JPS6256405A - Insecticidal composition for agriculture and horticulture - Google Patents

Abstract

PURPOSE:The titled composition effective especially for controlling insects, having low toxicity to cultivated plants and to warm-blooded animals, containing a mixture of a nitromethylene derivative and a well-known insecticide such as S,S'-2-dimethylaminotrimethylenebis(thiocarbamate), etc. CONSTITUTION:The titled composition containing an active ingredient obtained by blending (A) a nitromethylene derivative shown by the formula(X is lower alkyl, lower alkoxy or halogen; l is 0, 1 or 2; m is 2 or 3), such as 1-(3- pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine, etc.,] with (B) a well- known insecticide selected from N,N-dimethyl-1,2,3-trithian-5-ylamine, 2-tert- butylimno-3-iso-propyl-5-phenyl-1,3,5-thiadiazinan-4-one, etc. The blending ratio is preferably 0.1-5pts.wt. active component of the well-known insecticide based on 1pt.wt. compound shown by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel agricultural and horticultural active compound mixture of a nitromethylene derivative and a known insecticide having an excellent insecticidal action.

It was discovered by the present applicant that nitromethylene derivatives have excellent insecticidal activity, and an application has already been filed (Japanese Patent Application No. 59-26020, 59-72966.59-
132943).

It has already been described that the following insecticides have insecticidal activity. For example, S, S'-2-dimethylaminotrimethylenebis(thiocarbamate), 2-1crt-butylimino-3-1so-propyl-5-phenyl-1,3
,5-thiacyacyinan-4-one, N-(2,6-difluorobenzoyl)-N'-(3,5-diquaa-4-
(3-ri o.

-5-trifluoromethyl-2-pyridyloxy)phenyl]urea, etc.

However, the action of these known insecticidal compounds is limited, especially when the concentration of active compound is low and when only small amounts are applied.
If /-1, then (- is also unsatisfactory.

(1) A nitromethylene derivative of the general formula, where X represents a lower alkyl group, a lower alkoxy group, or a halogen atom, l represents 0, 1 or 2, and m represents 2 or 3, and (2) S, S'-2-dimethylaminotrimethylenebis(thiocarbamate), NlN-dimethyl-1,2,3
-Trithian-5-ylamine, 2-t6rt-butylimino-3-iso-propyl-5-phenyl-1,3
, 5-thiacyacyinan-4-one, 1-(4-chlorophenyl)-3-(2゜6-difluorobenzoyl)urea, N-(2j6-difluorobenzoyl)-N'-[
3,5-cyclo-4-(3-chloro-5-)IJfluoromethyl-2-pyridyloxy)phenyltourea and 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether. It has now been found that novel active compound mixtures consisting of at least one selected from the group exhibit excellent insecticidal activity.

Conventionally, various pesticides have been developed as agricultural and horticultural insecticides, and have been used as single agents or mixtures. In particular, organophosphorus insecticides and carbamate insecticides are mainly used, and subsequently pyrethroid insecticides have been used. However, although conventional insecticides each have a certain type of insecticidal effect, they differ in their insecticidal spectrum, insecticidal effect (insecticidal effect on various growth stages, such as eggs, larvae, and adult insects), residual effect, and immediate effect. However, they do not fully satisfy various properties such as low toxicity, systemic transferability, low toxicity to fish and warm-blooded animals, reduced environmental pollution, and reduced number of applications and amount of applied drugs.

Furthermore, as a result of the reverse use of conventional drugs, various insect pests that have acquired resistance to various insect pests have appeared. In particular, planthoppers and leafhoppers (e.g., leafhoppers), which are hemiptera pests, have recently acquired resistance to organophosphorus insecticides and force-permeate insecticides in rice fields in various areas including the warm southwest region of Japan. have appeared and it has become difficult to control them, and the development of superior drugs is desired. In addition, pests such as aphids F, Q% mites, cruciferous wisteria greens, and cotton ballworms, which are vegetable pests, have acquired drug resistance. It is desired to develop an excellent drug that can simultaneously control resistant pests.

