FR2649295A1 - Solid pesticidal and acaridical formulation based on an ether derivative and process for preparing it - Google Patents

Abstract

The invention relates to a solid pesticidal and acaricidal formulation based on an ether derivative and process for preparing it. This formulation comprises a solution of an ether derivative represented by the general formula I: in which R represents a lower alkyl or a halomethyl group and R<1> represents a hydrogen or fluorine atom in an alkyl phthalate having an alkyl group with 9 to 13 carbon atoms, which is applied onto a solid support. The invention also relates to a process for preparing the formulation which comprises the dissolution of the ether derivative in the alkyl phthalate and the application of the solution onto a solid support.

Description

FORMULATION PESTICIDE AND SOLID ACARICIDE BASED ON DERIVATIVE OF HOUR AND ITS PREPARATION PROCESS
The present invention relates to a solid pesticide and acaricide formulation and a process for its preparation. More specifically, the present invention relates to a solid pesticide and acaricide formulation which comprises an ether derivative carried by a solid support and its method of preparation.

dans laquelle R représente un groupe alkyle inférieur ou un groupe halogénométhyle et R1 représente un atome d'hydrogène ou de fluor. Les dérivés d'éther sont les composants efficaces de pesticides et d'acaricides qui ont des activités pesticides et acaricides extrêmement élevées, une efficacité immédiate et une activité résiduelle excellentes et une faible toxicité pour les humains et les animaux y compris les poissons.Japanese Laid-Open Patent No. 21615/1986 and Japanese Laid-Open Patent Application No. 45233/1988 describe ether derivatives represented by the general formula I:

wherein R represents a lower alkyl group or a halogenomethyl group and R1 represents a hydrogen or fluorine atom. Ether derivatives are the effective components of pesticides and acaricides which have extremely high pesticidal and acaricidal activities, excellent immediate efficacy and residual activity, and low toxicity to humans and animals including fish.

In the practical applications of the effective components of agricultural chemicals, etc., it is generally usual to use them in the form of various formulations such as emulsions, wettable powders, dusts, granules, and these various have been improved. formulations in different ways.

For example, granules are obtained by applying effective amounts to mineral carriers and by performing granulation. Depending on the granulation techniques and the carriers, different adjuvants such as binders, disintegrants, wetting agents, dispersants, absorbents, solvents, lubricants and stabilizers can be used.

In particular, in order to allow a large amount of the carrier to uniformly absorb and carry a small amount of an effective component, to maintain the high efficiency of the effective component and to stabilize the efficiency thereof, it is customary to use different high boiling point solvents, for example hydrocarbons like heavy oil and kerosene, aromatic hydrocarbons like methylnaphthalene, plasticizers like dibutylphthalate, dioctylphthalate and tricresylphosphate, glycol derivatives like diethylene glycol and butylcellosolve, and animal and vegetable oils such as soybean oil.

Japanese Laid-Open Patent Application NT.171402 / 1986 describes solid agrochemical formulations which contain an alkyl phthalate comprising an alkyl group of 1 to 12 carbon atoms as an agrochemical formulation of reduced toxicity for. fish, alkyl esters of 1 to 8 carbon atoms being particularly preferred. Further, Japanese Patent Application Laid-Open NP.107902 / 1988 discloses an agrochemical formulation capable of preventing degradation over time, which is obtained by dissolving agrochemical components in an aromatic carboxylic ester and applying solution on a solid support, this application citing alkyl phthalates of 1 to 12 carbon atoms as a carboxylic ester.In the examples of this reference, ethyl benzoate is shown as an example of an aromatic carboxylic ester .

However, the properties of these conventional pesticide and acaricidal formulations are not fully satisfactory, so that it is desired to improve their pesticidal and acaricidal activity and their stability.

The object of the present invention is to provide a solid pesticide and acaricidal formulation which possesses higher pesticide and acaricidal activity, more stable and greater pesticide and acaricidal effects and which has lower toxicity to fish than the pesticide and acaricidal formulations. conventional solids.

Another object of the present invention is to provide a process for the preparation of solid pesticide and acaricide formulations making it possible to produce the above formulation in a favorable manner.

