JPH03141203A - Insecticidal composition and killing insect - Google Patents

Abstract

PURPOSE:To obtain an insecticidal composition useful as an insecticide against insect pests in paddy field, plowed field, orchard, forest and stock farm and environmental sanitary insect pests, having synergistically increased insecticidal effects by using both a crude extract of Phryma leptostachya L. and piperonyl butoxide. CONSTITUTION:Piperonyl butoxide is added to a crude extract of Phryma leptostachya L., preferably an extract prepared by immersing the plant in an organic solvent and extracting, more preferably a substance prepared by concentrating the extract, separating the concentrated solution between an arbitrary organic solvent and an alkali, acidic or neutral aqueous solution to remove substances soluble in the aqueous solution, concentrating the organic solvent phase, partitioning the concentrated solution between a polar solvent and a nonpolar solvent to remove substances soluble in the nonpolar solvent and concentrating the solution comprising the polar solvent to give an insecticidal composition having increased insecticidal effects of the crude extract having low insecticidal effects because of low concentration of insecticidal component without passing through a complicated separating process of the insecticidal component.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an insecticidal composition containing tobiperonyl butoxide (PB), a crude extract of P. elegans. The insecticidal composition according to the present invention can be used in rice fields, fields, orchards, forests,
It can be used as an insecticide against livestock farm and environmental pests.

[Conventional technology]

It has been used to kill flies since ancient times, but reports about its effectiveness are mixed. (
Insect Control Science No. 17, p. 10, 1952) Also, regarding the components extracted from Tetrahedron 1.ett, an example of leptostachiol acetate (Tetrahedron 1.ett,
(1972, p. 65), but its insecticidal activity was unknown.

However, in recent years, the present inventors have isolated and determined the structure of a class of insecticidal cylindrical insects from the cylindrical beetle. (
Japanese Patent Publication No. 62-207278. Bioorganic chemistry and molecular design of pesticides, page 202, edited by Mamoru Eto, Soft Science Co., Ltd. 198
5 years) [Problems to be solved by the invention] The above-mentioned Haedoxans are found in the crude extract of Haedoxan, which contains only a small amount of spores, and it takes time and effort to separate them, and the insecticidal effect of the crude extract is It also had the disadvantage of being weak.

[Means to solve the problem]

As a result of intensive studies to solve the above-mentioned problems, we found that an insecticidal activity that could not be expected from the use of Prunus spp. alone can be obtained by mixing the crude extract of Prunus spp. with piperonyl butoxide (hereinafter abbreviated as PB). find out,
The present invention has now been completed.

The present invention will be explained in detail below.

The crude extract of the present invention can be obtained as follows.

First of all, Phryma Ieptostac.
hya, T., ), preferably the whole plant (preferably the root part) from cowhide or dried, is mixed with an organic solvent, preferably 1 to 10 times the fresh weight, such as lower alcohols such as methanol and ethanol, acetone, and methyl ethyl ketone. ketones, esters such as ethyl acetate and butyl acetate, ethers such as diethyl ether and isopropyl ether, aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, methylene chloride, and percrene. Immersion extraction, shaking and 5-extraction using organic solvents such as halogenated hydrocarbons or mixed solvents thereof,
Extraction is generally performed according to a plant component extraction method, such as continuous extraction using a Knockley extractor.

Then, the obtained extract is concentrated to an appropriate amount (preferably 1/10 or less of the original extract) under normal pressure or reduced pressure.

Then, the concentrated solution concentrated to an appropriate amount is distributed between an appropriate organic solvent and an appropriate acid, alkali, or neutral aqueous solution. Suitable organic solvents include ethyl acetate, butyl acetate, diethyl ether, isopropyl ether, benzene, toluene, xylene, p-cymene, chloroform, methylene chloride, perchloride, and the like.

Suitable acidic, alkaline or neutral aqueous solutions include water or preferably 0.5 to 2.0% aqueous mineral acids such as hydrochloric acid, 2 to 5% aqueous sodium bicarbonate, 0.5 to 5%; 2.
0% sodium hydroxide aqueous solution, etc.

