CN104650061B - A kind of thiazole aldoxime ether compound and its production and use - Google Patents
A kind of thiazole aldoxime ether compound and its production and use Download PDFInfo
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- CN104650061B CN104650061B CN201410809371.4A CN201410809371A CN104650061B CN 104650061 B CN104650061 B CN 104650061B CN 201410809371 A CN201410809371 A CN 201410809371A CN 104650061 B CN104650061 B CN 104650061B
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
Abstract
The invention provides a kind of thiazole aldoxime ether compound and its production and use, and the present invention relates to isothiazole oximido ether compound, and they have the chemical structure of general formula as shown in I.
Description
Technical field
Technical scheme is related to thiazole and piperidines heterocyclic compounds containing N and containing S, and in particular to thiazole piperidines
The oximido ether compound of aldehyde.
Background technology
Nitrogen-containing heterocycle compound generally has unique bioactivity, hypotoxicity and high absorbability, is medicine and agricultural chemicals
Active structure unit；Nitrogen-containing heterocycle compound is easy to carry out structural modification, it is convenient to introduces various functions base and (opens, wait to contain
The progress petrochemical industries of nitrogen heterocyclic, 2011,40 (6)：1000-8144.).Thiazole ring is a kind of important nitrogenous
Five yuan of heteroaromatics of sulfur heteroatom, its special structure cause thiazole compound in chemistry, pharmacy, biology and material science
Had broad application prospects Deng numerous areas, show that huge Development volue (Cui Shengfeng, waits thiazole compound applications
New research progress Chinese sciences, 2012,42 (8)：1105-1131.).Oxime ether compound has excellent desinsection, sterilizes and remove
Careless activity, many kinds also have the advantages that low toxicity, low-residual；The MOLECULE DESIGN of such compound and synthesis and bioactivity are ground
Study carefully one of focus of pesticides discovery (model is built, and waits to have the progress moderns of the oximido ether compound of bioactivity,
2011,7 (2)：1671-5284.).
Piperidines group is introduced into thiazole compound by the present invention using the principle of pesticide molecule design, and design has synthesized one
Thiazole oxime ether noval chemical compound 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.
The content of the invention
The technical problems to be solved by the invention are：The synthetic method of new thiazole aldoxime ether compound is provided, there is provided
This kind of compound modulates agricultural, gardening and health and the bioactivity and its measure side of forestry plant insect 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 scheme is used by the present invention solves the technical problem：With agriculture field, horticultural field, forestry and
Health field insecticidal activity, bactericidal activity, anti-phytoviral activity, induction plant produce the thiazole aldoxime ethers of anti-disease activity
The general structure of compound is I：
Wherein, A is selected from tertbutyloxycarbonyl, H, HHCl；It is pungent that R is selected from H, 3- phenyl -2- propine -1- bases, propargyl, 2-
Alkynes -1- bases, 2- butine -1- bases, pi-allyl, the thiadiazoles -4- methylene of 5- chloro- 1,2,3-, 2- chloropyridine -5- methylene, 2- second
Oxygen carbonyl methylene；
Chemical structure of general formula can be specifically divided into VI and VII kind forms for the compound of Formulas I：
Wherein, A is selected from tertbutyloxycarbonyl, H, HHCl；It is pungent that R is selected from H, 3- phenyl -2- propine -1- bases, propargyl, 2-
Alkynes -1- bases, 2- butine -1- bases, pi-allyl, the thiadiazoles -4- methylene of 5- chloro- 1,2,3-, 2- chloropyridine -5- methylene, 2- second
Oxygen carbonyl methylene；
The thiazole aldoxime ether compound I of present invention synthetic method is as follows：
Wherein, A is selected from tertbutyloxycarbonyl, H, HHCl；It is pungent that R is selected from H, 3- phenyl -2- propine -1- bases, propargyl, 2-
Alkynes -1- bases, 2- butine -1- bases, pi-allyl, the thiadiazoles -4- methylene of 5- chloro- 1,2,3-, 2- chloropyridine -5- methylene, 2- second
Oxygen carbonyl methylene；
It is specifically divided into following steps：
A. compound III preparation：
7.47 grams are added into 250 milliliters of round-bottomed flasks, i.e. 21.95 mMs of compound II, then into reaction bulb
The mixed solution of 110 milliliters of tetrahydrofurans and methanol is added, tetrahydrofuran: the volume ratio of methanol is 4: 1, after stirring 3 minutes,
1.66 grams, i.e. 43.89 mMs of sodium borohydrides are added portionwise under condition of ice bath into reaction bulb, after addition, ice bath stirring
30 minutes, finally heated backflow 1 hour；After reaction completely, reaction solution is first concentrated, 25 milliliter two is then added into reaction bulb
Chloromethanes and 25 milliliters of saturated ammonium chloride solutions, extraction separate dichloromethane layer, and dichloromethane mutually washes one with saturated sodium-chloride again
Time, after anhydrous magnesium sulfate is dried, filter, concentration, removal of solvent under reduced pressure, residue purifies through 200~300 mesh silica gel column chromatographies
5.11 grams of white powder compound III, eluant, eluent are 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1,
Yield 78.5%；Amount and the volume of reaction vessel prepared by compound III is expanded or shunk by corresponding proportion.
