FR2701630A1 - Soil insecticide based on a cyclopropanecarboxylic acid ester - Google Patents

Abstract

Soil insecticide containing as active ingredient a carboxylic acid ester having the formula (I): in which Y represents a hydrogen atom or a methyl group, and when Y is a hydrogen atom, X represents an isobutenyl or 2,2-dihalovinyl group, and when Y is a methyl group, X represents a methyl group.

Description

 The present invention relates to a soil insecticide.

 Pyrethroid compounds are widely used as insecticides because of their low toxicity to mammals. In general, however, there are none that have sufficient control effect on soil insects when used in soil treatment, only tefluthrin being used in practice as a soil insecticide.

 In general, products with the following various characteristics may be considered suitable for use as soil insecticides. The characteristics that the soil insecticide must exhibit include, for example: 1. Excellent soil insect control.

2. Long-term, long-term effectiveness (long-term persistence).

3. Repellent or impeding action to feed.

 An object of the present invention is to provide a soil insecticide that satisfies these characteristics.

dans laquelle Y représente un atome d'hydrogène ou un groupe méthyle, et lorsque Y est un atome d'hydrogène, X représente un groupe isobutényle (groupe 2-méthyl-I-propényle) ou un groupe 2,2-dihalogénovinyle (par exemple un groupe 2,2-dichlorovinyle, 2,2-difluorovinyle, 2-chloro-2-fluorovinyle), et lorsque Y est un groupe éthyle, X représente un groupe méthyle, a une propriété remarquable en tant qu'insecticide du sol.In consideration of the situation described above, the present inventors have conducted extensive research to find an excellent compound for use as a soil insecticide. As a result, they have found that a carboxylic acid ester having the formula (I):

in which Y represents a hydrogen atom or a methyl group, and when Y is a hydrogen atom, X represents an isobutenyl group (2-methyl-1-propenyl group) or a 2,2-dihalogenovinyl group (for example 2,2-dichlorovinyl, 2,2-difluorovinyl, 2-chloro-2-fluorovinyl), and when Y is ethyl, X is methyl, has remarkable property as a soil insecticide.

The present inventors have thus realized the present invention.

Soil insects that can be controlled with the soil insecticide of the present invention include soil dwelling insects that damage crops, for example:
Chrysomelidae:
Kind Diabrotica: Diabrotiea larvae such as
Diabrotica virgifera virgifera Leconte, Diabrotica barberi
Smith and Lawrence, and Diabrotica undeeimpunetata howardi
Barber; AuZaeophora geese: AuZacophora femoralis (Motschulsky); and genus Phyllotreta: Phyllotreta str @ olata (Fabricius).

 The carboxylic acid ester of formula (I) used as an active ingredient in the present invention can be prepared for example by the method described in Japanese Patent Application Laid-Open No. 56-156238.

 The carboxylic acid ester of formula (I) comprises, for example, the following compounds: 2,2-methyl-3-propyl-2-methyl-4-methylidene-3- (2-propynyl) cyclopent-2-enyl 2,2,3,3-tetramethylcyclopropanecarboxylate; 2-methyl-4-methylidene-3- (2-propynyl) cyclopent-2-enyl chrysanthemate; 2- (2, 2-dichlorovinyl) -2,2-methyl-4-methylidene-3- (2-propynyl) cyclopent-2-enyli 3- (2,2-difluorovinyl) -2,2-dimethylcyclopropanecarboxylate 2-methyl-4-methylidene-3- (2-propynyl) cyclopent-2-enyl dimethylcyclopropanecarboxylate); and 2-methyl-4-methylidene-3- (2-propynyl) cyclopent-2-6nyl 3- (2-chloro-2-fluorovinyl) -2,2-dimethylcyclopropanecarboxylate.

 These carboxylic acid esters have geometric and / or optical isomers, and these isomers and mixtures thereof are also included in the present invention.