・In recent years, paddy rice cultivation in Japan has mainly been carried out by mechanical transplantation using seedling transplanters. It is desired to develop a drug that is free from this.

Furthermore, there is a desire to develop an excellent drug against pests, such as the rice weevil, which have become a particular problem in recent years.

Therefore, important pests of food crops including rice and other grains, pests of horticultural crops such as vegetables, flower petals, and fruit trees, pests of craft crops such as tobacco, cotton, and tea, forest pests, and certain types of facilities among these are important pests. There is a desire to develop a drug that has even better effects against horticultural crop pests, earthen pests such as nematodes, sweat-absorbing and feeding insects such as grain storage pests, and other pests.

As a result of intensive research aimed at solving the various problems described above, the present inventors surprisingly found that the insecticidal activity of the active compound mixture according to the present invention, which is a combination of a nitromethylene derivative and the above-mentioned known insecticides, is different from that of each individual. It has been discovered that the active compounds exhibit cooperative and synergistic effects that are superior to the sum of their effects, and have residual effects.

That is, by applying the insecticidal composition according to the present invention,
For example, only a single active compound is effective against paddy field pests, such as Hemiptera pests such as planthoppers (e.g., the brown planthopper), Lepidoptera larvae known as the Knot borer moth, and horticultural crop pests such as fruit trees and medical vegetables, such as the Lepidoptera larvae Diamondback moth. It has been found that this can be achieved cooperatively and synergistically at lower concentrations than in the case of , and that it has a residual effect.

Therefore, the insecticidal composition of the present invention is very effective in the cultivation of agricultural and horticultural crops, and provides extremely outstanding technical progress in terms of its usefulness.

The nitromethylene derivatives of the general formula (■) used in the active compound mixtures according to the invention are defined as below.

In the formula, X represents a lower alkyl group, a lower alkoxy group or a halogen atom, l represents 0, 1 or 2, and m represents 2 or 3.

Particularly preferred nitromethylene derivatives of general formula (I) for use in the active compound mixtures of the invention are defined as below.

In the general formula (I), X preferably represents a methyl group, a methoxy group, a chloro atom, a bromine atom or a fluoro atom, and ! represents 1 or 2, m represents 2 or 3, and the bonding position of the pyridine ring is the 3-position (or 5-position).

The nitromethylene derivative of the general formula (1) can also exist in the form of a salt, such as an inorganic acid salt, a sulfonate, an organic acid salt, a metal salt, etc., preferably, for example, a hydrochloride, a p - Toluenesulfonate, acetic acid &J, copper salt, succinate, etc. can be mentioned. Therefore, the nitromethylene derivative of formula (1) used in the present invention is a term that includes the salt form thereof.