A further object of the present invention is to provide a solid pesticidal and acaricidal formulation in which an ether derivative represented by the general formula I is applied to a solid support as an effective component, which allows the ether derivative to develop in the compounds. practical applications the maximum of its characteristics such as high pesticidal and acaricidal activity and low toxicity to humans and animals including fish and to have stable and significant pesticidal effects, as well as a process for its preparation .

The present inventors have been investigating various adjuvants for formulation in order to achieve the above objects. As a result of this research they have found that a solid pesticide and acaricide formulation which is prepared by applying to a solid support an ether derivative represented by the general formula I dissolved in a solvent consisting of an alkyl phthalate having a An alkyl group of 9 to 13 carbon atoms exhibits stable and substantial pesticidal and acaricidal activity as well as reduced toxicity to fish. The present invention is based on this finding.

dans laquelle R représente un groupe alkyle inférieur ou halogénométhyle et R1 représente un atome d'hydrogène ou de fluor dans un phtalate d'alkyle ayant un groupe alkyle de 9 à 13 atomes de carbone est appliquée sur un support solide.The present invention provides a solid pesticide and acaricidal formulation wherein a solution of an ether derivative represented by the general formula I:

wherein R represents a lower alkyl or halogenomethyl group and R1 represents a hydrogen or fluorine atom in an alkyl phthalate having an alkyl group of 9 to 13 carbon atoms is applied to a solid support.

In addition, the present invention provides a process for preparing solid pesticide and acaricidal formulations which comprises dissolving an ether derivative of general formula I in an alkyl phthalate having an alkyl group of 9 to 13 carbon atoms and the application of the alkyl phthalate solution containing the ether derivative on a solid support.

The solid pesticide and acaricidal formulation according to the present invention allows a more attractive use of the effective components represented by formula I than before, the formulation exhibiting stable and significant long-term pesticide and acaricidal effects compared to conventional formulations. According to the process of the present invention, it is possible to produce the formulation advantageously.

As noted above, it is known that alkyl phthalates are used as solvents to dissolve effective components in the preparation of solid formulations of agricultural chemicals. However, it has surprisingly been found that the solid pesticide and acaricidal formulation described above, which contains an alkyl phthalate having an alkyl group of 9 to 13 carbon atoms, unexpectedly exhibits not only pesticidal and acaricidal activity. improved but also stable and significant pesticide and acaricidal effects as well as an extremely reduced toxicity to fish, compared to known conventional solid pesticide and acaricide formulations in which a solution of an ether derivative of general formula I in a Alkyl phthalate having an alkyl group of 1 to 8 carbon atoms is applied on a solid support.

It is not clear why the number of carbon atoms of an alkyl group of an alkyl phthalate produces such a difference in effect on the part of the resulting formulation. It is believed, however, that due to the physicochemical similarity between the ether derivative and an alkyl phthalate having an alkyl group of 9 to 13 carbon atoms, their mutual solubility is high and that they behave in such a manner. the like in water or the like, so that the unexpected effects of the pesticide and acaricidal formulation according to the present invention are obtained.

Such effects cannot be obtained when an alkyl phthalate having an alkyl group of 1 to 8 carbon atoms is used as the solvent. On the other hand, using an alkyl phthalate having an alkyl group of 14 or more carbon atoms as a solvent results in low solubility of the effective components.

The R substituent of the ether derivative represented by the general formula I represents a lower alkyl group such as a methyl, ethyl, n-propyl, isopropyl, nbutyl or tert-butyl group, or a halogenomethyl group such as a group difluoromethyl, trifluoromethyl, chlorodifluoromethyl or bromodifluoromethyl. Examples of ether derivatives are shown in Table 1.
Table 1

