CN1044071C

CN1044071C - Insecticidal agents

Info

Publication number: CN1044071C
Application number: CN90101188A
Authority: CN
Inventors: 坪井真一
Original assignee: Nihon Bayer Agrochem KK
Current assignee: Bayer CropScience KK
Priority date: 1989-03-10
Filing date: 1990-03-03
Publication date: 1999-07-14
Anticipated expiration: 2005-03-03
Also published as: KR0167337B1; CN1045333A; KR900013850A

Abstract

To obtain an excellent insecticidal composition by combining specific insecticidal nitro compound with one of acephate, cartap, thiocyclam, propoxur, BPMC, chloropyrifos methyl or ethofenprox. A nitro compound expressed by the formula [R<1> is H or 1-4C alkyl; R<2> is -S-R<3> or -N(R<4>)R<5> (R<3> is alkyl; R<4> and R<5> are H or alkyl); Y is CH or N] [e.g. 1-(2-chloro-5-pyridylmethylamino)-1-methylthio-2-nitroethylene] and at least one selected from the group such as O,S-dimethyl acetylphosphoroamide thioate (acephate), S,S'-[2-(dimethylamino) trimethylene] bis(thiocarbamate) (cartap) and N,N-dimethyl-1,2,3-trithian-5-ilamine (thiocyclam) are contained the aimed insecticidal composition. The insecticidal composition exhibits co-operative and synergistic effect in a low concentration.

Description

The insecticide combination agent

The present invention relates to the composition of the new tool desinsection synergism activity that combines by known nitro compound and known insecticides.

These nitro compounds and as being applied as of insecticide known (seeing Japanese PatentApplication 299419/1988).

Known following compounds has agriculture insecticidal activity:

Acetyl group thio-phosphamide O, the S-dimethyl ester;

S, S '-[2-(dimethylamino)-1,3-propylidene] two (thiocarbamates);

N, N-dimethyl-1,2,3-trithiane-5-base amine;

Methyl carbamic acid 2-isopropoxy phenyl ester;

Methyl carbamic acid 2-secondary butyl phenenyl ester;

O-3,5,6-trichloro-2-pyridyl D2EHDTPA O, O-dimethyl ester;

2-(4-ethoxyphenyl)-2-methyl-propyl 3-benzyloxy phenoxy base ether

(seeing Pesticidal Manual, 7th ed, 1983, published by The BritishCrop Protection Council).

But when above-mentioned Pesticidal compound used with low dosage concentration, its insecticidal effect can not be satisfactory.

In addition, these insecticides do not reach satisfied deinsectization effect owing to the insect of different genera all develops immunity to drugs after using continuously for many years.

Have found that, below the composition of new active substance have extra high insecticidal activity, that is:

(1) by the nitro compound of formula (I):

R wherein ¹Be hydrogen or C ₁-C ₄Alkyl; R ²Be-S-R ³Or R ⁴-N-R ⁵, R wherein ³Be C ₁-C ₄Alkyl; R ⁴And R ⁵Each is hydrogen or C naturally ₁-C ₄Alkyl; Y is CH or N;

With the composition of selecting to (8) from following (2) that at least a insect killing substance became:

(2) acetyl group thio-phosphamide O, the S-dimethyl ester;

(3) S, S '-[2-(dimethylamino)-1,3-propylidene] two (thiocarbamates);

(4) N, N-dimethyl-1,2,3-trithiane-5-base amine;

(5) methyl carbamic acid 2-isopropoxy phenyl ester;

(6) methyl carbamic acid 2-secondary butyl phenenyl ester;

(7) O-3,5,6-trichloro-2-pyridyl D2EHDTPA O, O-dimethyl ester;

(8) 2-(4-ethoxyphenyl)-2-methyl-propyl 3-benzyloxy phenoxy base ether.

Be surprised to find that, much bigger by the summation of the indivedual active matter effects of specific activity of active matter composition of the present invention.So have favourable synergistic effect.In addition, by active matter composition of the present invention performance simultaneously to the excellent insecticidal effect of insect.