 When carboxylic acid esters having the formula (I) are used as active ingredients for soil insecticides, they usually come in oil spray formulations, emulsifiable concentrates, wettable powders, granules, fine powders, aerosols and the like by mixing with solid supports liquid carriers or gaseous supports and, if necessary, addition of surfactants and other auxiliaries for the formulation.

 It is desirable that these preparations contain as active ingredient the carboxylic acid esters of formula (I) in an amount of 0.1 to 99.9% by weight, preferably 1 to 80% by weight.

 Solid supports include, for example, fine powders or clay granules such as kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, Fubasami clay and terra alba, talcs, other inorganic minerals such as sericite , quartz, sulfur, activated carbon, calcium carbonate and hydrated silica and chemical fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride. Liquid carriers include, for example, water , alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as toluene, xylene, ethylbenzene and methylnaphthalene, aliphatic hydrocarbons such as hexane, cyclohexane, kerosene and gas oil, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and isobutyronitrile and ethers such as diisopropyl ether, and dioxane and acyl amides. such as dimethylformamide and dimethylacetamide. Gaseous carriers, ie propellants, include, for example, gaseous freon, butane gas or gaseous carbon dioxide.

 Surfactants include, for example, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl and aryl oxides and polyoxyethylenated products thereof, polyethylene glycol oxides, polyhydric alcohol esters, or alcoholic derivatives of sugar.

 Formulation aids such as adhesive agents and dispersing agents include, for example, casein, gelatin, polysaccharides, such as starch powder, gum arabic, cellulose derivatives and alginic acid, lignin derivatives. , bentonite, sugars, and water-soluble synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polyacrylic acid. Stabilizers include PAP (isopropyl acid phosphate), (2,6-di-tert-butyl-4-methylphenol), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl- 4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids and esters thereof.

 The preparations thus obtained are applied as such or after dilution in the water to the surface of the soil, and if necessary the soil is mixed with them after application or the soil is imbibed by them. The preparations can be applied on leaves. These preparations may also be used in combination with other insecticides, nematocides, acaricides, fungicides, herbicides, plant growth regulators, fertilizers, microbial pesticides such as BT formulations, entomopathogenic viruses, insect hormones and skin enhancers. ground.

 According to another embodiment, the preparations and these pesticidal compositions can also be used simultaneously without mixing them. When the carboxylic acid esters of formula (I) are used as active ingredients for soil insecticides, their dosage is usually 1 to 500 g / 10 ares, preferably 5 to 200 g / 10 ares. When emulsifiable concentrates, wettable powders, etc. are used in dilution in batten, the concentration to be used is from 0.5 ppm to 30%, and the fine powders, granules, oily sprays or aerosols are used as such without being diluted in water .

 For all of these, the dosages and concentrations of applications vary depending on the type of preparation, the timing, location and manner in which these preparations are used, the type of pest or the extent of the damage, and may be increased or decreased outside the fields described above.

 If necessary, synergistic agents and stabilizers incorporated in known pyrethroid insecticides may be added to the soil insecticides of the present invention. The synergistic agents include piperonylbutoxides, MGK-264 CN- (2-ethylhexyl) bicyclol2,2,1l-hept-5-ene-2,3-dicarboxinintdeff, and S-421 Ebis (2,3,3 , 3-tetrachloropropyl) ether, and the stabilizing agents include organic acids and phenolic antioxidants. The amount of these added compounds is usually 1/100 to 10 times the weight of the active ingredient.

 The present invention is illustrated in more detail with reference to the following examples.

 The compounds are represented by the numbers of compounds described in Table 1.