<tb><SEP> Compound <SEP> constituting <SEP> the effective <SEP> component <SEP>
<tb> A <SEP> ether <SEP> of <SEP> 2- (4-difluoromethoxyphenyl) -2
<tb><SEP> methylpropyl <SEP> and <SEP> from <SEP> 3-phenoxybenzyl
<tb> B <SEP> ether <SEP> of <SEP> 2- (4-trifluoromethoxyphenyl) -2- <SEP>
<tb><SEP> methylpropyl <SEP> and <SEP> from <SEP> 3-phenoxybenzyl <SEP>
<tb> C <SEP> ether <SEP> of <SEP> 2- (4-difluorobromomomethoxyphenyl) - <SEP>
<tb><SEP> 2-methylpropyl <SEP> and <SEP> from <SEP> 3-phenoxybenzyl
<tb> D <SEP><SEP> 2- (4-chlorodifluromethoxyphenyl) <SEP> ether <SEP>
<tb><SEP> -2-methylpropyl <SEP> and <SEP> from <SEP> 3-phenoxybenzyl
<tb> E <SEP> ether <SEP> of <SEP> 2- (4-methoxyphenyl) -2-methyl- <SEP>
<tb><SEP> propyl <SEP> and <SEP> from <SEP> 3-phenoxybenzyl <SEP>
<tb> F <SEP> ether <SEP> of <SEP> 2- (4-ethoxyphenyl) -2-methyl- <SEP>
<tb><SEP> propyl <SEP> and <SEP> from <SEP> 3-phenoxybenzyl
<tb> G <SEP> ether <SEP> of <SEP> 2- (4-difluoromethoxyphenyl) -2- <SEP>
<tb><SEP> methylpropyl <SEP> and <SEP> from <SEP> 3-phenoxy-4-fluoro
<tb><SEP> benzyl
<tb> H <SEP> ether <SEP> of <SEP> 2- (4-trifluoromethoxyphenyl) -2- <SEP>
<tb><SEP> methyl-propyl <SEP> and <SEP> from <SEP> 3-phenoxy-4-fluoro
<tb><SEP> benzyl
<tb> I <SEP> ether <SEP> of <SEP> 2- (4-difluorobronomethoxyphenyl) - <SEP>
<tb><SEP> 2-methylpropyl <SEP> and <SEP> from <SEP> 3-phenoxy-4-fluoro
<tb><SEP> benzoyl <SEP>
<tb> J <SEP> ether <SEP> of <SEP> 2- (4-chlorodifluoromethoxyphenyl) <SEP>
<tb><SEP> -2-methylpropyl <SEP> and <SEP> from <SEP> 3-phenoxy-4-fluoro
<tb><SEP> benzyl
<tb> K <SEP> ether <SEP> of <SEP> 2- (4-methoxyphenyl) -2-methyl- <SEP>
<tb><SEP> propyl <SEP> and <SEP> from <SEP> 3-phenoxy-4-fluorobenzyl
<tb> L <SEP> ether <SEP> of <SEP> 2- (4-ethoxyphenyl) -2-methyl- <SEP>
<tb><SEP> propyl <SEP> and <SEP> from <SEP> 3-phenoxy-4-fluorobenzyl
<tb>
The alkyl phthalate which contains an alkyl group of 9 to 13 carbon atoms according to the present invention can include di-n-nonyl phthalate, diisononyl phthalate, di-n-decyl phthalate, diisodecyl phthalate. , di-n-undecyl phthalate, di-n-dodecyl phthalate, di-n-tridecyl phthalate, etc. The alkyl phthalate can include any of different alkyl groups, as long as these contain 9 to 13 carbon atoms, however, it is sufficient to use the alkyl phthalates which are readily available as industrial and natural products.

These alkyl phthalates can be used alone or in the form of a mixture of several of them.

The solid pesticidal and acaricidal formulation according to the present invention preferably contains 0.1 to 40% by weight of effective component, i.e. an ether derivative, 0.1 to 40% by weight of sodium phthalate. alkyl, the remainder being constituted by a solid support. The formulation can also include various adjuvants such as surfactants, tackifiers and stabilizers, as needed.

The solid support can be constituted by vegetable powders such as soybean flour and wheat flour, mineral powders such as bentonite, clay, talc, calcium carbonate, diatomaceous earth, powder of stone, radiolarite and a zeolite, and in some cases water soluble solids such as potassium chloride, sodium chloride, ammonium sulfate and urea. These products can be used alone or as a mixture of two or more of them.