Formula (I) the nitro compound example that is used for active matter composition of the present invention comprises:

1-(2-chloro-5-pyridylmethyl amino)-1-methyl mercapto-2-nitroethylene;

1-(2-chloro-5-pyridylmethyl amino)-1-methylamino-2-nitroethylene;

1-(2-chloro-5-pyridylmethyl)-3-nitro-2-methyl isothiourea;

3-(2-chloro-5-pyridylmethyl)-1-methyl-2-nitroguanidine;

1-(2-chloro-5-pyridylmethyl)-1-dimethylamino-2-nitroethylene;

1-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-1-methylamino-2-nitroethylene;

1-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-1-dimethylamino-2-nitroethylene;

3-(2-chloro-5-pyridylmethyl)-1,1-dimethyl-2-nitroguanidine;

1-(2-chloro-5-pyridylmethyl amino)-1-ethylamino-2-nitroethylene;

1-amino-1-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-the 2-nitroethylene;

3-(2-chloro-5-pyridylmethyl)-1,3-dimethyl-2-nitroguanidine;

3-(2-chloro-5-pyridylmethyl)-1,1,3-trimethyl-2-nitroguanidine;

1-amino-1-[N-(2-chloro-5-pyridylmethyl)-N-ethylamino]-the 2-nitroethylene;

1-[N-(2-chloro-5-pyridylmethyl)-N-ethylamino]-1-methylamino-2-nitroethylene;

1-[N-(2-chloro-5-pyridylmethyl)-N-n-pro-pyl amino]-1-methylamino-2-nitroethylene;

1-[N-(2-chloro-5-pyridylmethyl)-N-ethylamino]-1-ethylamino-2-nitroethylene;

3-(2-chloro-5-pyridylmethyl)-3-ethyl-1-methyl-2-nitroguanidine.

The insecticidal activity of formula (I) nitro compound is described in Japanese Patent Application 299419/1988 to some extent.

Below the insecticidal activity of (2) to (8) each material be that second is known:

(2) acetyl group thio-phosphamide O, S-dimethyl ester (orthene);

(3) S, S '-[2-(dimethylamino)-1,3-propylidene] two (thiocarbamate) (Padan);

(4) N, N-dimethyl-1,2,3-trithiane-5-base amine (Thiocyclam);

(5) methyl carbamic acid 2-isopropoxy phenyl ester (unden);

(6) methyl carbamic acid 2-secondary butyl phenenyl ester (BPMC);

(7) O-3,5,6-trichloro-2-pyridyl D2EHDTPA O, O-dimethyl ester (methyl Chlorpyrifos);

(8) 2-(4-ethoxyphenyl)-2-methyl-propyl 3-benzyloxy phenoxy base ether (Ethofenprox);

For example be found in " The Pesticide Manual ", 7th ed., 1983, publishedbyThe British Crop Protection Council.

Weight rate in the above-mentioned active matter composition can change in a big way.Generally, every part of weight of active matter (1) is used at least a active matter that is selected from (2)-(8) of 0.05 to 20 part of weight, is preferably and uses 0.1 to 10 part of weight.

These active matter compositions can be held by fine ground cover plant, also are favourable to the toxic level of warm blooded animal, and they can be used for preventing and treating arthropod, particularly the insect that runs into of agricultural, forestry, warehousing goods and materials, health field.They all have activity for normal susceptibility and pesticide resistance kind, and the insect that grows each stage is all had activity.Described insect comprises:

Isopoda, for example damp worm, pillworm and Yang Chao worm;

Doubly sufficient order is for example had a zebra land;

Lip foot order, for example DIWUGONG and common house centipede;

Comprehensive order does not for example have the spot common house centipede;

Thysanoptera, for example silverfiss;

Collembola, for example armoring springtail;

Orthoptera, for example Lian, American cockroach, Madeira Lian, Groton bug, cricket, mole cricket, African migratory locust, different black locust and desert locust are deceived in east;

Dermaptera, for example European ball locust;

Isoptera, for example termite;

Anoplura, grape phylloxera for example, woolly aphid, body louse, a blood lice and a hair lice;

Mallophaga is for example chewed lice and poultry lice;

Thrips, for example chamber pattern thistle horse and onion thrips;

Heteroptera, Eurygasterspp for example, middle red cotton bug, square butt stinkbug, bed bug, phodnius prolixus and triatomid;

Homoptera, wild cabbage aleyrodid for example, cassava aleyrodid, greenhouse whitefly, cotten aphid, cabbage aphid, the tea Fischer conceals knurl aphid, aphis fabae, Bao Shi angle aphid, apple cotten aphid, mealy plum aphid, English grain aphid, the knurl aphid, phorodon aphid, rhopalosiphum padi, jassids, the double leaf leafhopper, rice leafhopper, the hard a red-spotted lizard black scale of water wood, small brown rice planthopper, brown planthopper, red kidney Aspidiotus, ivy Aspidiotus, mealybug and wood louse;

