CN105123738A - Pest repellent powder and application thereof - Google Patents

Abstract

The present invention provides a pest repelling powder, which is composed of 0.01% to 5% of the total weight of the pest repelling powder and a powdery carrier as the balance, and the insect repelling active ingredient is represented by the following formula: Pyrethroid compound A, wherein R is a hydrogen atom or a methoxymethyl group; the powdery carrier is an inert component acceptable in pesticides that can load or dilute pesticides. The pest repelling powder of the invention can effectively inhibit the infestation of crawling pests and flying pests, and has a long-lasting medicinal effect. The invention also provides the application of the pest repellent powder.

Description

A kind of pest repellent powder and its application

This application is a divisional application of a patent application with an application date of October 18, 2010, an application number of 201010510326.0, and an invention title of "A Pest Repellent Powder and Its Application".

technical field

The invention relates to a pest repellent, in particular to a pest repellent powder containing a pyrethroid compound and an application thereof.

Background technique

In the past, the powders with repellent effect were all spread in a certain range to repel the invasion of reptiles. However, due to the low vapor pressure of the active ingredients used in this type of powder, they were not enough to volatilize into the air to repel flying pests. As a result, it will still be infested by flying pests within the range of spraying powder. The published patent CN101478880A proposes an insecticide composition, wherein the active ingredient adopts metofluthrin (metofluthrin), which can prevent flying insects from infesting, but we still feel that its medicinal effect is Not ideal.

Therefore, in order to achieve the effect of repelling both reptiles and flying insects, it must have excellent vapor pressure and high activity against pests. We have found through research that certain pyrethroid compounds with the structure of formula (A) have a very high vapor pressure.

Among them, in descending order of vapor pressure, 2,3,5,6-tetrafluoro-4-methoxybenzyl-3-(3,3,3-trifluoro-1-propenyl)-2, 2-Dimethylcyclopropanecarboxylate (2176.6Pa)＞2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3,3,3-trifluoro-1-propene base)-2,2-dimethylcyclopropanecarboxylate (1713.8Pa) > Mefluthrin (1323.8Pa). The vapor pressure here is to use Donovan's method (published by StephenF.Donovan in Journal of Chromatography A, 749 (1996) 123-129 " New method forestinating vapor pressure by the use of gaschromatography (new method for estimating vapor pressure with gas chromatography " method reported in the article) to find out in 200 Vapor pressure at °C. Simultaneously, the compound of formula (A) also has higher insecticidal activity, therefore, the inventor of the present invention tries to develop the pest repellent containing formula (A) compound, finds that it can volatilize under the help of normal temperature volatile agent A certain amount of active ingredients can be released to achieve the effect of repelling flying insects and reptiles at the same time.

Contents of the invention

The object of the present invention is to provide a pest repellent powder, which can effectively repel flying pests while effectively repelling crawling pests, and has a long-lasting effect.

Above-mentioned purpose of the present invention is achieved through the following technical solutions:

A pest repelling powder is provided, which is composed of 0.01% to 5% of the total weight of the pest repelling powder and the rest of the powdery carrier. The insect repelling active ingredient is pyrethroid shown in the following formula Ester compound A, wherein R is a hydrogen atom, a methyl group or a methoxymethyl group; the powdery carrier is an inert ingredient acceptable in pesticides that can load or dilute pesticides,

The pyrethroid compound (A) includes all compounds satisfying the above formula, and all their stereoisomers caused by cyclopropane plane asymmetry and olefin double bond asymmetry or their mixtures. Specifically, the following compounds can be selected:

Compound 1: 2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxylate;

Compound 2: 2,3,5,6-tetrafluoro-4-methylbenzyl-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxylate;

Compound 3: 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxy acid ester;

Compound 4: 2,3,5,6-Tetrafluorobenzyl-1R,trans-(Z)-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropane Carboxylate;

Compound 5: 2,3,5,6-tetrafluoro-4-methylbenzyl-1R,trans-(Z)-2,2-dimethyl-3-(3,3,3-trifluoro- Propyl)cyclopropanecarboxylate;

