JPH0250081B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to the general formula (In the formula, X represents a chlorine atom or a bromine atom.R
is a hydrogen atom or a cyano group, Y is a hydrogen atom,
Represents a fluorine atom, chlorine atom or bromine atom. ) The present invention relates to an insecticide and acaricide characterized by containing a cyclopropanecarboxylic acid ester derivative having the (1R, cis) configuration represented by (1R, cis). In recent years, research has been widely conducted on analogs with modified chemical structures of pyrethrin, a natural insecticidal ingredient, and the general formula (In the formula, R and Y represent the same meanings as above,
R' represents various carboxylic acids constituting synthetic pyrethroids, including chrysanthemum acid and dihalobinyl chrysanthemum acid. )
A series of compounds represented by are already known, and some of them are widely used as household, epidemic prevention, and agricultural insecticides. The present inventors continued their research to search for more useful insecticidal ingredients, and developed a series of compounds in which the phenoxy group of the compound represented by the general formula (iv) was replaced with a substituted anilino group (in a broad sense, the compound represented by the general formula ()). After learning that the insecticidal efficacy of the compound (including the compound) was significantly enhanced compared to the original compound, while the toxicity to warm-blooded animals and seafood was reduced, I applied for a patent earlier (application numbers 55-185758 and 56). −
13147). The present inventors further focused on the structural activity of the isomers, and as a result of intensive research on the optical and geometrical isomers of halobinyl chrysanthemum acid, the general formula ()
2, which has the (1R, cis) configuration represented by
Insecticides containing 2-dimethyl-3-(2,2-dihalobinyl)cyclopropanecarboxylic acid ester derivatives have significantly superior insecticidal efficacy against various pests compared to those with other steric configurations. They discovered this and completed the present invention. Regarding the study of each isomer of 3-phenoxybenzyl alcohol ester and 3-phenoxy-α-cyanobenzyl alcohol ester of dihalobinyl chrysanthemum acid, the insecticidal activity of the (IR, trans) or d-cis form is ), that is, 1.5 to 2.5 times higher than the d-trans form (Pestic.Sci.1974,
5791, 1975, 6 537, 1978, 9 112).
However, according to the results of the present inventors' study of 3-anilinobenzyl alcohol ester derivatives, surprisingly, the insecticidal efficacy of the d-cis form is higher than that of the d-trans form, against house flies, German cockroaches, In each case, it was more than three times as strong as that of Spodoptera spp., which was an unexpected increase in efficacy based on conventional knowledge. Furthermore, when comparing the knock-down effects of both, it was revealed that the d-cis form had an extremely high knockdown effect. In recent years, from the standpoint of environmental pollution, there has been a trend toward spraying small amounts of highly insecticidal agents, and the discovery of such isomers with extremely excellent insecticidal activity is extremely useful. Furthermore, methods for selectively synthesizing cis-dihalovinyl chrysanthemum acid and improved methods for splitting dl-isomer have recently been developed one after another (Pestic.Sci.1980,
11180), both the acid and alcohol components constituting the compound of the present invention can now be obtained easily and inexpensively, and its practical application is fully expected. The compound represented by the above formula (I) used as an active ingredient in the present invention can be prepared using the general formula (In the formula, X represents a chlorine atom or a bromine atom.)
Cyclopropanecarboxylic acid or its reactive derivative with the (IR, cis) configuration shown by and the general formula (In the formula, R is a hydrogen atom or a cyano group, and Y
represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom. ) or a reactive derivative thereof.
Examples of reactive derivatives of cyclopropanecarboxylic acid include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts. Examples of reactive derivatives of alcohol include chloride, bromide, and P-toluenesulfonic acid ester. 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, and if necessary with heating. Note that when R in the alcohol component is a cyano group, a non-satile carbon is present, and the RS racemate obtained by ordinary synthesis methods is also included in the present invention. As in the case of the phenoxybenzyl alcohol ester derivatives, the S form is more preferred as it is the insecticidal form. The above formula ()
Representative examples of the compounds represented by are shown below, but the present invention is of course not limited to these. [Table] The compound used as an active ingredient in the present invention is a new compound, is solid or liquid at room temperature, and is generally easily soluble in 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 as an insecticide for fumigation such as mosquito coils. can be used. Also, when used as a so-called electric mosquito repellent, in which the active ingredient is dissolved in an appropriate organic solvent and soaked in a mount, or dissolved in an appropriate solvent and heated and evaporated with an appropriate heating element, it is as good as a mosquito coil. This shows the effect of The compound used as an active ingredient in the present invention is more stable to light than conventional chrysanthemum acid ester-based pyrethroids, has a broad insecticidal spectrum, has low toxicity, and is inexpensive, so it is not suitable for conventional organic phosphorus agents, organic It can be used as an agricultural and horticultural insecticide in place of chlorine-based insecticides. The insecticide of the present invention can be used for flies,
In addition to sanitary pests such as mosquitoes and cockroaches, organophosphorus and carbamate resistant leafhoppers, planthoppers, stinkbugs, armyworms, diamondback moths, tobacco moths, bean weevils, nocturnal moths, cabbage moths, chestnut beetles, leafhoppers, aphids, and scale insects. It is extremely useful for the control of agricultural pests such as, grain storage pests such as brown elephant, mites, etc.
