CN104650059B

CN104650059B - A kind of thiazolone oxime ether derivative and its preparation method and application

Info

Publication number: CN104650059B
Application number: CN201410809127.8A
Authority: CN
Inventors: 范志金; 李凤云; 王海霞; 朱玉洁; 郭晓凤; 宗广宁; 陈来; 钱晓琳; 马刘勇; 宋胤奇; 徐京华; 王家然
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 2014-12-17
Filing date: 2014-12-17
Publication date: 2018-06-22
Anticipated expiration: 2034-12-17
Also published as: CN104650059A

Abstract

The present invention provides a kind of thiazolone oxime ether derivatives and its preparation method and application, and the present invention relates to isothiazole oximido ether compounds, they have the chemical structure of general formula as shown in VI.

Description

A kind of thiazolone oxime ether derivative and its preparation method and application

Technical field

Technical scheme of the present invention is related to the oxime ether derivative containing thiazolone, and in particular to 2- piperidines thiazol -4-one oximes Ether derivative.

Background technology

Heterocyclic compound is the mainstream of current new drug development, and in heterocyclic compound based on nitrogen heterocyclic ring.Thiazoles Compound is a kind of important nitrogenous sulfur heterocyclic compound, has desinsection, weeding, sterilization, the anti-inflammatory and biology such as antitumor living Property (it wears red, waits the synthesis of the novel pyrazol oxime ether derivatives containing thiazole ring of and its bioactivity organic chemistry, 2013,33： 1104-1107.), highly important role is play in human health care and agricultural production.What success both at home and abroad was developed contains thiazole The pesticide new variety of ring structure has insecticide clothianidin, fungicide benzene metsulfovax etc..

Oxime ether derivatives are a kind of compounds with excellent bioactivity, are not only had a wide range of applications in medicine, It is also a kind of important reactive compound on pesticide.Related oxime ether reactive compound, having a large amount of reports both at home and abroad, (Song is precious Peace, waits the synthesis of oxime derivatives and the progress organic chemistry of pesticide bioactivity, 2005,25 (5)：507-525.), Also there are many commodity simultaneously to come out, for example, to downy mildew effective cymoxanil (cymoxanil), have to northern house and housefly compared with The insect growth regulator, IGR S-21149 and S-21150 of high activity, the fenpyroximate quite high to pears red spider, citrus red mite activity (fenpyroximate), there is the propaquizafop of preferable preventive effect to many main annual and perennial grassy weeds (propa quizafop) etc. (model is built, and waits the progress moderns of the biologically active oximido ether compounds of, 2008,7 (2)：6-11.).Oxime ether structure is introduced in frequently as good pharmacophore in parent compound molecule, to improve it Bioactivity.

Oxime ether group is introduced into thiazole compound by the present invention using the principle of pesticide molecule design, and design has synthesized one Thiazolone oxime ether derivative of the class containing piperidine ring, and the bioactivity screening of system has been carried out, to the initiative for novel pesticide More efficient candidate compounds are provided.

Invention content

The technical problems to be solved by the invention are：The synthetic method of new thiazolone oxime ether derivative is provided, is provided This kind of compound modulates agricultural, gardening and health and the bioactivity and its measure side of forestry plant pest and the phytopathy original Method, while middle application of these compounds in agriculture field, horticultural field, field of forestry and health field is provided.

Technical solution is used by the present invention solves the technical problem：With agriculture field, horticultural field, forestry and The thiazole ketoxime ether that health field insecticidal activity, bactericidal activity, anti-phytoviral activity, induction plant generate anti-disease activity spreads out The chemical structure of general formula of biology is shown in Formula IV：

Wherein, R is selected from tertbutyloxycarbonyl, the bromo- 1- of H, HHCl, 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- carbonyls； R¹Selected from methyl, 3,4- Dimethoxyphenyls；R²Selected from hydrogen, propargyl, 2- chloropyridine -5- methylene, chloro- 1,2,3- thiophenes two of 5- Azoles -4- methylene, 3- phenyl -2- propine -1- bases, hepta-fluoroiso-propyl, 3,4-, bis- chloroisothiazole -5- methylene.

The synthetic method of the 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- bases) -1H- pyrazoles -5- carbonyls； R¹Selected from methyl, 3,4- Dimethoxyphenyls；R²Selected from hydrogen, propargyl, 2- chloropyridine -5- methylene, chloro- 1,2,3- thiophenes two of 5- Azoles -4- methylene, 3- phenyl -2- propine -1- bases, hepta-fluoroiso-propyl, 3,4-, bis- chloroisothiazole -5- methylene；X is selected from Cl, Br.

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

When R is the bromo- 1- of 3- (3- chloropyridine -2- base -1H- pyrazoles -5- carbonyls, R¹For methyl, R²For propargyl, when X is Br, The synthetic method of the thiazolone oxime ether derivative VI of the present invention is as follows：

It is specifically divided into following steps：

A. the preparation of intermediate II：

1.00 grams, i.e., 3.20 mMs of I are added in 100 milliliters of two mouthfuls of round-bottomed flasks, with 20 milliliters of dichloromethane Dissolving, rear to add in 0.36 gram, i.e., 3.52 mMs of triethylamine, nitrogen protection is stirred at room temperature, is added in after ten minutes into reaction 0.68 gram, i.e., 3.52 mMs 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides are abbreviated as EDCI, finally 10 milligrams of 4-dimethylaminopyridine is added in, is stirred overnight at room temperature, reaction solution is washed one time with 30 milliliters after having reacted, and has been separated Machine layer is washed one time with saturated sodium-chloride, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 Mesh silica gel column chromatography purifies to obtain intermediate II, and eluant, eluent volume ratio is the petroleum ether of ethyl acetate/60~90 degree Celsius fraction =1/4；With gained sterling calculated yield, yield 90-100%；Amount and the volume of reaction vessel prepared by intermediate II is by corresponding Ratio is expanded or shunk.

B. the preparation of intermediate III：

0.77 gram is added in 100 milliliters of two mouthfuls of round-bottomed flasks, i.e., 2.17 mMs of intermediate II, nitrogen is protected, instead System is answered to vacuumize, 20 milliliters of dry tetrahydrofurans are added in into reaction, react on -78 degrees Celsius of stirrings, backward reactant 1.08 mMs of methyl-magnesium-bromide or 3,4- Dimethoxyphenyl magnesium bromide are slowly added dropwise in system, is taken the photograph after being added dropwise -78 Continue stirring 1 hour under family name's degree, after be stirred at room temperature instead 1 hour, react in backward reaction solution the saturation chlorine of 30 milliliters of addition Change ammonium salt solution and 30 milliliters of ethyl acetate, stirring separates organic layer afterwards a little while, and organic layer is washed one time with saturated sodium-chloride, anhydrous Sodium sulphate is dried, and is filtered, and rotary evaporation removes solvent, and residue purifies to obtain intermediate through 200~300 mesh silica gel column chromatographies III, eluant, eluent volume ratio are petroleum ether=1/4 of ethyl acetate/60~90 degree Celsius fraction；With gained sterling calculated yield, Yield 80-93%；Amount and the volume of reaction vessel prepared by intermediate III is expanded or shunk by corresponding proportion.

C. the preparation of intermediate compound IV：

Sequentially add 0.50 gram in 100 milliliters of single necked round bottom flask, i.e., 1.61 mMs of intermediate III, 0.16 gram, I.e. 1.61 mMs of triethylamine is dissolved with 20 milliliters of absolute ethyl alcohols, in 80 degrees Centigrade back flow reaction 2 hours, has been reacted Reaction solution is concentrated afterwards and removes solvent, 20 milliliters of water of residue and 20 milliliters of dichloromethane dissolvings separate organic layer, organic layer Saturated common salt is washed one time, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silica gel Column chromatography purifies to obtain intermediate compound IV, and eluant, eluent volume ratio is petroleum ether=1/3 of ethyl acetate/60~90 degree Celsius fraction； With gained sterling calculated yield, yield 79-90%；Amount and the volume of reaction vessel prepared by intermediate compound IV is expanded by corresponding proportion Or it reduces.

D. the preparation of intermediate V

Sequentially add 0.36 gram in 100 milliliters of two mouthfuls of round-bottomed flasks, i.e., 1.10 mMs of intermediate compound IV, 0.19 gram, I.e. 1.66 mMs of potassium tert-butoxide and 10 milligrams of tetrabutylammonium bromide, with 20 milliliters of tetrahydrofurans and 4 milliliters of N, N- diformazans Base formyl amine solvent, nitrogen protection, is stirred at room temperature after ten minutes, is added in into reaction defined in 1.66 mMs of the present invention Different halides, be stirred at room temperature reaction 2 hours, react afterwards reaction solution washed one time with 20 milliliters of chloroforms, separate organic layer according to Secondary to be washed 3 times with saturated sodium bicarbonate, saturated common salt is washed one time, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, Residue purifies to obtain intermediate V through 200~300 mesh silica gel column chromatographies, and according to the difference of product, eluant, eluent volume ratio is acetic acid Petroleum ether=1/3 to 1/1 of ethyl ester/60~90 degree Celsius fraction；With gained sterling calculated yield, yield 47-91%；Intermediate Amount and the volume of reaction vessel prepared by V is expanded or shunk by corresponding proportion.