Compound 6: 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R, trans-(Z)-2,2-dimethyl-3-(3,3,3-tri Fluoro-propenyl)cyclopropanecarboxylate;

Compound 7: 2,3,5,6-tetrafluorobenzyl-1R-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxylate;

Compound 8: 2,3,5,6-Tetrafluoro-4-methylbenzyl-cis-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxy acid ester;

Compound 9: 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R,cis-2,2-dimethyl-3-(3,3,3-trifluoro-propene base) cyclopropane carboxylate;

Compound 10: 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R,trans-2,2-dimethyl-3-(3,3,3-trifluoro-propene base) cyclopropane carboxylate;

Compound 11: 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R, (cis/trans=2/8)-2,2-dimethyl-3-(3,3 ,3-trifluoro-propenyl)cyclopropanecarboxylate;

Compound 12: 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R, trans-(Z/E=9/1)-2,2-dimethyl-3-( 3,3,3-Trifluoro-propenyl)cyclopropanecarboxylate; or

Compound 13: 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R, trans-(Z/E=7/3)-2,2-dimethyl-3-( 3,3,3-Trifluoro-propenyl)cyclopropanecarboxylate.

In the preferred compound (A), R is methoxymethyl, that is, the preferred compound 3.

The single stereoisomers of 1R, trans, and Z configurations of compound 3 are further preferred, that is, compound 6 is preferred.

The compound (A) is an existing compound, which can be prepared by various methods of the prior art, for example: tetrafluorobenzyl alcohol (wherein, R is hydrogen, methyl or methyl) with the following structural formula (X) Oxymethyl) and chrysanthemic acid chloride of structural formula (Y) are esterified to prepare the compound (A).

The esterification reaction can be carried out in an organic solvent such as toluene, xylene or cyclohexane, and pyridine is added as an acid-binding agent; the molar ratio of chrysanthemic acid chloride to tetrafluorobenzyl alcohol is 0.8-1.5:1.

In the pest repelling powder of the present invention, the powdery carrier refers to the inert component of loading or diluting pesticides, which can be selected from attapulgite, diatomaceous earth, bentonite, sepiolite, zeolite, vermiculite, kaolin, talc, leaf wax Stone, white carbon black, calcium carbonate, coal gangue, rice husk, walnut shell powder, sawdust powder or lignin or a mixture of two or more.

The optimum particle size range of the powder carrier is 10-1000 μm, preferably 60-600 μm.

The pest repelling powder of the present invention can be prepared by a conventional method for preparing pesticide powder, that is, the active ingredient is mixed with the powdery carrier by spraying liquid crude oil onto the carrier; the liquid crude oil can be dissolved by compound (A) In alcohols (such as methanol, ethanol, isopropanol, glycerol or polyethylene glycol), ketones (such as acetone, methyl ethyl ketone or cyclohexanone), ethers (such as tetrahydrofuran), aliphatic hydrocarbons (such as hexane, kerosene, petroleum ether), esters (such as ethyl acetate), nitriles (such as acetonitrile), etc., to form a solution with a weight percentage of 1 to 50%.

After the pest repelling powder of the present invention is applied, 0.0625mg-250mg of the compound of formula (A) will naturally volatilize per square meter per hour, and this dose is generally sufficient to repel pests at normal temperature.

The present invention also provides an application method of the pest repelling powder, that is, applying the pest repelling powder to an outdoor area at an application rate of 5g/m ² -40g/m ² to repel pest infestation.

Said pests include invasive reptiles, specifically mentioned here are gnats (Scutigeracole optrata), millipedes (Spirobolus Bungii), centipedes (Scolopendra subspinipes), ants (Formicidae), mouse women (Porcellioscaber Latreille) etc.; also include invasive flying insects, such as Muscadomestica, Muscainastabulans, Drosophilidae, Culex, Aedes, Anopheles, Chironomidae, Simuliidae, Chironmidae ), midges (Psychodidae), horseflies (Tabanidaetabanus), etc.