Lepidoptera, pink bollworm for example, loose looper, the winter looper, the thin moth of apple, apple ermine moth, diamond-back moth, malacosoma neustria, the pornography and drug moth, gypsymoth, cotton lyonetid, tangerine lyonetid, cutworm, root eating insect, noctuid, earias insulana, real noctuid, beet armyworm, tomato moth, pine beauty, prodenia litura, spodoptera, cabbage looper, Caprocapsa pomonella, imported cabbageworm, dogstail snout moth's larva, corn borer, Anagasta kuehniella, greater wax moth, curtain rain moth, bag rain moth, brownly knit moth, the yellow volume of flax moth, cigarette moth, spruce bunworm, grape codling moth (Clysia ambiguella), the green volume of tea long paper moth and oak moth;

Coleoptera, furniture death watch beetle for example, lesser grain borer, cover bean weevil, North America house longhorn beetle, willow firefly leaf worm, colorado potato beetles, the horseradish ape is chrysomelid, chrysomelid genus kind, rape golden head flea beetle, the big Epilachna spp of Mexico, latent food first belongs to kind, saw-toothed grain beetle, flower resembles the genus kind, and grain weevil belongs to kind, black grape ear image, the banana collar resembles, and tortoise resembles the Chinese cabbage seed, alfalfa leaf resembles, and khapra beetle belongs to kind, and the spot khapra beetle belongs to kind, the Anthrenus kind, the moth-eaten kind that belongs to of fur, the moth-eaten kind that belongs to of powder, pollen beetle, Ptinus kind, golden spider beetle, globose spider beetle, Tribolium kind, bloom head, the Agriotes spp kind, wide chest Agriotes spp kind, the west melolonthid in May, the potato melolonthid and the brown New Zealand rib wing melolonthid;

Hymenoptera, for example Neodiprion spp belongs to kind, the tenthredinidae kind, ant belongs to kind, monomorium pharaonis and Vespa kind;

Diptera, Aedes kind for example, Anopheles kind, Culex kind, black-tailed fruit flies, the Musca kind, the Fannia kind, calliphora erythrocephala, green head belongs to kind, the Carysomyia kind, cuterbrid belongs to kind, the Gasterophilus kind, ox abdomen fly belongs to kind, the Stomoxys kind, the Oestrus kind, the Hypoderma kind, the horsefly fly belongs to kind, the Gadfly kind, a smaller kind of cicada cicada belongs to kind, forest land march fly, Sweden's wheat stem chloropid fly, grass Hylemyia kind, beet spring fly, Mediterranean Ceratitis spp, big trypetid of olive and European daddy-longlegs;

These active matter compositions can be processed into habitual preparaton, for example solution, emulsion, wetting powder, suspension, pulvis, foam, paste, particle, aerosol, be impregnated with the natural and synthetic material of active matter, the superfine microcapsules in polymer, be used for seed coating composition, be used for combustion apparatus preparaton for example sootiness box, sootiness jar and sootiness incense coil, also have cold droplet of ULV (ultra-small volume) and warm droplet preparaton.

These preparatons can be by the known way manufacturing, for example active matter can be mixed with incremental agent, said incremental agent is meant the diluent or carrier of liquid, liquid gas or solid, and can choose the use surfactant wantonly, i.e. emulsifier and/or dispersant and/or a foaming agent.When making water, for example also can use organic solvent as secondary solvent as incremental agent.

About liquid flux, diluent or carrier, the suitable aromatic hydrocarbon that mainly contains is as dimethylbenzene, toluene, Fluhyzon; Chloro aromatic hydrocarbon or chloro aliphatic hydrocarbon are as chlorobenzene, vinyl chloride or carrene; Aliphatic hydrocarbon is as cyclohexane or paraffin hydrocarbon, for example mineral oil fractions; Alcohols, as butanols or ethylene glycol, and their ether, ketone, as acetone, MEK, first isobutyl ketone or cyclohexanone; Or intensive polar solvent, as dimethyl formamide, dimethyl sulfoxide (DMSO); Can also water.