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：

10 mMs of intermediate V is placed in 100 milliliters of two-mouth bottles, is dissolved with 20 milliliters of dry dichloromethane, nitrogen Gas shielded, ice bath stirring, into reaction system, the trifluoroacetic acid of 4 milliliters of dropwise addition, is stirred at room temperature 1 hour after being all added dropwise, The sodium hydroxide that 1 mol/L is added dropwise in backward reaction solution has been reacted, pH value is adjusted to separate organic layer, organic layer is used full to 10 or so Primary with salt washing, anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silicagel columns Chromatographic purifying obtains intermediate VI, and eluant, eluent is methylene chloride/methanol, according to product difference, volume ratio 50: 1 to 6: 1；With institute Obtain sterling calculated yield, yield 66-100%；Intermediate VI prepare amount and reaction vessel volume by corresponding proportion expand or It reduces.

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

1 mM of compound V is added in 50 milliliters of single necked round bottom flask, is dissolved with 5 milliliters of absolute methanols, room temperature Stirring, the hydrogen chloride dioxane solutions of 4 excessive mol/Ls are added in into reaction, and room temperature continues stirring 3 hours, reacted Reaction solution directly concentrates removing organic solvent afterwards, and suitable absolute ethyl alcohol is added in into flask, continues concentration and removes a small amount of water, Finally obtain product as light yellow solid VI, yield 100%；Amount and the volume of reaction vessel prepared by compound VI is expanded by corresponding proportion Big or diminution.The chemical constitution and physical and chemical parameter of compound VI is shown in Table 1.

When R for the bromo- 1- of 3- (during 3- chloropyridine -2- base -1H- pyrazoles -5- carbonyls, the system of thiazolone oxime ether derivative VI Preparation Method is as follows：The method that intermediate X I is prepared by intermediate X is as follows：

Sequentially add 0.39 gram in 100 milliliters of two mouthfuls of round-bottomed flasks, i.e., 1.28 mMs of bromo- 1- of 3- (3- chloropyridines- 2- base -1H- pyrazoles -5- carboxylic acids, 0.28 gram, i.e. 1.47 mMs of 1- (3- dimethylamino-propyls) -3- ethyl carbodiimide hydrochlorides Salt is abbreviated as EDCI, 0.17 gram, i.e. 1.28 mMs of I-hydroxybenzotriazoles, is abbreviated as HOBT, vacuumizes, nitrogen protection, 30 milliliters of dichloromethane a heatable brick bed steamed again are added under ice bath into reaction system, ice bath stirring removes ice bath, is stirred at room temperature 1 after five minutes Hour, 0.26 gram be dissolved in 10 milliliters of dry methylene chlorides, i.e. 1.22 mmoles are added in into reaction system under ice bath stirring Your intermediate X, is finally added dropwise 0.15 gram, i.e., 1.47 mMs of triethylamine removes ice bath room temperature after all adding in and stirs It mixes overnight, after reaction, enough water is added in into reaction solution, isolate organic layer, water layer is stripped twice with dichloromethane a heatable brick bed, Organic layer after merging is respectively washed one time respectively with saturated sodium bicarbonate and saturated sodium-chloride, and anhydrous magnesium sulfate drying filters, decompression Solvent is removed, residue is purified through 200~300 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether/acetic acid second Ester=2/1 obtains yellow solid XI, yield 56%；Amount and the volume of reaction vessel prepared by compound XI is expanded by corresponding proportion Or it reduces.

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

Sequentially add 0.24 gram in 100 milliliters of single necked round bottom flask, i.e., 0.48 mM of intermediate X I, 0.049 gram, I.e. 0.48 mM of triethylamine is dissolved with 20 milliliters of absolute ethyl alcohols, in 80 degrees Centigrade back flow reaction 2 hours, has been reacted Reaction solution is concentrated afterwards and removes solvent, 20 milliliters of water of residue and 20 milliliters of dichloromethane dissolvings separate organic layer, organic layer Saturated common salt is washed one time, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silica gel Column chromatography purifies to obtain intermediate X II, and eluant, eluent volume ratio is petroleum ether=1/4 of ethyl acetate/60~90 degree Celsius fraction； With gained sterling calculated yield, yield 61%；Intermediate X II prepare amount and reaction vessel volume by corresponding proportion expand or It reduces.

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

Sequentially add 0.42 gram in 100 milliliters of two mouthfuls of round-bottomed flasks, i.e., 0.82 mM of intermediate X II, 0.14 gram, I.e. 1.22 mMs of potassium tert-butoxide and 10 milligrams of tetrabutylammonium bromide, with 20 milliliters of tetrahydrofurans and 4 milliliters of N, N- diformazans Base formyl amine solvent, nitrogen protection, is stirred at room temperature after ten minutes, 0.15 gram is added in into reaction, i.e., 1.22 mMs of alkynes third Reaction 2 hours is stirred at room temperature in bromide, and reaction solution is washed one time with 20 milliliters of chloroforms after having reacted, and is separated organic layer and is used saturation successively Sodium bicarbonate is washed 3 times, and saturated common salt is washed one time, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, residue warp 200~300 mesh silica gel column chromatographies purify to obtain thiazolone oxime ether derivative VI, eluant, eluent volume ratio for ethyl acetate/60~ Petroleum ether=1/5 of 90 degrees Celsius of fractions, yield 63%；Amount and the volume of reaction vessel prepared by compound VI presses corresponding proportion It expands or shrinks.The chemical constitution and physical and chemical parameter of compound VI is shown in Table 1.

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

The sterilization of the thiazolone oxime ether derivative VI of the present invention or bacteriostatic activity use thalli growth rate measuring method, specifically Step is：1.8 milligrams of samples is taken to be dissolved in appropriate dimethylformamide, then with water-soluble containing a certain amount of polysorbas20 emulsifier Liquid is diluted to the medicament of 500 mcg/mls, and reagent agent is aseptically respectively drawn in 1 milliliter of injection culture dish, then divide Not Jia Ru 9 milliliters of PDA culture mediums, 50 mcg/ml drug containing tablets are made after shaking up, with add 1 milliliter of aqua sterilisa tablet do Blank control cuts bacterium disk along mycelia outer rim with 4 millimeters of card punch of diameter, moves on drug containing tablet, put in equilateral triangle It puts, often processing is repeated 3 times, and culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and is cultivated, and colony diameter to be compareed expands to Each processing bacterium disk extension diameter is investigated after 2-3 centimetres, averages, opposite bacteriostasis rate is calculated compared with blank control, for trying bacterium The kind of most of typical plant pathogen that kind is actually occurred for field in China's agricultural production, code name and title are as follows： AS：Tomato early blight bacterium, Latin are entitled：Alternaria solani、BC：Botrytis cinerea pers, Latin are entitled： Botrytis cinerea、CA：Peanut Cercospora bacteria, Latin are entitled：Cercospora arachidicola、GZ：Wheat is red Mildew bacterium, Latin are entitled：Gibberella zeae、PI：Phytophthora infestans, Latin are entitled：Phytophthora infestans(Mont.)de Bary、PP：Botryosphaeria berengeriana f. sp, Latin are entitled：Physalospora piricola、PS： Rhizoctonia solani Kuhn, Latin are entitled：Pellicularia sasakii、RC：Rhizoctonia cerealis, Latin are entitled： Rhizoctonia cerealis、SS：Sclerotinia sclerotiorum, Latin are entitled：Sclerotinia sclerotiorum.G. originally The inducing anti-disease activity of the thiazolone oxime ether derivative VI of invention measures：

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

(1) positive controls activating plants agent：It is positive control to select tiadinil of the quality purity purity more than 99.5% Activating plants agent；Tiadinil is abbreviated as TDL；

(2) screening technique of the anti-TMV activity of the evoking tobacco of thiazolones oxime ether derivative VI：It is in vitro directly antiviral The measure of activity is carried out using half leaf method；Live body induction is by the consistent common cigarette of seedling age, and 3 basins are one group, 7 before inoculation The tobacco seedlings of its pre-treatment, processing mode include：Spray test compounds solution 2 to 3 times, every time 10 milliliters or soil treatment, 10 milliliters every time, measured concentration is 50 mcg/mls, in frictional inoculation TMV on the tobacco leaf newly grown, tobacco seedlings is placed within the 7th day After being cultivated 3 days under growth preference temperature and illumination, incidence is checked, comprehensive scab number is calculated as follows out for examination chemical combination For object to the induction antiviral effect of TMV, each processing sets 3 repetitions, blank control and standard agent control respectively selection water and TDL：

Wherein, inducing effects of the R for noval chemical compound anti-TMV to tobacco, unit：%；CK is that clear water compares being averaged for blade Withered spot number, unit：It is a；I is that the average withered spot number for handling rear blade is induced through compound, unit：It is a；

Other than carry out the measure of above-mentioned induced activity, the anti-TMV for being carried out at the same time thiazolone oxime ether derivative VI is controlled Treat the measure of activity, passivation activity and protection activity.