B. compound IV preparation：
3 grams, i.e. 10.05 mMs of compound III are sequentially added into 100 milliliters of round-bottomed flasks, then add 30 milliliters
Dichloromethane, 4.7 grams, i.e., 11.06 mMs are worn this Martin's oxidant, are stirred overnight at room temperature；After reaction completely, filter, decompression
Solvent is removed, residue purifies to obtain 2.8 grams of compound as white solid IV through 200~300 mesh silica gel column chromatographies, and eluant, eluent is 60~
90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1, yield 94%；Amount and the body of reaction vessel prepared by compound IV
Product is expanded or shunk by corresponding proportion.
C. compound V preparation：
0.7 gram, i.e. 2.36 mMs of compound IV are sequentially added into 100 milliliters of round-bottomed flasks, 0.33 gram, i.e., 4.72 in the least
Mole hydroxylamine hydrochloride, 0.24 gram, i.e., 2.36 mMs of triethylamine, be stirred at room temperature 2 hours；After reaction completely, first concentrate, so
Appropriate water and ethyl acetate extraction are added afterwards, separate ethyl acetate layer, organic layer is washed one time with saturated sodium-chloride again, anhydrous sulphur
Sour magnesium is dried, and concentration filters, removal of solvent under reduced pressure, residue through 200~300 mesh silica gel column chromatographies purify 0.56 gram of white is consolidated
Body V, eluant, eluent are 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1, yield 80.5%；It is prepared by compound V
Amount and the volume of reaction vessel expanded or shunk by corresponding proportion.
D. compound VI preparation：
0.3 gram is sequentially added into 100 milliliters of round-bottomed flasks, i.e. 0.96 mM of compound V, 1.45 mMs of R institutes are right
The different chloros or bromo-derivative answered, 30 milliliters of acetonitrile solutions are then added into bottle, then add 0.68 into reaction bulb successively
MM cesium carbonate, 0.01 gram of KI are finally added dropwise two drop N, N-2- NMFs, i.e. DMF, in 65-80 degrees Celsius plus
Thermal response is stayed overnight；After reaction completely, first concentrate, 20 milliliters of saturated sodium bicarbonate solution and 20 millis are then added into residue
Dichloromethane is risen, separates dichloromethane layer, dichloromethane is mutually washed with saturated sodium-chloride again, and anhydrous magnesium sulfate is dried, and is filtered, dense
Contracting, removal of solvent under reduced pressure, residue purify through 200~300 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether
: ethyl acetate, according to the difference of product, volume ratio 2: 1 to 1: 1, yield 50-90%；Amount and reaction prepared by compound VI
Volume of a container is expanded or shunk by corresponding proportion.
E. compound VII preparation：
0.18 mM of compound VI is added in 100 milliliters of two mouthfuls of round-bottomed flasks, 25 millis are then added into reaction bulb
The dichloromethane after fumigating is risen, 5 milliliters of trifluoroacetic acid is slowly added dropwise under condition of ice bath into reaction bulb, rear room temperature is added dropwise
Stirring 1 hour, after reaction completely, it is 8-9 that reaction solution adjusts pH value with the sodium hydroxide solution of 1 mol/L, then separates dichloromethane
Alkane layer, dichloromethane are mutually washed one time with saturated sodium-chloride again, and anhydrous magnesium sulfate is dried, and are filtered, concentration, and removal of solvent under reduced pressure is residual
Excess purifies through 200~300 mesh silica gel column chromatographies, and eluant, eluent is dichloromethane: methanol, according to the difference of product, volume ratio is
40: 1 to 30: 1, yield 50-80%；Amount and the volume of reaction vessel prepared by compound VII is expanded or shunk by corresponding proportion.