As surfactant, mention may be made of anionic surfactants such as lignosulphonate, alkylbenzenesulphonates, alkylsulphates, polyoxyalkylene alkylsulphates and polyoxyalkylene alkylphosphates, nonionic surfactants such as polyoxyalkylene alkylethers, polyoxyalkylene alkylethers, polyoxyalkylene alkylphosphates, polyoxyalkylene alkylamines, polyoxyalkylene alkylamides, polyoxyalkylene alkylthioethers, esters of fatty acids and of polyoxyalkylene, esters of fatty acids and of glycerol and esters of fatty acids and sorbitan, etc.

Adjuvants can be added as appropriate as long as the properties of the final product are not deteriorated.

It is preferable to appropriately adjust the proportions of the different constituents taking into account the shape and stability of the desired formulation and the stability and persistence of its effect.

In the method according to the present invention, it is preferable that the effective component is dissolved in the above phthalate by heating and the resulting solution is uniformly applied to the support.

The present invention will be illustrated by the following Examples, Comparative Examples and Test Examples. However, it is understood that the present invention is not limited thereto or by them. The effective components used are identified by the letters shown in Table 1.

Example 1:
In 0.4 part by weight of diisononyl phthalate was dissolved 0.2 part by weight of 2- 2- (4-difluorobromomomomethoxyphenyl) - 2-methylpropyl ether and 3-phenoxy-4fluorobenzyl (compound I) , and 10 parts by weight of white carbon, 0.5 part by weight of Driless A (flocculant manufactured by the company Sankyo) and 88.9 parts by weight of clay were added. These components were mixed and ground to obtain 100 parts by weight of a dust-like powder.

Example 2:
2- (4-trifluoromethoxyphenyl) -2-methylpropyl and 3-phenoxybenzyl ether (compound B), diisododecyl phthalate and Irganox 1010 (antioxidant manufactured by the company Ciba Geigy) were mixed in respective amounts of 0.5 part, 0.5 part and 0.05 part by weight. The resulting composition was heated and melted, to which were added 5 parts by weight of white carbon and 93.95 parts by weight of clay. These components were mixed and ground to obtain 100 parts by weight of a dust-like powder.

Exerrrole3:
0.5 part by weight of each of the compounds C, D, F, J, K and L was taken separately, to which 0.8 part by weight of Agrisole AC-100 was mixed each time (registered trademark: phthalate consisting mainly of phthalates having an alkyl group of 10 to 12 carbon atoms; manufactured by the company Kao) and 0.1 part by weight of Irganox 1010. To each of these mixtures, 10 parts by weight of white carbon, 0, 0, were added. 5 part by weight of
Driless B and a further 88.9 parts by weight of clay. These components were mixed and ground uniformly to obtain each dust-like powder in an amount of 100 parts by weight.

Example 4:
20 parts by weight of 2- (4-difluorobromomomethoxyphenyl) -2-methylpropyl and 3-phenoxybenzyl ether (compound C) were heated and melted in 15 parts by weight of diisononyl phthalate, and 5 parts were added. by weight of Dexsol NF (surfactant manufactured by the company Dai-here Kogyo Seiyaku), 25 parts by weight of white carbon and 35 parts by weight of radiolarite. These products were mixed and ground to obtain 100 parts by weight of a wettable powder.

Example 5:
10 parts by weight of 2- (4-ethoxyphenyl) -2-methylpropyl and 3-phenoxybenzyl ether (compound F) were heated and melted in 10 parts by weight of Agrisol-AC-100, and added 3 parts by weight of
Dexsol WK (surfactant manufactured by the company Dai-here
Kogyo Seiyaku) and 10 parts by weight of white carbon. These components were mixed and ground to obtain 100 parts by weight of a wettable powder.

Example 6:
10 parts by weight of di-n-decyl phthalate were individually heated and dissolved in 10 parts by weight of each of compounds A, B, H, I, J and K, and 5 parts by weight were added each time uniformly. dEmal 10 (surfactant manufactured by the company Kao), 20 parts by weight of white carbon and 55 parts by weight of radiolarite. These mixtures were ground to obtain 100 parts by weight of wettable powders each time.