Compared with the prior art, the pest repellent powder of the present invention has the following beneficial effects: not only can effectively repel crawling pests, but also can effectively repel flying pests, and the drug effect is more durable.

Description of drawings

FIG. 1 is a test schematic diagram of test examples 1 and 2. FIG.

FIG. 2 is a test schematic diagram of test examples 3 and 4. FIG.

Detailed ways

The technical solutions and effects of the present invention are explained in detail below in the form of examples, but the present invention is not limited to the following examples.

Preparation Examples 1-18

With 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R, trans-(Z)-2,2-dimethyl-3-(3,3,3-trifluoro- Propyl) cyclopropane carboxylate (compound 6) is used as the active ingredient in the pest repellent powder, according to the formula of each formulation embodiment in Table 1, adopts the liquid crude oil spraying method, mixes with the powdery carrier, obtains the pest repellent Powder embodiment 1～18.

Table 1

Formulation Examples 19-32

With 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R, trans-(Z)-2,2-dimethyl-3-(3,3,3-trifluoro- Propyl) cyclopropane carboxylate (compound 6) is used as the active ingredient in the pest repelling powder, according to the formula of each preparation in Table 2, adopts the liquid crude oil spraying method, mixes with the powdery carrier, obtains the pest repelling powder and implements Examples 19-32.

Table 2

Formulation Example 33

With 1.0g of 2,3,5,6-tetrafluorobenzyl-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxylate (compound 1), dissolve in 3.0 g of acetone, the solution was evenly sprayed onto 99.0 g of kaolin carrier, mixed thoroughly and then air-dried for 24 hours to obtain pest repellent powder 33.

Formulation Example 34

With 0.5g 2,3,5,6-tetrafluoro-4-methylbenzyl-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxylate (compound 2) Dissolved in 3.0g of acetone, sprayed the solution evenly onto 99.5g of kaolin carrier, mixed well and air-dried for 24 hours to obtain pest repellent powder 34.

Formulation Example 35

With 0.3g 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxylic acid The ester (compound 3) was dissolved in 2.0 g of ethanol, and the solution was evenly sprayed onto 99.7 g of kaolin carrier, mixed thoroughly and then naturally air-dried for 24 hours to obtain pest repellent powder 35.

Formulation Example 36

With 3.0g 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R,trans-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl ) cyclopropane carboxylate (compound 10), was dissolved in 8.0 g of acetonitrile, and the solution was evenly sprayed onto 97.0 g of kaolin carrier, mixed well and then naturally air-dried for 36 hours to obtain pest repellent powder 36.

Formulation Example 37

With 4.5g2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R, trans-(Z/E=7/3)-2,2-dimethyl-3-(3 , 3,3-trifluoro-propenyl)cyclopropanecarboxylate (compound 13), was dissolved in 10.0g ethyl acetate, and the solution was evenly sprayed onto 95.5g kaolin carrier, fully mixed and air-dried for 36 hours to obtain Pest repellent powder37.

Comparative Example 1

Using centrin as the active ingredient in the pest repellent powder, the comparative room temperature volatilization formulation 1 was produced as in formulation example 2.

Comparative Example 2

Using centrin as the active ingredient in the pest repellent powder, the comparative room temperature volatilization formulation 2 was produced just like formulation example 22.

Comparative Example 3

Methofluthrin was used as the active ingredient in the pest repellent powder, and a comparative normal temperature volatilization formulation 3 was produced just like in formulation example 2.

Comparative Example 4

Methofluthrin was used as the active ingredient in the pest repellent powder, and a comparative normal temperature volatilization formulation 4 was produced as in formulation example 1.

Test Example 1

On flat ground without vegetation coverage, sprinkle 5 g of the pest repellent powder of Preparation Example 2, and circle a 2m×2m square, as shown in FIG. 1 . People stood in the center to observe the number of ants entering the circle and the number of times people in the circle were bitten by mosquitoes within 30 minutes after 1 hour, 4 hours, and 8 hours.