The organic solvent-soluble fraction obtained in this way from which the water-soluble fraction has been removed is distributed using a non-polar solvent and a polar solvent, and the non-polar soluble fraction is removed.

In this case, the non-polar solvent may be petroleum ether or
”, C5 to C+Z aliphatic hydrocarbons such as butane, n-hexane, n-octane, n-undecane, etc.
In addition, as a polar solvent, methanol (preferably 0 to 2
(containing 0% v/v water), ethanol (preferably 5 to
20% v/v of water), acetonitrile (preferably containing 0-20% y/v of water) and methylselonulp (
Preferably, methanol or acetonitrile is used.

The method of removing the solvent of the polar solvent-soluble fraction obtained in this manner under normal pressure or reduced pressure to separate the resinous fraction can also be simplified by the following method. In other words, after removing the water-soluble fraction, a suitable organic solvent-soluble fraction is concentrated to an appropriate amount, and the liquid is dropped into a large amount of non-polar solvent while stirring, to obtain the desired crude extract as a precipitate. It will be done. This crude extract contains compounds represented by the following formulas mixed in various proportions.

(In the formula, X3 is hydrogen or methoxy, X4 is hydrogen or methoxy, R is hydrogen or acetyl, n is O or 1,
Ar represents (Z represents hydrogen or hydroxy) or λ2 (X+ represents hydrogen or methoxy, X2 represents hydrogen or methoxy).

A compound in which Ar is ICOZ in formula (I) is a sesquilignan derivative, such as the compound disclosed in JP-A-62-207278.

λ2 is a run-based compound, for example, JP-A-63-270609
This is the compound shown in No. Specifically, JP-A-62-2
Examples include the compounds shown in Example 2 of No. 07278 (pages 10 to 15) and Table 1 (pages 20 and 21) of JP-A-63-270609.

The compound of formula (I) can be isolated by various types of adsorption chromatography and partition chromatography alone or in combination.

Next, preferred among the sesquilignan derivatives Sesquilignans isolated from the crude extract of P. elegans are shown in Table 2.

Table 1 Furofuran Compounds Table H: Furofuran Compounds Table H shows preferred furofuran compounds separated from the crude extract of Rhododendron alba.

The crude extract of N. edokusou collected from nature or obtained through cultivation/culture is a mixture of these N. nidoxanes and furofuran compounds, and it was found that the insecticidal activity differs depending on the mixing ratio. The mixing ratio of the haedoxanes and the furofuran compound is preferably 1 to 10x for the former and 90 to 99x for the latter in terms of weight ratio, but is not limited to this range. At this time, each component can be analyzed by various methods, but the analysis method shown in the following examples was determined under the following HPLC analysis conditions.

The ratio of the peak area ratio corresponding to each component was defined as the composition ratio.

Next, in the insecticidal composition of the present invention, the mixing ratio of the crude extract and PB is usually 1:1000 to 10:1 (weight ratio), assuming that the solvent has been completely removed from the crude extract. ), preferably in a ratio of 1:100 to 1:1.

The insecticidal composition of the present invention is produced as follows. In other words, depending on the purpose of use, the above-mentioned mixed active ingredients can be used as they are, or agrochemical auxiliaries can be used to prepare emulsions, wettable powders, powders, granules, and aerosols using methods commonly used in the field of agrochemical formulations. It can be used in the form of formulations such as , flowable agents, and high-concentration micro-dispersants. When these various preparations are actually used, they can be used directly as they are, or they can be diluted with water to a desired concentration.

The agrochemical auxiliaries mentioned herein include inert solvents and/or carriers (diluents), as well as various surfactants and/or organic raw materials. Examples of solvents include petroleum fractions such as kerosene and light oil, aromatic hydrocarbons such as toluene, xylene, and methylnaphthalene, alcohols such as methyl selon, methanol, butanol, and glycol, ketones such as acetone, cyclohexane, and isophorone, Examples include amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, animal and vegetable oils, fatty acids, and esters such as isoamyl acetate.