Example 7:
86 parts by weight of clay and 2 parts by weight of clay were ground, mixed, added with water, granulated and dried.
Serogen 7A (carboxymethylcellulose manufactured by the company
Dai-ici Kogyo Seiyaku) to obtain granular kernels.

These granular cores were impregnated with a liquid obtained by heating and melting 1 part by weight of 2 - (4 - ethoxyphenyl) -2-methylpropyl and 3 -phenoxybenzyl ether (compound F) and Irganox 1010 in 10.9 parts by weight of diisododecyl phthalate, to obtain 100-parts by weight of granules.

Examples:
Using a mixture of clay and talc (mixing ratio = 7: 3), 88 parts by weight of granular cores were obtained in the same manner as in Example 7. These granular cores were impregnated with a liquid. obtained by heating and melting 0.5 part by weight of 2- (4-ethoxyphenyl) -2-methylpropyl ether of 3-phenoxy-4-fluorobenzyl (compound L) and 0.05 part by weight of Irganox 1010 in 11.45 parts by weight of Agrisol AC-110 (di-n-decyl phthalate manufactured by the company Kao) to thereby obtain 100 parts by weight of granules.

Example 9:
86 parts by weight of a mixture of clay and talc (mixing ratio = 7: 3) and 2 parts by weight of Serogen were ground, mixed, added with water, granulated and dried.
PR (carboxymethylcellulose manufactured by the company Dai-ici
Kogyo Seiyaku) to obtain granular kernels. These granular cores were separately impregnated with the liquid obtained by heating and dissolving 1 part by weight of compound B, C, D, H, I or J and 0.1 part by weight of Irganox 1010 in 8.9 parts by weight. weight of dinonyl phthalate, thereby obtaining each time 100 parts by weight of granules.

Comparative example 1:
A dust-like powder was obtained by following the procedure of Example 1 except that dimethyl phthalate was used in place of diisononyl phthalate.

Comparative example 2:
A dust-like powder was obtained by following the procedure of Example 2 except that di-2-ethylhexyl phthalate was used in place of diisodecyl phthalate.

Comparative example 3:
A wettable powder was obtained by following the procedure of Example 4, except that dimethyl phthalate was used in place of diisononyl phthalate.

Comparative example 4:
A wettable powder was obtained by following the procedure of Example 5, except that di-n-octyl phthalate was used in place of Agrisol AC-100.

Comparative example 5:
Granules were obtained in the same way as in Example 7, except that dimethyl phthalate was used in place of diisodecyl phthalate.

Comparative example 6:
Granules were obtained in the same way as in Example 8, except that di-noctyl phthalate was used instead of Agrisol AC-110.

Test example 1:
In a resin pot of 1 dm2 (1/10000 are) rice was planted, water was filled and a poly (vinyl chloride) cylinder was installed, then a powder similar to dust using a Berger sprinkler at a rate of 3 kg / 10 ares. The pot thus treated was placed in a greenhouse and covered daily with a cylindrical wire mesh into which 10 adult females of small brown delphacids (Delphacides striattola) were released. After 24 hours the number of dead insects was counted to determine the mortality rate. The test was repeated three times. The results of the test are shown in Table 2.

Table 2

<tb> Example <SEP> of <SEP> Mortality <SEP> (%)
<tb> formulation <SEP> at <SEP> end <SEP> of
<tb><SEP> 1 <SEP> day <SEP> 3 <SEP> days <SEP> 5 <SEP> days
<tb> Example <SEP> 1 <SEP> 100 <SEP> 100 <SEP> 100
<tb> Example
<tb> comparative <SEP> 1 <SEP> 100 <SEP> 80 <SEP> 50
<tb> Example <SEP> 2 <SEP> 100 <SEP> 100 <SEP> 100
<tb> Example
<tb> comparative <SEP> 2 <SEP> 100 <SEP> 77 <SEP> 53
<tb>
From the test, the dust-like powders of Examples 1 and 2, in which diisononyl phthalate and diisodecyl phthalate were used respectively, show better and more stable effects than the dust-like powders of Comparative Examples 1 and 2 in which dimethyl phthalate and di-n-ethylhexyl phthalate were used respectively.