F. the bactericidal activity measure of thiazole aldoxime ether compound of the invention：
The sterilization of the thiazole aldoxime ether compound of the present invention or bacteriostatic activity use thalli growth rate determination method, specific step
Suddenly it is：1.8 milligrams of samples are taken to be dissolved in 2 drop dimethylformamides, then with water-soluble containing a certain amount of polysorbas20 emulsifying agent
Liquid is diluted to the medicament of 500 mcg/mls, reagent agent is aseptically respectively drawn to 1 milliliter in culture dish, then distinguish
9 milliliters of PDA culture mediums are added, 50 mcg/ml drug containing flat boards are made after shaking up, sky is done to add the flat board of 1 milliliter of aqua sterilisa
White control, cuts bacterium disk along mycelia outer rim with 4 millimeters of card punch of diameter, moves on drug containing flat board, put in equilateral triangle,
Often processing is repeated 3 times, and culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivated, and colony diameter to be compareed expands to 2-3
Each processing bacterium disk extension diameter is investigated after centimetre, averages, relative bacteriostasis rate is calculated compared with blank control, for trying strain
The kind of the most of typical plant pathogen actually occurred for field in China's agricultural production, its code name and entitled AS：Kind
Eggplant early epidemic germ, entitled Alternaria solani of its Latin, BC：Botrytis cinerea pers, the entitled Botrytis of its Latin
cinerea、CA：Peanut Cercospora bacteria, entitled Cercospora arachidicola of its Latin, GZ：Fusarium graminearum, its
Entitled Gibberella zeae of Latin, PI：Phytophthora infestans, the entitled Phytophthora infestans of its Latin
(Mont.)de Bary、PP：Botryosphaeria berengeriana f. sp, its Latin entitled Physalosporapiricola, PS：Rice sheath blight disease
Bacterium, entitled Pellicularia sasakii of its Latin, RC：Rhizoctonia cerealis, the entitled Rhizoctonia of its Latin
cerealis、SS：Sclerotinia sclerotiorum, the entitled Sclerotinia sclerotiorum of its Latin.
G. the inducing anti-disease activity measure of thiazole aldoxime ether compound of the invention：
The screening technique of the thiazole aldoxime ether compound evoking tobacco activity of resisting tobacco mosaic virus of the present invention is as follows, cigarette
Showy flowers of herbaceous plants mosaic virus 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 thiazoles aldoxime ether compound：In vitro directly antiviral work
Property measure using half leaf method carry out；Live body induction is that 3 basins are one group, 7 days before inoculation by the consistent common cigarette of seedling age
The tobacco seedlings of pre-treatment, processing mode include：Spray test compounds solution 2 to 3 times, 10 milliliters every time, or soil treatment, often
Secondary 10 milliliters, measure concentration is 100 mcg/mls, in frictional inoculation TMV on the tobacco leaf newly grown, tobacco seedlings is placed in into it within the 7th day
After being cultivated 3 days under growth preference temperature and illumination, incidence is checked, test compound is calculated as follows out in comprehensive scab number
Induction antiviral effect to TMV, each processing set 3 repetitions, blank control and standard agent control select respectively water and
TDL：
Wherein, R be noval chemical compound TMV anti-to tobacco inducing effect, unit：%；CK is that clear water compares being averaged for blade
Withered spot number, unit：It is individual；I is that the average withered spot number for handling rear blade is induced through compound, unit：It is individual；
In addition to carrying out the measure of above-mentioned induced activity, while the anti-TMV of thiazole aldoxime ether compound treatment is carried out
Activity, passivation activity, the measure of protection activity.
