.3-trimethyl-
3-(2,2-dichloroethoxy)-cyclopropanecarboxylate n201.5651 The compound of the present invention is a new compound, which is solid or liquid at room temperature and easily soluble in general organic solvents. Therefore, as an insecticide for spraying, it can be used as an emulsion, oil, powder, wettable powder, aerosol, etc. It can also be mixed with wood flour or other suitable base material and used as an insecticide for fumigation such as mosquito coils. be able to. 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 effective as a mosquito coil. shows. The compound of the present invention is extremely stable to light compared to conventional pyrethroids and can be used as a horticultural insecticide. The stability can be further improved by adding an antioxidant such as IT) or 2,5-ditertiary-glutylhydroquinone (DBHQ). In addition, the compounds of the present invention include N-octylbicyclohebutene dicarboximide (trade name MGK-264), a mixture of N-octylbicyclohebutene dicarboximide and an arylsulfonate (trade name MGK-s 026), octa The insecticidal effect can be further enhanced by adding a synergist such as chlorodipropyl ether or piperonyl ptoxide. The compounds of the present invention may also be used with other insecticides such as organic phosphorus agents such as sumithion, DDVP, diazinon, 1-
Carbamate agents such as 7-thi-N-methyl carbamate and 3,4-dimethyl-N-methyl carbamate, conventional pyrethroid insecticides such as pyrethrin, allethrin, 7 courthrin, 7 lametrin, and phenothrin, badan, galefron, lannate, etc. By mixing insecticides, acaricides, fungicides, nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, a multipurpose composition with excellent efficacy is obtained, which saves labor. We can also fully expect synergistic effects between these drugs. 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 piveronyl ptoxide 0.8
% white light solution (B), 0.1% and Fucurthrin 0.1
% white light solution (C) and 0.2% white light solution of allethrin and phthalthrin, the drop-upside-down rate of house flies was calculated and the relative effectiveness of the test drug was calculated, and after 24 hours, the test example 2. Insecticidal test by fumigation Mosquito coils containing 0.5% of the insecticidal ingredient were produced and tested for their effectiveness in making Culex Culex adults fall and roll over. This experiment was carried out in accordance with the method of Insect Control Science Vol. 16 (1951), p. 176, Nagasha, Katsuta et al., and the relative effectiveness of the incense sticks was calculated as follows. The test drug number is the effective test example 3 mentioned above. Insecticidal test by microdropping method. Allethrin and the compound of the present invention were added to each of them, and piveronyl ptoxide was added in an amount twice the amount of the active ingredient to make an acetone solution of a predetermined concentration. The product was 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 piveronyl guttoxide were determined from the mortality rate after 24 hours. Examples of the present invention are shown below. . The compound names are the same as those in the active ingredient examples above.

Example 1 2.2.3-)limethyl-3-(2,2-dichlorovinyloxy)-cyclopropanecarboxylic acid chloride 5
．． Dissolve 1g in dry benzene 15rlT1 and add 5-
A solution of 3.8 g of hensyl-3-furyl methyl alcohol dissolved in 20% of dry benzene is added, and further, dry pyridine 3-3 is added 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 over sulfur, and the benzene was distilled off under reduced pressure to obtain 5'-benzyl-3'-furylmethyl 2,2.3- )limethyl-3-(2゜2-
7.2 g of 990-vinyloxy)-cyclopropane carboxylate were obtained.

Example & 2.2. 42 g of 3-trimethyl-3-n-butoxycyclopropanecarboxylic acid and 3.8 g of 5-benzyl-3-furylmethyl alcohol were mixed with 150 rId of benzene! Dissolve and add 5 d 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 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 then benzene was distilled off under reduced pressure to obtain 5'-benzyl-3'-furylmethyl2.
2.6.8 g of 3-trimethyl-3-n-butoxycyclopropane rupoxylate was obtained.

Example 3 3.9 g of sodium salt of 2.2.3-trimethyl-3-ethoxycyclopropanecarboxylic acid and 5-benzyl-3
-4.1g of furyl methyl chloride in 50me of benzene
After reacting under reflux in a nitrogen stream for 3 hours, the reaction solution was cooled, and the precipitated salt was separated, thoroughly washed with brine, dried over nitric acid, and the benzene was distilled off under reduced pressure. 5
'-benzyl-3'-furylmethyl 2,2.3-)
6.3 g of dimethyl-3-ethoxycyclopropanecarpoxylate was obtained.

2.2.43 g of methyl ester of 3-trimethyl-3-n-propoxine chloropropanecarboxylic acid and 3.8 g of 5-benzyl-3-furyl methyl alcohol were added to 1500
Heat to G. . When the temperature reaches 1500C, 0.25 g of sodium is added and methanol distillation is started.