The liquid gas thinner is meant at normal temperature and pressure it is those liquid of gaseous state, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbonic acid gas.

Solid carrier can be with the natural minerals that grinds, and as kaolin, clay, talcum powder, chalk, quartz, atlapulgite, imvite, diatomite, the synthetic that grinds in addition is as silicic acid, aluminium oxide and the silicate of high degree of dispersion.The solid carrier that granule is used, can use and grind and through the natural rock of sorting, as calcite, marble, float stone, sepiolite, dolomite, can also be with the synthetic particle of inorganic and organic flour, and the particle of some organic substances such as sawdust, coconut husk, corncob and offal.

Can use nonionic and anion emulsifier about emulsification and/or blowing agent, as the polyoxyethylene fatty acid ester, the polyoxyethylene fatty alcohol ether, for example, alkylaryl polyglycol ether, alkyl sulfate, alkylsulfonate, arylsulphonate, and albumin hydrolysate.Dispersant for example has lignin lignosulfite and methylcellulose.

For example carboxymethyl cellulose and natural and synthetic polymer of available adhesive can be powder, particle or latex in preparaton, for example gum Arabic, polyvinyl alcohol and polyvinyl acetate.

Can also use colouring matter, for example inorganic pigment such as iron oxide, titanium oxide, Prussian blue, organic dyestuff such as alizarin dyes, azo dyes or metal phthalocyanine dyestuff, and micronutrient branch are as the salt of iron, manganese, boron, copper, cobalt, molybdenum, zinc.

Generally contain 0.1-95% (weight) active matter in this preparaton, be preferably 0.5-90% (weight).

By active matter composition of the present invention can be that they discuss the dosage form of selling, and be mixed into practical form, other reactive compounds such as insecticide, poison bait, disinfectant, miticide, nematocide, fungicide, growth regulator, the agent of cutting weeds by these preparations and other reactive compounds.Described insecticide for example has phosphate, carbamate, carboxylate, chlorohydrocarbon, phenylurea, by the material of micro-organisms.

Can also sell in the preparation and joined in the useful form as existing its merchant by active matter composition of the present invention with the mixture of synergist by these preparations.So-called synergist is the compound that can increase this reactive compound effect, and added synergist itself must not be activated.

The active matter content of selling in the useful form that preparation is made into of going into business can change in wide scope.Activity concentration can be 0.00001-100% (weight) in the useful form, is preferably 0.0001-5% (weight).

The method of application of these materials can be the ways customary that is suitable for this useful form.

Following example is further illustrated the present invention, but these examples are not limitation of the invention.

The biologic test example:

Test-compound:

Press the compound of general formula (I):

(1) 1-(2-chloro-5-pyridylmethyl amino)-1-methylamino-2-nitroethylene;

(2) 1-(2-chloro-5-pyridylmethyl amino)-1-dimethylamino-2-nitroethylene;

(3) 1-[N-(2-chloro-5-pyridylmethyl)-N-methylamino]-1-methylamino-2-nitroethylene;

(4) 3-(2-chloro-5-pyridylmethyl)-1,1-dimethyl-2-nitroguanidine;

(5) 3-(2-chloro-5-pyridylmethyl)-1,3-dimethyl-2-nitroguanidine;

Known Fungicidally active thing:

(A) orthene;

(B) Padan;

(C) thiocyclarn;

(D) unden;

(E) Osbac;

(F) methyl Chlorpyrifos;

(G)Ethofenprox。

The test of example 1 cnaphalocrocis tick

The preparation of test chemicals

Solvent: 3 parts of (weight) dimethylbenzene

Emulsifier: 1 part of (weight) polyoxyethylene alkyl phenyl ether

With the active matter of 1 part (weight) and the solvent and the emulsifier of above-mentioned amount, water releases mixture alkene to predetermined concentration then, becomes the preparation of this active matter.

Test method

The rice seedling of 15 centimetres of three plant height degree is planted in the polyvinyl chloride dish of 9 centimetres of diameters.Planted back 10 days, will be sprayed on the plant with spray gun by above-mentioned preparation and the active matter that is diluted to predetermined concentration, discharge rate is 20 milliliters on every dish.After institute's spraying liquid drying, on each dish, cover 9 centimetres of diameters, high 25 centimetres plastic wire tube, in each dish, put into the 4th instar larvae of 10 rice leaf roller (Cnaphalocrosis medinalis Gueneer) then.These dishes are placed thermostatic chamber, after two days, count out dead borer population order, calculate lethality then.Above-mentioned test is the result with two groups of parallel tests.