H. the measure of thiazole aldoxime ether compound of the invention to aphid cytotoxicity：
The thiazole aldoxime ether compound of the present invention is determined as follows to aphid cytotoxicity：Using proofing method, black bean aphid,
The entitled Aphis laburni Kaltenbach (ALK) of its Latin, the normal population of indoor feeding；Weigh test compound 2.5
Milligram is added dropwise 1 drop DMF, is i.e. DMF, adds 5 milliliters of acetone vibration dissolving samples, added and told in beaker
The water of temperature 80 is configured to the solution to be measured of 200 mcg/mls；By the confession examination bean plant with least 60 black bean aphids from basin
Cut, impregnated 5 seconds in each decoction to be measured, unnecessary decoction is gently got rid of in taking-up, is inserted in by water saturated sponge
Moisturizing, escaped, trained to prevent aphid with cloche cover, the opening of cloche upper end is sealed with gauze after decoction natural air drying
Support after indoor feeding is placed 48 hours and check aphid death state, standard is：It can be creeped or can stood or six leg energy with test worm
Strenuous exercise is 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 to thiazole aldoxime ether compound I, and to newization of synthesis
Compound has carried out the screening of insecticidal activity, bacteriostatic activity and antiviral activity.
The present invention passes through specific preparation and the more specific explanation thiazole aldoxime ether compound I of biological activity determination embodiment
Synthesis 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 raw
Thing activity is merely illustrative of, and unrestricted this patent, embodiment are as follows：
Embodiment 1
Compound III preparation：
7.47 grams are added into 250 milliliters of round-bottomed flasks, i.e. 21.95 mMs of compound II, then into reaction bulb
The mixed solution of 110 milliliters of tetrahydrofurans and methanol is added, tetrahydrofuran: the volume ratio of methanol is 4: 1, after stirring 3 minutes,
1.66 grams, i.e. 43.89 mMs of sodium borohydrides are added portionwise under condition of ice bath into reaction bulb, after addition, ice bath stirring
30 minutes, finally heated backflow 1 hour；After reaction completely, reaction solution is first concentrated, 25 milliliter two is then added into reaction bulb
Chloromethanes and 25 milliliters of saturated ammonium chloride solutions, extraction separate dichloromethane layer, and dichloromethane mutually washes one with saturated sodium-chloride again
Time, anhydrous magnesium sulfate is dried, and is filtered, and concentration, removal of solvent under reduced pressure, residue purifies through 200~300 mesh silica gel column chromatographies
5.11 grams of white powder compound III, eluant, eluent are 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1, are received
Rate 78.5%；1HNMR(CDCl3)：δ 7.04 (s, 1H), 4.26-4.12 (m, 2H), 3.90 (s, 2H), 3.35 (br, 1H),
3.21-3.09 (m, 1H), 2.93-2.77 (m, 2H), 2.15-2.00 (m, 2H), 1.79-1.66 (m, 2H), 1.45 (s, 9H)
Embodiment 2
Compound IV preparation：
3 grams, i.e. 10.05 mMs of compound III are sequentially added into 100 milliliters of round-bottomed flasks, then add 30 milliliters
Dichloromethane, 4.7 grams, i.e., 11.06 mMs are worn this Martin's oxidant, are stirred overnight at room temperature, and after reaction completely, are filtered, decompression
Solvent is removed, residue purifies to obtain 2.8 grams of white powder compound IV through 200~300 mesh silica gel column chromatographies, and eluant, eluent is 60~
90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1, yield 94%；1HNMR(CDCl3)：δ 8.12 (s, 1H), 7.29
(s, 1H), 4.32-4.19 (m, 2H), 3.27-3.2,1H), 2.97-2.85 (m, 2H), 2.19-2.12 (m, 2H), 1.81-1.77
(m, 2H), 1.50 (s, 9H)
Embodiment 3
Compound V preparation：
0.7 gram, i.e. 2.36 mMs of compound IV are sequentially added into 100 milliliters of round-bottomed flasks, 0.33 gram, i.e., 4.72 in the least
Mole hydroxylamine hydrochloride, 0.24 gram, i.e., 2.36 mMs of triethylamine, be stirred at room temperature 2 hours；After reaction completely, first concentrate, so
The water and 15 milliliters of ethyl acetate for adding 15 milliliters afterwards extract, and separate ethyl acetate layer, ethyl acetate phase uses saturated sodium-chloride again
Wash one time, anhydrous magnesium sulfate is dried, and concentration filters, and removal of solvent under reduced pressure, residue purifies through 200~300 mesh silica gel column chromatographies