In addition, the insecticide of the present invention 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), Cinepine 500, octachlorodipropyl ether, or piperonyl butoxide. If necessary, use the insecticide of the present invention.
Stability can be further improved by adding stabilizers and antioxidants such as BHT and DBHQ. In addition, the insecticide of the present invention may include other insecticides such as organic phosphorus agents such as fenitrothion, DDVP, diazinon, propaphos, and pyridafentione;
Carbamate agents such as NAC, MTMC, BPMC, and PHC, conventional pyrethroid insecticides such as pyrethrin, allethrin, phthalthrin, flamethrin, phenothrin, permethrin, cypermethrin, decametrin, fuenvalerate, and fuenpropanate, cartap, and chlorphenamide. A highly effective multi-purpose composition can be obtained by mixing insecticides such as gin, methomyl, acaricides, fungicides, nematicides, herbicides, plant growth regulators, fertilizers and other agricultural chemicals. , labor savings, and synergistic effects between drugs can be fully expected. Next, synthetic examples will be shown for representative examples. Synthesis Example 1 (IR, cis)2,2-dimethyl-3-(2,2
-Dichlorovinyl) cyclopropanecarboxylic acid Synthesis of dl-cis-2,2 - dimethyl-3-(2,2-
dichlorovinyl)cyclopropanecarboxylic acid 7.3
g was dissolved in 100 ml of benzene, and 4.2 g of l-α-methylbenzylamine dissolved in 15 ml of benzene was mixed at 50°C and left overnight at room temperature. The obtained crystals were recrystallized three times from benzene to obtain 3.0 g of l-α-methylbenzylamine salt of d-cis acid. [mp147゜〔α〕 ²⁰ _D −26.1゜(C, 1.9in EtoH)] Add 25 ml of benzene and 25 ml of 3N-HCl to the amine salt, shake well, wash the benzene layer thoroughly, remove the solvent, and add d-cis. i.e. (1R, cis)2,2
1.7 g of -dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid was obtained. [mp90゜[α] ²⁰ _D +27.2゜ (C, 2.1in CHCl ₃ )] Synthesis Example 2 Synthesis of 3-anilino-α-cyanobenzyl alcohol Described in Zhur. Obshchei Khim 30 , 2693 (1960) According to the method, methyl 3-acetylaminobenzoate and iodobenzene were reacted in nitromethane in the presence of potassium carbonate and activated copper powder to produce 3-
Anilinobenzoic acid was obtained and synthesized by the route shown in the figure below. 4.2 g of 3-anilinobenzoic acid was dissolved in 40 ml of methanol, 40 ml of 1N HCl methanol solution was added thereto, and the mixture was refluxed for 2 hours. Methanol was removed and ether was added to extract the ester. The ether layer was washed with 2% NaOH and saturated brine to remove ether, yielding 4.2 g of 3-anilinobenzoic acid.
(mp110-112℃) Dissolve 4.5g of methyl 3-anilinobenzoate in 20ml of methanol and add sodium borohydroxide under ice cooling.