Examples of nitromethylene derivatives of the general formula (I) used in the active compound mixtures according to the invention include the following compounds (1-(3-pyridylmethyl)-2-tromethylene)
Tetrahydropyrimidine, ]-(2-methyl-5-pyridylmethyl)-2-tromethylene)imidazolidine, 1-(2-methyl-5-pyridylmethyl)-2-tromethylene)tetrahydropyrimidine, 1-(2- Metquin-5-pyridylmethyl)-2-totromethylene)imidazolidine, 1-(2-methoxy-5-pyridylmethyl)-2-totromethylene)tetrahydropyrimidine, 1
-(2-chloro-5-pyridylmethyl)-2-tromethylene)imidazolidine, 1-(2-chloro-5-pyridylmethyl)-2-tromethylene)tetrahydropyrimidine, 1-(2-yfluoro- 5-pyridylmethyl)-2-tromethylene)imidapridine, 1-(2-fluoro-5-pyridylmethyl)-2-tromethylene)tetrahydropyrimidine,
1-(2-Bromo-5-pyridylmethyl)-2-tromethylene)imidazolidine, 1-(2-bromo-5-pyridylmethyl)-2-tromethylene)tetrahydropyrimidine, 1-(5-chloro-2) -pyridylmethyl)-2-tromethylene)imidazolidine, 1-(5-chloro-2-pyridylmethyl)-2-tromethylene)tetrahydropyrimidine, 1-(2,4-dichloro-5-pyridylmethyl)-2 -tromethylene)
Tetrahydropyrimidine, 1-(2,4-dibromo-5-pyridylmethyl)-2-
Tromethylene) imidazolidine, 1-(2,3-dichloro-5-pyridylmethyl)-2-tromethylene) imidapridine, 1-(3-pyridylmethyl)-2-tromethylene) tetrahydropyrimidine hydrochloride, 1- (
2-methyl-5-pyridylmethyl)-2-totromethylene)-tetrahydropyrimidine-p-toluenesulfonate, 1-(2-methoxy-5-pyridylmethyl)-2-totromethylene)-tetrahydropyrimidine-succinate, 1-(2-chloro-5-pyridylmethyl)-2-tromethylene)imigzolidine-hydrochloride, 1-(2-fluoro-5-pyridylmethyl)-2-tromethylene)tetrahydropyrimidine-cupric acetate salt, -(2-Bromo-5-pyridylmethyl)-2-totromethylene)imidapridine-succinate, 1-(2,4-dichloro-5-pyridylmethyl)-2-
The present applicant has already discovered that the nitromethylene derivative of the general formula (1) has insecticidal activity and has filed an application (Japanese Patent Application No. 59-26020). 59-72966
．． 59-132943).

Among the insecticides used in the active compound mixture according to the invention, mention may be made of the following compounds: S, S'-
2-dimethylaminotrimethylenebis(thiocarbamate) (eartap), N,N-dimethyl-1,2,3-)dithian-5-ylamine (thioeyelam), 2-tert-butylimino-3-1so-propyl -5-phenyl-1,3
,5-thiacyasinan-4-one (pbuo7z Schiff
buprofezin), ]-(4-chlorophenyl)
-3-(2,6-difluorobenzoyl)urea (diflubenzuron)
, N-(2,6-difluorobenzoyl)-N'-[3
, S-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]urea, 3-phenoxy/benzyl 2-(4-ethoxyphenyl)
-2-methylpropyl ether.

The abovementioned insecticides, which are a component of the active compound mixture according to the invention, are already known. That is, for example, The Pesticide Manual.
l) 7th edition 1983 (The Br1tishCr
op Protection Cnunc issue) etc. (
(Already described and known as an insecticide.

The weight ratio of the active compounds of each group in the active compound mixture can be varied within a relatively wide range. −For the role, (
1) 1 part by weight of the active compound of the active compound group of the nitromethylene derivative of general formula H) 11, (2) The active compound group of the active compound group of the insecticide A is 0.05 to 10 parts by weight,
Weight: 0.1 to 5 parts per month.

The active compound mixtures according to the invention exhibit excellent insecticidal activity. Therefore, the active compound mixture can be used as an insecticide.
It can be used by foliage spraying, underwater or water surface application, soil application, soil mixing treatment, growing box application, etc.

The active compound mixtures according to the invention exhibit a strong insecticidal action. Therefore, it can be used primarily as a role. Furthermore, the active compound according to the present invention has no phytotoxicity to cultivated plants, has low toxicity to warm-blooded animals,
It can be used to precisely control pests, especially insects, in the protection of stored crops and products. They are usually active against sensitive and resistant species and against all or some growth stages.

