CN102246777B - Composition containing aromatic group pyrroline compound - Google Patents

Abstract

The invention relates to a composition containing an aromatic group pyrroline compound. The composition comprises two types of active components, namely a compound shown in a formula (I) and fipronil, wherein the compound shown in the formula (I) and the fipronil exist in the synergy effective dose proportion; particularly, the weight ratio of the compound shown in a formula (I) to the fipronil is 1:(0.01-100); when the two active components of pesticide are mixed, under the condition of achieving the same prevention effect, the application amount of each pesticide can be respectively reduced; and the two active components of the pesticide present a synergistic effect when used for an insecticidal purpose.

Description

A kind of composition that comprises aryl-pyrrolidine quinoline compound

Technical field

The invention belongs to the composition pesticide field, relate to particularly a kind of agricultural chemical composition for disinsection and application thereof, particularly relate to a kind of purposes that comprises composition and the control crop pest thereof of aryl-pyrrolidine quinoline compound.

Background technology

Ethiprole is a kind of Phenylpyrazole insecticides, and the desinsection wide spectrum take stomach toxicity as main, has certain tagging and systemic action to insect concurrently.To striped rice borer, paddy stem borer, diamond-back moth, plant hopper, flea beetle has good insecticidal activity.

Aryl-pyrrolidine quinoline compound useful as pesticides, the control efficiency very strong to harmful insect, and can not apply to cultivated plant any harmful seondary effect of medicine, can be used for preventing and treating the insect of relative broad range, such as harmful sucking mouth parts insect, biting mouthparts insect and other phytotrophy nuisances, Stored Grain Insects, health nuisance etc., and can be used for their elimination and extinction.

The composition of different cultivars carries out composite, is control resistant insect or the very common way of evil mite.Heterogeneity is carried out composite, according to the effect of practical application, judge certain composite be synergy, add and or antagonism.Compound synergic is well filled a prescription, owing to obviously improved actual control efficiency, reduced the usage amount of agricultural chemicals, thereby delayed greatly the generation of pest resistance to insecticide, and be the important means of integrated control insect.

Summary of the invention

The technical problem to be solved in the present invention provides a kind of insecticidal synergistic composition that comprises aryl-pyrrolidine quinoline compound, with the usage amount that reduces agricultural chemicals, the insecticidal spectrum that enlarges agricultural chemicals, reduce insect to single resistance of planting agricultural chemicals, prolong the preventive effect phase when guaranteeing quick desinsection, reduce a large amount of applying pesticides to the harmful effect of environment.Overcome the defective such as single plant that pesticide species is applied to that the dosage in farmland is large, resistance, insecticidal spectrum are narrow.

For solving the problems of the technologies described above, the present invention has obtained a kind of insecticidal synergistic composition through great many of experiments, two kinds of active components of said composition inclusion compound A and compd B, and wherein compd A is as shown in the formula (I) compound,

Chemical name is: 5-[3-(3, the 5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole-5-yl]-2-(1H-1,2, the 4-triazol-1-yl) benzonitrile, compd B is ethiprole, wherein compd A and compd B exist with the ratio of synergy effective dose, preferably, the weight ratio of compd A and compd B is 1 in the composition: (0.01-100) especially preferred, the weight ratio of compd A and compd B is 1: (0.05-20), particularly preferred, the weight ratio of compd A and compd B is 1: (0.1-10).

The composition of above-mentioned inclusion compound A and compd B can also comprise other one or more pesticide activity components, other pesticide activity component such as insecticides, fungicide, synergist, weed killer herbicide or plant growth regulator etc., preferably, above-mentioned composition comprises one or more other pesticide active ingredients.

Other suitable insecticide can be pyrethroid, natural pyrethrins, tetramethrin, S-bioallethrin, fenfluthrin, prallethrin etc.; Organophosphorus ester is such as the first Toyodan; Carbamates, such as carbofuran, furathiocarb etc.; Macrolide, such as Olivomitecidin, the close mycin that compares; Organochlorine compound, such as 5a,6,9,9a-hexahydro-6,9-methano-2,4, lindane etc.; The amidine class is such as galecron, two worm amidines etc.; The chlorine nicotinyl compounds, such as Imidacloprid, thiacloprid, pyridine worm miaow etc.