7.2g was added gradually. Gradually raise the temperature and
After refluxing for an hour, the reaction solution was poured into an ice-cooled 10% aqueous H ₂ SO ₄ solution. Ether extraction was performed to collect 5.0 g of oil, and further hydrolysis was performed by adding a 5% KOH methanol solution to remove unreacted methyl ester. By-product 3-anilinobenzoic acid was removed from the reaction solution by alkali washing to obtain 3.5 g of 3-anilinobenzyl alcohol. 3.0 g of the above alcohol was dissolved in 30 ml of benzene, 6.0 g of activated MnO ₂ was added, and after refluxing for 3 hours, the generated MnO was removed by filtration. The filtrate was concentrated and passed down a 40 g silica gel column to obtain 2.7 g of 3-anilinobenzaldehyde. Dissolve 2.5g of the obtained aldehyde in 40ml of ethanol and make KCN1.5
After adding 1.8 ml of acetic acid and stirring overnight, 2N-KCl100
ml and extracted with benzene. The benzene layer was washed with brine and concentrated to obtain 2.7 g of 3-anilino-α-cyanobenzyl alcohol. Bromide, a reactive derivative of alcohol, was obtained by reacting thionyl bromide in the presence of pyridine in benzene under ice cooling. Synthesis Example 3 Synthesis of ester by reaction of alcohol and carboxylic acid halide (1R, cis)2,2-dimethyl-3-(2,2
-Dichlorovinyl) cyclopropanecarboxylic acid chloride (4.8 g) was dissolved in 15 ml of dry benzene, to which was added 4.5 g of 3-anilino-α-cyanobenzyl alcohol dissolved in 20 ml of dry benzene, and then dry pyridine was added as a condensation aid. When 3 ml is added, pyridine hydrochloride precipitates out. After sealing the cap and leaving it overnight at room temperature, the crystals of pyridine hydrochloride were filtered, the benzene solution was dried with nitric acid, and the benzene was distilled off under reduced pressure to obtain 3'-anilino-α'-cyanobenzyl (1R, cis). 2,2-dimethyl-3-(2,2
-dichlorovinyl) cyclopropane carboxylate 7.7 g were obtained. Synthesis Example 4 Synthesis of ester by reaction of alcohol and carboxylic acid (1R, cis)2,2-dimethyl-3-(2,2
-dibromovinyl)cyclopropanecarboxylic acid
Dissolve 6.0 g and 4.4 g of 3-(4-fluoroanilino)benzyl alcohol in 50 ml of dry benzene.
6.2 g of dicycloxylcarbodiimide 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 filtered off. The oily substance obtained by concentrating the filtrate was passed down a 100 g silica gel column to 3'-
(4-fluoroanilino)benzyl (1R, cis)
9.7 g of 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate was obtained. Synthesis Example 5 (1R,4R,5S)-4-hydroxy-6,6 was synthesized according to the method described in Pestic.Sci.1980, 11 188.
-dimethyl-3-oxabicyclo[3,1,0]
Lactone ether was obtained by reacting hex-2-one and 3-anilino-α-cyanobenzyl alcohol in the presence of toluene-4-sulfonic acid. Column chromatography (S)-
2-[(1R,4R,5S)-6,6-dimethyl-2-
Using (S) 3-anilino-α-cyanobenzyl alcohol obtained by separating and hydrolyzing oxo-3-oxabicyclo[3,1,0]hex-4-yloxy]-2-(3-anilinophenyl)acetonitrile According to Synthesis Example 4, (S)3'-anilino-α'-cyanobenzyl (1R, cis)2,2
-Dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate was synthesized. Synthesis Example 6 Synthesis of ester by reaction of alcohol halide and organic tertiary base carboxylate (1R, cis)2,2-dimethyl-3-(2,2
-dichlorovinyl)cyclopropanecarboxylic acid
Dissolve 4.2g in 50ml of acetone and add 3-(4-
Add 7.4 g of bromoanilino-α-cyanobenzyl bromide. Add 4 ml of triethylamine under stirring, react at 60-80°C for 3 hours, then dissolve in ether, wash the ether solution thoroughly with diluted hydrochloric acid, aqueous sodium bicarbonate, and brine, dry over sulfuric acid, and distill off the ether under reduced pressure. and 3'-(4-bromoanilino)-α'-cyanobenzyl (1R, cis)2,2-dimethyl-
8.6 g of 3-(2,2-dichlorovinyl)cyclopropanecarboxylate was obtained. Next, in order to make it clearer that the insecticide of the present invention is excellent, we will show the results of efficacy tests. Test Example 1 Insecticidal test by spraying A 0.02% white light solution of the compound used as an active ingredient in the present invention and its reference compound (A), a white light solution of 0.02% and piperonyl butoxide 0.1% (B),
White light solution of 0.01% and Phthalthrin 0.01% (C)
A white lamp solution of 0.02% each of allethrin and phthalthrin was sprayed using a turntable device.