As a carrier (diluent), clay kaolin, Merck,
Diatomaceous earth, silica, calcium carbonate, montmorillonite,
Examples include bentonite, feldspar, quartz, and alumina.

Examples of surfactants include anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, and laurylbentine, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Examples include ionic surfactants.

In addition, auxiliary agents other than carriers normally used for agricultural chemicals, such as spreading agents, emulsifiers, wetting agents, dispersants, fixing agents, disintegrants, etc., can be appropriately mixed as necessary to ensure the insecticidal effect. .

The concentration of the mixture (active ingredient) of the crude extract and PB in the composition of the present invention is usually 1.0 to 80% (by weight), preferably 5.0 to 60% (by weight).

The amount of the composition of the present invention to be used is 5 to 800 g, preferably 5 to 600 g as the amount of active ingredient per 10 ares.
It is.

In addition, all formulations can not only be used alone, but also mixed with fungicides, herbicides, plant growth regulators, agricultural and horticultural fungicides, soil fungicides, soil conditioners, or other insecticides and acaricides. You may do so.

The composition of the present invention can be applied to a wide range of insect pests as shown below, and examples thereof are shown below, but the composition is not limited thereto.

(1) Lepidoptera Phyllonorycter, Diamondback moth (
Plutella xylostella), cotton moth (Promalactisinonisema),
Adoxophyesorana
), Leguminivora GL
yoin-ivorella), Kubno borer moth (Cn
apharocrocis med-1nalis)
, Chilo 5uppressal
is ), 7 Qstrinia fur
ncalis), armyworm (Mamesatra)
brassicae), fall armyworm (pseud-
aletia 5eparata), Japanese armyworm (5podoptera 1itura), parnara guttata (parnara guttata), white cabbage butterfly (pieris rapae crucivor)
a) etc.

(2) Coleoptera (7+, nomala cuprea), −
7 Popillia japonica
, rice weevil (Echinocnemus squa)
meus), rice weevil (Li5sorhop
trus oryzophilus), Qulema oryzae, Anthrenus verbasci
), Tenebrioi-des ma
uritanicus), brown weevil (Sitop
hiluszeamais), Henosepilachna vigint
ioctopunctata), Adzuki bean weevil (C
a1losobruchus chinensis)
, Monochamus al.
ternatus), Au1acoph
ora femoralis) etc.

(3) Diptera (1) iptera) C11ex pipiens, Aedes aegypti, Hulemy3platura, EverT
- (Musca domestica), Urimiba -
r- (Dacus cucurbitae), rice leafminer (Agromyza oryzae), etc.

(4) Orthoptera (G)
ryllotalpa africana), Tonosama locust, (I, ocusta migratori)
a), Japanese locust (Oxyajaponica)
, German cockroach (131attella germ)
-anica), black cockroach (periplane)
ta fuliginosa) etc.

(5) Hymenoptera Athalia rosae japonensi
s), Arge 51m1
lis) etc.

(6) Acarina, two-spotted spider mite (T
etranychus urticae ), orange spider mite ( Panonychus citri ), apple spider mite ( Pan.

nychus ulmi), Nasisabida = (Epi
trimerus pyri), P. trimerus pyri (
Eaemaphysalis bispinosa) etc.

[Effects of the Invention] As is clear from the examples below, the insecticidal composition of the present invention exhibits an excellent synergistic effect that cannot be expected from the insecticidal effects of each single agent.

〔Example〕

Next, examples of the present invention will be shown, but the present invention is not limited thereto.

[Extraction example]

(Extraction Example 1) 143 g of the roots of Rhododendron algae (green type 'i) were crushed and extracted by immersion in 12 methanol for 2 days.

This was repeated three times and the resulting methanol solution was concentrated to obtain 10.5 g of extract. Ether 1 for this
50 ml of water and 5 Q ml of water were added, liquid-liquid partitioning was repeated twice, and the ether layer was concentrated to obtain 3.14 g of crude extract. 50 ml of acetonitrile and 100 ml of petroleum ether were added to this for liquid-liquid partitioning, and the acetonitrile layer was concentrated to obtain 2.21 g of crude extract.