TABLE 1
Compounds represented by the formula:

<SEP> index of
<tb> Structural <SEP> Formula <SEP> Isomer <SEP> Refraction <SEP> nD
<tb> Compound <SEP> n
<tb> x- <SEP> y- <SEP> Fragment <SEP> alcohol <SEP> Fragment <SEP> acid <SEP> (C)
<tb> (1) <SEP> CH3- <SEP> CH3- <SEP> S <SEP> - <SEP> 1.5137 (22)
<tb> (2) <SEP> (CH3) 2C = CH- <SEP> H- <SEP> S <SEP> (1R) -cis, <SEP> trans <SEP> 1.5177 (25)
<tb> (3) <SEP> Cl2C = CH- <SEP> H- <SEP> S <SEP> (1R) -trans <SEP> 1.5344 (25)
<tb> (4) <SEP> F2C = CH- <SEP> H- <SEP> S <SEP> (1RS) -trans <SEP> 1.4972 (25)
<tb> (5) <SEP> CH3- <SEP> CH3- <SEP> RS <SEP> - <SEP> 1.5032 (29)
<tb> (6) <SEP> F2C = CH- <SEP> H- <SEP> S <SEP> (1R) -trans
<Tb>
The compounds used for comparison in the test examples are represented by the compound symbols (A) to (D) described below. The compounds of Table 2 are described in USP Patent No. 4,356,187 and the application Published Japanese Patent Application No. 56-156238.

TABLE 2

Symbp <SEP> the <SEP> Structural <SEP> Formula <SEP> Isomer
<tb> of <SEP> composed
<tb> x- <SEP> y- <SEP> Fragment <SEP> alcohol <SEP> Fragment <SEP> acid
<tb> (A) <SEP> CH3- <SEP> CH3- <SEP> RS <SEP> (B) <SEP> (CH3) 2C = CH- <SEP> H- <SEP> RS <SEP> (1R ) -cis, <SEP> trans
<tb> (C) <SEP> Cl2C = CH- <SEP> H- <SEP> RS <SEP> (1R) -trans
<Tb>
Tefluthrin Compound (D); (Z) - (1RS) -cis-3- (2-chloro-3,3,3-trifluoro-prop-1-enyl) -2,2-dimethylcyclopropanecarboxylate 2,3,5,6-tetrafluoro-4- Methylbenzyl, which is commercially available as a soil insecticide among the pyrethroid compounds, is also used as a compound for comparison.

 In the first place, examples of formulation are indicated. In the examples, all parts are by weight.

EXAMPLE OF FORMULATION 1. EMULSIFIABLE CONCENTRATE
20 parts of each of the compounds (1) to (6) are dissolved in 65 parts of xylene, and 15 parts of
Sorpol 3005X, an emulsifier, (trademark registered in the name of
Toho Kagaku Co.) are added. The resulting mixture is suitably stirred to obtain a 20% emulsifiable concentrate of each of the compounds.

EXAMPLE OF FORMULATION 2. WET POWDER
To 40 parts of each of the compounds (1) to (6) are added 5 parts of Sorpol 3005X (described above), and after vigorous mixing, 32 parts of Carplex &num; 80 (trademark registered in the name of Shionogi & Co., Ltd; a fine powder of synthetic hydrated silicon dioxide) and 23 parts of 300 mesh diatomaceous earth are added. The resulting mixture is stirred using a juice mixer to obtain a 40% wettable powder of each compound.

FORMULATION EXAMPLE 3. PELLETS
1.5 parts of each of the compounds (1) to (6) are added to 98.5 parts of AGSORB LVM-MS 24/48 (montmorillonite calcination product manufactured by Oil Dri Co; particles of 24 to 48 mesh). The resulting mixture is suitably mixed to obtain 1.5% granules of each compound.

EXAMPLE OF FORMULATION 4. PELLETS
1.5 parts of each of the compounds (1) to (6) are added to 98.5 parts of Attapulgite LVM 24/48 (attapulgite calcination product manufactured by ENGELHARD Co .; granular support having a particle size from 24 to 48 mesh). The resulting mixture is suitably mixed to obtain 1.5% granules of each compound.

EXAMPLE OF FORMULATION 5. GRANULES.

 1.5 parts of each of the compounds (1) to (6) are added to 98.5 parts of BIODAC 25/50 (pulp waste product made by OIL DRI Co; from 25 to 50 mesh).

The resulting mixture is suitably mixed to obtain 1.5% granules of each compound.

EXAMPLE OF FORMULATION 6. GRANULES.