The relative effectiveness of the knockdown effect of the test drug was calculated from the falling and turning rates of houseflies after 1, 2, 5, 10, and 20 minutes, and the mortality rate after 24 hours was calculated as follows. It is like that. The control drugs are indicated by the symbols A, B, and C after the compound number, and the alcohol component in each drug is the same as the original compound.
The numbers in parentheses represent the mortality rate after 24 hours. [Table] The test results (1R, cis) show that the knock-down effect of the insecticide of the present invention is very good;
trans), that is, 3 to 5 compared to the trans form.
The activity was twice as high. Test Example 2 Insecticidal test using microdropping method Phenothrin, the compound of the present invention, and its control compound, and Cinepirin 500 were added to each of them in an amount twice the amount of the active ingredient to make an acetone solution of a predetermined concentration, and the mixture was infected with house flies using a microsyringe. It was applied to adult cockroaches, adult German cockroaches, and 3rd instar larvae of Spodoptera japonica, and the relative insecticidal efficacy against phenotrin and the synergistic effect with cinepirin 500 were investigated from the mortality rate after 24 hours, and the results are as follows. Note that the symbols A, B, and C of the control compounds have the same meanings as in Test Example 1. [Table] As a result of the test, the insecticidal activity of the insecticide of the present invention against house flies, German cockroaches, and Spodoptera was more than three times that of the corresponding trans form or dl-cis, trans form. The effect was further enhanced. Next, examples of formulation are shown.The formulation can be prepared by a method well known to those skilled in the art without requiring any special conditions in accordance with general agricultural chemicals. 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 (2) of the present invention 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 (4) of the present invention, 10 parts of Solpol SM-200 (registered trademark of Toho Chemical) and 70 parts of xylol were added and stirred and mixed to dissolve, 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 refined kerosene.
After dissolving 28 parts of the solution 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 compound (7) of the present invention and 0.5 g of BHT were uniformly mixed with 99.0 g of a base material for mosquito coils such as pyrethrum extract lees powder, wood flour, starch powder, etc., and a mosquito repellent was prepared by a known method. Get some incense. Reference Example 6 0.4 g of the compound (9) 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 0.3 parts of the compound (10) of the present invention and 99.7 parts of clay are thoroughly ground and mixed to obtain a 0.3% powder. Reference example 8 40 parts of the present compound (12), 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 3 5 to 5 on a surface where a large number of green peach aphids appeared
A 1000-fold dilution with water of each emulsion containing the compounds (1), (3), (6), and (9) of the present invention among the emulsions obtained in Reference Example 3 was applied to a radish field at the 6-leaf stage. Scattered per 100/count. A parasitic rate survey two days later showed that the density had decreased to less than 1/10 of the pre-spraying density in each plot. Test Example 4 One day before applying the insecticidal ingredient to potted fava beans, one tree was infested with approximately 200 aphids. Among the hydrating agents obtained in Reference Example 8, (2)
A 4000-fold dilution of solutions (7), (10), and (12) was sprayed on leaves infested with insects using a compressed air spray method (10 ml/pot), and the degree of damage was observed 2 days later. As a result, no increase in the degree of damage was observed in any of the cases. Test Example 5 1 for 4 leaves of potted green beans 5 days after sowing
Each leaf is infested with 10 female adult spider mites and stored in a constant temperature room at 27°C. After 6 days, the active ingredients were added to emulsions (4), (5), (8) and (10) obtained in Reference Example 3 with water.
A chemical solution diluted to 100 ppm was sprayed on a turntable at 10 ml per pot. After 10 days, the number of parasitized spider mites on the plants was less than 10 for all drugs. Test Example 6 Each of the powders (1), (4), (7), and (11) obtained in Reference Example 7 was uniformly sprinkled at a rate of 2 g/m ² on the bottom of a waist-high glass tray with a diameter of 14 cm. Spread butter on the wall, leaving about 1cm at the bottom. If adult German cockroaches were released into the container in groups of 10, and the cockroaches were left in contact for 30 minutes and then transferred to a new container, more than 80% of the cockroaches could be killed by either powder after three days.

Claims (1)

[Claims] 1. General formula (In the formula, X represents a chlorine atom or a bromine atom.R
is a hydrogen atom or a cyano group, Y is a hydrogen atom,
Represents a fluorine atom, chlorine atom or bromine atom. ) An insecticide and acaricide characterized by containing a cyclopropanecarboxylic acid ester derivative having the configuration (1R, cis). 2. The insecticide and acaricide according to claim 1, which contains a pyrethroid synergist as an adjuvant.