When the distillation power of methanol is stopped by 5, sodium is added by 0.
Add 25 g and increase the temperature to 1 until the theoretical amount of methanol is obtained.
Keep the temperature around 50'C and repeat the above operation. 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 sulfuric acid, and the ether was distilled off under reduced pressure to give 5'-benzyl 3/-furylmethyl 2.
, 2,3-)rimethyltLt-3-n-proboxycyclopropane hydroxylate (6.6 g) was obtained.

Example 5゜2.2.3-) 43 g of dimethyl-3-taloloethoxycycloprohanecarboxylic acid anhydride and 5-benzyl-3-
Mix 3.8g of 7lyl methyl alcohol and add 98% while stirring.
Gradually add 8 g of % sulfuric acid and react at 80 to 100°C for 3 hours, then dissolve in ether and dilute the ether solution with sodium bicarbonate water,
After washing thoroughly with brine, drying with salt water and distilling off the ether under reduced pressure, 5'-benzyl-3'-furylmethyl 2,2
．． 3-) 5.9 g of dimethyl-3-taloloethoxycyclopropane rupoxylate was obtained.

Reference Example 1゜ White kerosene was added to 0.2 parts of the compound of the present invention (1) to obtain a 0.2% oil solution, making the total 100 parts.

Reference Example 2 White kerosene was added to 0.2 parts of the compound (2) of the present invention and 0.8 parts of piveronyl ptoxide to make a total of 100 parts to obtain an oil solution.

Reference Example 3 20 parts of the compound of the present invention (4) and Tsurupol 5M-200
(Toho Chemical registered trademark) and 70 parts of Kijirole were added and mixed and dissolved with stirring to obtain a 20% emulsion.

Reference Compound of the Invention (5) 0.4 parts, resmethrin 0.1 part, octachlorodiprobyl ether t, dissolved in 28 parts of 54R11 lamp solution, filled into an aerosol container and attached with the pulp part. 70 parts of propellant (liquefied petroleum gas) is charged under pressure through the pulp portion to obtain an aerosol.

Reference example 5゜Compound of the present invention (6) 0.5 g SB HT 0.5
g as a base material for mosquito coils such as pyrethrum extracted lees powder, wood flour, and starch powder99. A mosquito coil is obtained by uniformly mixing with Og and using a known method.

Reference Example 6゜Compound (7) of the present invention, 0.4 g, MGK-50261,
0 g was uniformly mixed with 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 lacryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder.

Test Example Table Compounds (3), (4), (7) and (9) of the present invention among the emulsions obtained in Reference Example 3 were applied to a field of radish at the 5-6 leaf stage where a large number of green peach aphids were infested. A 1000-fold dilution of each emulsion containing water was applied at a rate of 1 OOl/count. Parasitism rate survey after 2 days showed 1/1 of the density before spraying.
The number decreased to below 0 in each ward.

Test Example 5 Approximately 200 aphids were infested on one day before applying the insecticidal active ingredient to potted fava beans. Two days after spraying 4000 times diluted solutions of (2), (6) and (9) of the hydrating powders obtained in Reference Example 8 onto leaves infested with pests using a compressed air spray method, 1 ove/bottle was applied. The degree of damage was observed. As a result, no increase in the degree of damage was observed in either case.

Test Example 6 Among the emulsions obtained in Reference Example 3, the compound of the present invention (1),
(4), (8), and (lO) fresh leaves were immersed in the 2000-fold diluted solution for about 5 seconds, and after the solution dried, they were placed in a petri dish and 10 healthy larvae of fall armyworm were released. The test insects were released twice, once on the day of soaking the fresh leaves and once 5 days later.
Dead insects test example 7 after 4 hours Each of the powders (2), (5), (8) and (9) obtained in Reference Example 7 was placed on the bottom of a waist-height chalice dish with a diameter of 14c+++ at a concentration of 2 g/rd. Apply the putter to the wall surface by spreading it evenly at the same rate and leaving the bottom part 1cIn't.

When adult cockroaches of -f-herbaceous cockroaches were released into the container in groups of 10, they were left in contact for 30 minutes, and the cockroaches were transferred to a new container. After 3 days, more than 80% of the cockroaches could be killed by any of the powders.

Claims (4)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) (In the formula, R is an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group or haloalkenyl group having 1 to 3 carbon atoms. ) and its optical and geometric isomers. (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼... (II) (In the formula, R is an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms, haloalkenyl A general formula characterized by reacting cyclopropanecarboxylic acid or a reactive derivative thereof represented by 5-benzyl-3-furylmethyl alcohol or a reactive derivative thereof ▲Mathematical formula, chemical formula, table, etc. ▼...(I) (Here, R has the same meaning as above.) A method for producing a cyclopropane carboxylic acid ester derivative. (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) (In the formula, R is an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or a haloalkenyl group An insecticide characterized by containing a cyclopropanecarboxylic acid ester derivative represented by: (4) The insecticide according to claim (3), which contains a pyrethroid synergist as an adjuvant.