For example, the insecticidal composition of the present invention can be applied to paddy field pests such as Hemiptera pests such as planthoppers (e.g. brown planthopper, brown planthopper, and brown planthopper), leafhoppers L, DtM order larvae such as the larvae of the larvae, brown leafhopper, and Coleoptera pests such as the rice water weevil. and Lepidoptera larvae such as mealybugs, armyworms, and leaf beetles, and Hemiptera pests such as scale insects on fruit trees;
It can be effectively used to control pests of fixed crops such as wisteria.

Furthermore, in addition to the above-mentioned pests, it can also be effectively used against, for example, the pests listed below.

Insects include Coleoptera pests, such as the bean weevil (Callosobruchus ch.
ine-nsis), brown weevil (Sitophile)
us Zeama-IS), and Tri
bolium casta-n6unl), Japanese lady beetle (Epi lachnavigitio)
ctomaculata),) Agriotes fusctcollis, Anomala rufocuprea, Colorado pore) Beetle (Lepttnotarsa)
decemkineata), Diabrotica (Dia
brotiea spp, ), -27/Monochamus afternatus,
Rice weevil (Lfssorhoptrus o)
ryzo-philus), oyster chrysanthemum (Lyc
tus bru-neus): Lepidopteran insects, such as Lymantria dispar, Malacosoma neustria
, Pieris rapae, Pieris rapae) (8podo-pteca 1itura)
, Armyworm (Mamestra bra-88ICae)
, Chilo 5uppre-ssa
lis), 7wa/,' (ga(Pyraustan)
ubi-1alis), Kof-q Darameiga (Ephe
stiacautella), :] Kakumonha-7ki (
Aaoxophyesorana), Codri moth (Ca.
rpoeapsa pornon611a), Agrotis fueosa, and honey hemlock (Agrotis fueosa).
Gallery me! 1 on 6th a), Diamondback moth (P
lute-11a maculipennis), Ilelin-this vireseen
s), Phyllocnistis
citrella); for Hemiptera, such as N6photettix eine
ticeps), brown planthopper (Nilaparva)
ta lugens), brown-bottomed planthopper (Laode
lohax 5triate11us), Sogatella furcifera, Pseudococcus eoms
to-cki), Unaspis
yano-nenSiS), peach aphid (M
yzus persi-CaC), apple aphid (
Aph is pomi) cotton aphid (Ap
His gossypii), Rhopalosiphum pseudobra-
ssicas), Nasi Gunpai (Stephaniti)
snashi), green stink bug (Nazara sp.
p, ), whitefly (Tria14urod)
es vapora-riorum), Ps.
ylla spp, ): Orthoptera insects, e.g.
, locust (Locusta migratoria m)
igratoriodes): etc.

The active compound mixture according to the invention can be in the form of a mixture of components (1) and (2) or in the customary formulation form of each individual for extemporaneous mixing. Such forms include solutions, emulsions, suspensions, powders, foams,
Pastes, granules, aerosols, active compound infiltration - natural and synthetic products, microcapsules, seed coatings, preparations with combustion devices (e.g. combustion devices: fumigation and fume cartridges, cans and coils); Then U L
V [cold mist (cold m1st), warm mist (warm m1st))].

These formulations can be manufactured by known methods. Such a method comprises, for example, combining the active compound with a vehicle, i.e. a liquid diluent; a liquefied gas diluent; a solid diluent; or a carrier, optionally a surfactant, i.e. an emulsifier and/or a dispersant and/or This is done by mixing using a foam-forming agent.

When using water as a developing agent, for example, organic solvents can also be used as co-solvents.

The liquid diluent or carrier is generally an aromatic hydrocarbon.
n (e.g. xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (
For example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [e.g., cyclohexane, etc., paraffins (e.g., mineral oil fractions, etc.)], alcohols (e.g., butanol, glycols and their ethers, esters, etc.), ketones (e.g., acetone,
(such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), strongly polar solvents (such as dimethyl formamide, dimethyl sulfoxide, etc.) and water.

Liquefied gas diluents or carriers are gases at normal temperature and pressure, and include, for example, butane, propane, nitrogen gas, carbon dioxide, and aerosol propellants such as halogenated hydrocarbons.