0.56 gram of white solid V is obtained, eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1, yield
80.5%；1HNMR(CDCl3): δ 9.43 (br, 1H), 8.15 (s, 1H), 7.35 (s, 1H), 4.24-4.04 (m, 2H), 3.20-
3.07 (m, 1H), 2.97-2.71 (m, 2H), 2.09-1.98 (m, 2H), 1.72-1.57 (m, 2H), 1.40 (s, 9H)
Embodiment 4
Compound VI preparation：
0.3 gram, i.e. 0.96 mM of compound V, 1.45 mMs of RX are sequentially added into 100 milliliters of round-bottomed flasks, so
30 milliliters of acetonitrile solutions are added in backward bottle, then add 0.68 mM of cesium carbonate into reaction bulb successively, 0.01 gram of KI,
Two drop N are finally added dropwise, N-2- NMFs, i.e. DMF are in the reaction of 65-80 degrees Centigrades overnight, first dense after reaction completely
Contracting, 20 milliliters of saturated sodium bicarbonate and 20 milliliters of dichloromethane are then added into residue, separates dichloromethane layer, dichloro
Methane is mutually washed with saturated sodium-chloride again, and anhydrous magnesium sulfate is dried, and is filtered, and concentration, removal of solvent under reduced pressure, residue is through 200~300
Mesh silica gel column chromatography purifies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, according to the difference of product, volume ratio
For 2: 1 to 1: 1, yield 50-90%；Its physical and chemical parameter and structural parameters are shown in Table 1.
Embodiment 5
Compound VII preparation：
0.18 mM of compound VI is added in 100 milliliters of two mouthfuls of round-bottomed flasks, 25 millis are then squeezed into reaction bulb
Stifling dichloromethane is risen, 5 milliliters of trifluoroacetic acid is slowly added dropwise under condition of ice bath into reaction bulb, rear room temperature is added dropwise and stirs
Mix 1 hour, after reaction completely, it is 8-9 that reaction solution adjusts pH value with 1 mole every liter of sodium hydride solution, then separates dichloromethane
Layer, dichloromethane are mutually washed one time with saturated sodium-chloride again, and anhydrous magnesium sulfate is dried, and are filtered, concentration, and removal of solvent under reduced pressure is remaining
Thing purifies through 200~300 mesh silica gel column chromatographies, and eluant, eluent is dichloromethane: methanol, according to the difference of product, volume ratio 40:
1 to 30: 1, yield 50-80%；Its physical and chemical parameter and structural parameters are shown in Table 1.
Embodiment 6
The Antibacterial Activity result of the thiazole aldoxime ether compound of the present invention：
The code name and the following AS of title for the frequently seen plants disease fungus that the present invention tests：Tomato early blight bacterium, its latin name
For Alternaria solani, CA：Peanut Cercospora bacteria, entitled Cercospora arachidicola of its Latin, GZ：Wheat
Gibberellic hypha, entitled Gibberella zeae of its Latin, PP：Botryosphaeria berengeriana f. sp, the entitled Physalospora of its Latin
piricola、SS：Sclerotinia sclerotiorum, its Latin entitled Sclerotinia sclerotiorum, BC：Botrytis cinerea pers,
Entitled Botrytis cinerea of its Latin, PI：Phytophthora infestans, the entitled Phytophthora infestans of its Latin
(Mont.)de Bary、RC：Rhizoctonia cerealis, entitled Rhizoctonia cerealis of its Latin, PS：Rhizoctonia solani Kuhn,
Entitled Pellicularia sasakii of its Latin, these strains have representativeness well, can represent field in agricultural production
Between the kind of most of pathogen that occurs.It is worth noting that compound lfy006-39 is patent document in the present invention
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 present invention in synthesized this structure closest to target compound of the present invention and its active highest of patent literature it is similar
Compound lfy006-39.Thalli growth rate method measurement result is shown in Table 2, and table 2 shows, majority of compounds of the invention have compared with
The activity of good bactericidal activity, in 50 mcg/ml, all compounds that the present invention synthesizes have different degrees of sterilization
Activity.For tomato early blight bacterium, compound zyj002-41, zyj002-47, zyj002-42, zyj003-2 suppression are lived
For property more than 48%, the bactericidal activity of above-claimed cpd is higher than lfy006-39 and Fluoxastrobin, and to be higher by structure similar, literary for activity
The best compound lfy006-39 of report activity is offered more than 10%, compound zyj002-42 activity is up to 72.73%.