 1.5 parts of each of the compounds (1) to (6) and 5 parts of polypropylene glycol (average molecular weight 1000) are suitably mixed, and then 93.5 parts of AGSORB LVM-MS 24/48 (calcination product) are added. montmorillonite manufactured by OIL DRI Co; granular support having a particle size of 24 to 48 mesh) to obtain 1.5% granules of each compound.

EXAMPLE OF FORMULATION 7. WZCROCAPSULES

10 parts of each of the compounds (1) to (6), 10 parts of phenylxylylethane and 0.5 part of Sumidur L-75 (tolylene diisocyanate manufactured by Sumitomo-Bayer Urethane
Co.) are mixed, then the mixture is added to 20 parts of an aqueous solution of 20% gum arabic. The resulting mixture is stirred using a web homogenizer mixer to obtain an emulsion having an average particle size of 20 m. Then, 2 parts of ethylene glycol are added, and the reaction is carried out for 24 hours in a water bath at 600C so as to obtain a suspension of microcapsules.

 Separately, 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate manufactured by Sanyo Kasei Co.) were dispersed in 56.3 parts of ion-exchanged water. in order to obtain a solution of thickening agent.

 Then, 42.5 parts of the suspension of the above microcicrocapsules and 57.5 parts of the thickening agent solution are mixed so as to obtain microcapsules containing each compound in a proportion of 10%.

EXAMPLE OF FURMULATION 8. FLUID FORMULATION
10 parts of each of the compounds (1) to (6) and 10 parts of phenylxylylethane are mixed, and then the mixture is added to 20 parts of a 10% aqueous polyethylene glycol solution. The resulting mixture is stirred with a homogenizer mixer to obtain an emulsion having a mean particle size of 3 μm.

 Separately, 0.2 part of xanthan gum and 1.0 part of Veegum R (magnesium aluminum silicate manufactured by Sanyo Kasei Co.) were dispersed in 58.8 parts of ion-exchanged water. so as to obtain a solution of thickening agent.

 Next, 40 parts of the above emulsion and 60 parts of the thickener solution are mixed to obtain a 10% fluid formulation of each compound.

EXAMPLE OF FORMULATION 9. FINE POWDERS
5 parts of each of the compounds (1) to (6), 3 parts of Carplex &num; 80 (described above), 0.3 part of PAP and 91.7 parts of 300 mesh talc, and the resulting mixture is stirred with a juice mixer so as to obtain a fine powder containing each compound at 25%. %.

EXAMPLE OF FORMULATION 10. OIL SPRAY
0.2 parts of each of the compounds (1) to (6) are dissolved in 99.8 parts of methylnaphthalene so as to obtain an oily spray containing each compound in an amount of 0.2%.

 The test examples are shown.

EXAMPLE OF TEST 1
The emulsifiable concentrate of each test compound prepared according to Formulation Example I is diluted in batten, and 5 ml of the dilute aqueous solution is mixed with 50 g of sterile (16 mesh) sol to adjust the concentration of the test compound. soil active ingredient at 1.0 or 0.5 ppm.

This soil is transferred to a polyethylene section 5.6 cm in diameter and 5.8 cm in height, and two maize plants are planted in the soil in which the roots have grown to a length of approximately 2 cm. Then 10 larvae: in the third instar stage of Diabrotica undeeimpunetata howardi Barber are introduced into the cut. Three days after treatment, the number of myrtle and live larvae and the feeding stage of the als plant are observed. The feeding stage is assessed from the standards described in Table 3.

The results, ie mortality (%) and feeding stage, are reported in Tables 4 and 5, respectively.