Solid diluents include soil natural minerals (e.g. kaolin, clay, talc, chalk, quartz, attapulgite,
Examples include montmolinite (or montmorinite), soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.).

Solid carriers for granules include crushed and fractionated rocks (e.g. calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic powders, and fine granules or organic substances ( (for example, sawdust, coconut berries, corn cobs, tobacco stalks, etc.).

Examples of emulsifiers and/or foaming agents include nonionic and anionic emulsifiers [e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (
Examples: Eva, alkylaryl polyglycol ethers,
(alkyl sulfonates, alkyl sulfates, aryl sulfonates, etc.)] and albumin hydrolysis products.

Dispersants include, for example, lignin sulfide waste liquor and methylcellulose.

Fixing agents can also be used in the formulations (powders, granules, emulsions), such fixing agents include carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate. I can do it.

Coloring agents may also be used, and such coloring agents and 17
Inorganic pigments such as iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, ab dyes or metal phthalocyanine dyes, and also iron,
Mention may be made of such trace elements as manganese, zolon, copper, cobalt, molybdenum, their salts of zinc.

The formulation may generally contain 0.1 to 95 parts by weight, preferably 0.5 to 90 parts by weight of the active ingredient.

The active compound mixtures of the invention are useful in their commercially useful formulations and in their t! ! ! present as a mixture with other active compounds, such as insecticides, poison baits, fungicides, acaricides, nematocides, fungicides, growth regulators or herbicides. You can also do that.

Here, examples of the insecticide include organic phosphorus agents, carbamate agents, carboxylate agents, chlorinated hydrocarbon agents, and insecticidal substances produced from microorganisms.

Furthermore, the active compound mixtures according to the invention can also be present as admixtures with synergists, the formulations and usage forms being those which are commercially useful. The synergist need not be active itself, but is a compound that amplifies the action of the active compound.

The content of the active compound mixtures according to the invention in commercially useful use forms can vary within wide limits.

The working concentration of the active compound mixture according to the invention is, for example, 0.
．． 00001 to 100, preferably 0
．． 0004 to IM quantity.

The active compound mixtures according to the invention can be used in the customary manner adapted to the intended use.

When used against stored pests, the active compound is
Due to its good stability against alkalis on lime materials, as well as its excellent residual effect on wood and soil,
It is highlighted.

Next, the content of the present invention will be specifically explained with reference to Examples.
The present invention should not be limited to this only.

Example 1 Preparation of a test solution against the Knot borer moth Solvent: 3 parts by weight of xylene Emulsifier: 1 part by weight of holoxyethylene alkylphenyl ether To prepare a suitable active compound formulation, 1 part of each active compound was added to the above amount. The emulsifier was mixed with the above amount of solvent and the mixture was diluted with water to the desired concentration.

Test drive method: Plant height approximately 150 cm planted in a vinyl pot with a diameter of 9CrJL
10 days after planting, the active compound diluted in water with a predetermined concentration prepared as above was sprayed at 20 #l per pot using a spray gun.
The pot was covered with a plastic mesh tube with a height of 25 cm, and 10 larvae of the 4th instar of the brown borer moth were inoculated per pot.The pot was placed in a constant temperature room, and after 2 days, death was determined and the insect kill rate was calculated. Note that the test was conducted in duplicate.

The results are shown in Table 1.

Table 1 Tests against the Japanese snail borer (Note) 16 No drug damage was observed in all the mixtures and single agents used in the tests in the examples.