Furthermore, the above tests were repeated once using formulation example 22, comparative example 1, comparative example 2 and comparative example 3, and the blank control was only powdery carrier kaolin, and the results were recorded in Table 3.

As can be seen from the results, compared with the blank control, Preparation Example 2 and Preparation Example 22 play the role of repelling reptiles and flying insects within 0 to 8 hours, while Comparative Example 1 and Comparative Example 2 can only play a role in repelling reptiles and flying insects. Repels reptiles but not flying insects. Comparative Example 3 has the effect of repelling reptiles and flying insects within 0-4 hours, but the effect of repelling flying insects decreases within 4-8 hours.

table 3

Test Example 2

Select the insect repellent powder of any one of the formulation examples 1, 3-21 or 23-37, and carry out the test according to the method described in the test example 1. The results all can play a role in repelling within 0-8 hours. Reptiles and flying insects.

Test Example 3

Evenly spread 25g of preparation embodiment 1 in 1 square meter around the person, as shown in FIG. 2 . People stood in the center to observe the number of mosquito bites within 30 minutes starting from 1 hour, 4 hours, and 8 hours.

Furthermore, the above tests were repeated once using formulation example 26 and comparative example 4, and the blank control was only powder. The results are shown in Table 4.

It can be seen from the results that compared with the blank control, Preparation Example 1 and Preparation Example 26 have the effect of repelling flying insects within 0 to 8 hours, while Comparative Example 4 has the effect of repelling flying insects within 0 to 4 hours effect, but the effect of repelling flying insects decreases within 4 to 8 hours.

Table 4

Test Example 4

Any one of Examples 2-25, 27-37, according to the method described in Test Example 3, can play the role of repelling mosquitoes within 0-8 hours.

Claims (10)

1. A pest repellent powder, characterized in that it consists of 0.01% to 5% of the total weight of the pest repellent powder and a powdery carrier of the remaining amount, and the insect repellent active ingredient is of the following formula The pyrethroid compound A shown, wherein R is a hydrogen atom or a methoxymethyl group; the powdery carrier is an inert component that can be loaded or diluted in pesticides 2. The pest repelling powder according to claim 1, characterized in that: in the pyrethroid compound, R is methoxymethyl, that is, compound A is 2,3,5,6-tetrafluoro-4 - Methoxymethylbenzyl-2,2-dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxylate. 3. The pest repellent powder according to claim 2, characterized in that: the pyrethroid compound is 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-1R, trans- (Z)-2,2-Dimethyl-3-(3,3,3-trifluoro-propenyl)cyclopropanecarboxylate. 4. The pest repelling powder according to claim 1, characterized in that: the powdery carrier is selected from attapulgite, diatomaceous earth, bentonite, sepiolite, zeolite, vermiculite, kaolin, talc, leaf wax Stone, white carbon black, calcium carbonate, coal gangue, rice husk, walnut shell powder, sawdust powder or lignin or a mixture of two or more. 5. The pest repellent powder according to claim 1, characterized in that: the particle size of the powder carrier is in the range of 10-1000 μm. 6. The pest repelling powder according to claim 5, characterized in that: the particle size of the powdery carrier is in the range of 60-600 μm. 7. The application of the pest repelling powder according to claim 1, characterized in that: the application is to apply the pest repelling powder to the outdoor area at an application rate of 5g/m ² -40g/m ² Repel pest infestation. 8. The application of the pest repelling powder according to claim 7, characterized in that: the pests are invasive reptiles or invasive flying insects. 9. The application of the pest repellent powder according to claim 8, characterized in that: said invasive reptiles include gnats, millipedes, centipedes, ants or ratworts. 10. The application of the pest repellent powder according to claim 8, characterized in that: said intrusive flying insects include houseflies, dung flies, fruit flies, Culex mosquitoes, Aedes mosquitoes, Anopheles mosquitoes, chironomids, gnats, Midges, midges, or flies.