The Activity Results of peanut Cercospora asparagagas are shown, compound zyj002-3, zyj002-41, zyj002-47, zyj002-42,
Zyj002-38, zyj002-43, zyj002-44, zyj002-40, zyj003-10 inhibitory activity are more than 40%, above-mentionedization
The bactericidal activity of compound be higher by structure is similar, the active best compound lfy006-39 of document report more than 10%, compound
Zyj002-3, zyj002-41, zyj002-42, zyj002-43, zyj002-44, zyj003-10 inhibitory activity 60% with
On, activity is higher than comparison medicament Fluoxastrobin；The active testing result of fusarium graminearum is shown, compound zyj002-32,
For zyj002-41, zyj004-4, zyj002-43 inhibitory activity more than 46%, the bactericidal activity of above-claimed cpd is higher by structure
Similar, the active best compound lfy006-39 of document report is more than 10%；To the test result table of Botryosphaeria berengeriana f. sp
Bright, compound zyj002-41, zyj004-4, zyj002-44, zyj002-4 inhibitory activity are more than 50%, compound
Zyj004-4, zyj002-44 activity are higher by that structure is similar, the active best compound lfy006-39 of document report is 10%
More than；And compound zyj004-4 activity is up to 100%, higher than comparison medicament Fluoxastrobin, and bactericidal activity is higher by structure
Similar, the active best compound lfy006-39 of document report is more than 10%；To the active testing table of Sclerotinia sclerotiorum
It is bright, compound zyj002-3, zyj002-15, zyj002-10, zyj004-4, zyj002-43, zyj003-9, zyj003-10's
For inhibitory activity more than 54%, the bactericidal activity of above-claimed cpd is higher by that structure is similar, the active best compound of document report
Lfy006-39 is more than 10%, and for compound zyj002-3, zyj003-9, zyj003-10 activity more than 77%, activity is high
In comparison medicament Fluoxastrobin, compound zyj002-3 activity is up to 82.35%；To the active testing table of botrytis cinerea pers
It is bright, compound zyj002-3, zyj002-47, zyj002-42, zyj004-4, zyj004-44, zyj002-40, zyj003-2,
For zyj003-10 activity more than 45%, the active of above-claimed cpd is higher by that structure is similar, document report is active best
Compound lfy006-39 is more than 10%, compound zyj002-3, zyj004-4, zyj004-44, zyj003-2, zyj003-
10 activity is higher than 55%, and bactericidal activity is higher by that structure is similar, the active best compound lfy006-39 of document report is 10%
More than, compound zyj003-10 activity is up to 100%；The active testing of Phytophthora infestans shows, compound
Zyj004-4, zyj002-38, zyj002-44, zyj003-2, zyj003-9, zyj003-10 inhibitory activity more than 45%,
The bactericidal activity of above-claimed cpd is higher by that structure is similar, the active best compound lfy006-39 of document report is more than 10%；
The active testing of Rhizoctonia cerealis is shown, compound zyj002-47, zyj004-4, zyj002-38, zyj002-43 suppression
For activity more than 70%, the activity of compound zyj002-47, zyj002-38 is higher than 80%, bactericidal activity be higher by structure it is similar,
More than 10%, compound zyj002-47 activity is up to the best compound lfy006-39 of document report activity
84.62%；The active testing of Rhizoctonia solani Kuhn is shown, for compound zyj003-2 activity more than 60%, activity is close
In control drug lfy006-39.