TABLE 3

<tb> Stage <SEP> Power Supply <SEP> Appreciation Standard <SEP>
<tb><SEP> ++ <SEP> Align <SEP> equals <SEP> to <SEP><SEP> observed <SEP> in
<tb><SEP> processed sample <SEP> no <SEP>
<tb><SEP> + <SEP> Supply <SEP> frankly <SEP> marked <SEP>
<tb><SEP> + <SEP> Low <SEP> power <SEP>
<tb><SEP> - <SEP> not <SEP> supply
<Tb>
TABLE 4

<tb><SEP> Test <SEP> Compound <SEP> Mortality <SEP> (%)
<tb><SEP> 1.0 <SEP> ppm <SEP> 0.5 <SEP> ppm
<tb><SEP> (1) <SEP> 100 <SEP> 100
<tb><SEP> (2) <SEP> 100 <SEP> 80
<tb><SEP> (3) <SEP> 100 <SEP> 80
<tb><SEP> (4) <SEP> 100 <SEP> 100
<tb><SEP> (5) <SEP> 100 <SEP> 85
<tb><SEP> (A) <SEP> 70 <SEP> 40
<tb><SEP> (B) <SEP> 0 <SEP> 0
<tb><SEP> (C) <SEP> 50 <SEP> 20
<tb><SEP> (D) <SEP> 80 <SEP> 20
<tb> No <SEP> of <SEP> treatment <SEP> 0
<Tb>
TABLE 5

stadium <SEP> feeding
<tb><SEP> Test compound <SEP>
<tb><SEP> 1.0 <SEP> ppm <SEP> 0.5 <SEP> ppm
<tb><SEP> (1)
<tb> (2) <SEP> - <SEP>
<tb><SEP> (3) <SEP> - <SEP>
<tb><SEP> (4) <SEP> - <SEP>
<tb><SEP> (5) <SEP> - <SEP>
<tb><SEP> (A) <SEP>#<SEP><SEP> ++
<tb><SEP> (B) <SEP> ++ <SEP><SEP>!<SEP> ++ <SEP>
<tb><SEP> (C) <SEP> + <SEP> +
<tb><SEP> (D) <SEP> + <SEP>#
<tb><SEP> not <SEP> of <SEP> processing <SEP> ++
<Tb>
EXAMPLE OF TEST 2
The emulsifiable concentrate of each test compound prepared according to Formulation Example 1 is diluted in water, and 5 ml of the dilute aqueous solution is mixed with 50 g of sterile (16 mesh) sol to adjust the pH. soil active ingredient concentration at 4.0 ppm. This treated soil is stored at 250C under conditions of total darkness. This treated soil is transferred to a polyethylene section (diameter 5.6 cm, height 5.8 cm) one, two, three and five weeks after the soil treatment; and two maize plants were planted in the soil in which the roots grew to an approximate length of 2 cm. Then 10 larvae of the third instar stage of Diabrotica undecimpunctata howardi Barber are introduced into the section. Three days after the introduction of the larvae, the number of dead and living larvae is examined in order to obtain a mortality rate (*). The results are shown in Table 6.

TABLE 6

mortality <SEP> (%)
<tb> composed
<tb> test
<tb> after <SEP> after <SEP> after <SEP> after
<tb> one <SEP> week <SEP> two <SEP> weeks <SEP> three <SEP> weeks <SEP> five <SEP> weeks
<tb> (1) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 90
<tb> (3) <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 80
<tb> not <SEP> of <SEP> processing <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0
<Tb>

Claims (5)

 in which Y represents a hydrogen atom or a methyl group, and when Y is a hydrogen atom, X represents an isobutenyl or dihalogenovinyl group, and when Y is a methyl group, X represents a methyl group, and a support or inert diluent.

 1. soil insecticide containing as active ingredient an amount effective in insecticidal activity of a carboxylic acid ester having the formula (I) The soil insecticide according to claim 1, wherein X and Y are both methyl. A method of controlling soil insects which comprises applying a soil insecticide according to claim 1 or 2 to the soil occupied by the insects. 4. The method of claim 3 wherein the soil insects are Diabrotica larvae. 5. Use of a carboxylic acid ester having the formula (I):

 in which Y represents a hydrogen atom or a methyl group, and when Y is a hydrogen atom, X represents an isobutenyl or dihalogenovinyl group, and when Y is a methyl group, X represents a methyl group, as a soil insecticide .