2 Compound of general formula (1) used in the present invention: Compound A
11-(2-Methoxy-5-pyridylmethyl)-2-totromethylene)tetrahydropyrimidine compound 2l-(2-methoxy-5-pyridylmethyl)-2-totromethylene)tetrahydropyrimidine compound 431-(2-bromo- 5-pyridylmethyl)-2-totromethylene)tetrahydropyrimidine compound 4l-(2-chloro-5-pyridylmethyl)-2-totromethylene)imidazolidine compound A31-(2-fluoro-5-pyridylmethyl)-2 - (tromethylene) imidazolidine 3, Compound used in the present invention: [A]: Cartap [B]: Thiocyclam Example 2 Test method: Plant 3 rice plants with a diameter of about 13 crIL and a plant height of about 150, and plant 10 After 1 day, 2 (M) of the active compound diluted in water with a predetermined concentration prepared as in Example 1 was sprayed on each pot using a spray gun. 10 and 20 days after spraying, a HC grid was applied to 3-year-old white-bottomed planthoppers. Ten larvae were inoculated per pot, placed in a thermostatic chamber, and deaths were counted after 2 and 7 days to calculate the insecticidal rate.The test was conducted in duplicate.

The results are shown in Table 2.

Note) 1. No phytotoxicity was observed in all the mixtures and single agent uses of the samples in Example 2.

2 Compound layer of general formula H used in the present invention 1.42.4
3, A4 and Grave 5 indicate the same compounds as in Example 1.

3. Compounds used in the present invention: [A]: Buprofezin Example 3 Test method: Planted in a pot with a diameter of 9 cmrn at a height of about 15 CI! A water-diluted solution of a predetermined concentration of the active compound prepared as in [Example] was sprayed on non-heading cabbage seedlings of L. using a spray gun at an amount of 1 Qal per pot.
Ten instar larvae were inoculated per pot, placed in a constant temperature room, and dead and alive were counted after 2 and 7 days to calculate the insecticidal rate. Note that the test was conducted in duplicate.

The results are shown in Table 3.

Note) 1. No phytotoxicity was observed in all mixtures and single agent use in the test of Example 3.

λ Compound 1, A2 of general formula (1) used in the present invention
, JE3.44 and x5 indicate the same compounds as in Example 1.

3. Compounds used in the present invention: [A] Nidiflubenzuron [B]: N-(2,6-difluorobenzoyl)-
N'-[: 3.5-dichloro-4-(3-chloro-
5-Trifluoromethyl-2-pyridyloxy)phenyl]urea Example 4 Test method: A predetermined concentration of the active compound prepared as in Example 1 was applied to non-heading cabbage seedlings approximately 15 crIt in height planted in pots with a diameter of 9c7n. Spray 20 d of water diluted solution per pot using a spray gun, and after air-drying the sprayed chemical solution, υ1 per pot.
Zero 4th instar larvae of organophosphate-resistant diamondback moth were inoculated, placed in a constant temperature room, and 2 days later, dead and alive were counted to calculate the insecticidal rate. still,
The first test was conducted in two consecutive sessions.

The results are shown in Table 4.

Table 4 Test notes for diamondback moth) 1. No phytotoxicity was observed in all of the mixtures and single agent uses tested in Example 4.

2. Compound M1 of general formula (1) used in the present invention, &
2, A 3 , A 4 and Wash 5 indicate the same compounds as in Example 1.

3. Compounds used in the present invention: [:A]: 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether and one other compound

Claims (1)

[Claims] 1. (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) In the formula, X represents a lower alkyl group, a lower alkoxy group, or a halogen atom, and l is 0, 1, or 2 and m represents 2 or 3, and (2) S,S'-2-dimethylaminotrimethylene bis(thiocarbamate), N,N-dimethyl-1,2,3- Trithian-5-ylamine, 2-te
rt-Butylimino-3-iso-propyl-5-phenyl-1,3,5-thiadiazinan-4-one, 1-(
4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea, N-(2,6-difluorobenzoyl)-N'-[3,5-cyclo-4-(3-chloro-5
-trifluoromethyl-2-pyridyloxy)phenyl]urea and at least one selected from the group consisting of 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether. An agricultural and horticultural insecticidal composition characterized by the following.