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

The thiazolone oxime ether derivative VI of the present invention is as follows to the assay method of aphid cytotoxicity：Using infusion process, Black bean aphid, Latin are entitled：Aphis laburni Kaltenbach (ALK), the normal population of indoor raising；It weighs for examinationization 2.5 milligrams of object is closed in beaker, 1 drop n,N-Dimethylformamide is added dropwise, i.e. DMF adds 5 milliliters of acetone oscillation dissolving samples, then The water that adding in has Tween 80 is configured to the solution to be measured of 100 mcg/mls；The broad bean that supplies to try at least 60 black bean aphids is planted Strain is cut from basin, is impregnated 5 seconds in each liquid to be measured, and extra liquid is gently got rid of in taking-up, is inserted in by water saturation Sponge on moisturizing, on cloche cover after liquid is done, the opening of cloche upper end is sealed with gauze escapes to prevent aphid, raises It supports and aphid death state is checked after placing 48 hours, standard is：It can be creeped or can stood or six Tiao Tuineng strenuous exercises with test worm Be worm living；Using clear water as control, imidacloprid is positive control, calculates corrected mortality.

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

The present invention is by specific preparation and biological activity determination embodiment is more specific illustrates thiazolone oxime ether derivative The synthesis of VI and bioactivity and application, the embodiment, which is only used for illustrating the present invention, to be not intended to limit the present invention, especially Bioactivity is merely illustrative of, and unrestricted this patent, specific embodiment are as follows：

Embodiment 1

The preparation of intermediate II：

1 gram, i.e., 3.20 mMs of I of addition, molten with 20 milliliters of dichloromethane in 100 milliliters of two mouthfuls of round-bottomed flasks Solution, rear to add in 0.36 gram, i.e., 3.52 mMs of triethylamine, nitrogen protection is stirred at room temperature, is added in after ten minutes into reaction 0.68 gram, i.e., 3.52 mMs 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides are abbreviated as EDCI, finally 10 milligrams of 4-dimethylaminopyridine is added in, is stirred overnight at room temperature, reaction solution is washed one time with 30 milliliters after having reacted, and has been separated Machine layer is washed one time with saturated sodium-chloride, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 Mesh silica gel column chromatography purifies to obtain intermediate II, and eluant, eluent volume ratio is the petroleum ether of ethyl acetate/60~90 degree Celsius fraction =1/4；With gained sterling calculated yield, yield 90-100%；¹H NMR(CDCl₃)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, i.e., 2.17 mMs of intermediate II, nitrogen is protected, instead System is answered to vacuumize, 20 milliliters of dry tetrahydrofurans are added in into reaction, react on -78 degrees Celsius of stirrings, backward reactant 1.08 mMs of methyl-magnesium-bromide or 3,4- Dimethoxyphenyl magnesium bromide are slowly added dropwise in system, is taken the photograph after being added dropwise -78 Continue stirring 1 hour under family name's degree, after be stirred at room temperature instead 1 hour, react in backward reaction solution the saturation chlorine of 30 milliliters of addition Change ammonium salt solution and 30 milliliters of ethyl acetate, stirring separates organic layer afterwards a little while, and organic layer is washed one time with saturated sodium-chloride, anhydrous Sodium sulphate is dried, and is filtered, and rotary evaporation removes solvent, and residue purifies to obtain intermediate through 200~300 mesh silica gel column chromatographies III, eluant, eluent volume ratio are petroleum ether=1/4 of ethyl acetate/60~90 degree Celsius fraction；With gained sterling calculated yield, Yield 80-93%；¹H NMR(CDCl₃)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：

Sequentially add 0.5 gram in 100 milliliters of single necked round bottom flask, i.e., 1.61 mMs of intermediate III, 0.16 gram, I.e. 1.61 mMs of triethylamine is dissolved with 20 milliliters of absolute ethyl alcohols, in 80 degrees Centigrade back flow reaction 2 hours, has been reacted Reaction solution is concentrated afterwards and removes solvent, 20 milliliters of water of residue and 20 milliliters of dichloromethane a heatable brick bed dissolvings separate organic layer, organic layer Saturated common salt is washed one time, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silica gel Column chromatography purifies to obtain intermediate compound IV, and eluant, eluent volume ratio is petroleum ether=1/3 of ethyl acetate/60~90 degree Celsius fraction； With gained sterling calculated yield, yield 79-90%；¹H NMR(CDCl₃)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：

Sequentially add 0.36 gram in 100 milliliters of two mouthfuls of round-bottomed flasks, i.e., 1.10 mMs of intermediate compound IV, 0.19 gram, I.e. 1.66 mMs of potassium tert-butoxide and 10 milligrams of tetrabutylammonium bromide, with 20 milliliters of tetrahydrofurans and 4 milliliters of N, N- diformazans Base formyl amine solvent, nitrogen protection, is stirred at room temperature after ten minutes, is added in into reaction defined in 1.66 mMs of the present invention Different halides, be stirred at room temperature reaction 2 hours, react afterwards reaction solution washed one time with 20 milliliters of chloroforms, separate organic layer according to Secondary to be washed 3 times with saturated sodium bicarbonate, saturated common salt is washed one time, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, Residue purifies to obtain intermediate V through 200~300 mesh silica gel column chromatographies, and according to the difference of product, eluant, eluent volume ratio is acetic acid Petroleum ether=1/3 to 1/1 of ethyl ester/60~90 degree Celsius fraction, 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

10 mMs of intermediate V is placed in 100 milliliters of two-mouth bottles, is dissolved with 20 milliliters of dry dichloromethane, nitrogen Gas shielded, ice bath stirring, into reaction system, the trifluoroacetic acid of 4 milliliters of dropwise addition, is stirred at room temperature 1 hour after being all added dropwise, The sodium hydroxide that 1 mol/L is added dropwise in backward reaction solution has been reacted, pH value is adjusted to separate organic layer, organic layer is used full to 10 or so Primary with salt washing, anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silicagel columns Chromatographic purifying obtains intermediate VI, and eluant, eluent is methylene chloride/methanol, according to product difference, volume ratio 50: 1-10: 1；With institute Obtain sterling calculated yield, yield 66-100%.The chemical constitution and physical and chemical parameter of compound VI is shown in Table 1.

1 mM of compound V is added in 50 milliliters of single necked round bottom flask, is dissolved with 5 milliliters of absolute methanols, room temperature Stirring, the hydrogen chloride bis- Evil a heatable brick bed solution of 4 excessive mol/Ls is added in into reaction, and room temperature continues stirring 3 hours, reacted Reaction solution directly concentrates removing organic solvent afterwards, and suitable absolute ethyl alcohol is added in into flask, continues concentration and removes a small amount of water, Finally obtain product as light yellow solid VI, yield 100%；Amount and the volume of reaction vessel prepared by compound VI is expanded by corresponding proportion Big or diminution.The chemical constitution and physical and chemical parameter of compound VI is shown in Table 1.

Sequentially add 0.39 gram in 100 milliliters of two mouthfuls of round-bottomed flasks, i.e., 1.28 mMs of bromo- 1- of 3- (3- chloropyridines- 2- base -1H- pyrazoles -5- carboxylic acids, 0.28 gram, i.e. 1.47 mMs of 1- (3- dimethylamino-propyls) -3- ethyl carbodiimide hydrochlorides Salt is abbreviated as EDCI, 0.17 gram, i.e. 1.28 mMs of I-hydroxybenzotriazoles, is abbreviated as HOBT, vacuumizes, nitrogen protection, 30 milliliters of dichloromethane steamed again are added under ice bath into reaction system, ice bath stirring removes ice bath, is stirred at room temperature 1 after five minutes Hour, 0.26 gram be dissolved in 10 milliliters of dry methylene chlorides, i.e. 1.22 mmoles are added in into reaction system under ice bath stirring Your intermediate X, is finally added dropwise 0.15 gram, i.e., 1.47 mMs of triethylamine removes ice bath room temperature after all adding in and stirs It mixes overnight, after reaction, enough water is added in into reaction solution, isolate organic layer, water layer is stripped twice with dichloromethane, Organic layer after merging is respectively washed one time respectively with saturated sodium bicarbonate and saturated sodium-chloride, and anhydrous magnesium sulfate drying filters, decompression Solvent is removed, residue is purified through 200~300 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether/acetic acid second Ester, volume ratio 2/1 obtain yellow solid XI, yield 56%；¹H NMR(CDCl₃)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).

Sequentially add 0.24 gram in 100 milliliters of single necked round bottom flask, i.e., 0.48 mM of intermediate X I, 0.049 gram, I.e. 0.48 mM of triethylamine is dissolved with 20 milliliters of absolute ethyl alcohols, in 80 degrees Centigrade back flow reaction 2 hours, has been reacted Reaction solution is concentrated afterwards and removes solvent, 20 milliliters of water of residue and 20 milliliters of dichloromethane dissolvings separate organic layer, organic layer Saturated common salt is washed one time, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silica gel Column chromatography purifies to obtain intermediate X II, and eluant, eluent volume ratio is petroleum ether=1/4 of ethyl acetate/60~90 degree Celsius fraction； With gained sterling calculated yield, yield 61%；¹H NMR(CDCl₃)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).