Test example 2:
A cabbage which had been grown in a greenhouse for 20 days after transplanting was placed on a turntable, and a wettable powder of equivalent concentration of 50 ppm was applied to this cabbage using a spray gun. . The pot thus treated was placed in a greenhouse and leaves were cut daily and placed in a round container into which 10 caterpillars of tobacco moth in the third larval instar were released. After 24 hours the number of dead insects was counted to determine the mortality rate. The test was repeated twice. The results of the test are shown in Table 3.

Table 3

<tb> Example <SEP> of <SEP> Mortality <SEP> (%)
<tb> formulation <SEP> at <SEP> end <SEP> of
<tb><SEP> 1 <SEP> day <SEP> 3 <SEP> days <SEP> 5 <SEP> days
<tb> Example <SEP> 4 <SEP> 100 <SEP> 100 <SEP> 100
<tb> Example
<tb> comparative <SEP> 3 <SEP> 100 <SEP> 90 <SEP> 65
<tb> Example <SEP> 5 <SEP> 100 <SEP> 100 <SEP> 100
<tb> Example
<tb> comparative <SEP> 4 <SEP> 100 <SEP> 95 <SEP> 70
<tb>
According to the test, the wettable powders of Examples 4 and 5, in which diisononyl phthalate and Agrisol AC-100 (number of carbon atoms: 10-12) were used respectively, show better effects and more stable than the wettable powders of Comparative Examples 3 and 4 in which dimethyl phthalate and di-n-octyl phthalate were used respectively.

Test example 3:
In a resin pot of 1 dm2 (1/10000 are) rice was planted, water was filled and granules were applied at a rate of 2 kg / are on the surface of the water. The pot thus treated was placed in a greenhouse and covered daily with a cylindrical wire mesh into which 10 adult rice field weevils were released. After 24 hours the number of dead insects was counted to determine the mortality rate. The test was repeated three times. The results of the test are shown in Table 4.

Table 4

<tb><SEP> Example <SEP> of <SEP> Mortality <SEP> (%)
<tb><SEP> formulation <SEP> at the <SEP> end <SEP> of
<tb><SEP> 1 <SEP> day <SEP> 7 <SEP> days <SEP> 14 <SEP> days
<tb><SEP> Example <SEP> 7 <SEP> 100 <SEP> 100 <SEP> 100
<tb><SEP> Example
<tb> comparative <SEP> 5 <SEP> 53 <SEP> 20 <SEP> 0
<tb><SEP> Example <SEP> 8 <SEP> 100 <SEP> 100 <SEP> 100
<tb><SEP> Example
<tb><SEP> comparative <SEP> 6 <SEP> 100 <SEP> 80 <SEP> 15
<tb>
According to the test, the granules of Examples 7 and 8, in which diisodecyl phthalate and Agrisol AC-110 (di-n-decyl phthalate) were used respectively, show better and more stable effects than the granules. Comparative Examples 5 and 6 in which dimethyl phthalate and di-n-octyl phthalate were used respectively.

Claims (4)

1. Solid pesticide and acaricide formulation characterized in that it comprises a solution of an ether derivative represented by the general formula I:

wherein R represents a lower alkyl or halogenomethyl group and R1 represents a hydrogen or fluorine atom in an alkyl phthalate having an alkyl group of 9 to 13 carbon atoms which is coated on a solid support. 2. Formulation according to claim 1, characterized in that the content of the ether derivative and the content of the alkyl phthalate.d'alkyl are both in the range of 0.1 to 40% by weight. 3. Process for preparing a solid pesticide and acaricide formulation characterized in that it comprises dissolving an ether derivative represented by the general formula I:

wherein R represents a lower alkyl or halogenomethyl group and R1 represents a hydrogen or fluorine atom in an alkyl phthalate having an alkyl group of 9 to 13 carbon atoms, and applying the solution to a solid support of the ether derivative in alkyl phthalate. 4. Method according to claim 3 characterized in that the ether derivative and the alkyl phthalate are used individually in the range of 0.1 to 40% by weight relative to the total amount of the formulation.