The present composition can be used for preventing and treating insect and the evil mite that harms the crops, and especially prevents and treats the resistance lepidoptera pest.Above-mentioned composition can be used for resisting and Control pests such as Lepidoptera, diptera, and Semiptera, Thysanoptera, orthoptera, Dictyoptera, coleoptera, Siphonaptera, Hymenoptera and Isoptera and other invertebral insect, for example, acarid, the infringement of nematode and mollusk insect.

Particularly, the insect that above-mentioned composition can be prevented and treated has black peach aphid, cotten aphid, and beans winged euonymus aphid, lygus bug belongs to, red cotton bug belongs to, brown planthopper, and rice leafhopper, Bemisia spp, Leptocorisa spp belongs to, Frankliniella occidentalis, Thrips, colorado potato beetles, cotton boll resembles, the kidney Aspidiotus belongs to, Aleyrodes, sweet potato whitefly, European corn borer, mythimna separata, Spodoptera littoralis, tobacco budworm, cotton bollworm, the real noctuid of paddy, the wild snout moth's larva of lap leaf, Pieris brassicae, diamond-back moth, the ground Noctua, striped rice borer, Australia epidemic disease locust, panonychus ulmi, citrus red mite (crm), Tetranychus urticae, Tetranychus cinnabarinus, citrus wrinkle leaf Aculus, Polyphagotarsonemus latus Banks, short whisker Acarapis, boophilus microplus, Dermacentor variabilis, cat flea, Liriomyza, housefly, Aedes aegypti, Anopheles, Culex, Lucilia, Groton bug, American cockroach, oriental cockroach, Mastotermitidae, Kalotermitidae, Rhinotermitidae, Meloidogyne, ball Heterodera, Heterodera, Pratylenchidae belongs to, pulvinulus sword Turbatrix, haemonchus contortus, Trichostrongylus.Preferably, above-mentioned composition is used for the control diamond-back moth.

The present invention also provides a kind of method of pest control, and the method comprises with the insecticidal effective dose above-mentioned composition processes above-mentioned insect, its provand source, its habitat or its breeding spot or wherein insect growth or may growing plants, seed, soil, zone, material or environment or will prevent the insect invasion and attack or material, plant, seed, soil, surface or the space of infecting.

Above-mentioned composition of the present invention also comprises suitable inert diluent or other non-active ingredients such as carrier and surfactant.Preferably, the active component sum accounts for the 0.0001-95% of composition total weight in the composition, preferred 1-80%, especially preferred 1-10%

The composition that comprises other non-active ingredients can be mixed with the powder (DP) that can dust, soluble powder (SP), water-soluble granular formulation (SG), the dispersible pellet of water (WG), wetting powder (WP), pellet (GR), solubility concentrate thing (SL), oily compatibility liquid (OL), ultra low volume liquid (UL), emulsifiable concentrate (EC), dispersible concentrate (DC), emulsion, microemulsion (ME), suspending agent (SC), aerosol, capsule suspension liquid (CS) and seed treatment etc.

Above-mentioned composition of the present invention can also use with fertiliser mixtures, comprises in the composition of fertilizer, contains at the most the active component that accounts for gross weight 15%.

Above-mentioned composition of the present invention is used after two or more active components can being mixed, perhaps with two or more active components with use after other non-active ingredients mix, also can be with active component successively, can first administered compound A, then administered compound B is in insect, perhaps first administered compound B, again administered compound A, perhaps two or more active components are mixed with respectively certain formulation, bucket is used after mixing immediately before pest control.

Composition pesticide of the present invention compared with prior art produces following beneficial effect:

(1) two kind of agricultural chemicals mixes when using, reaching in the situation of identical preventive effect, can reduce respectively the amount of application of every kind of agricultural chemicals, namely two kinds of agricultural chemicals show the effect of synergy when being used for desinsection, the part by weight of compd A and compd B is in 1: in the time of (0.05-20), co-toxicity coefficient shows synergistic effect greater than 120;

(2) be mixed after, with respect to single defective of planting the applications of pesticide, accelerated on the one hand the control time of diamond-back moth, prolonged on the other hand the control efficiency to diamond-back moth.

(3) it is remarkable to mix the preventive effect effect use the antagonism insect, the especially control of antagonism diamond-back moth, and effect is remarkable.

Embodiment

In order to understand the present invention, the below further specifies the present invention with embodiment, but does not limit the present invention.

Embodiment 1:

Formula (I) compound 5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3, the 4-dihydro-2 h-pyrrole -5-yl]-2-(1H-1,2,4-triazol-1-yl) benzonitrileSynthesizing of (compd A)

Synthesizing of step 1:N-(3-bromo-4-fluorobenzene methyl) formamide

Ethyl formate (1.48g) is added dropwise in ice-cooled (0 ℃) 1-(3-bromo-4-fluorophenyl) methylamine (3.40g) under stirring.Reactant mixture stirred 2 hours with its original state, then returned to room temperature, stirred 2 hours again.By silica gel chromatography this reactant mixture is directly carried out purifying, obtain N-(3-bromo-4-fluorobenzene methyl) formamide (2.7g), yield is 69%.

1H-NMR(CDCl3)δ：4.47(2H，d)，7.06-7.33(3H，m)，8.26(1H，s)。

Step 2:2-(3-bromo-4-fluorophenyl)-4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole synthetic

N-(3-bromo-4-fluorobenzene methyl) formamide (2.70g) and triethylamine (3.50g) are stirred in toluene (40ml) at ice-cooled lower (0 ℃), simultaneously to wherein adding phosphoryl chloride phosphorus oxychloride (1.90g).Then this reactant mixture was at room temperature stirred 3 hours.In this reactant mixture, carefully add water (100ml), and add saturated sodium bicarbonate aqueous solution with this reactant mixture that neutralizes.Separate water layer and use toluene (60ml * 2) extraction.With the organic layer that saturated sodium bicarbonate aqueous solution and saturated brine washing merge, use subsequently dried over mgso, and by the isolated by filtration desiccant.In filtrate, adding 1,3-, two chloro-5-[1-(trifluoromethyl) vinyl] benzene (2.1g) and copper oxide (II) are (0.2g).This mixture was added hot reflux 3 days.Make this reactant mixture return to room temperature, with saturated aqueous solution and the saturated brine wash filtrate of sodium bicarbonate, then use dried over mgso.After this reactant mixture filtration, solvent distillation under the pressure that reduces obtains thick 2-(3-bromo-4-fluorophenyl)-4-(3,5-dichlorophenyl)-4-(trifluoromethyl) 3,4-dihydro-2 h-pyrrole (0.88g).

Step 3:5-(3-bromo-4-fluorophenyl)-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole synthetic

Ice-cooled lower, to 2-(3-bromo-4-fluorophenyl)-4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3, add t-BuOK (0.24g) in the solution of 4-dihydro-2 h-pyrrole (0.88g) in THF (13ml).This mixture is returned to room temperature and stirred 16 hours.In this reactant mixture, add entry, separate water layer, and use ethyl acetate extraction.With the organic layer of saturated brine washing merging, and use dried over mgso.After filtering this reactant mixture, under the pressure that reduces, distill solvent, mixture by the formation of silica gel chromatography purifying, obtain 5-(3-bromo-4-fluorophenyl)-3-(3, the 5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole (0.88g), yield are 100%.

1H-NMR(CDCl3)δ：3.42(2H，d)，3.75(2H，d)，4.43(2H，d)，4.88(2H，d)，7.10-7.39(3H，m)，7.86-8.08(3H，m)。

Step 4:5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole-5-yl]-2-fluorine benzonitrile synthetic

With 5-(3-bromo-4-fluorophenyl)-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole (0.88g) is dissolved among the DMF (10ml), makes this solution degassed, then places under the argon atmosphere.In this reactant mixture, add Zn (CN) 2 (0.45g) and Pd (PPh3) 4 (0.67g).Under 90 ℃, this mixture was stirred 4 hours.This reactant mixture is returned to room temperature, then to wherein adding ethyl acetate.Saturated aqueous solution with sodium bicarbonate washs this reactant mixture, then uses dried over mgso.After filtering this reactant mixture, under the pressure that reduces, distill solvent, by the mixture of silica gel chromatography purifying formation, obtain 5-[3-(3, the 5-dichlorophenyl)-and 3-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole-5-yl]-2-fluorine benzonitrile (0.25g), yield is 32%.

1H-NMR(CDCl3)δ：3.44(1H，d)，3.76(1H，d)，4.46(1H，d)，4.91(1H，d)，7.12-8.16(6H，m)。

Step 5:5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole 5-yl]-2-(1H-1,2,4-triazol-1-yl) benzonitrile synthetic

Under 80 ℃ with 5-[3-(3, the 5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole-5-yl]-2-fluorine benzonitrile (250g), 1H-1,2,4-triazole (52mg) and potash (103mg) mixed solution in DMF (1ml) stirred 3 hours.Reactant mixture is returned to room temperature, to wherein adding entry, and with this mixture of ethyl acetate extraction.Wash organic layer with saturated brine, then use dried over mgso.After filtering this reactant mixture, under the pressure that reduces, distill solvent, mixture by the formation of silica gel chromatography purifying, obtain 5-[3-(3, the 5-dichlorophenyl)-and 3-(trifluoromethyl)-3,4-dihydro-2 h-pyrrole-5-yl]-2-(1H-1,2, the 4-triazol-1-yl) benzonitrile (compd A) (130mg), yield is 46%.

1H-NMR(CDCl3)δ：3.50(1H，d)，3.82(1H，d)，4.51(1H，d)，4.96(1H，d)，7.41(1H，m)，7.93-8.33(4H，m)，8.90(1H，d)。

Embodiment 2: emulsion

Compd A

2 grams

Compd B	2 grams
		The polyoxyethylene alkyl phenyl ether	8 grams
Alkyl benzene calcium sulfonate	7 grams
		Dimethylbenzene	Complement to 100 grams

Various compositions in the form are weighed up weight, mix, obtain 4% emulsion.

According to the compd A of the described methods preparation of above-described embodiment 2 Different Weight ratios and the emulsion of compd B composition, then add solution that entry is mixed with corresponding weight concentration and be used for the farmland and use.

Embodiment 3: the insecticidal effect of composition

Formula (I) compound (compd A) is mixed with emulsion (according to embodiment 2 described method preparations) from ethiprole (compd B) according to different weight ratios, be diluted to required concentration, take diamond-back moth as object, adopt spraying directly to spray, according to the method that toxicity index is calculated the mixture co-toxicity of passing through of the propositions such as Sun Yunpei, the co-toxicity coefficient of two kinds of active components in the test composition.Concrete outcome is as follows:

According to above-mentioned experiment, two kinds of compounds to the co-toxicity coefficient of diamond-back moth all greater than 120, illustrate that compd A and compd B are synergy in the effect of killing diamond-back moth, have synergistic effect after two kinds of compound.

Claims (3)

1. insecticidal synergistic composition, two kinds of active components of said composition inclusion compound A and compd B, wherein compd A is as shown in the formula (I) compound,

Compd B is ethiprole, and wherein the weight ratio of compd A and compd B is 1: (0.05-20).

2. insecticidal synergistic composition according to claim 1, wherein the weight ratio of compd A and compd B is 1: (0.1-10).

3. insecticidal synergistic composition according to claim 1, said composition is emulsion, this emulsion is prepared by the component of following weight:

Compd A 2 grams

Compd B 2 grams

Polyoxyethylene alkyl phenyl ether 8 grams

Alkyl benzene calcium sulfonate 7 grams

Dimethylbenzene complements to 100 grams.