Embodiment 6

The thiazolone oxime ether derivative VI Antibacterial Activity results of the present invention：

The code name and title for the frequently seen plants disease fungus that the present invention tests are as follows：AS：Tomato early blight bacterium, latin name For：Alternariasolani、BC：Botrytis cinerea pers, Latin are entitled：Botrytis cinerea、CA：The cercospora brown spot of peanut Bacterium, Latin are entitled：Cercospora arachidicola、GZ：Fusarium graminearum, Latin are entitled：Gibberella zeae、PI：Phytophthora infestans, Latin are entitled：Phytophthora infestans(Mont.)de Bary、PP：Apple Fruit Target spot pathogen, Latin are entitled：Physalospora piricola、PS：Rhizoctonia solani Kuhn, Latin are entitled： Pellicularia sasakii、RC：Rhizoctonia cerealis, Latin are entitled：Rhizoctonia cerealis、SS：Sclerotina Sclerotiorum in Winter Rape Core germ, Latin are entitled：Sclerotinia sclerotiorum, these strains have representativeness well, can represent The kind for most of pathogen that field occurs in agricultural production.It is worth noting that compound lfy006-39 is patent document The known compound for the high activity reported in WO2008091594, it is living for the biology of the noval chemical compound more of the invention synthesized Property, the closest target compound of the present invention of this structure has been synthesized in of the invention and its activity of patent literature is highest similar Compound lfy006-39.Thalli growth rate method measurement result is shown in Table 2, and table 2 shows in 50 mcg/ml, present invention synthesis All compounds have different degrees of bactericidal activity.For Phytophthora infestans, compound lfy007-7, lfy007-34、lfy007-14、lfy007-31、lfy007-25、lfy007-44、lfy008-27、lfy008-40、lfy008- 41st, for the inhibiting rate of lfy008-1, lfy008-20, lfy008-31 more than 40%, the bactericidal activity of above compound is higher by knot Structure is similar, the active best compound lfy006-39 of document report is more than 10%, wherein compound lfy007-34, The inhibiting rate of lfy008-1, lfy007-25, lfy008-40, lfy008-31, lfy008-20, lfy007-14 more than 50%, Activity is higher than comparison medicament Fluoxastrobin.For peanut Cercospora bacteria, compound lfy007-7, lfy007-34, lfy007-47, The inhibiting rate of lfy008-24, lfy007-31, lfy007-25, lfy007-44, lfy007-39, lfy008-20, lfy007-14 More than 40%, the bactericidal activity of above compound is higher by that structure is similar, the active best compound lfy006-39 of document report More than 10%, wherein the inhibiting rate of compound lfy007-34, lfy007-14, lfy007-44, lfy007-7 60% with On, activity is higher than comparison medicament Fluoxastrobin.For tomato early blight bacterium, compound lfy007-7, lfy007-34, lfy007- 14th, the inhibition of lfy008-46, lfy007-44, lfy008-41, lfy008-31, lfy008-42, lfy009-5, lfy008-1 For rate more than 50%, the bactericidal activity of above compound is higher by that structure is similar, the active best compound lfy006- of document report 39 more than 10%, but less than comparison medicament Fluoxastrobin.For botrytis cinerea pers, compound lfy007-7, lfy007- 34、lfy007-14、lfy008-19、lfy007-44、lfy008-27、lfy008-41、lfy008-31、lfy008-1、 The inhibiting rate of lfy008-46, lfy008-34, fy009-5, lfy009-6, lfy008-42 are more than 50%, wherein compound For the inhibiting rate of lfy007-34, lfy007-14, lfy008-19, lfy008-34 more than 62%, activity is higher than known compound The activity of lfy006-39, compound lfy008-19 are 100%, and activity is higher than comparison medicament Fluoxastrobin and is higher by structure class Seemingly, the best compound lfy006-39 of document report activity is more than 30%.For fusarium graminearum, compound The inhibiting rate of lfy007-7, lfy007-47, lfy008-3, lfy008-40, lfy008-41, lfy008-20, lfy008-1 exist More than 40%, for the wherein inhibiting rate of compound lfy008-40, lfy008-41, lfy008-1 more than 55%, activity is higher by knot Structure is similar, the active best compound lfy006-39 of document report is more than 10%.For Botryosphaeria berengeriana f. sp, compound The inhibiting rate of lfy007-7, lfy007-14, lfy007-31, lfy007-25, lfy008-1, lfy007-44 more than 50%, Activity is higher than higher than known compound lfy006-39, the inhibiting rate of compound lfy007-7, lfy007-14, lfy007-44 60%, activity is higher by that structure is similar, the active best compound lfy006-39 of document report is more than 10%.To rape sclerotium For germ, 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 Inhibiting rate more than 40%, activity be higher by structure is similar, the active best compound lfy006-39 of document report 10% with On, wherein the inhibiting rate of compound lfy007-7, lfy008-38, lfy007-44, lfy007-47 is higher than 80%.To cereal silk For pyrenomycetes, compound lfy007-7, lfy007-34, lfy007-14, lfy007-31, lfy007-25, lfy007-44, The inhibiting rate of lfy008-40, lfy008-1, lfy009-5, lfy009-6, lfy008-46 are more than 40%, wherein compound The activity of lfy008-1 is higher than 80%, and activity is higher by that structure is similar, the active best compound lfy006-39 of document report exists 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- 6th, the inhibiting rate of lfy007-14 is more than 40%, and wherein the inhibiting rate of compound lfy007-7, lfy007-44 is higher than 70%, lives Property higher than known compound lfy006-39, for the inhibiting rate of compound lfy007-44 higher than 80%, it is similar, literary that activity is higher by structure The best compound lfy006-39 of report activity is offered more than 10%.Therefore, the noval chemical compound of present invention design synthesis is due to drawing Enter the difference of substituent group, the bactericidal activity of target compound compared with the similar compound for the high activity reported in patent document, Bactericidal activity has obtained significant raising, this is the place that the invention is different from existing invention.

Embodiment 7

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

The measurement result of TMV activity is shown in Table 3, and table 3 shows that majority of compounds of the invention has preferable anti-TMV's Activity；In 100 mcg/ml, all compounds that the present invention synthesizes have different degrees of anti-TMV activity.In treatment mould Under formula, 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、 The inhibiting rate of lfy008-34, lfy008-38, lfy009-6 are higher than 45%, and activity is higher than 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、lfy009-6 Inhibiting rate higher than 50%, activity be higher by structure is similar, the active best compound lfy006-39 of document report 10% with On, compound lfy007-34, lfy008-32, lfy008-33, lfy008-41, lfy008-1, lfy007-39, lfy008-31 Inhibiting rate higher than 60%, activity is higher than comparison medicament Ningnanmycin.Under passivation pattern, compound lfy007-34, lfy007-14、lfy008-18、lfy008-32、lfy008-27、lfy008-33、lfy008-40、lfy008-31、lfy008- 14th, the inhibiting rate of lfy008-34, lfy008-38 are higher than 40%, activity higher than comparison medicine BTH and activity be higher by structure it is similar, Best compound lfy006-39 is more than 10% for document report activity, wherein compound lfy007-14, lfy008-27, The inhibiting rate of lfy008-40, lfy008-34 are higher than 60%, and activity is higher than comparison medicament SZG-7.In protected mode, compound lfy007-7、lfy008-18、lfy007-25、lfy008-19、lfy008-32、lfy008-3、lfy008-41、lfy008- 31st, the inhibiting rate of lfy008-14, lfy009-6, lfy009-5, lfy008-42 are higher than 62%, and activity is higher than known compound Lfy006-39 and comparison medicament Ningnanmycin, wherein compound lfy007-7, lfy009-6, lfy008-32, lfy008-31, The inhibiting rate of lfy007-25 is higher than 75%, and activity is higher by that structure is similar, the active best compound lfy006-39 of document report 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、 The inhibiting rate of lfy008-1, lfy008-46, lfy008-24, lfy008-38, lfy008-42 are higher than 60%, and activity is higher than control Medicament Ningnanmycin and SZG-7, wherein compound lfy007-34, lfy008-38, lfy007-31, lfy008-19, lfy007- 44、lfy008-27、lfy008-33、lfy008-41、lfy008-31、lfy007-39、lfy008-1、lfy008-46、 The inhibiting rate of lfy008-24, lfy007-47 are higher than 70%, and activity is higher than comparison medicament TDL and known compound lfy006-39, Compound lfy007-34, lfy007-47, lfy007-31, lfy008-27, lfy008-33, lfy008-31, lfy007-39, The inhibiting rate of lfy008-24, lfy008-1 are higher than 80%, and it is similar, literary that activity higher than comparison medicament BTH and activity is higher by structure The best compound lfy006-39 of report activity is offered more than 10%.As it can be seen that the thiazolone oxime ether derivative VI tools of the present invention There is preferable anti-TMV activity.

Embodiment 8

The insecticidal activity result of the 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, and table 4 is visible：It is a concentration of in reagent agent During 100mg/L, after observation acts on 72 hours, and structure of the present invention is closest, the active best compound lfy006- of document report For 39 pairs of aphids substantially without toxic action, the compound having in of the invention has aphid certain toxic action, wherein compound The cytotoxicity of lfy007-14, lfy007-31, lfy007-44, lfy007-39, lfy008-20 are more than 20%, respectively 26.79%th, 26.81%, 28.15%, 24.95% and 25.00%.

Embodiment 9

The thiazolone oxime ether derivative of the present invention is killed with agriculturally acceptable auxiliary agent and following one or more commodity The purposes in compounded pesticides are prepared is combined in worm agent：

The commodity insecticide is selected from：Chlopyrifos, Asia Nong, Acetamiprid, emamectin benzoate, milbemectin, AVM hereinafter Rhzomorph, pleocidin, fenvalerate, esfenvalerate, cypermethrin, effective cypermethrin, Cyhalothrin, bromine cyanogen chrysanthemum Ester, Fenpropathrin, Beta- cyfloxylates, cyfloxylate, Lambda- Cyhalothrins, Permanone, benzyl chloride Chrysanthemum ester, allethrin, cyhalothrin, Biphenthrin, Permethrin, ethofenprox, flumethrin, fluvalinate, pyrrole worm Quinoline, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin, dinotefuran, clothianadin, Da Tenan, diflubenzuron, goes out at Acetamiprid Young urea, Teflubenzuron, deinsectization are grand, flubenzuron, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron are more Fluorine urea, CAS 121451-02-3, flucycloxuron, Novaluron, that is, Rimon, chlorfluazuron, Bay sir 6874 are { 1- [(bis- chloro- 4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzenes)-ureas of 3.5- }, Bay SIR-8514 be [1- (4- trifluoromethoxies Phenyl) -3- (2- chlorobenzenes)-urea], piperazine worm urea, Bistrifluron, that is, bistrifluron, furan tebufenozide, tebufenozide, chlorine worm acyl Hydrazine, methoxyfenozide, ring tebufenozide, Rogor, flolimat, DDVP, orthene, Hostathion, quinalphos, pyridazine sulphur Phosphorus, isazofos, isoprocarb, sevin, Aphox, MTMC, confer the third prestige, cartap, Bassa, leaf disperse, carbaryl, rosickyite Carbofuran, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, third Carbosulfan, pymetrozine, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, phonamiphos, fluorine worm Nitrile, Cupric sulfate, dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromine worm Nitrile, pyrazinones, etoxazole, tebufenpyrad, rattle away young ketone, Nylar, emaricin；The thiazolone oxime ether derivative of the present invention is in institute The total mass percentage obtained in compounded pesticides is 1%-90%, thiazolone oxime ether derivative of the invention and the quotient The ratio of product insecticide is mass percent 1%: 99% to 99%: 1%；The dosage form that the compounded pesticides are applicable in is selected from seed Handle emulsion, aqueous emulsion, big granula, microemulsion, suspension emulsion, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, Aerosol, blocky 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 stick, seed treatment suspending agent, cigarette Mist piece, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, solid-liquid mix dress agent, liquid liquid mixing fills agent, Solid harl agent, solid/mixing dress agent, medicine paint, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, it is bold and vigorous pour agent, Seed coat agent, liniment, fritter poison bait, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, super-low capacity Measure any one in suspending agent, tracking pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water-dispersible powder；It is described The plant that compounded pesticides are applicable in be selected from paddy, wheat, barley, oat, corn, 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, can Can, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tuber, 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 insect pest of compounded pesticides prevention be selected from Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, Oriental burmeister, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipes thrips, greenhouse Trialeurodes vaporariorum, 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 are flat Angle plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, pears circle A red-spotted lizard, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, rice spider edge Stinkbug, niphe elongata, scotinophora lurida, green rice bug, green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, Casemaking clothes moth, oriental moth, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, diamondback moth, small heart-eating peach worm, the soybean food heart Worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, corn borer, Yellow rice borer, Oeobia undalis, rice leaf roller, snout moth's larva, Notarchaderogata, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, the small bridging of cotton Worm, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point spark, black cutworm, big cutworm, yellow cutworm, steal poison moth, gypsymoth, Palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, cabbage butterfly, pyrameis indica, ramie A Chinese ephedra a kind of butterfly harmful to crop plants, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, casting skin It is moth, the small buprestid beetle of citrus, golden edge buprestid beetle, yellow meal worm, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, black dull Cockchafer, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, Huang are kept Melon, 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 hang cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, wheat Huang and inhale Slurry worm, pachydiplosis oryzae, citrus fruit fly, melonfly, wheat leaf ash are dived fly, Americal rice leaf miner, Soybean stem borer, frit fly, Hylemyia Platura Meigen, green onion Fly, radish fly, full skirt Exorista civilis, corn borer are strict to post fly, armyworm.

Embodiment 10

In the thiazolone oxime ether derivative of the present invention and agriculturally acceptable auxiliary agent and following commodity fungicide Purposes of any one or more combination in composite bactericide is prepared：

The commodity fungicide is selected from diazosulfide, tiadinil, first thiophene and lures amine, 4- methyl-1s, 2,3- thiadiazoles -5- Formic acid, 4- methyl-1s, 2,3- thiadiazoles -5- sodium formates, 4- methyl-1s, 2,3- thiadiazoles -5- Ethyl formates, 4- bromomethyl -1, 2,3- thiadiazoles -5- Ethyl formates, 4- iodomethyls -1,2,3- thiadiazoles -5- Ethyl formates, 4- bromomethyl -5- methyl-1s, 2,3- Thiadiazoles, 4- iodomethyl -5- methyl-1s, 2,3- thiadiazoles, 4,4- dibromo methyl-1s, 2,3- thiadiazoles -5- Ethyl formates, 3,4- Two chloroisothiazole -5- formic acid, 3,4-, bis- chloroisothiazole -5- sodium formates, 3,4-, bis- chloroisothiazole -5- Ethyl formates, DL- beta-aminos Butyric acid, isotianil, virazole, antofine, Ningnanmycin, first thiophene lure amine, salicylic acid, cytosintetidemycin, dichloro-isonicotinic acid, allyl Isothiazole, cymoxanil, thiram, ziram, Mancozeb, aliette, thiophanate-methyl, Bravo, enemy can pine, procymidone, Fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, salicylic acid, flumorph, dimethomorph, mefenoxam, efficient benzene frost Spirit, double chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, ring acyl Bacterium amine, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, second Bacterium profit, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, azoles bacterium amine Ester, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, Cyproconazole, difenoconazole, olefin conversion, efficient alkene azoles Alcohol, epoxiconazole, benzoxazole, Fluquinconazole, Flusilazole, Flutriafol, hexaconazole, glyoxalin, kind bacterium azoles, metconazole, nitrile bacterium azoles, penta bacterium Azoles, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Triadimenol, triticonazole, bitertanol, probenazole, wheat Fringe is peaceful, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, Evil imidazoles, pefurazoate, famoxadones, The spirit of oxazole, hymexazo, Evil frosts, Guardian, Grandox fumigant, octhilinone, benthiozole, dodemorph, butadiene morpholine, ten Morpholine, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, Boscalid, fluopicolide, pyridine bacterium amine, phonetic collarium Amine, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, Fenarimol, nuarimol, chinomethionat, dithianon, ethoxyquin Quinoline, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, Different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, well ridge are mould Element, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, carbendazim, benomyl, thiophanate-methyl, triazolone, Bupirimate, dimethirimol, ethirimol, difoltan, captan, folpet, vinclozolin, fluoromide, sclerotium Only, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, Mancozeb, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, Copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, loop coil bacterium Amine, tricyclazole, triforine, more fruit pyridines, 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, grams hundred Prestige, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole；The thiazolone oxime ether derivative of the present invention is compounded in gained Total mass percentage in fungicide is 1%-90%, and thiazolone oxime ether derivative of the invention is sterilized with the commodity The ratio of agent is mass percent 1%: 99% to 99%: 1%；The dosage form that the composite bactericide is applicable in is in following dosage forms Any one：Wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment breast Agent, aqueous emulsion, big granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, moisture Dissipate property granula, poison grain, aerosol, blocky 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 stick, seed treatment suspending agent, cigarette Mist piece, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, solid-liquid mix dress agent, liquid liquid mixing fills agent, Gu harl agent, medicine paint, seed treatment liquor, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, is sprinkled at solid/mixing dress agent It pours agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, chase after Track pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water-dispersible powder；The plant choosing that the composite bactericide is applicable in From paddy, wheat, barley, oat, corn, 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, fritillaria, rubber, coconut, Oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tuber, 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 controlling disease that the composite bactericide is applicable in is selected from：It is wheat rust, wheat scab, wheat powdery mildew, wheat virus disease, small The compacted spore leaf spot of the mould leaf blights of Mai Xue, wheat, flag smut of wheat, take-all, wheat sharp eyespot, wheat downy mildew, Ma Ling Potato late blight, wart of potatoes, potato scab, target, bacterial ring rot o potato, potato bacterial wilt, horse Bell potato balck shank, Potyvirus and viroid disease, bacterial soft rot of potato, dry rot of potato, potato verticillium wilt, Ma Ling Potato tar spot, 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, rice Bakanae disease, downymildewofrice, rice green smut, rice leaf sheath corruption, bacterial blight of rice, bacterial leaf streak of rice, water Rice bacterial Footrot, stripe disease, black streaked dwarf virus of rice, 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 sclerotiorum, Rape virus disease, rape downy mildew It is disease, white rust of colza, root rot, soybean sclerotinia crown rot, grey speck of soybean, soybean Mosaic, soy bean cyst roundworm, big Beans root-knot nematode, soybean rust, soybean anthracnose, bacterial pustule of soybean, soybean spot blight, downy mildew, peanut are green Blight, Diplodia gossypina, peanut root rot, the cercospora brown spot of peanut, Peanut Web Blotch Disease, activity of peanuts disease, Peanut Scab, tobacco are green Blight, wildfire, tobacco hollw stalk, Tobacco Angular Leaf Spot Disease, tobacco black shank, Alternaria alternate, frog-eye leaf spot of tobacco, tobacco charcoal Subcutaneous ulcer disease, black root of tobacco, fusarium tabacinum root rot, Tobacco seedling diseases, tobacco damping-off, tobacco junk leaf spot, tobacco Powdery mildew, tobacco southern blight, tobacco black spot, tobacco mosaic disease, cucumber mosaic virus, etch virus of tobacco, Chinese cabbage downy mildew, Chinese cabbage Soft rot, Chinese cabbage Tipburn Disease, Chinese cabbage virosis, Cabbage Leaf Spot, Seed detection, Chinese cabbage anthracnose, cabbage clubroot, kind Eggplant bacterial speck, 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 With damping-off, tomato deformation 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, kind Eggplant low temperature obstacle, tomato bolter, tomato physiological leaf curl, tomato samping off, tomato fruit drop disease, tomato bud are withered Disease, 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, tomato navel corruption fruit, tomato sesame pinta bacterium, bacterial spot of tomato, tomato are fainted leaf Virosis, tomato yellow leaf curl virus disease, eggplant cotton disease, eggplant sclerotiniose, eggplant bacterial wilt, eggplant Phomopisis vexans, eggplant are yellow Wither disease, eggplant leaf spot, eggplant early blight, eggplant virosis, eggplant leaf spot disease, eggplant leaf mold, eggplant powdery mildew, eggplant spot Select 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, eggplant base rot disease, capsicum green pepper virosis, capsicum early blight, capsicum Leucoplakia, capsicum White star, capsicum leaf spot, capsicum Scald, capsicum sooty mold, capsicum wilt, capsicum sclerotiniose, capsicum sunscald, capsicum Virosis, capsicum malformed fruit, capsicum blossom-end rot, capsicum soft rot, bacterial spot of pepper, capsicum item virus scab, capsicum pythium rot, Macrosporium leaf spot of red pepper, capsicum spot blight, capsicum black spot, capsicum verticillium wilt, pepper bacterial leaf spot, capsicum brown rot, capsicum Root rot, capsicum damping-off, pepper anthracnose, capsicum brown spot, capsicum downy mildew, Botrytis cinerea, capsicum leaf blight, capsicum Leaf mold, capsicum samping off, capsicum epidemic disease, downy mildew of garpe, uncinula necator, brown spot of grape, grapevine leafroll disease, grape fan Leaf disease, grape rust, grape ring spot, grape leaf spot, the small brown spot of grape, grape zonate spot, grape graywall, grape are new The golden yellow disease of tip wasting disease, grape mosaic disease, grape wasting disease, grape stripe disease, grape, grape infectivity necrosis disease, grape are yellow Select disease, grape ear projection disease, the downright bad disease of grape vein, Grapevine fleck virus disease, the starlike mosaic disease of grape, grape Pearls, Portugal Grape white rot, bitter rot or anthracnose of grape, grape room blight, grape grey mould, grapevine anthracnose, black rot of grape, the big room blight of grape, Grape coal selects that disease, grape are brown to select the mould dirty disease of disease, grape, grape bitter rot, grape branch spore mildew, 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, apple die back disease, apple branch-rot, apple anthracnose, Apple Mould Core, rust of apple (Gymnosporangium yamadai), apple blossom rot, apple Fruit brown rot, black fruit rot of apple, apple phytophthora rot, Apple Sooty, sick apple marssonina leaf spot, alternaria leaf spot of apple, apple wheel Pinta, 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 rust Fruit 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, apple pulp Powder silk floss disease, 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 Maize ear 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, peach reality maize ear rot, peach fruit rot, peach soft rot, peach canker, peach powdery mildew, peach brown rot, peach sore The abnormal fruit disease of scall, 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 disease, peach gummosis, peach wood rot, peach do Blight, Peach crown gall, peach root rot, peach root knot nematode disease, Citrus Huanglongbing pathogen, exocortis, the broken leaf disease of citrus, mandarin orange Tangerine decline disease, Satsuma dwarf virus, citrus bacterial canker disease, citrus scab, citrus anthracnose, citrus foot rot, citrus resin Disease, citrus bleeding disease, Citrus fuliginous, citrus powdery mildew, citrus fat select maculopathy, citrus intends fat and selects the red clothing of maculopathy, citrus Disease, citrus felt fungus, citrus seedling blight, citrus seedling epidemic disease, banana bunchy top disease, Banana Mosaic Disease, banana sickle-like bacteria Droop, Cercospora musae bacterium leaf spot, the banana secretly mould leaf spot of double spores, the mould leaf spots of the small 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, wild cabbage blackspot Disease, wild cabbage brown spot, wild cabbage blastomere disease, wild cabbage virosis, wild cabbage soft rot, wild cabbage bolting disease, cabbage downy mildew, wild cabbage in advance Anthracnose, black leg of cabbage, sugarcane pineapple disease, smut of sugarcane, sugarcane ratoon stunting disease, sugarcane brown streak, sugarcane rust, height Beam smut, jowar leaf spot, jowar anthracnose, jowar leaf blight, jowar virosis.

Embodiment 11

The thiazolone oxime ether derivative of the present invention with agriculturally acceptable auxiliary agent and with following commodity antivirotic In any one or more combination preparing compounding anti-plant virus agent, the purposes in activating plants agent：

The commodity antivirotic is selected from：Diazosulfide, tiadinil, first thiophene lure amine, 4- methyl-1s, 2,3- thiophenes two Azoles -5- formic acid, 4- methyl-1s, 2,3- thiadiazoles -5- sodium formates, 4- methyl-1s, 2,3- thiadiazoles -5- Ethyl formates, 4- bromine first Base -1,2,3- thiadiazoles -5- Ethyl formates, 4- iodomethyls -1,2,3- thiadiazoles -5- Ethyl formates, 4- bromomethyl -5- methyl - 1,2,3- thiadiazoles, 4- iodomethyl -5- methyl-1s, 2,3- thiadiazoles, 4,4- dibromo methyl-1s, 2,3- thiadiazoles -5- formic acid second Ester, 3,4- dichloros confer thiazole -5- formic acid, 3,4-, bis- chloroisothiazole -5- sodium formates, 3,4-, bis- chloroisothiazole -5- Ethyl formates, DL- beta-aminobutyric acids, virazole, antofine, Ningnanmycin, first thiophene lure amine, salicylic acid, cytosintetidemycin, dichloro-isonicotinic acid, allyl Isothiazole, well ridge azanol, jinggangmeisu；The thiazolone oxime ether derivative of the present invention compounds anti-plant virus agent, plant in gained Total mass percentage in object activator is 1%-90%, and thiazolone oxime ether derivative of the invention resists with the commodity The ratio of viral agent is mass percent 1%: 99% to 99%: 1%；The compounding anti-plant virus agent, activating plants agent Dosage form is selected from wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, water Emulsion, big granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, water dispersible grain Agent, poison grain, aerosol, blocky poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, oil Packet aqueous emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog stick, seed treatment suspending agent, smog piece, Smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, harl Gu agent, medicine paint, seed treatment liquor, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, is sprinkled and is poured at solid/mixing dress agent Agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, tracking Any one in pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water-dispersible powder；The anti-phytopathy of compounding The plant that toxic agent, activating plants agent are applicable in be selected from paddy, wheat, barley, oat, corn, 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 Coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tuber, 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 virus disease that the compounding anti-plant virus agent, activating plants agent are applicable in is selected from Rice dwarf virus disease, yellow dwarf, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease, tobacco veinal necrosis virus disease, Any one of maize dwarf mosaic, cauliflower mosaic virus, citrus virosis, cymbidium mosaic virus, cybidium ring spot virus. Embodiment 12

The thiazolone oxime ether derivative of the present invention with agriculturally acceptable auxiliary agent and in following commodity acaricide Any one or more combination preparing Compositional acaricide and its prevention plant mites evil in purposes：

The commodity acaricide is selected from azacyclotin, plictran, fenbutatin oxide, three phosphor tins, chlorfenviphos, dimethylvinphos, bar poison Phosphorus, DDVP, heptenophos, Menite, Azodrin, 2-dichloroethylk dimethyl phosphate, chlopyrifos, Diothyl, imino-formyl chloride sulphur phosphorus, omethoate, enemy kill Phosphorus, Ethodan, malathion, methacrifos, Phosalone, phoxim, methylpyrimidine sulphur phosphorus, quinalphos, sulfotep, Hostathion, Kilval, isocarbophos, acephatemet, propetamphos, dialifos, phosmet, acrinathrin, Biphenthrin, chlorine fluorine cyanogen chrysanthemum Ester, smart gamma cyhalothrin, Fenpropathrin, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, biphenyl hydrazine Ester, fenothiocarb, Aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, benomyl, sok, carbofuran, fourth sulphur gram hundred Prestige, MTMC, promacyl, Carzol, single carbonamidine, medimeform, Amitraz, Spanon, Ergol, fenisobromolate, fourth fluorine mite Ester, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, avermectin, Doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, Rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, Hexythiazox, Envidor, fluacrypyrim, chlorfenizon, propargite, Pyridaben；Total mass percentage of the thiazolone oxime ether derivative of the present invention in gained Compositional acaricide in the composition It is 1%-90%, thiazolone oxime ether derivative of the invention and the acaricidal ratio of the commodity are mass percent 1%: 99% to 99%: 1%；The dosage form of the Compositional acaricide is selected from wettable powder, micro-capsule suspension, dispersible system Agent, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, big granula, microemulsion, oil-suspending agent, the kind with coated pesticidal Son, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, blocky poison bait, sustained-release block, dense poison bait, capsule Granula, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, cigarette Mist cylinder, smog stick, seed treatment suspending agent, smog piece, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, hot mist Solid agent, the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, harl agent, solid/mixing fill agent, medicine paint, seed treatment liquor, fine granule, Oil-dispersing property pulvis, dense jelly, sprinkles and pours agent, liniment, suspended emulsion, film forming finish, soluble powder, seed sheet poison bait Treatment of water-soluble pulvis, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water dispersible Any one in pulvis；The plant that the Compositional acaricide is applicable in is selected from paddy, wheat, barley, oat, corn, sorghum, sweet Potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Xiang Certain herbaceous plants with big flowers, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tuber, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, hill Dish, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape；Mite that the Compositional acaricide is applicable in evil selected from Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae, tetranychus telarius category, Eriophyidae evil mite, these evil mites be worldwide Agricultural Mites, forestry evil Mite, gardening evil mite and hygienic evil mite.

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

Serial number	Compound	PI	CA	AS	BC	GZ	PP	SS	RC	PS
											1	lfy007-7	42.90	75.00	54.50	59.40	41.70	62.90	84.20	42.90	75.00
2	lfy007-34	50.00	62.50	54.50	65.60	25.00	40.00	73.70	50.00	62.50
											3	lfy007-47	22.70	46.70	47.60	37.90	41.70	40.00	83.30	22.70	46.70
4	lfy007-14	53.60	68.80	63.60	65.60	25.00	60.00	71.10	53.60	68.80
											5	lfy007-31	42.90	56.30	40.90	25.00	16.70	54.30	42.10	42.90	56.30
6	lfy008-18	0.00	30.00	15.79	19.44	12.82	9.21	9.86	0.00	30.00
											7	lfy007-25	50.00	43.80	31.80	46.90	8.30	54.30	71.10	50.00	43.80
8	lfy008-19	33.33	12.50	50.00	100	30.43	23.81	0	23.81	31.25
											9	lfy008-32	26.92	25.00	5.26	11.11	15.38	10.53	21.13	26.92	25.00
10	lfy007-44	42.90	81.30	63.60	56.30	0.00	68.60	92.10	42.90	81.30
											11	lfy008-27	47.62	18.75	31.25	55.56	30.43	28.57	27.78	23.81	6.25
12	lfy008-33	7.69	25.00	10.53	13.89	7.69	11.84	8.45	7.69	25.00
											13	lfy008-3	22.73	7.14	26.67	40.00	44.44	39.58	6.38	22.73	7.14
14	lfy008-40	57.14	0.00	12.50	41.67	60.00	24.39	63.41	57.14	0.00
											15	lfy008-41	47.62	31.25	50.00	55.56	78.26	23.81	52.78	0.00	50.00
16	lfy008-31	57.14	31.25	56.25	55.56	30.43	0.00	0.00	23.81	62.50
											17	lfy007-39	32.10	56.30	22.70	34.40	25.00	22.90	44.70	32.10	56.30
18	lfy008-20	71.43	43.75	43.75	100	52.17	23.81	41.67	38.10	31.25
											19	lfy008-1	81.82	14.29	6.67	56.67	55.56	52.08	14.89	81.82	14.29
20	lfy008-24	15.38	50.00	21.05	47.22	30.77	23.68	14.08	15.38	50.00
											21	lfy008-38	14.29	7.14	18.75	16.67	0.00	24.39	85.37	14.29	7.14
22	lfy008-42	23.81	31.25	62.50	52.78	30.43	23.81	13.89	0.00	6.25
											23	lfy008-34	23.81	7.14	0.00	62.50	28.00	36.59	63.41	23.81	7.14
24	lfy009-5	23.81	6.25	50.00	55.56	21.74	23.81	0.00	42.86	31.25
											25	lfy009-6	33.33	31.25	31.25	50.00	30.43	23.81	47.22	47.62	62.50
26	lfy008-14	31.82	21.43	6.67	23.33	0.00	16.67	0.00	31.82	21.43
											27	lfy008-46	38.10	31.25	68.75	61.11	34.78	23.81	27.78	47.62	43.75
28	lfy006-39	10.00	11.11	33.33	61.40	44.83	42.25	31.58	67.50	68.29
											29	Fluoxastrobin	46.88	55.56	75.00	91.18	71.43	100	88.10	84.06	80.77

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

Serial number	Compound	Treatment	Passivation	Induction	Protection
						1	lfy007-7	57.50±2.50	34.19±5.42	64.00±2.00	82.86±7.70
2	lfy007-34	65.00±5.00	47.44±8.97	80.00±6.00	43.73±3.36
						3	lfy007-47	47.50±0.83	17.09±6.68	90.67±2.24	56.97±2.80
4	lfy007-14	40.83±2.50	64.10±7.69	31.00±1.00	42.73±2.73
						5	lfy007-31	58.33±1.67	37.18±6.41	82.00±4.00	25.45±1.82
6	lfy008-18	55.83±4.17	57.69±3.85	12.00±2.00	63.64±3.64
						7	lfy007-25	47.50±2.50	28.21±7.69	11.00±1.00	75.45±2.73
8	lfy008-19	57.50±0.83	26.67±4.00	79.17±4.04	64.55±0.91
						9	lfy008-32	63.89±4.21	58.97±5.13	47.00±3.00	77.58±6.08
10	lfy007-44	52.78±2.74	37.18±1.28	73.00±1.00	49.70±3.36
						11	lfy008-27	29.17±0.83	68.67±0.67	83.33±3.22	53.64±0.91
12	lfy008-33	61.67±1.67	59.33±0.67	83.33±2.45	41.82±4.77
						13	lfy008-3	40.56±3.95	33.33±2.56	61.00±1.00	64.85±4.12
14	lfy008-40	37.50±4.17	69.23±7.69	47.00±1.00	23.03±5.17
						15	lfy008-41	66.67±2.13	16.00±2.67	73.33±9.54	68.18±0.91
16	lfy008-31	69.17±0.83	59.33±0.67	85.83±3.14	82.73±0.91
						17	lfy007-39	80.56±5.78	28.21±7.69	80.00±7.36	50.00±4.55
18	lfy008-20	40.22±0.83	33.54±2.64	43.00±1.93	33.64±5.64
						19	lfy008-1	69.44±2.67	26.92±1.28	86.00±6.72	40.91±4.55
20	lfy008-24	39.17±0.83	25.64±2.56	81.00±3.00	57.27±2.73
						21	lfy008-38	55.00±5.00	42.31±8.97	73.33±1.64	10.00±0.91
22	lfy008-42	1.67±1.67	24.67±2.00	69.17±4.93	68.18±0.91
						23	lfy008-34	52.50±0.83	64.10±7.69	44.00±2.00	43.64±7.64
24	lfy009-5	30.00±1.67	36.44±1.09	23.75±1.25	62.73±2.73
						25	lfy009-6	52.50±5.83	3.56±1.60	50.83±9.08	78.18±1.82
26	lfy008-14	40.83±0.83	46.15±5.13	50.00±4.00	69.09±3.89
						27	lfy008-46	4.44±2.01	35.56±2.64	75.00±4.71	25.45±1.82
28	lfy006-39	40.22±5.65	15.33±0.67	65.00±5.00	71.82±0.91
						29	Ningnanmycin	60.83±2.50	45.64±2.35	28.36±2.99	62.42±4.04
30	TDL	29.17±4.17	89.33±2.67	66.67±6.66	88.48±2.97
						31	BTH	51.67±1.67	35.33±2.00	77.50±2.50	53.94±2.80
32	SZG-7	33.33±3.33	60.26±3.85	48.75±1.25	83.64±4.94

The insecticidal activity (the target death rate (%), 100 mg/litres) of the thiazolone oxime ether derivative VI of 4 present invention of table

Number	Compound	Aphid death rate %	Number	Compound	Aphid death rate %
						1	lfy007-7	4.52	15	lfy008-41	7.95
2	lfy007-34	4.58	16	lfy008-31	18.60
						3	lfy007-47	15.21	17	lfy007-39	24.95
4	lfy007-14	26.79	18	lfy008-20	25.00
						5	lfy007-31	26.81	19	lfy008-1	12.34
6	lfy008-18	3.88	20	lfy008-14	8.30
						7	lfy007-25	2.86	21	lfy008-46	2.94
8	lfy008-19	14.07	22	lfy008-24	6.25
						9	lfy008-32	6.94	23	lfy008-38	0.00
10	lfy007-44	28.15	24	lfy008-42	5.83
						11	lfy008-27	17.69	25	lfy008-34	14.84
12	lfy008-33	3.17	26	lfy009-5	3.94
						13	lfy008-3	12.01	27	lfy009-6	7.42
14	lfy008-40	5.14	28	lfy006-39	4.94

Claims

1. a kind of thiazolone oxime ether derivative, it is characterised in that：With the general structure as shown in Formula IV：

Wherein, R is selected from tertbutyloxycarbonyl, the bromo- 1- of H, HHCl, 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- carbonyls；R¹It is selected from Methyl, 3,4- Dimethoxyphenyls；R²Selected from hydrogen, propargyl, 2- chloropyridine -5- methylene, chloro- 1,2,3- thiadiazoles -4- of 5- Methylene, 3- phenyl -2- propine -1- bases, hepta-fluoroiso-propyl, 3,4-, bis- chloroisothiazole -5- methylene.

2. the synthetic method of thiazolone oxime ether derivative described in claim 1, specific synthetic route are as follows：

3. the synthetic method of thiazolone oxime ether derivative, is divided into following steps described in claim 2：

A. the preparation of intermediate II：

1.00 grams, i.e., 3.20 mMs of I are added in 100 milliliters of two mouthfuls of round-bottomed flasks, is dissolved with 20 milliliters of dichloromethane, 0.36 gram is added in afterwards, i.e., 3.52 mMs of triethylamine, nitrogen protection is stirred at room temperature, adds in 0.68 into reaction after ten minutes Gram, i.e., 3.52 mMs 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides are abbreviated as EDCI, are eventually adding 10 milligrams of 4-dimethylaminopyridine, is stirred overnight at room temperature, and reaction solution is washed one time with 30 milliliters after having reacted, and separates organic layer It is washed one time with saturated sodium-chloride, anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silicon Gel column chromatography eluting to obtain intermediate II, eluant, eluent volume ratio is petroleum ether=1/ of ethyl acetate/60~90 degree Celsius fraction 4；With 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, i.e., 2.17 mMs of intermediate II, nitrogen is protected, reactant System vacuumizes, and 20 milliliters of dry tetrahydrofurans are added in into reaction, react on -78 degrees Celsius of stirrings, in backward reaction system 1.08 mMs of methyl-magnesium-bromide or 3,4- Dimethoxyphenyl magnesium bromide is slowly added dropwise, at -78 degrees Celsius after being added dropwise Under continue stirring 1 hour, after be stirred at room temperature instead 1 hour, react in backward reaction solution the saturated ammonium chloride of 30 milliliters of addition Solution and 30 milliliters of ethyl acetate, stirring separate organic layer afterwards a little while, and organic layer washes one time with saturated sodium-chloride, anhydrous slufuric acid Sodium is dried, and is filtered, and rotary evaporation removes solvent, and residue is purified to obtain intermediate III, be washed through 200~300 mesh silica gel column chromatographies De- agent volume ratio is petroleum ether=1/4 of ethyl acetate/60~90 degree Celsius fraction；With gained sterling calculated yield, yield 80- 93%；

C. the preparation of intermediate compound IV：

Sequentially add 0.50 gram in 100 milliliters of single necked round bottom flask, i.e., 1.61 mMs of intermediate III, 0.16 gram, i.e., 1.61 mMs of triethylamine is dissolved with 20 milliliters of absolute ethyl alcohols, in 80 degrees Centigrade back flow reaction 2 hours, after having reacted Reaction solution is concentrated and removes solvent, 20 milliliters of water of residue and 20 milliliters of dichloromethane dissolvings separate organic layer, organic layer is satisfied It is washed one time with salt, anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silicagel columns Chromatographic purifying obtains intermediate compound IV, and eluant, eluent volume ratio is petroleum ether=1/3 of ethyl acetate/60~90 degree Celsius fraction；With Gained sterling calculated yield, yield 79-90%；

D. the preparation of intermediate V

Sequentially add 0.36 gram in 100 milliliters of two mouthfuls of round-bottomed flasks, i.e., 1.10 mMs of intermediate compound IV, 0.19 gram, i.e., 1.66 mMs of potassium tert-butoxide and 10 milligrams of tetrabutylammonium bromide, with 20 milliliters of tetrahydrofurans and 4 milliliters of N, N- dimethyl Formyl amine solvent, nitrogen protection, is stirred at room temperature after ten minutes, is added in into reaction defined in 1.66 mMs of the present invention not Reaction 2 hours is stirred at room temperature in same halides, and reaction solution is washed one time with 20 milliliters of chloroforms after having reacted, and separates organic layer successively It is washed 3 times with saturated sodium bicarbonate, saturated common salt is washed one time, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, residual Excess purifies to obtain intermediate V through 200~300 mesh silica gel column chromatographies, and according to the difference of product, eluant, eluent volume ratio is acetic acid second Petroleum ether=1/3 to 1/1 of ester/60~90 degree Celsius fraction；With gained sterling calculated yield, yield 47-91%；

E. the preparation of thiazolone oxime ether derivative VI：

10 mMs of intermediate V is placed in 100 milliliters of two-mouth bottles, is dissolved with 20 milliliters of dry dichloromethane, nitrogen is protected Shield, ice bath stirring, into reaction system, the trifluoroacetic acid of 4 milliliters of dropwise addition, is stirred at room temperature 1 hour after being all added dropwise, and reacts The sodium hydroxide of 1 mol/L is added dropwise in complete backward reaction solution, pH value is adjusted to separate organic layer, organic layer is eaten with saturation to 10 or so Salt washing is primary, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silica gel column chromatographies Intermediate VI is purified to obtain, eluant, eluent is methylene chloride/methanol, according to product difference, volume ratio 50: 1-6: 1；With gained sterling Calculated yield, yield 66-100%；

1 mM of compound V is added in 50 milliliters of single necked round bottom flask, is dissolved with 5 milliliters of absolute methanols, room temperature is stirred It mixes, the hydrogen chloride dioxane solutions of 4 excessive mol/Ls is added in into reaction, room temperature continues stirring 3 hours, after having reacted Reaction solution directly concentrates removing organic solvent, and suitable absolute ethyl alcohol is added in into flask, continues concentration and removes a small amount of water, most Product as light yellow solid VI, yield 100% are obtained afterwards.

4. when R is the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- carbonyls, R¹For methyl, R²For propargyl, when X is Br, The synthetic method of thiazolone oxime ether derivative VI described in claim 2, specific reaction route are as follows：

When R is the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- carbonyls, the preparation side of thiazolone oxime ether derivative VI Method is as follows：The method that intermediate X I is prepared by intermediate X is as follows：

0.39 gram is sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks, i.e., 1.28 mMs of the bromo- 1- of 3- (3- chloropyridines -2- Base) -1H- pyrazoles -5- carboxylic acids, 0.28 gram, i.e. 1.47 mMs of 1- (3- dimethylamino-propyls) -3- ethyl carbodiimide hydrochlorides Salt is abbreviated as EDCI, 0.17 gram, i.e. 1.28 mMs of I-hydroxybenzotriazoles, is abbreviated as HOBT, vacuumizes, nitrogen protection, 30 milliliters of dichloromethane steamed again are added under ice bath into reaction system, ice bath stirring removes ice bath, is stirred at room temperature 1 after five minutes Hour, 0.26 gram be dissolved in 10 milliliters of dry methylene chlorides, i.e. 1.22 mmoles are added in into reaction system under ice bath stirring Your intermediate X, is finally added dropwise 0.15 gram, i.e., 1.47 mMs of triethylamine removes ice bath room temperature after all adding in and stirs It mixes overnight, after reaction, enough water is added in into reaction solution, isolate organic layer, water layer is stripped twice with dichloromethane, Organic layer after merging is respectively washed one time respectively with saturated sodium bicarbonate and saturated sodium-chloride, and anhydrous magnesium sulfate drying filters, decompression Solvent is removed, residue is purified through 200~300 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether/acetic acid second Ester=2/1 obtains yellow solid XI, yield 56%；

Sequentially add 0.24 gram in 100 milliliters of single necked round bottom flask, i.e., 0.48 mM of intermediate X I, 0.049 gram, i.e., 0.48 mM of triethylamine is dissolved with 20 milliliters of absolute ethyl alcohols, in 80 degrees Centigrade back flow reaction 2 hours, after having reacted Reaction solution is concentrated and removes solvent, 20 milliliters of water of residue and 20 milliliters of dichloromethane dissolvings separate organic layer, organic layer is satisfied It is washed one time with salt, anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200~300 mesh silicagel columns Chromatographic purifying obtains intermediate X II, and eluant, eluent volume ratio is petroleum ether=1/4 of ethyl acetate/60~90 degree Celsius fraction；With Gained sterling calculated yield, yield 61%；

Sequentially add 0.42 gram in 100 milliliters of two mouthfuls of round-bottomed flasks, i.e., 0.82 mM of intermediate X II, 0.14 gram, i.e., 1.22 mMs of potassium tert-butoxide and 10 milligrams of tetrabutylammonium bromide, with 20 milliliters of tetrahydrofurans and 4 milliliters of N, N- dimethyl Formyl amine solvent, nitrogen protection, is stirred at room temperature after ten minutes, 0.15 gram is added in into reaction, i.e., 1.22 mMs of propargyl Reaction 2 hours is stirred at room temperature in bromine, and reaction solution is washed one time with 20 milliliters of chloroforms after having reacted, and is separated organic layer and is used saturated carbon successively Sour hydrogen sodium is washed 3 times, and saturated common salt is washed one time, and anhydrous sodium sulfate drying filters, and rotary evaporation removes solvent, and residue is through 200 ~300 mesh silica gel column chromatographies purify to obtain thiazolone oxime ether derivative VI, and eluant, eluent volume ratio is taken the photograph for ethyl acetate/60~90 Petroleum ether=1/5 of family name's degree fraction, yield 63%.

5. purposes of the thiazolone oxime ether derivative described in claim 1 in insecticide is prepared.

6. purposes of the thiazolone oxime ether derivative described in claim 1 in fungicide is prepared.

7. purposes of the thiazolone oxime ether derivative described in claim 1 in resisting tobacco mosaic virus agent is prepared.

8. purposes of the thiazolone oxime ether derivative described in claim 1 in activating plants agent is prepared.