C Extraction Example 2) 730 g (fresh weight) of the root of A. japonica was air-dried in the shade for 2 days, and extracted by immersion in 6 volumes of ethanol for 2 days. Repeat this 3 times and add 200ml of the resulting ethanol solution.
1, 500 ml of ethyl acetate and water le were added, and liquid-liquid distribution was repeated twice. The ethyl acetate layer was concentrated to obtain 10 g of crude extract. Add 3 methanol to this
00 ml and 600 ml of n-hexane were added for liquid-liquid partitioning, and the methanol layer was concentrated to obtain 6.6 g of crude extract.

[Example of crude extract analysis]

Although the components contained in the "C. longleaf" vary depending on the region and time of collection, cultivation method, etc., a typical analysis example is shown in Table 2.

Table IH [Formulation Example] Formulation Example 1. (Emulsion) 10 parts (by weight, the same applies hereinafter) of the extract obtained in Extraction Example 2, 50 parts of biperonyl ptoxide, 20 parts of dimethyl sulfoxide, a mixture of alkylphenol oxidation ethylene condensate and calcium alkylbenzenesulfonate ( Add 20 parts of New Cardan 1515-2H (product name, New Cardan 1515-2H, manufactured by Takemoto Yushi) to make an emulsion.
Alternatively, dilute it 10 to 50 times with water and use it as a spraying agent.

parts by weight, 50 parts of piperonyl butoxide, 15 parts of xylene, 5 parts of isopropanol, a mixture of alkylphenol oxidized ethylene condensate and calcium alkylbenzenesulfonate (trade name, New Calgen 15)
15-2H.

Add 20 parts of Monomoto Yushi Co., Ltd. to make an emulsion. The basic rule is to use it as it is or dilute it 10 to 5000 times with water and use it as a spraying agent.

[Test example]

A test example of the effect of piperonyl butoxide on the crude extract of Haedokunwu is shown. The crude extract used here is shown in the analysis example.

[Test Example 1] Insecticidal effect on adult house flies: A solution prepared by diluting the crude extract of Edocus spp. with acetone to a predetermined concentration and a solution containing 0.5% piperonyl butoxide (PB) diluted with acetone were prepared. An adult house fly was anesthetized with ether, and more than 1 drug solution of a predetermined concentration was applied locally to the dorsal surface of the thorax using a micro applicator. After treatment, the animals were transferred to plastic cups and fed with Schiff's sugar solution soaked in absorbent cotton as bait. Abnormal man-hours and number of dead insects were investigated 3 hours, 24 hours, and 48 hours after treatment. The test was conducted in two consecutive sessions with 10 animals per section. The results are shown in Table ■.

〔Effect of the invention〕

As is clear from the above test examples, it is clear that the insecticidal effect is enhanced by the addition of baby peronyl butoxide to the crude extract of P. elegans.

Claims (4)

[Claims] (1) An insecticidal composition characterized by containing a crude extract of P. elegans and piperonyl butoxide. (2) Claim 1, in which the crude extract of Rhinoceros vulgaris is obtained by immersing Rhinoceros vulgare in an organic solvent and extracting it.
The insecticidal composition described in Section 1. (3) The crude extract of the Japanese commonweed is obtained by immersing the Japanese commonweal in an organic solvent, extracting it, removing the solvent and concentrating the extract, and [2] adding the concentrated liquid obtained in [1] to any Partitioning between an organic solvent and an acidic, alkaline or neutral aqueous solution, removing the substances soluble in the aqueous solution, then removing the solvent and concentrating the organic solvent phase [3](a)[2] The obtained concentrated liquid is distributed between a polar solvent and a non-polar solvent, the substance soluble in the non-polar solvent is removed, and the solution consisting of a polar solvent is concentrated, or the solution consisting of a polar solvent according to (b) [2] The insecticidal composition according to claim 1, which is a crude extract obtained by adding a large amount of non-polar solvent and stirring, and removing the non-polar solvent by decantation. (4) An insecticidal method characterized by using a mixture of a crude extract of P. elegans and piperonyl butoxide.