Result of the test is shown in table 1.

Table 1

Tried composition	Activity concentration (ppm)	Insect lethality (%)
Tried composition	Activity concentration (ppm)	Insect lethality (%)	No.1+(B) No.1+(C) No.2+(B) No.2+(C) No.3+(B) No.3+(C) No.4+(B) No.4+(C) No.5+(B) No.5+(C) No.1 No.2 No.3 No.4 No.5 (B) (C)	40+8 40+8 40+8 40+8 40+8 40+8 40+8 40+8 40+8 40+8 40 40 40 40 40 8 8	100 100 100 100 100 100 100 100 100 100 40 15 20 35 10 30 35
Be untreated	-	0

Annotate: used single or mixed chemical medicine does not all show phytotoxicity in example 1.

The test of example 2 diamond-back moths

To be sprayed on (about 15 cm heights) the cabbage seedling that does not grow leaf-head as yet by the active matter water diluent of the predetermined concentration of example 1, this seedling is to be implanted in the dish of 9 centimetres of diameters, and every dish sprays 20 milliliters with spray gun.After institute's spraying liquid was air-dry, putting into 10 in each dish had drug-fast diamond-back moth (P1utella maculipennis) 4 instar larvaes to organophosphorous pesticide.Dish is placed thermostatic chamber.After two days, count out dead borer population order, calculate lethality.Above-mentioned test is the result with two groups of parallel tests.

The results are shown in table 2.

Table 2

Tried composition	Activity concentration (ppm)	Insect lethality (Z)
Tried composition	Activity concentration (ppm)	Insect lethality (Z)	N0.1+(A) No.1+(F) N0.1+(G) No.2+(A) No.2+(F) No.2+(G) N0.3+(A) No.3+(F) N0.3+(G) No.4+(A) No.4+(F) No.4+(G) N0.5+(A) No.5+(F) No.5+(G) N0.1 NO.2 No.3 N0.4 N0.5 (A) (F) (C)	40+40 40+40 40+40 40+40 40+40 40+40 40+40 40+40 40+40 40+40 40+40 40+40 40+40 40+40 40+40 40 40 40 40 40 40 40 40	100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 30 15 20 30 5 30 25 25
Be untreated	-	O

The test of example 3 brown plant-hoppers

Test method

In the dish of each 13 cm diameter, plant the rice seedling of 15 centimetres of three plant heights.Planted back 10 days, and will be sprayed on the plant, with 20 milliliters of the every dish sprays of spray gun by the active matter water diluent of the predetermined concentration of example 1.After institute's spraying liquid is air-dry, on each dish, put a cage, put into 4 instar larvaes of 10 brown plant-hoppers (Nilaparvata lugens) in each dish.Dish is placed thermostatic chamber.After three days, count out dead borer population order, calculate lethality.Above-mentioned test is the result with two groups of parallel tests.

The results are shown in table 3.

Table 3

Tried composition	Activity concentration (ppm)		Insect lethality (%)
Tried composition	Activity concentration (ppm)		Insect lethality (%)	No.1+(D) No.1+(E) No.2+(D) No.2+(E) No.3+(D) No.3+(E) No.4+(D) No.4+(E) No.5+(D) No.5+(E) No.1 No.2 No.3 No.4 No.5 (D) (E)	8+100 8+100 8+100 8+100 8+100 8+100 8+100 8+100 8+100 8+100 8 8 8 8 8 100 100		100 100 100 100 100 100 100 100 100 100 45 20 15 40 20 40 40

Claims

1. insecticides is characterized in that containing the active matter by following combination: (A) (1) is by the nitro compound of formula (I):

R wherein ¹Be hydrogen or C ₁-C ₄Alkyl; R ²Be R ⁴-N-R ⁵, R wherein ⁴And R ⁵Each is hydrogen or C naturally ₁-C ₄Alkyl; Y is CH or N;

(B) the tool insecticidal effective dose be selected from following at least a killing:

(2) orthene;

(3) Padan;

(4) thiocyclarn;

(5) unden;

(6) Osbac;

(7) methyl Chlorpyrifos;

(8)Ethofenprox。

2. by the insecticides of claim 1, wherein the nitro compound by formula (I) is: