CN104650059A - Thiazolone oxime ether derivatives, and preparation method and use thereof - Google Patents

Abstract

The invention provides a class of thiazolone oxime ether derivatives, and a preparation method and use thereof, and relates to an isothiazole oxime ether compound having a chemical structure general formula shown in the specification. The invention discloses a structural general formula and a synthetic method of the compound, use as an insecticide, a bactericide, an anti-plant virus agent and a plant activator, use of the compound for preventing and treating agricultural, forestall and horticultural diseases, insect attack, mite damage and virus diseases in combination with agriculturally acceptable auxiliaries or synergists and commercial insecticides, miticides, bactericide, anti-plant virus agents and plant activators, and a preparation method.

Description

One class thiazolone oxime ether derivative and its production and use

Technical field

Technical scheme of the present invention relates to the oxime ether derivative containing thiazolone, is specifically related to 2-piperidines thiazol-4-one oxime ether derivative.

Background technology

Heterogeneous ring compound is the main flow of current new drug development, and based on nitrogen heterocyclic ring in heterogeneous ring compound.Thiazole compound is the important nitrogenous sulfur heterocyclic compound of a class, having desinsection, weeding, sterilization, anti-inflammatory and the biological activity such as antitumor (wears red, Deng. the synthesis of the novel pyrazol oxime ether derivatives containing thiazole ring and biological activity thereof. organic chemistry, 2013,33:1104-1107.), in human health care and agriculture production, play very important role.The pesticide new variety containing thiazole ring structure that domestic and international success is developed has sterilant clothianidin, sterilant benzene metsulfovax etc.

Oxime ether derivatives is that a class has excellent bioactive compound, is not only pharmaceutically having a wide range of applications, and agricultural chemicals is also the important active compound of a class.Relevant oxime ether active compound, existing a large amount of report (Song Baoan both at home and abroad, Deng. the synthesis of oxime derivatives and the progress of pesticide bioactivity. organic chemistry, 2005, 25 (5): 507-525.), also there are many commodity to come out simultaneously, such as to the effective white urea cyanogen (cymoxanil) of downy mildew, northern house and housefly are had to insect growth regulator(IGR) S-21149 and S-21150 of greater activity, to pears red spider, the active quite high fenpyroximate (fenpyroximate) of citrus red mite, (model is built to have the propaquizafop (propaquizafop) of better preventive effect etc. to many annual and perennial gramineous weedss mainly, Deng. there is the progress of bioactive oximinoether. modern, 2008, 7 (2): 6-11.).The good pharmacophore of oxime ether structure Chang Zuowei is introduced in parent compound molecule, to improve its biological activity.

Oxime ether group is introduced in thiazole compound by the principle that the present invention utilizes pesticide molecule to design, design and synthesis one class is containing the thiazolone oxime ether derivative of piperidine ring, and carried out the bioactivity screening of system, to providing how efficient candidate compounds for the initiative of novel pesticide.

Summary of the invention

Technical problem to be solved by this invention is: the synthetic method providing new thiazolone oxime ether derivative, this kind of compound modulates agricultural, the biological activity of gardening and health and forestry plant insect and the phytopathy original and measuring method thereof are provided, provide these compounds to apply in agriculture field, horticultural field, field of forestry and health field simultaneously.

The present invention solves this technical problem adopted technical scheme: have agriculture field, chemical structure of general formula that horticultural field, forestry and health field insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant produce the thiazolone oxime ether derivative of anti-disease activity is shown in formula VI:

Wherein, R is selected from tertbutyloxycarbonyl, the bromo-1-of H, HHCl, 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-carbonyl; R ¹be selected from methyl, 3,4-Dimethoxyphenyls; R ²be selected from hydrogen, propargyl, 2-chloropyridine-5-methylene radical, chloro-1,2, the 3-thiadiazoles-4-methylene radical of 5-, 3-phenyl-2-propine-1-base, seven fluorine sec.-propyls, 3,4-bis-chloroisothiazole-5-methylene radical.

The synthetic method of thiazolone oxime ether derivative VI of the present invention is as follows:

Wherein, R is selected from tertbutyloxycarbonyl, the bromo-1-of H, HHCl, 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-carbonyl; R ¹be selected from methyl, 3,4-Dimethoxyphenyls; R ²be selected from hydrogen, propargyl, 2-chloropyridine-5-methylene radical, chloro-1,2, the 3-thiadiazoles-4-methylene radical of 5-, 3-phenyl-2-propine-1-base, seven fluorine sec.-propyls, 3,4-bis-chloroisothiazole-5-methylene radical; X is selected from Cl, Br.

Due to the difference of radicals R, the synthetic method of compound VI is different, specifically comprises following synthetic method:

When R is the bromo-1-of 3-(3-chloropyridine-2-base-1H-pyrazoles-5-carbonyl, R ¹for methyl, R ²for propargyl, when X is Br, the synthetic method of thiazolone oxime ether derivative VI of the present invention is as follows:

Specifically be divided into following steps:

A. the preparation of intermediate II:

1.00 grams are added in two mouthfuls of round-bottomed flasks of 100 milliliters, the i.e. I of 3.20 mmoles, dissolve with 20 milliliters of methylene dichloride, after add 0.36 gram, the i.e. triethylamine of 3.52 mmoles, nitrogen protection, stirring at room temperature, 0.68 gram is added in backward reaction in 10 minutes, i.e. 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride of 3.52 mmoles, be abbreviated as EDCI, finally add the DMAP of 10 milligrams, stirred overnight at room temperature, the 30 milliliters of washings one time of rear reaction solution are reacted, separate organic layer saturated sodium-chloride and wash one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate II through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/4 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 90-100%, the volume of amount prepared by intermediate II and reaction vessel expands by corresponding proportion or reduces.

B. the preparation of intermediate III:

0.77 gram is added in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. intermediate II of 2.17 mmoles, nitrogen protection, reaction system vacuumizes, 20 milliliters of dry tetrahydrofuran (THF)s are added in reaction, react on-78 degrees Celsius of stirrings, the methyl-magnesium-bromide or 3 of 1.08 mmoles is slowly dripped in backward reaction system, 4-Dimethoxyphenyl magnesium bromide, under-78 degrees Celsius, stirring 1 hour is continued after dropwising, after make stirring at room temperature into 1 hour, the saturated ammonium chloride solution and 30 milliliters of ethyl acetate that add 30 milliliters are reacted in backward reaction solution, stir and separate organic layer afterwards a little while, organic layer saturated sodium-chloride washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate III through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/4 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 80-93%, the volume of amount prepared by intermediate III and reaction vessel expands by corresponding proportion or reduces.

C. the preparation of intermediate compound IV:

0.50 gram is added successively in 100 milliliters of single necked round bottom flask, the i.e. intermediate III of 1.61 mmoles, 0.16 gram, the i.e. triethylamine of 1.61 mmoles, with 20 milliliters of anhydrous alcohol solutions, in 80 degrees Centigrade back flow reaction 2 hours, desolventizing is removed by concentrated for reaction solution after having reacted, resistates 20 ml waters and 20 milliliters of methylene dichloride dissolve, separate organic layer, organic layer saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate compound IV through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/3 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 79-90%, the volume of amount prepared by intermediate compound IV and reaction vessel expands by corresponding proportion or reduces.

D. the preparation of intermediate V

0.36 gram is added successively in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. intermediate compound IV of 1.10 mmoles, 0.19 gram, the i.e. potassium tert.-butoxide of 1.66 mmoles and the Tetrabutyl amonium bromide of 10 milligrams, with 20 milliliters of tetrahydrofuran (THF)s and 4 milliliters of N, dinethylformamide dissolves, nitrogen protection, stirring at room temperature is after 10 minutes, the different halides defined is added in the present invention of 1.66 mmoles in reaction, stirring at room temperature reacts 2 hours, react rear reaction solution 20 milliliters of chloroforms and wash one time, separate organic layer and wash 3 times with saturated sodium bicarbonate successively, saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate V through 200 ~ 300 order purification by silica gel column chromatography, according to the difference of product, eluent volume ratio is sherwood oil=1/3 to 1/1 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 47-91%, the volume of amount prepared by intermediate V and reaction vessel expands by corresponding proportion or reduces.

E. the preparation of thiazolone oxime ether derivative VI:

When R is H, the preparation method of thiazolone oxime ether derivative VI is as follows:

The intermediate V of 10 mmoles is placed in 100 milliliters of two-mouth bottles, dissolve with 20 milliliters of dry methylene dichloride, nitrogen protection, ice bath stirs, the trifluoroacetic acid of 4 milliliters is dripped in reaction system, all dropwise rear stirring at room temperature 1 hour, react the sodium hydroxide dripping 1 mol/L in backward reaction solution, about adjust pH to 10, separate organic layer, organic layer saturated common salt is washed once, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate VI through 200 ~ 300 order purification by silica gel column chromatography, eluent is methylene chloride/methanol, different according to product, volume ratio is 50: 1 to 6: 1, by gained sterling calculated yield, yield 66-100%, the volume of amount prepared by intermediate VI and reaction vessel expands by corresponding proportion or reduces.

When R is HHCl, the preparation method of thiazolone oxime ether derivative VI is as follows:

The compound V of 1 mmole is added in the single necked round bottom flask of 50 milliliters, dissolve with 5 milliliters of anhydrous methanols, stirring at room temperature, in reaction, add the hydrogenchloride dioxane solution of 4 excessive mol/L, room temperature continues stirring 3 hours, has reacted rear reaction solution directly concentrated removing organic solvent, appropriate dehydrated alcohol is added in flask, continue the water that concentrated removing is a small amount of, finally obtain product as light yellow solid VI, yield 100%; The volume of amount prepared by compound VI and reaction vessel expands by corresponding proportion or reduces.The chemical structure of compound VI and physical and chemical parameter are in table 1.

When R be the bromo-1-of 3-(during 3-chloropyridine-2-base-1H-pyrazoles-5-carbonyl, the preparation method of thiazolone oxime ether derivative VI is as follows: the method being prepared intermediate X I by intermediate X is as follows:

0.39 gram is added successively in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. bromo-1-of the 3-of 1.28 mmoles (3-chloropyridine-2-base-1H-pyrazoles-5-carboxylic acid, 0.28 gram, i.e. 1.47 mmole 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, be abbreviated as EDCI, 0.17 gram, i.e. 1.28 mmole I-hydroxybenzotriazoles, be abbreviated as HOBT, vacuumize, nitrogen protection, 30 milliliters of methylene dichloride heavily steamed are added in ice bath downhill reaction system, ice bath stirs the bath of 5 minutes recession deicings, stirring at room temperature 1 hour, stir in downhill reaction system at ice bath and add 0.26 gram that is dissolved in 10 milliliters of dry methylene chloride, the i.e. intermediate X of 1.22 mmoles, finally drip 0.15 gram, the i.e. triethylamine of 1.47 mmoles, ice bath stirred overnight at room temperature is removed after all adding, after reaction terminates, enough water is added in reaction solution, isolate organic layer, water layer methylene dichloride back extraction twice, organic layer after merging respectively washes one time with saturated sodium bicarbonate and saturated sodium-chloride respectively, anhydrous magnesium sulfate drying, suction filtration, removal of solvent under reduced pressure, resistates is through 200 ~ 300 order purification by silica gel column chromatography, eluent is petrol ether/ethyl acetate=2/1 of 60 ~ 90 degrees Celsius, obtain yellow solid XI, yield 56%, the volume of amount prepared by compounds X I and reaction vessel expands by corresponding proportion or reduces.

The method being prepared intermediate X II by intermediate X I is as follows:

0.24 gram is added successively in 100 milliliters of single necked round bottom flask, the i.e. intermediate X I of 0.48 mmole, 0.049 gram, the i.e. triethylamine of 0.48 mmole, with 20 milliliters of anhydrous alcohol solutions, in 80 degrees Centigrade back flow reaction 2 hours, desolventizing is removed by concentrated for reaction solution after having reacted, resistates 20 ml waters and 20 milliliters of methylene dichloride dissolve, separate organic layer, organic layer saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate X II through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/4 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 61%, the volume of amount prepared by intermediate X II and reaction vessel expands by corresponding proportion or reduces.

The method being prepared thiazolone oxime ether derivative VI by intermediate X II is as follows:

0.42 gram is added successively in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. intermediate X II of 0.82 mmole, 0.14 gram, the i.e. potassium tert.-butoxide of 1.22 mmoles and the Tetrabutyl amonium bromide of 10 milligrams, with 20 milliliters of tetrahydrofuran (THF)s and 4 milliliters of N, dinethylformamide dissolves, nitrogen protection, stirring at room temperature is after 10 minutes, 0.15 gram is added in reaction, the i.e. propargyl bromide of 1.22 mmoles, stirring at room temperature reacts 2 hours, react rear reaction solution 20 milliliters of chloroforms and wash one time, separate organic layer and wash 3 times with saturated sodium bicarbonate successively, saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains thiazolone oxime ether derivative VI through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/5 of ethyl acetate/60 ~ 90 degree Celsius cut, yield 63%, the volume of amount prepared by compound VI and reaction vessel expands by corresponding proportion or reduces.The chemical structure of compound VI and physical and chemical parameter are in table 1.

F. the fungicidal activity of thiazolone oxime ether derivative VI of the present invention measures:

The sterilization of thiazolone oxime ether derivative VI of the present invention or bacteriostatic activity adopt thalli growth rate assay method, concrete steps are: get 1.8 milligrams of sample dissolution in appropriate dimethyl formamide, then with the medicament being diluted to 500 mcg/ml containing a certain amount of polysorbas20 emulsifier aqueous solution, reagent agent is aseptically respectively drawn in 1 milliliter of injection culture dish, add 9 milliliters of PDA substratum more respectively, 50 mcg/ml pastilles are made dull and stereotyped after shaking up, blank is done with the flat board adding 1 milliliter of aqua sterilisa, bacterium dish is cut along mycelia outer rim with the punch tool of diameter 4 millimeters, move on pastille flat board, put in equilateral triangle, often process repetition 3 times, culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivates, treat that contrast colony diameter expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, compare with blank and calculate relative bacteriostasis rate, for the kind that examination bacterial classification is most of typical plant pathogenic bacteria of the actual generation in field in China's agriculture production, its code name and title as follows: AS: tomato early blight bacterium, its Latin is called: Alternaria solani, BC: botrytis cinerea pers, its Latin is called: Botrytis cinerea, CA: peanut Cercospora bacteria, its Latin is called: Cercospora arachidicola, GZ: fusarium graminearum, its Latin is called: Gibberella zeae, PI: phytophthora infestans, its Latin is called: Phytophthora infestans (Mont.) de Bary, PP: Botryosphaeria berengeriana f. sp, its Latin is called: Physalosporapiricola, PS: Rhizoctonia solani Kuhn, its Latin is called: Pellicularia sasakii, RC: Rhizoctonia cerealis, its Latin is called: Rhizoctonia cerealis, SS: Sclerotinia sclerotiorum, its Latin is called: Sclerotinia sclerotiorum.

G. the inducing anti-disease activity of thiazolone oxime ether derivative VI of the present invention measures:

The screening method of thiazolone oxime ether derivative VI evoking tobacco activity of resisting tobacco mosaic virus of the present invention is as follows, and tobacco mosaic virus (TMV) is abbreviated as TMV:

(1). positive control activating plants agent: the tiadinil selecting quality purity purity to be greater than 99.5% is the activating plants agent of positive control; Tiadinil is abbreviated as TDL;

(2). the screening method of the anti-TMV activity of evoking tobacco of thiazolone oxime ether derivative VI: the mensuration of in vitro directly antiviral activity adopts half leaf method to carry out, live body induction is by common cigarette consistent for seedling age, 3 basins are one group, respectively at the cigarette seedling of inoculation pre-treatment in first 7 days, processing mode comprises: spray test compounds solution 2 to 3 times, each 10 milliliters, or soil treatment, each 10 milliliters, measuring concentration is 50 mcg/ml, 7th day frictional inoculation TMV on the tobacco leaf newly grown, cultivate under cigarette seedling being placed in its growth optimal temperature and illumination after 3 days, check incidence, comprehensive scab number is calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, 3 repetitions are established in each process, blank and standard agent contrast select water and TDL respectively:

$R=\frac{\mathrm{CK}-I}{\mathrm{CK}}\×100$

Wherein, R is the inducing effect of new compound to Resistance In Tobacco TMV, unit: %; CK is the average withered spot number of clear water contrast blade, unit: individual; I is the average withered spot number through compound induction process rear blade, unit: individual;

Except carrying out the mensuration of above-mentioned induced activity, carry out the mensuration of the therapeutic activity of the anti-TMV of thiazolone oxime ether derivative VI, inactivate activity and prolection simultaneously.

H. thiazolone oxime ether derivative VI of the present invention is to the mensuration of aphid cytotoxicity:

The measuring method of thiazolone oxime ether derivative VI of the present invention to aphid cytotoxicity is as follows: adopt pickling process, black bean aphid, and its Latin is called: Aphis laburni Kaltenbach (ALK), the normal population of indoor feeding; Take test compound 2.5 milligrams in beaker, drip 1 DMF, i.e. DMF, add 5 milliliters of acetone vibrations and dissolve sample, then add the solution to be measured having the water of tween 80 to be mixed with 100 mcg/ml; By cutting from basin for examination bean plant with at least 60 black bean aphids, flooded for 5 seconds in each liquid to be measured, take out and get rid of unnecessary liquid gently, be inserted in by moisturizing on water saturated sponge, with on lens cover after liquid is dry, the opening of lens upper end is with gauze sealing in case aphid escapes, and raise placement and check aphid death state after 48 hours, standard is: with try worm can creep maybe can stand or six Tiao Tuineng strenuous exercises be worm alive; Take clear water as contrast, Provado is positive control, calculation correction mortality ratio.

The invention has the beneficial effects as follows: guide's optimization has been carried out to thiazolone oxime ether derivative VI, and the screening of insecticidal activity and bacteriostatic activity and antiviral activity has been carried out to the new compound of synthesis.

The present invention illustrates the synthesis of thiazolone oxime ether derivative VI and biological activity and application more by specific preparation and biological activity determination embodiment, described embodiment is only for illustrating the present invention and unrestricted the present invention, especially biological activity only illustrates, and unrestricted this patent, embodiment is as follows:

Embodiment 1

The preparation of intermediate II:

1 gram is added in two mouthfuls of round-bottomed flasks of 100 milliliters, the i.e. I of 3.20 mmoles, dissolve with 20 milliliters of methylene dichloride, after add 0.36 gram, the i.e. triethylamine of 3.52 mmoles, nitrogen protection, stirring at room temperature, 0.68 gram is added in backward reaction in 10 minutes, i.e. 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride of 3.52 mmoles, be abbreviated as EDCI, finally add the DMAP of 10 milligrams, stirred overnight at room temperature, the 30 milliliters of washings one time of rear reaction solution are reacted, separate organic layer saturated sodium-chloride and wash one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate II through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/4 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 90-100%, ¹h NMR (CDCl ₃) δ: 7.93 (s, 1H), 4.32-4.10 (m, 2H), 3.81 (s, 3H), 3.44 (s, 3H), 3.24-3.16 (m, 1H), 2.93-2.87 (m, 2H), 2.15-2.12 (m, 2H), 1.82-1.71 (m, 2H), 1.48 (s, 9H).

Embodiment 2

The preparation of intermediate III:

0.77 gram is added in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. intermediate II of 2.17 mmoles, nitrogen protection, reaction system vacuumizes, 20 milliliters of dry tetrahydrofuran (THF)s are added in reaction, react on-78 degrees Celsius of stirrings, the methyl-magnesium-bromide or 3 of 1.08 mmoles is slowly dripped in backward reaction system, 4-Dimethoxyphenyl magnesium bromide, under-78 degrees Celsius, stirring 1 hour is continued after dropwising, after make stirring at room temperature into 1 hour, the saturated ammonium chloride solution and 30 milliliters of ethyl acetate that add 30 milliliters are reacted in backward reaction solution, stir and separate organic layer afterwards a little while, organic layer saturated sodium-chloride washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate III through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/4 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 80-93%, ¹h NMR (CDCl ₃) δ: 8.06 (s, 1H), 4.32-4.14 (m, 2H), 3.25-3.18 (m, 1H), 2.95-2.89 (m, 2H), 2.66 (s, 3H), 2.16-2.13 (m, 2H), 1.82-1.72 (m, 2H), 1.50 (s, 9H).

Embodiment 3

The preparation of intermediate compound IV:

0.5 gram is added successively in 100 milliliters of single necked round bottom flask, the i.e. intermediate III of 1.61 mmoles, 0.16 gram, the i.e. triethylamine of 1.61 mmoles, with 20 milliliters of anhydrous alcohol solutions, in 80 degrees Centigrade back flow reaction 2 hours, desolventizing is removed by concentrated for reaction solution after having reacted, resistates 20 ml waters and 20 milliliters of methylene dichloride dissolve, separate organic layer, organic layer saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate compound IV through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/3 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 79-90%, ¹h NMR (CDCl ₃) δ: 7.32 (s, 1H), 4.10 (m, 2H), 3.15-3.09 (m, 1H), 2.81-2.79 (m, 2H), 2.23 (s, 3H), 2.03-2.00 (m, 2H), 1.69-1.63 (m, 2H), 1.38 (s, 9H).

Embodiment 4

The preparation of intermediate V:

0.36 gram is added successively in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. intermediate compound IV of 1.10 mmoles, 0.19 gram, the i.e. potassium tert.-butoxide of 1.66 mmoles and the Tetrabutyl amonium bromide of 10 milligrams, with 20 milliliters of tetrahydrofuran (THF)s and 4 milliliters of N, dinethylformamide dissolves, nitrogen protection, stirring at room temperature is after 10 minutes, the different halides defined is added in the present invention of 1.66 mmoles in reaction, stirring at room temperature reacts 2 hours, react rear reaction solution 20 milliliters of chloroforms and wash one time, separate organic layer and wash 3 times with saturated sodium bicarbonate successively, saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate V through 200 ~ 300 order purification by silica gel column chromatography, according to the difference of product, eluent volume ratio is sherwood oil=1/3 to 1/1 of ethyl acetate/60 ~ 90 degree Celsius cut, yield 47-91%.

Embodiment 5

The preparation of thiazolone oxime ether derivative VI:

When R is H, the preparation method of thiazolone oxime ether derivative VI is as follows

The intermediate V of 10 mmoles is placed in 100 milliliters of two-mouth bottles, dissolve with 20 milliliters of dry methylene dichloride, nitrogen protection, ice bath stirs, the trifluoroacetic acid of 4 milliliters is dripped in reaction system, all dropwise rear stirring at room temperature 1 hour, react the sodium hydroxide dripping 1 mol/L in backward reaction solution, about adjust pH to 10, separate organic layer, organic layer saturated common salt is washed once, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate VI through 200 ~ 300 order purification by silica gel column chromatography, eluent is methylene chloride/methanol, different according to product, volume ratio is 50: 1-10: 1, by gained sterling calculated yield, yield 66-100%.The chemical structure of compound VI and physical and chemical parameter are in table 1.

When R is HHCl, the preparation method of thiazolone oxime ether derivative VI is as follows:

The compound V of 1 mmole is added in the single necked round bottom flask of 50 milliliters, dissolve with 5 milliliters of anhydrous methanols, stirring at room temperature, in reaction, add the hydrogenchloride dioxane solution of 4 excessive mol/L, room temperature continues stirring 3 hours, has reacted rear reaction solution directly concentrated removing organic solvent, appropriate dehydrated alcohol is added in flask, continue the water that concentrated removing is a small amount of, finally obtain product as light yellow solid VI, yield 100%; The volume of amount prepared by compound VI and reaction vessel expands by corresponding proportion or reduces.The chemical structure of compound VI and physical and chemical parameter are in table 1.

When R be the bromo-1-of 3-(during 3-chloropyridine-2-base-1H-pyrazoles-5-carbonyl, the preparation method of thiazolone oxime ether derivative VI is as follows: the method being prepared intermediate X I by intermediate X is as follows:

0.39 gram is added successively in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. bromo-1-of the 3-of 1.28 mmoles (3-chloropyridine-2-base-1H-pyrazoles-5-carboxylic acid, 0.28 gram, i.e. 1.47 mmole 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, be abbreviated as EDCI, 0.17 gram, i.e. 1.28 mmole I-hydroxybenzotriazoles, be abbreviated as HOBT, vacuumize, nitrogen protection, 30 milliliters of methylene dichloride heavily steamed are added in ice bath downhill reaction system, ice bath stirs the bath of 5 minutes recession deicings, stirring at room temperature 1 hour, stir in downhill reaction system at ice bath and add 0.26 gram that is dissolved in 10 milliliters of dry methylene chloride, the i.e. intermediate X of 1.22 mmoles, finally drip 0.15 gram, the i.e. triethylamine of 1.47 mmoles, ice bath stirred overnight at room temperature is removed after all adding, after reaction terminates, enough water is added in reaction solution, isolate organic layer, water layer methylene dichloride back extraction twice, organic layer after merging respectively washes one time with saturated sodium bicarbonate and saturated sodium-chloride respectively, anhydrous magnesium sulfate drying, suction filtration, removal of solvent under reduced pressure, resistates is through 200 ~ 300 order purification by silica gel column chromatography, eluent is the petrol ether/ethyl acetate of 60 ~ 90 degrees Celsius, volume ratio is 2/1, obtain yellow solid XI, yield 56%, ¹h NMR (CDCl ₃) δ: 8.42 (d, J=1.4Hz, 1H), 8.06 (s, 1H), 7.91 (d, J=7.8Hz, 1H), 7.36 (dd, J=6.9,2.4Hz, 1H), 6.57 (s, 1H), 4.57-4.54 (m, 1H), 4.23-4.21 (m, 1H), 3.36-3,31 (m, 2H), 2.98-2.95 (m, 1H), 2.65 (s, 3H), 2.20-2.17 (m, 2H), 2.03-1.74 (m, 2H).

The method being prepared intermediate X II by intermediate X I is as follows:

0.24 gram is added successively in 100 milliliters of single necked round bottom flask, the i.e. intermediate X I of 0.48 mmole, 0.049 gram, the i.e. triethylamine of 0.48 mmole, with 20 milliliters of anhydrous alcohol solutions, in 80 degrees Centigrade back flow reaction 2 hours, desolventizing is removed by concentrated for reaction solution after having reacted, resistates 20 ml waters and 20 milliliters of methylene dichloride dissolve, separate organic layer, organic layer saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate X II through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/4 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 61%, ¹h NMR (CDCl ₃) δ: 8.25 (dd, J=4.7,1.5Hz, 1H), 7.72 (dd, J=8.0,1.5Hz, 1H), 7.24 (s, 1H), 7.17 (dd, J=8.0,4.7Hz, 1H), 6.40 (s, 1H), 4.38-4.35 (m, 1H), 4.04-4.01 (m, 1H), 3.19-3.12 (m, 2H), 2.85-2.72 (m, 1H), 2.14 (s, 3H), 2.02-2.00 (m, 2H), 1.83-1.55 (m, 2H).

The method being prepared thiazolone oxime ether derivative VI by intermediate X II is as follows:

0.42 gram is added successively in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. intermediate X II of 0.82 mmole, 0.14 gram, the i.e. potassium tert.-butoxide of 1.22 mmoles and the Tetrabutyl amonium bromide of 10 milligrams, with 20 milliliters of tetrahydrofuran (THF)s and 4 milliliters of N, dinethylformamide dissolves, nitrogen protection, stirring at room temperature is after 10 minutes, 0.15 gram is added in reaction, the i.e. propargyl bromide of 1.22 mmoles, stirring at room temperature reacts 2 hours, react rear reaction solution 20 milliliters of chloroforms and wash one time, separate organic layer and wash 3 times with saturated sodium bicarbonate successively, saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains thiazolone oxime ether derivative VI through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/5 of ethyl acetate/60 ~ 90 degree Celsius cut, yield 63%, the volume of amount prepared by compound VI and reaction vessel expands by corresponding proportion or reduces.The chemical structure of compound VI and physical and chemical parameter are in table 1.

Embodiment 6

Thiazolone oxime ether derivative VI Antibacterial Activity result of the present invention:

Code name and the title of the frequently seen plants pathogenic fungi of the present invention's test are as follows: AS: tomato early blight bacterium, its Latin is called: Alternaria solani, BC: botrytis cinerea pers, its Latin is called: Botrytis cinerea, CA: peanut Cercospora bacteria, its Latin is called: Cercospora arachidicola, GZ: fusarium graminearum, its Latin is called: Gibberellazeae, PI: phytophthora infestans, its Latin is called: Phytophthora infestans (Mont.) de Bary, PP: Botryosphaeria berengeriana f. sp, its Latin is called: Physalospora piricola, PS: Rhizoctonia solani Kuhn, its Latin is called: Pellicularia sasakii, RC: Rhizoctonia cerealis, its Latin is called: Rhizoctonia cerealis, SS: Sclerotinia sclerotiorum, its Latin is called: Sclerotinia sclerotiorum, these bacterial classifications have good representativeness, the kind of most of pathogenic bacteria that field occurs in agriculture production can be represented.It should be noted that compound lfy006-39 is the highly active known compound reported in patent documentation WO2008091594, in order to compare the biological activity of new compound of the present invention's synthesis, synthesize this structure in the present invention closest to target compound of the present invention and the highest similar compound lfy006-39 of its activity of patent literature.Thalli growth rate method measurement result is in table 2, and table 2 shows, when 50 mcg/ml, all compounds of the present invention's synthesis all have fungicidal activity in various degree.Phytophthora infestans, compound lfy007-7, lfy007-34, lfy007-14, lfy007-31, lfy007-25, lfy007-44, lfy008-27, lfy008-40, lfy008-41, lfy008-1, lfy008-20, the inhibiting rate of lfy008-31 is more than 40%, the fungicidal activity of above-claimed cpd exceeds similar, the active best compound lfy006-39 of bibliographical information is more than 10%, wherein compound lfy007-34, lfy008-1, lfy007-25, lfy008-40, lfy008-31, lfy008-20, the inhibiting rate of lfy007-14 is more than 50%, active in contrast medicament Azoxystrobin.For peanut Cercospora bacteria, the inhibiting rate of compound lfy007-7, lfy007-34, lfy007-47, lfy008-24, lfy007-31, lfy007-25, lfy007-44, lfy007-39, lfy008-20, lfy007-14 is more than 40%, the fungicidal activity of above-claimed cpd exceeds similar, the active best compound lfy006-39 of bibliographical information more than 10%, wherein the inhibiting rate of compound lfy007-34, lfy007-14, lfy007-44, lfy007-7 is more than 60%, active in contrast medicament Azoxystrobin.For tomato early blight bacterium, the inhibiting rate of compound lfy007-7, lfy007-34, lfy007-14, lfy008-46, lfy007-44, lfy008-41, lfy008-31, lfy008-42, lfy009-5, lfy008-1 is more than 50%, the fungicidal activity of above-claimed cpd exceeds similar, the active best compound lfy006-39 of bibliographical information more than 10%, but lower than contrast medicament Azoxystrobin.For botrytis cinerea pers, compound lfy007-7, lfy007-34, lfy007-14, lfy008-19, lfy007-44, lfy008-27, lfy008-41, lfy008-31, lfy008-1, lfy008-46, lfy008-34, fy009-5, lfy009-6, the inhibiting rate of lfy008-42 is more than 50%, wherein compound lfy007-34, lfy007-14, lfy008-19, the inhibiting rate of lfy008-34 is more than 62%, active in known compound lfy006-39, the activity of compound lfy008-19 is 100%, active in contrasting medicament Azoxystrobin and exceeding similar, the active best compound lfy006-39 of bibliographical information is more than 30%.For fusarium graminearum, the inhibiting rate of compound lfy007-7, lfy007-47, lfy008-3, lfy008-40, lfy008-41, lfy008-20, lfy008-1 is more than 40%, wherein the inhibiting rate of compound lfy008-40, lfy008-41, lfy008-1 is more than 55%, and activity exceeds similar, the active best compound lfy006-39 of bibliographical information more than 10%.For Botryosphaeria berengeriana f. sp, the inhibiting rate of compound lfy007-7, lfy007-14, lfy007-31, lfy007-25, lfy008-1, lfy007-44 is more than 50%, active in known compound lfy006-39, the inhibiting rate of compound lfy007-7, lfy007-14, lfy007-44 is higher than 60%, and activity exceeds similar, the active best compound lfy006-39 of bibliographical information more than 10%.For Sclerotinia sclerotiorum, the inhibiting rate of compound lfy007-7, lfy007-34, lfy007-47, lfy007-1, lfy007-31, lfy007-25, lfy007-4, lfy008-40, lfy008-4, lfy007-39, lfy008-20, lfy008-38, lfy009-6, lfy008-34 is more than 40%, activity exceeds similar, the active best compound lfy006-39 of bibliographical information more than 10%, and wherein the inhibiting rate of compound lfy007-7, lfy008-38, lfy007-44, lfy007-47 is higher than 80%.For Rhizoctonia cerealis, the inhibiting rate of compound lfy007-7, lfy007-34, lfy007-14, lfy007-31, lfy007-25, lfy007-44, lfy008-40, lfy008-1, lfy009-5, lfy009-6, lfy008-46 is more than 40%, wherein the activity of compound lfy008-1 is higher than 80%, and activity exceeds similar, the active best compound lfy006-39 of bibliographical information more than 10%.For Rhizoctonia solani Kuhn, compound lfy007-7, lfy007-34, lfy007-47, lfy008-46, lfy007-31, lfy007-2, lfy007-44, lfy008-41, lfy007-39, lfy008-31, lfy008-24, lfy009-6, the inhibiting rate of lfy007-14 is more than 40%, wherein compound lfy007-7, the inhibiting rate of lfy007-44 is higher than 70%, active in known compound lfy006-39, the inhibiting rate of compound lfy007-44 is higher than 80%, activity exceeds similar, the active best compound lfy006-39 of bibliographical information is more than 10%.Therefore, the new compound of design and synthesis of the present invention is owing to introducing substituent difference, the fungicidal activity of target compound compares with the highly active similar compound reported in patent documentation, and fungicidal activity obtains significant raising, and this is the place that the invention is different from existing invention.

Embodiment 7

The anti-TMV Activity Results of thiazolone oxime ether derivative VI of the present invention:

The measurement result of TMV activity is in table 3, and table 3 shows, majority of compounds of the present invention has the activity of good anti-TMV; When 100 mcg/ml, all compounds of the present invention's synthesis all have anti-TMV in various degree active.In the therapeutic mode, compound lfy007-7, lfy007-34, lfy007-47, lfy007-31, lfy008-18, lfy007-25, lfy007-44, lfy008-32, lfy008-19, lfy008-33, lfy008-41, lfy008-31, lfy007-39, lfy008-1, lfy008-34, lfy008-38, the inhibiting rate of lfy009-6 is higher than 45%, active in known compound lfy006-39, wherein compound lfy007-7, lfy007-34, lfy007-31, lfy008-18, lfy007-44, lfy008-32, lfy008-19, lfy008-33, lfy008-41, lfy008-31, lfy007-39, lfy008-1, lfy008-34, lfy008-38, the inhibiting rate of lfy009-6 is higher than 50%, and activity exceeds similar, the active best compound lfy006-39 of bibliographical information more than 10%, compound lfy007-34, lfy008-32, lfy008-33, lfy008-41, lfy008-1, lfy007-39, the inhibiting rate of lfy008-31 is higher than 60%, active in contrast medicament Ningnanmycin.Under passivation pattern, the inhibiting rate of compound lfy007-34, lfy007-14, lfy008-18, lfy008-32, lfy008-27, lfy008-33, lfy008-40, lfy008-31, lfy008-14, lfy008-34, lfy008-38 is higher than 40%, activity is higher than contrast medicine BTH and activity exceeds similar, the active best compound lfy006-39 of bibliographical information more than 10%, wherein the inhibiting rate of compound lfy007-14, lfy008-27, lfy008-40, lfy008-34 is higher than 60%, active in contrast medicament SZG-7.In protected mode, compound lfy007-7, lfy008-18, lfy007-25, lfy008-19, lfy008-32, lfy008-3, lfy008-4l, lfy008-3l, lfy008-14, lfy009-6, lfy009-5, the inhibiting rate of lfy008-42 is higher than 62%, active in known compound lfy006-39 and contrast medicament Ningnanmycin, wherein compound lfy007-7, lfy009-6, lfy008-32, lfy008-31, the inhibiting rate of lfy007-25 is higher than 75%, activity exceeds similar, the active best compound lfy006-39 of bibliographical information is more than 10%.Under induction pattern, compound lfy007-7, lfy007-34, lfy007-47, lfy007-31, lfy008-19, lfy007-44, lfy008-27, lfy008-33, lfy008-3, lfy008-41, lfy008-31, lfy007-39, lfy008-1, lfy008-46, lfy008-24, lfy008-38, the inhibiting rate of lfy008-42 is higher than 60%, active in contrast medicament Ningnanmycin and SZG-7, wherein compound lfy007-34, lfy008-38, lfy007-31, lfy008-19, lfy007-44, lfy008-27, lfy008-33, lfy008-4l, lfy008-31, lfy007-39, lfy008-1, lfy008-46, lfy008-24, the inhibiting rate of lfy007-47 is higher than 70%, active in contrast medicament TDL and known compound lfy006-39, compound lfy007-34, lfy007-47, lfy007-31, lfy008-27, lfy008-33, lfy008-3l, lfy007-39, lfy008-24, the inhibiting rate of lfy008-1 is higher than 80%, and activity is higher than contrast medicament BTH and activity exceeds similar, the active best compound lfy006-39 of bibliographical information is more than 10%.Visible, it is active that thiazolone oxime ether derivative VI of the present invention has good anti-TMV.

Embodiment 8

The insecticidal activity result of thiazolone oxime ether derivative VI of the present invention:

The insecticidal activity assay of thiazolone oxime ether derivative the results are shown in Table 4, table 4 is visible: when reagent agent concentration is 100mg/L, after observation acts on 72 hours, closest with structure of the present invention, the active best compound lfy006-39 of bibliographical information does not have toxic action substantially to aphid, the compound had in the present invention has certain toxic action to aphid, wherein compound lfy007-14, lfy007-31, lfy007-44, lfy007-39, the cytotoxicity of lfy008-20 is more than 20%, be respectively 26.79%, 26.81%, 28.15%, 24.95% and 25.00%.

Embodiment 9

Thiazolone oxime ether derivative of the present invention and agriculturally acceptable auxiliary agent and as follows one or more commodity insecticide compositions are preparing the purposes in compounded pesticides:

Described commodity sterilant is selected from: Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, esfenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-cyfloxylate, cyfloxylate, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron and noviflumuron, its CAS 121451-02-3, flucycloxuron, Novaluron and Rimon, chlorfluazuron, Bay sir 6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron and bistrifluron, furan tebufenozide, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, Cupric sulfate, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, to rattle away young ketone, Nylar, emaricin, the total mass percentage of thiazolone oxime ether derivative of the present invention in gained compounded pesticides is 1%-90%, and the ratio of thiazolone oxime ether derivative of the present invention and described commodity sterilant is mass percent 1%: 99% to 99%: 1%, the formulation that described compounded pesticides is suitable for is selected from seed treatment emulsion, aqueous emulsion, large granula, microemulsion, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, seed treatment suspension agent, smog sheet, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, microgranules, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, seed coat agent, basting agent, fritter poison bait, suspension emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, any one in wet-mixing kind water-dispersible powder, the plant that described compounded pesticides is suitable for is selected from paddy, wheat, barley, oat, corn, jowar, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, apple, citrus, peach, tea, wild vegetable, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape, the insect pest of described compounded pesticides control is selected from Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), singly sting mole cricket, Oriental burmeister, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipe thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, sugarcane flat angle plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, sorghum aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hangs cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, Soybean stem borer, frit fly, plant fly, onion fly, radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm.

Embodiment 10

Thiazolone oxime ether derivative of the present invention is preparing the purposes in composite bactericide with any one or the multiple combination in agriculturally acceptable auxiliary agent and following commodity sterilant:

Described commodity bactericide is selected from diazosulfide, tiadinil, first thiophene lures amine, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-Ethyl formate, 4-bromomethyl-1,2,3-thiadiazoles-5-Ethyl formate, 4-iodomethyl-1,2,3-thiadiazoles-5-Ethyl formate, 4-bromomethyl-5-methyl-l, 2,3-thiadiazoles, 4-iodomethyl-5-methyl isophthalic acid, 2,3-thiadiazoles, 4,4-, bis-bromomethyls-l, 2,3-thiadiazoles-5-Ethyl formate, 3,4-, bis-chloroisothiazoles-5-formic acid, 3,4-, bis-chloroisothiazoles-5-sodium formate, 3,4-, bis-chloroisothiazoles-5-Ethyl formate, DL-beta-aminobutyric acid, isotianil, virazole, antofine, Ningnanmycin, first thiophene lures amine, salicylic acid, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, frost urea cyanogen, thiram, ziram, Mancozeb, aliette, thiophanate-methyl, Bravo, enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, salicylic acid, flumorph, dimethomorph, mefenoxam, benalaxyl-M, two chlorine zarilamids, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, pyraclostrobin, oxime bacterium ester, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, Cyproconazole, Difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, own azoles alcohol, glyoxalin, plant bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Triadimenol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, Grandox fumigant, octhilinone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, Fenarimol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, IBP, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, difoltan, captan, folpet, vinclozolin, fluoromide, dimethachlon, Isoprothiolane, kitazine, Yekuzuo,Pentachloronitrobenzene, Mancozeb, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the pungent salt of biguanides, iminoctadine, botran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium, enemy's line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, isazofos, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole, the total mass percentage of thiazolone oxime ether derivative of the present invention in gained composite bactericide is 1%-90%, and the ratio of thiazolone oxime ether derivative of the present invention and described commodity bactericide is mass percent 1%: 99% to 99%: 1%, the applicable formulation of described composite bactericide is selected from any one in following dosage forms: wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, Seed Treatment emulsion, aqueous emulsion, large granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, Seed Treatment suspending agent, smog sheet, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/agent of mixing dress, medicine paint, Seed Treatment liquor, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, liniment, suspended emulsion, film forming finish, soluble powder, Seed Treatment water solube powder, ultra-low volume suspending agent, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water-dispersible powder, the applicable plant of described composite bactericide is selected from paddy, wheat, barley, oat, corn, jowar, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, to order certain herbaceous plants with big flowers, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape, the applicable controlling disease of described composite bactericide is selected from: wheat rust, wheat scab, wheat powdery mildew, wheat virus disease, wheat is avenged mould leaf blight, the wheat spore leaf spot of wriggling, flag smut of wheat, take-all, wheat sharp eyespot, wheat downy mildew, the late blight of potato, wart of potatoes, potato scab, target, bacterial ring rot o potato, potato bacterial wilt, blakleg of potato, Potyvirus and viroid disease, bacterial soft rot of potato, dry rot of potato,Potato verticillium wilt, black scurf of potato, potato bacterial wilt, bacterial ring rot o potato, blakleg of potato, bacterial soft rot of potato, cotton wilt, cotton verticillium wilt, angular leaf spot of cotton, red leaf blight, cotton seedling blight, cotton samping off, cotton anthracnose, cotton spoting verticillium wilt, cotton anthracnose, cotton spoting verticillium wilt, rice blast, rice sheath blight disease, water rice brown spot, small round sclerotial disease of rice, bakanae disease of rice, downymildewofrice, rice green smut, rice leaf sheath rot, bacterial blight of rice, bacterial leaf streak of rice, Characters of Erwinia chrysanthemi pv. zeae, stripe disease, the short volume of paddy rice secret note is sick, paddy rice rice black sclerotium stalk rot, the leaf blight of corn, corn southern leaf blight, Helminthosporium carbonum, maize brown spot, maize sheath blight, corn rust, maize head smut, Corn Stalk Rot, corn smut, corn dry rot, maize virus disease and corn stalk rot disease, sclerotinia rot of colza, Rape virus disease, oilseed rape downy mildew, white rust of colza, root rot, soybean sclerotinia crown rot, grey speck of soybean, soybean Mosaic, soy bean cyst roundworm, root-knot nematode, soybean rust, soybean anthracnose, bacterial pustule of soybean, soybean spot blight, downy mildew, bacterial wilt of peanut, Diplodia gossypina, Roots of Peanut maize ear rot, the cercospora brown spot of peanut, Peanut Web Blotch Disease, activity of peanuts disease, Peanut Scab, tobacco bacterial wilt, wildfire, tobacco hollw stalk, Tobacco Angular Leaf Spot Disease, black shank, Alternaria alternate, frog-eye leaf spot of tobacco, anthracnose of tobacco, black root of tobacco, fusarium tabacinum root rot, Tobacco seedling diseases, tobacco damping-off, the tattered leaf spot of tobacco, Powdery Mildew in Tobacco, tobacco southern blight, tobacco black spot, tobacco mosaic disease, cucumber mosaic virus, etch virus of tobacco, Chinese cabbage downy mildew, soft rot of cabbage, Chinese cabbage Tipburn Disease, Chinese cabbage virosis, Cabbage Leaf Spot, Seed detection, Chinese cabbage anthracnose, cabbage clubroot, bacterial spot of tomato, tomato late blight, tomato blossom-end rot, tomato powdery mildew, tomato samping off, tomato fish pelargonium mosaic disease, tomato bacterial speck, tomato yellow leaf curl virus, leaf muld of tomato, tomato virus disease, tomato late blight, tomato samping off and damping-off, tomato distortion fruit, tomato perforation fruit, tomato black ring virus disease, tomato rot stem nematodes disease, tamato fruit buphthalmos disease, tomato stain root rot, tomato stain root rot, tomato branch spore fruit rot, tomato heartrot, tomato Rhizopus fruit rot, tomato low temperature obstacle, tomato bolter, tomato physiological leaf curl, tomato samping off, tomato fruit drop disease, tomato bud blight, Tomato soft rot, tomato stem rot, tomato seedling damping-off, tomato order burns sick, tomato shot hole, tomato rouge and powder disease, tomato virus disease, tomato cracked fruit, canker of tomato, the rotten fruit of tomato navel, tomato sesame pinta bacterium, bacterial spot of tomato, tomato rot leaf viral disease, tomato yellow leaf curl virus disease, eggplant cotton disease, eggplant sclerotiniose, eggplant bacterial wilt, eggplant Phomopisis vexans, eggplant verticillium wilt, eggplant leaf spot, eggplant early blight, eggplant virosis, eggplant leaf spot disease, eggplant leaf mold, eggplant powdery mildew, eggplant spot disease, eggplant coal spot disease, cercospora leaf spot of egg plant, helminthosporium leaf blight and fruit rot of egg plant, eggplant epidemic disease, eggplant anthracnose, eggplant head mold soft rot,Wilt of eggplant, grey mould of egg plant, stem of eggplant basal stem rot, capsicum green pepper virosis, capsicum early blight, capsicum Leucoplakia, pepper white star disease, capsicum leaf spot, capsicum Scald, capsicum sooty mold, capsicum wilt, capsicum sclerotiniose, capsicum sunscald, pepper virus disease, capsicum malformed fruit, capsicum blossom-end rot, capsicum soft rot, bacterial spot of pepper, capsicum bar virus scab, capsicum pythium rot, macrosporium leaf spot of red pepper, cayenne pepper spots rot, capsicum black spot, capsicum verticillium wilt, pepper bacterial leaf spot, capsicum brown rot, Fusarium solani, capsicum damping-off, pepper anthracnose, capsicum brown spot, capsicum downy mildew, Botrytis cinerea, capsicum leaf blight, pepper leaf mold, capsicum samping off, capsicum epidemic disease, downy mildew of garpe, uncinula necator, brown spot of grape, grapevine leafroll disease, Grapevine Fan Leaf Virus Disease, grape rust, grape ring spot, grape leaf pinta, the little brown spot of grape, grape zonate spot, light grey and pinkish pinta, grape young sprout wasting disease, grape flower leaf disease, grape wasting disease, grape stripe disease, the golden yellow disease of grape, grape infectivity is downright bad sick, the yellow point of grape is sick, grape lug disease, grape vein is downright bad sick, Grapevine fleck virus disease, grape star-of-bethlehem leaf disease, grape Pearls, fruit white rot of grape, bitter rot or anthracnose of grape, grape room rot, grape grey mould, grapevine anthracnose, black rot of grape, the large room of grape rot, grape coal point is sick, grape is brown sick, grape is mould dirty sick, grape bitter rot, grape branch spore rot, grape penicilliosis, grape Alternaria rot, apple tree canker, dry rot of apple, ring rot of apple, apple branch canker, apple blister canker, Pink Disease of Apple, dried apple slices rot, apple branch-rot, apple anthracnose, Apple Mould Core, rust of apple (Gymnosporangium yamadai), apple flower maize ear rot, apple brown rot, black fruit rot of apple, apple phytophthora rot, Apple Sooty, sick apple marssonina leaf spot, alternaria leaf spot of apple, Glomerella cingulata, apple graywall, apple mildew, scab of apple, silver leaf of apple, apple infectivity root rot, armillariella root rot of apple, apple Root―rot disease, apple southern blight, apple violet root rot, rosellinia trunk rot of apple, Apple crown gall, apple decline disease, apple rough skin disease, apple mosaic, apple green wrinkle fruit disease, apple fruit-shrink disease, Apple little leaf, apple chlorosis, apple bitter pit, apple water core, apple superficial scald, carbuncle apple scab, Gold Delicious apple fruit russeting, green mold of apple, apple soft rot, Apples digested tankage is continuous sick, apple pulp brown stain disease, apple brown heart, pear scab, black rot of pear, Fungus of Pear Canker Disease, pears southern blight, pear tree wood rot, pears die back disease, rust of pear, Pear black spot, pears graywall, pears brown spot, pears Socty Blotch And Greasy Blotch, pears top rot, pears fruit-shrink disease, pears yellowtop, anthracnose of peach, the real maize ear rot of peach, peach fruit rot, peach soft rot, peach canker, peach powdery mildew, peach brown rot, peach scab, the abnormal fruit disease of peach, peach sooty mould, peach leaf-curl, peach fungoid shothole disease, peach Bacterial septicaemia syndrome, peach leaves pinta, peach leaf rust, peach mosaic disease, peach red-leaf disease, peach rot, peach gummosis, peach wood rot, peach die back disease, Peach crown gall, peach root rot, peach root knot nematode disease, Citrus Huanglongbing pathogen, exocortis, the broken leaf disease of oranges and tangerines,Citrus decline, Satsuma dwarf virus, citrus bacterial canker disease, citrus scab, citrus anthracnose, oranges and tangerines foot rot, oranges and tangerines resin disease, oranges and tangerines bleeding disease, Citrus fuliginous, oranges and tangerines powdery mildew, oranges and tangerines fat point maculopathy, oranges and tangerines are intended fat point maculopathy, the red clothing disease of oranges and tangerines, oranges and tangerines felt fungus, oranges and tangerines seedling blight, oranges and tangerines seedling epidemic disease, banana bunchy top disease, Banana Mosaic Disease, research of fusarium wilt disesase of banana, Cercospora musae bacterium leaf spot, the dark two mould leaf spots of spore of banana, the mould leaf spot of the little Dou Shi of banana, banana freckle, Banana Leaf seasonal febrile diseases, banana anthracnose, banana crown rot, wild cabbage bacterial black rot, cottony rot of cabbage, cabbage black rot, black spot of cabbage, wild cabbage brown spot, wild cabbage blastomere disease, wild cabbage virosis, wild cabbage soft rot, wild cabbage is bolting disease in advance, cabbage downy mildew, wild cabbage anthracnose, black leg of cabbage, sugarcane pineapple disease, smut of sugarcane, sugarcane ratoon stunting disease, sugarcane brown streak, sugarcane rust, jowar smut, jowar leaf spot, jowar anthracnose, jowar leaf blight, jowar virosis.

Embodiment 11

Thiazolone oxime ether derivative of the present invention and agriculturally acceptable auxiliary agent and preparing the purposes in composite anti-plant virus agent, activating plants agent with any one or multiple combination in following commodity antiviral agent:

Described commodity antiviral agent is selected from: diazosulfide, tiadinil, first thiophene lures amine, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 4-brooethyl-1, 2, 3-thiadiazoles-5-ethyl formate, 4-iodomethyl-1, 2, 3-thiadiazoles-5-ethyl formate, 4-brooethyl-5-methyl-l, 2, 3-thiadiazoles, 4-iodomethyl-5-methyl isophthalic acid, 2, 3-thiadiazoles, 4, 4-bis-brooethyl-l, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazole-5-formic acid, 3, 4-bis-chloroisothiazole-5-sodium formiate, 3, 4-bis-chloroisothiazole-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, first thiophene lures amine, Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, jingganmycin, the total mass percentage of thiazolone oxime ether derivative of the present invention in the composite anti-plant virus agent of gained, activating plants agent is 1%-90%, and the ratio of thiazolone oxime ether derivative of the present invention and described commodity antiviral agent is mass percent 1%: 99% to 99%: 1%, described composite anti-plant virus agent, the formulation of activating plants agent is selected from wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, large granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, seed treatment suspension agent, smog sheet, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, basting agent, suspension emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, any one in wet-mixing kind water-dispersible powder, described composite anti-plant virus agent, the plant that activating plants agent is suitable for is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, apple, citrus, peach, tea, wild vegetable, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape, the virus disease that described composite anti-plant virus agent, activating plants agent are suitable for is selected from any one in paddy rice short volume disease, yellow dwart, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease, tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, cybidium ring spot virus.

Embodiment 12

Thiazolone oxime ether derivative of the present invention and agriculturally acceptable auxiliary agent and preparing Compositional acaricide with any one or multiple combination in following commodity miticide and preventing and treating the purposes in plant mites evil:

Described commodity miticide is selected from azocyclotin, cyhexatin, fenbutatin oxide, three phosphor tins, Zaprawa enolofos, dimethylvinphos, crotoxyphos, SD-1750, heptenopos, Phosdrin, monocrotophos, naled, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, essence lambda-cyhalothrin, Fenvalerate, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, F-1991, sok, carbofuran, carbosulfan, meta-tolyl-N-methylcarbamate (MTMC), promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, survey positive mycin, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, pyridaben, thiazolone oxime ether derivative of the present invention is 1%-90% at gained Compositional acaricide total mass percentage in the composition, and thiazolone oxime ether derivative of the present invention and the acaricidal ratio of described commodity are mass percent 1%: 99% to 99%: 1%, the formulation of described Compositional acaricide is selected from wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, large granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, seed treatment suspension agent, smog sheet, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, basting agent, suspension emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, any one in wet-mixing kind water-dispersible powder, the plant that described Compositional acaricide is suitable for is selected from paddy, wheat, barley, oat, corn, jowar, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, apple, citrus, peach, tea, wild vegetable, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape, the mite evil that described Compositional acaricide is suitable for is selected from the harmful mite of Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae, tetranychus telarius genus, Eriophyidae, and these evil mites are worldwide Agricultural Mites, forestry harmful mites, gardening evil mite and health evil mite.

The bacteriostatic activity (inhibiting rate/% of 50 mcg/ml) of table 2 thiazolone oxime ether derivative of the present invention

The activity (inhibiting rate/% of 100 mcg/ml) of the resisting tobacco mosaic virus of table 3 thiazolone oxime ether derivative of the present invention VI

The insecticidal activity (target mortality ratio (%), 100 mg/litre) of table 4 thiazolone oxime ether derivative of the present invention VI

Claims (10)

1. a class thiazolone oxime ether derivative, is characterized in that: have such as formula the general structure shown in VI:

Wherein, R is selected from tertbutyloxycarbonyl, the bromo-1-of H, HHCl, 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-carbonyl; R ¹be selected from methyl, 3,4-Dimethoxyphenyls; R ²be selected from hydrogen, propargyl, 2-chloropyridine-5-methylene radical, chloro-1,2, the 3-thiadiazoles-4-methylene radical of 5-, 3-phenyl-2-propine-1-base, seven fluorine sec.-propyls, 3,4-bis-chloroisothiazole-5-methylene radical.

2. the synthetic method of thiazolone oxime ether derivative according to claim 1, concrete synthetic route is as follows:

Wherein, R is selected from tertbutyloxycarbonyl, the bromo-1-of H, HHCl, 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-carbonyl; R ¹be selected from methyl, 3,4-Dimethoxyphenyls; R ²be selected from hydrogen, propargyl, 2-chloropyridine-5-methylene radical, chloro-1,2, the 3-thiadiazoles-4-methylene radical of 5-, 3-phenyl-2-propine-1-base, seven fluorine sec.-propyls, 3,4-bis-chloroisothiazole-5-methylene radical;

Due to the difference of radicals R, the synthetic method of compound VI is different, specifically comprises following synthetic method:

When R is the bromo-1-of 3-(3-chloropyridine-2-base-1H-pyrazoles-5-carbonyl, R ¹for methyl, R ²for propargyl, when X is Br, the synthetic method of thiazolone oxime ether derivative VI of the present invention is as follows:

The synthesis of target compound of the present invention and the concrete grammar of biological activity determination are divided into following steps:

A. the preparation of intermediate II:

1.00 grams are added in two mouthfuls of round-bottomed flasks of 100 milliliters, the i.e. I of 3.20 mmoles, dissolve with 20 milliliters of methylene dichloride, after add 0.36 gram, the i.e. triethylamine of 3.52 mmoles, nitrogen protection, stirring at room temperature, 0.68 gram is added in backward reaction in 10 minutes, i.e. 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride of 3.52 mmoles, be abbreviated as EDCI, finally add the DMAP of 10 milligrams, stirred overnight at room temperature, the 30 milliliters of washings one time of rear reaction solution are reacted, separate organic layer saturated sodium-chloride and wash one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate II through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/4 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 90-100%,

B. the preparation of intermediate III:

0.77 gram is added in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. intermediate II of 2.17 mmoles, nitrogen protection, reaction system vacuumizes, 20 milliliters of dry tetrahydrofuran (THF)s are added in reaction, react on-78 degrees Celsius of stirrings, the methyl-magnesium-bromide or 3 of 1.08 mmoles is slowly dripped in backward reaction system, 4-Dimethoxyphenyl magnesium bromide, under-78 degrees Celsius, stirring 1 hour is continued after dropwising, after make stirring at room temperature into 1 hour, the saturated ammonium chloride solution and 30 milliliters of ethyl acetate that add 30 milliliters are reacted in backward reaction solution, stir and separate organic layer afterwards a little while, organic layer saturated sodium-chloride washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate III through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/4 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 80-93%,

C. the preparation of intermediate compound IV:

0.50 gram is added successively in 100 milliliters of single necked round bottom flask, the i.e. intermediate III of 1.61 mmoles, 0.16 gram, the i.e. triethylamine of 1.61 mmoles, with 20 milliliters of anhydrous alcohol solutions, in 80 degrees Centigrade back flow reaction 2 hours, desolventizing is removed by concentrated for reaction solution after having reacted, resistates 20 ml waters and 20 milliliters of methylene dichloride dissolve, separate organic layer, organic layer saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate compound IV through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/3 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 79-90%,

D. the preparation of intermediate V

0.36 gram is added successively in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. intermediate compound IV of 1.10 mmoles, 0.19 gram, the i.e. potassium tert.-butoxide of 1.66 mmoles and the Tetrabutyl amonium bromide of 10 milligrams, with 20 milliliters of tetrahydrofuran (THF)s and 4 milliliters of N, dinethylformamide dissolves, nitrogen protection, stirring at room temperature is after 10 minutes, the different halides defined is added in the present invention of 1.66 mmoles in reaction, stirring at room temperature reacts 2 hours, react rear reaction solution 20 milliliters of chloroforms and wash one time, separate organic layer and wash 3 times with saturated sodium bicarbonate successively, saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate V through 200 ~ 300 order purification by silica gel column chromatography, according to the difference of product, eluent volume ratio is sherwood oil=1/3 to 1/1 of ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 47-91%,

E. the preparation of thiazolone oxime ether derivative VI:

When R is H, the preparation method of thiazolone oxime ether derivative VI is as follows:

The intermediate V of 10 mmoles is placed in 100 milliliters of two-mouth bottles, dissolve with 20 milliliters of dry methylene dichloride, nitrogen protection, ice bath stirs, the trifluoroacetic acid of 4 milliliters is dripped in reaction system, all dropwise rear stirring at room temperature 1 hour, react the sodium hydroxide dripping 1 mol/L in backward reaction solution, about adjust pH to 10, separate organic layer, organic layer saturated common salt is washed once, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains intermediate VI through 200 ~ 300 order purification by silica gel column chromatography, eluent is methylene chloride/methanol, different according to product, volume ratio is 50: 1-6: 1, by gained sterling calculated yield, yield 66-100%,

When R is HHCl, the preparation method of thiazolone oxime ether derivative VI is as follows:

The compound V of 1 mmole is added in the single necked round bottom flask of 50 milliliters, dissolve with 5 milliliters of anhydrous methanols, stirring at room temperature, in reaction, add the hydrogenchloride dioxane solution of 4 excessive mol/L, room temperature continues stirring 3 hours, has reacted rear reaction solution directly concentrated removing organic solvent, appropriate dehydrated alcohol is added in flask, continue the water that concentrated removing is a small amount of, finally obtain product as light yellow solid VI, yield 100%;

When R be the bromo-1-of 3-(during 3-chloropyridine-2-base-1H-pyrazoles-5-carbonyl, the preparation method of thiazolone oxime ether derivative VI is as follows: the method being prepared intermediate X I by intermediate X is as follows:

0.39 gram is added successively in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. bromo-1-of the 3-of 1.28 mmoles (3-chloropyridine-2-base-1H-pyrazoles-5-carboxylic acid, 0.28 gram, i.e. 1.47 mmole 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, be abbreviated as EDCI, 0.17 gram, i.e. 1.28 mmole I-hydroxybenzotriazoles, be abbreviated as HOBT, vacuumize, nitrogen protection, 30 milliliters of methylene dichloride heavily steamed are added in ice bath downhill reaction system, ice bath stirs the bath of 5 minutes recession deicings, stirring at room temperature 1 hour, stir in downhill reaction system at ice bath and add 0.26 gram that is dissolved in 10 milliliters of dry methylene chloride, the i.e. intermediate X of 1.22 mmoles, finally drip 0.15 gram, the i.e. triethylamine of 1.47 mmoles, ice bath stirred overnight at room temperature is removed after all adding, after reaction terminates, enough water is added in reaction solution, isolate organic layer, water layer methylene dichloride back extraction twice, organic layer after merging respectively washes one time with saturated sodium bicarbonate and saturated sodium-chloride respectively, anhydrous magnesium sulfate drying, suction filtration, removal of solvent under reduced pressure, resistates is through 200 ~ 300 order purification by silica gel column chromatography, eluent is petrol ether/ethyl acetate=2/1 of 60 ~ 90 degrees Celsius, obtain yellow solid XI, yield 56%,

The method being prepared intermediate X II by intermediate X I is as follows:

0.24 gram is added successively in 100 milliliters of single necked round bottom flask, the i.e. intermediate X I of 0.48 mmole, 0.049 gram, the i.e. triethylamine of 0.48 mmole, with 20 milliliters of anhydrous alcohol solutions, in 80 degrees Centigrade back flow reaction 2 hours, desolventizing is removed by concentrated for reaction solution after having reacted, resistates 20 ml waters and 20 milliliters of methylene dichloride dissolve, separate organic layer, organic layer saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains through 200 ~ 300 order purification by silica gel column chromatography sherwood oil=1/4 that intermediate X II eluent volume ratio is ethyl acetate/60 ~ 90 degree Celsius cut, by gained sterling calculated yield, yield 61%,

The method being prepared thiazolone oxime ether derivative VI by intermediate X II is as follows:

0.42 gram is added successively in 100 milliliters of two mouthfuls of round-bottomed flasks, the i.e. intermediate X II of 0.82 mmole, 0.14 gram, the i.e. potassium tert.-butoxide of 1.22 mmoles and the Tetrabutyl amonium bromide of 10 milligrams, with 20 milliliters of tetrahydrofuran (THF)s and 4 milliliters of N, dinethylformamide dissolves, nitrogen protection, stirring at room temperature is after 10 minutes, 0.15 gram is added in reaction, the i.e. propargyl bromide of 1.22 mmoles, stirring at room temperature reacts 2 hours, react rear reaction solution 20 milliliters of chloroforms and wash one time, separate organic layer and wash 3 times with saturated sodium bicarbonate successively, saturated common salt washes one time, anhydrous sodium sulfate drying, suction filtration, rotary evaporation is except desolventizing, resistates obtains thiazolone oxime ether derivative VI through 200 ~ 300 order purification by silica gel column chromatography, eluent volume ratio is sherwood oil=1/5 of ethyl acetate/60 ~ 90 degree Celsius cut, yield 63%.

3. thiazolone oxime ether derivative according to claim 1 is preparing the purposes in sterilant.

4. thiazolone oxime ether derivative according to claim 1 is preparing the purposes in sterilant.

5. thiazolone oxime ether derivative according to claim 1 is preparing the purposes in resisting tobacco mosaic virus agent.

6. thiazolone oxime ether derivative according to claim 1 is preparing the purposes in activating plants agent.

7. thiazolone oxime ether derivative according to claim 1 and agriculturally acceptable auxiliary agent and as follows one or more commodity insecticide compositions preparing the purposes in compounded pesticides, described commodity sterilant is selected from: Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, esfenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-cyfloxylate, cyfloxylate, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron and noviflumuron, its CAS 121451-02-3, flucycloxuron, Novaluron and Rimon, chlorfluazuron, Bay sir 6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron and bistrifluron, furan tebufenozide, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, Cupric sulfate, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, to rattle away young ketone, Nylar, emaricin, the total mass percentage of thiazolone oxime ether derivative according to claim 1 in gained compounded pesticides is 1%-90%, and the ratio of thiazolone oxime ether derivative according to claim 1 and described commodity sterilant is mass percent 1%: 99% to 99%: 1%, the formulation that described compounded pesticides is suitable for is selected from seed treatment emulsion, aqueous emulsion, large granula, microemulsion, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, seed treatment suspension agent, smog sheet, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, microgranules, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, seed coat agent, basting agent, fritter poison bait, suspension emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, any one in wet-mixing kind water-dispersible powder, the plant that described compounded pesticides is suitable for is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, apple, citrus, peach, tea, wild vegetable, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape, the insect pest of described compounded pesticides control is selected from Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), singly sting mole cricket, Oriental burmeister, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipe thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, sugarcane flat angle plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hangs cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, Soybean stem borer, frit fly, plant fly, onion fly, radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm.

8. any one in thiazolone oxime ether derivative according to claim 1 and acceptable auxiliary agent agriculturally and following commodity bactericide or multiple combination are in the purposes of preparing in composite bactericide, described commodity bactericide is selected from diazosulfide, tiadinil, first thiophene lures amine, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-Ethyl formate, 4-bromomethyl-1,2,3-thiadiazoles-5-Ethyl formate, 4-iodomethyl-1,2,3-thiadiazoles-5-Ethyl formate, 4-bromomethyl-5-methyl isophthalic acid, 2,3-thiadiazoles, 4-iodomethyl-5-methyl isophthalic acid, 2,3-thiadiazoles, 4,4-dibromo methyl isophthalic acid, 2,3-thiadiazoles-5-Ethyl formate, 3,4-, bis-chloroisothiazoles-5-formic acid, 3,4-, bis-chloroisothiazoles-5-sodium formate, 3,4-, bis-chloroisothiazoles-5-Ethyl formate, DL-beta-aminobutyric acid, isotianil, virazole, antofine, Ningnanmycin, first thiophene lures amine, salicylic acid, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, frost urea cyanogen, thiram, ziram, Mancozeb, aliette, thiophanate-methyl, Bravo, enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, salicylic acid, flumorph, dimethomorph, mefenoxam, benalaxyl-M, two chlorine zarilamids, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, pyraclostrobin, oxime bacterium ester, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, Cyproconazole, Difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, own azoles alcohol, glyoxalin, plant bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Triadimenol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, Grandox fumigant, octhilinone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, Fenarimol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, IBP, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, carbendazim, benomyl,Thiophanate-methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, difoltan, captan, folpet, vinclozolin, fluoromide, dimethachlon, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, Mancozeb, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the pungent salt of biguanides, iminoctadine, botran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium, enemy's line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, isazofos, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole, the total mass percentage of thiazolone oxime ether derivative according to claim 1 in gained composite bactericide is 1%-90%, and the ratio of thiazolone oxime ether derivative according to claim 1 and described commodity bactericide is mass percent 1%: 99% to 99%: 1%, the applicable formulation of described composite bactericide is selected from any one in following dosage forms: wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, Seed Treatment emulsion, aqueous emulsion, large granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, Seed Treatment suspending agent, smog sheet, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/agent of mixing dress, medicine paint, Seed Treatment liquor, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, liniment, suspended emulsion, film forming finish, soluble powder, Seed Treatment water solube powder, ultra-low volume suspending agent, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water-dispersible powder, the applicable plant of described composite bactericide is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape, the applicable controlling disease of described composite bactericide is selected from: wheat rust, wheat scab, wheat powdery mildew, wheat virus disease, wheat avenge mould leaf blight, wheat wriggle spore leaf spot, flag smut of wheat, take-all, wheat sharp eyespot, wheat downy mildew,The late blight of potato, wart of potatoes, potato scab, target, bacterial ring rot o potato, potato bacterial wilt, blakleg of potato, Potyvirus and viroid disease, bacterial soft rot of potato, dry rot of potato, potato verticillium wilt, black scurf of potato, potato bacterial wilt, bacterial ring rot o potato, blakleg of potato, bacterial soft rot of potato, cotton wilt, cotton verticillium wilt, angular leaf spot of cotton, red leaf blight, cotton seedling blight, cotton samping off, cotton anthracnose, cotton spoting verticillium wilt, cotton anthracnose, cotton spoting verticillium wilt, rice blast, rice sheath blight disease, water rice brown spot, small round sclerotial disease of rice, bakanae disease of rice, downymildewofrice, rice green smut, rice leaf sheath rot, bacterial blight of rice, bacterial leaf streak of rice, Characters of Erwinia chrysanthemi pv. zeae, stripe disease, black streaked dwarf virus of rice, paddy rice rice black sclerotium stalk rot, the leaf blight of corn, corn southern leaf blight, Helminthosporium carbonum, maize brown spot, maize sheath blight, corn rust, maize head smut, Corn Stalk Rot, corn smut, corn dry rot, maize virus disease and corn stalk rot disease, sclerotinia rot of colza, Rape virus disease, oilseed rape downy mildew, white rust of colza, root rot, soybean sclerotinia crown rot, grey speck of soybean, soybean Mosaic, soy bean cyst roundworm, root-knot nematode, soybean rust, soybean anthracnose, bacterial pustule of soybean, soybean spot blight, downy mildew, bacterial wilt of peanut, Diplodia gossypina, Roots of Peanut maize ear rot, the cercospora brown spot of peanut, Peanut Web Blotch Disease, activity of peanuts disease, Peanut Scab, tobacco bacterial wilt, wildfire, tobacco hollw stalk, Tobacco Angular Leaf Spot Disease, black shank, Alternaria alternate, frog-eye leaf spot of tobacco, anthracnose of tobacco, black root of tobacco, fusarium tabacinum root rot, Tobacco seedling diseases, tobacco damping-off, the tattered leaf spot of tobacco, Powdery Mildew in Tobacco, tobacco southern blight, tobacco black spot, tobacco mosaic disease, cucumber mosaic virus, etch virus of tobacco, Chinese cabbage downy mildew, soft rot of cabbage, Chinese cabbage Tipburn Disease, Chinese cabbage virosis, Cabbage Leaf Spot, Seed detection, Chinese cabbage anthracnose, cabbage clubroot, bacterial spot of tomato, tomato late blight, tomato blossom-end rot, tomato powdery mildew, tomato samping off, tomato fish pelargonium mosaic disease, tomato bacterial speck, tomato yellow leaf curl virus, leaf muld of tomato, tomato virus disease, tomato late blight, tomato samping off and damping-off, tomato distortion fruit, tomato perforation fruit, tomato black ring virus disease, tomato rot stem nematodes disease, tamato fruit buphthalmos disease, tomato stain root rot, tomato stain root rot, tomato branch spore fruit rot, tomato heartrot, tomato Rhizopus fruit rot, tomato low temperature obstacle, tomato bolter, tomato physiological leaf curl, tomato samping off, tomato fruit drop disease, tomato bud blight, Tomato soft rot, tomato stem rot, tomato seedling damping-off, tomato sun burn, tomato shot hole, tomato rouge and powder disease, tomato virus disease, tomato cracked fruit, canker of tomato, the rotten fruit of tomato navel, tomato sesame pinta bacterium, bacterial spot of tomato, tomato rot leaf viral disease, tomato yellow leaf curl virus disease, eggplant cotton disease, eggplant sclerotiniose, eggplant bacterial wilt, eggplant Phomopisis vexans, eggplant verticillium wilt, eggplant leaf spot,Eggplant early blight, eggplant virosis, eggplant leaf spot disease, eggplant leaf mold, eggplant powdery mildew, eggplant spot disease, eggplant coal spot disease, cercospora leaf spot of egg plant, helminthosporium leaf blight and fruit rot of egg plant, eggplant epidemic disease, eggplant anthracnose, eggplant head mold soft rot, wilt of eggplant, grey mould of egg plant, stem of eggplant basal stem rot, capsicum green pepper virosis, capsicum early blight, capsicum Leucoplakia, pepper white star disease, capsicum leaf spot, capsicum Scald, capsicum sooty mold, capsicum wilt, capsicum sclerotiniose, capsicum sunscald, pepper virus disease, capsicum malformed fruit, capsicum blossom-end rot, capsicum soft rot, bacterial spot of pepper, capsicum bar virus scab, capsicum pythium rot, macrosporium leaf spot of red pepper, cayenne pepper spots rot, capsicum black spot, capsicum verticillium wilt, pepper bacterial leaf spot, capsicum brown rot, Fusarium solani, capsicum damping-off, pepper anthracnose, capsicum brown spot, capsicum downy mildew, Botrytis cinerea, capsicum leaf blight, pepper leaf mold, capsicum samping off, capsicum epidemic disease, downy mildew of garpe, uncinula necator, brown spot of grape, grapevine leafroll disease, Grapevine Fan Leaf Virus Disease, grape rust, grape ring spot, grape leaf pinta, the little brown spot of grape, grape zonate spot, light grey and pinkish pinta, grape young sprout wasting disease, grape flower leaf disease, grape wasting disease, grape stripe disease, the golden yellow disease of grape, grape infectivity is downright bad sick, the yellow point of grape is sick, grape lug disease, grape vein is downright bad sick, Grapevine fleck virus disease, grape star-of-bethlehem leaf disease, grape Pearls, fruit white rot of grape, bitter rot or anthracnose of grape, grape room rot, grape grey mould, grapevine anthracnose, black rot of grape, the large room of grape rot, grape coal point is sick, grape is brown sick, grape is mould dirty sick, grape bitter rot, grape branch spore rot, grape penicilliosis, grape Alternaria rot, apple tree canker, dry rot of apple, ring rot of apple, apple branch canker, apple blister canker, Pink Disease of Apple, dried apple slices rot, apple branch-rot, apple anthracnose, Apple Mould Core, rust of apple (Gymnosporangium yamadai), apple flower maize ear rot, apple brown rot, black fruit rot of apple, apple phytophthora rot, Apple Sooty, sick apple marssonina leaf spot, alternaria leaf spot of apple, Glomerella cingulata, apple graywall, apple mildew, scab of apple, silver leaf of apple, apple infectivity root rot, armillariella root rot of apple, apple Root―rot disease, apple southern blight, apple violet root rot, rosellinia trunk rot of apple, Apple crown gall, apple decline disease, apple rough skin disease, apple mosaic, apple green wrinkle fruit disease, apple fruit-shrink disease, Apple little leaf, apple chlorosis, apple bitter pit, apple water core, apple superficial scald, carbuncle apple scab, Gold Delicious apple fruit russeting, green mold of apple, apple soft rot, Apples digested tankage is continuous sick, apple pulp brown stain disease, apple brown heart, pear scab, black rot of pear, Fungus of Pear Canker Disease, pears southern blight, pear tree wood rot, pears die back disease, rust of pear, Pear black spot, pears graywall, pears brown spot, pears Socty Blotch And Greasy Blotch, pears top rot, pears fruit-shrink disease, pears yellowtop, anthracnose of peach, the real maize ear rot of peach, peach fruit rot, peach soft rot, peach canker, peach powdery mildew, peach brown rot, peach scab, the abnormal fruit disease of peach, peach sooty mould, peach leaf-curl, peach fungoid shothole disease, peach Bacterial septicaemia syndrome, peach leaves pinta, peach leaf rust,Peach mosaic disease, peach red-leaf disease, peach rot, peach gummosis, peach wood rot, peach die back disease, Peach crown gall, peach root rot, peach root knot nematode disease, Citrus Huanglongbing pathogen, exocortis, the broken leaf disease of oranges and tangerines, citrus decline, Satsuma dwarf virus, citrus bacterial canker disease, citrus scab, citrus anthracnose, oranges and tangerines foot rot, oranges and tangerines resin disease, oranges and tangerines bleeding disease, Citrus fuliginous, oranges and tangerines powdery mildew, oranges and tangerines fat point maculopathy, oranges and tangerines are intended fat point maculopathy, the red clothing disease of oranges and tangerines, oranges and tangerines felt fungus, oranges and tangerines seedling blight, oranges and tangerines seedling epidemic disease, banana bunchy top disease, Banana Mosaic Disease, research of fusarium wilt disesase of banana, Cercospora musae bacterium leaf spot, the dark two mould leaf spots of spore of banana, the mould leaf spot of the little Dou Shi of banana, banana freckle, Banana Leaf seasonal febrile diseases, banana anthracnose, banana crown rot, wild cabbage bacterial black rot, cottony rot of cabbage, cabbage black rot, black spot of cabbage, wild cabbage brown spot, wild cabbage blastomere disease, wild cabbage virosis, wild cabbage soft rot, wild cabbage is bolting disease in advance, cabbage downy mildew, wild cabbage anthracnose, black leg of cabbage, sugarcane pineapple disease, smut of sugarcane, sugarcane ratoon stunting disease, sugarcane brown streak, sugarcane rust, jowar smut, jowar leaf spot, jowar anthracnose, jowar leaf blight, jowar virosis.

9. thiazolone oxime ether derivative according to claim 1 and agriculturally acceptable auxiliary agent and preparing the purposes in composite anti-plant virus agent, activating plants agent with any one or multiple combination in following commodity antiviral agent, described commodity antiviral agent is selected from: diazosulfide, tiadinil, first thiophene lures amine, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 4-brooethyl-1, 2, 3-thiadiazoles-5-ethyl formate, 4-iodomethyl-1, 2, 3-thiadiazoles-5-ethyl formate, 4-brooethyl-5-methyl isophthalic acid, 2, 3-thiadiazoles, 4-iodomethyl-5-methyl isophthalic acid, 2, 3-thiadiazoles, 4, 4-dibromo methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazole-5-formic acid, 3, 4-bis-chloroisothiazole-5-sodium formiate, 3, 4-bis-chloroisothiazole-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, first thiophene lures amine, Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, jingganmycin, the total mass percentage of thiazolone oxime ether derivative according to claim 1 in the composite anti-plant virus agent of gained, activating plants agent is 1%-90%, and the ratio of thiazolone oxime ether derivative according to claim 1 and described commodity antiviral agent is mass percent 1%: 99% to 99%: 1%, described composite anti-plant virus agent, the formulation of activating plants agent is selected from wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, large granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, seed treatment suspension agent, smog sheet, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, basting agent, suspension emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, any one in wet-mixing kind water-dispersible powder, described composite anti-plant virus agent, the plant that activating plants agent is suitable for is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, apple, citrus, peach, tea, wild vegetable, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape, the virus disease that described composite anti-plant virus agent, activating plants agent are suitable for is selected from any one in rice dwarf virus disease, yellow dwart, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease, tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, cybidium ring spot virus.

10. thiazolone oxime ether derivative according to claim 1 and agriculturally acceptable auxiliary agent and preparing Compositional acaricide with any one or multiple combination in following commodity miticide and preventing and treating the purposes in plant mites evil, described commodity miticide is selected from azocyclotin, cyhexatin, fenbutatin oxide, three phosphor tins, Zaprawa enolofos, dimethylvinphos, crotoxyphos, SD-1750, heptenopos, Phosdrin, monocrotophos, naled, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, essence lambda-cyhalothrin, Fenvalerate, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, F-1991, sok, carbofuran, carbosulfan, meta-tolyl-N-methylcarbamate (MTMC), promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, pyridaben, thiazolone oxime ether derivative according to claim 1 is 1%-90% at gained Compositional acaricide total mass percentage in the composition, and thiazolone oxime ether derivative according to claim 1 and the acaricidal ratio of described commodity are mass percent 1%: 99% to 99%: 1%, the formulation of described Compositional acaricide is selected from wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, large granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, seed treatment suspension agent, smog sheet, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, basting agent, suspension emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, any one in wet-mixing kind water-dispersible powder, the plant that described Compositional acaricide is suitable for is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, apple, citrus, peach, tea, wild vegetable, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape, the mite evil that described Compositional acaricide is suitable for is selected from the harmful mite of Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae, tetranychus telarius genus, Eriophyidae, and these evil mites are worldwide Agricultural Mites, forestry harmful mites, gardening evil mite and health evil mite.