Embodiment 7
The anti-TMV activity of the thiazole aldoxime ether compound of the present invention：
The measurement result of TMV activity is shown in Table 3, and table 3 shows, 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 zyj002-3, zyj002-15, zyj002-47, zyj002-38, zyj002-43, zyj002-40, zyj003-
9th, zyj003-10 inhibiting rate height is more than 45%, and active is higher by that structure is similar, the active best compound of document report
Lfy006-39 more than 10%, compound zyj002-15, zyj002-47, zyj002-38, zyj002-43, zyj002-40,
For zyj003-10 activity more than 52%, activity is higher by that structure is similar, the active best compound lfy006-39 of document report
More than 10%, compound zyj002-15, zyj002-47, zyj002-40, zyj003-10 activity are high more than 65%
In comparison medicament Ningnanmycin；Under passivation pattern, the activity of all compounds is all higher by that structure is similar, document report is active most
Good compound lfy006-39 more than 10%, wherein, compound zyj002-32, zyj002-38, zyj002-44 activity
More than 65%, activity is higher than comparison medicament virazole；Under induction pattern, compound except compound zyj002-10,
Outside zyj002-47, zyj003-10, remaining compound activity is all more than 50%, and activity is higher than comparison medicament SZG-7, wherein changing
Compound zyj002-3, zyj002-15, zyj002-33, zyj002-42, zyj004-4, zyj002-43, zyj002-40,
For zyj003-2 activity more than 65%, activity is higher by that comparison medicament TDL is similar with structure, the active best chemical combination of document report
Thing lfy006-39 is more than 10%, and compound zyj002-43, zyj002-40, zyj003-2 activity are more than 75%, activity
Higher than comparison medicament BTH, and activity is all higher by that structure is similar, the active best compound lfy006-39 of document report is 10%
More than.
Embodiment 8
The thiazole aldoxime ether compound insecticidal activity of the present invention：
The insecticidal activity assay of thiazole aldoxime ether compound the results are shown in Table 4, and table 4 is visible：It is 100 in reagent agent concentration
During mg/litre, after observation acts on 72 hours, it is known that compound lfy006-39 does not have toxic action to aphid substantially, in of the invention
Compound have weaker toxic action to aphid, wherein, compound zyj002-15, zyj002-10, zyj002-32,
zyj002-41、.For zyj002-42, zyj002-43, zyj002-43 activity more than 15%, insecticidal activity is all higher by structure
Similar, the active best compound lfy006-39 of document report is more than 10%.
Embodiment 9
The thiazole aldoxime ether compound of the present invention kills 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, sub- 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, Acetamiprid, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, go out
Young urea, Teflubenzuron, deinsectization are grand, HEXAFLUMURON, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron are
Noviflumuron, its CAS 121451-02-3, flucycloxuron, Novaluron are Rimon, chlorfluazuron, Bay sir 6874 i.e. { 1-
[(3.5- bis- chloro- 4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzenes)-urea }, Bay SIR-8514 be [1- (4- trifluoromethoxies
Phenyl) -3- (2- chlorobenzenes)-urea], piperazine worm urea, Bistrifluron be 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, Mobucin, 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 thiazole aldoxime ether compound of the present invention is in institute
The total weight/mass percentage composition obtained in compounded pesticides is 1%-90%, thiazole aldoxime ether compound of the invention and the business
The ratio of product insecticide is mass percent 1%: 99% to 99%: 1%；The applicable formulation of the compounded pesticides 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, 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 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 applicable plant of compounded pesticides 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 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 insect pest of compounded pesticides preventing and treating be selected from Asiatic migrotory locust, reading room management, Chinese rice grasshopper,
Patanga japonica (l.Bol.), single thorn mole cricket, Oriental burmeister, rice thripses, 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, bar 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 the yellow suction of cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, wheat
Starch worm, pachydiplosis oryzae, citrus fruit fly, melonfly, the latent fly of wheat leaf ash, 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 thiazole aldoxime ether compound of the present invention and agriculturally acceptable auxiliary agent and following commodity bactericide
Purposes of any one or more combination in composite bactericide is prepared：
The commodity bactericide is selected from diazosulfide, tiadinil, first thiophene and lures amine, 4- methyl isophthalic acids, 2,3- thiadiazoles -5-
Formic acid, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 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 isophthalic acids, 2,3-
Thiadiazoles, 4- iodomethyl -5- methyl isophthalic acids, 2,3- thiadiazoles, 4,4- dibromo methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, 3,4-
Two chloroisothiazole -5- formic acid, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- Ethyl formates of 3,4- bis-, 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, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, azoles alcohol, 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 SYP-Z048, 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, ethoxy
Quinoline, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, enemy's pest
Phosphorus, different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, Jing Gang
Mycin, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, carbendazim, benomyl, thiophanate-methyl, triazole
Ketone, bupirimate, dimethirimol, ethirimol, difoltan, captan, folpet, vinclozolin, fluoromide, bacterium
Core is net, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, Mancozeb, Propineb, phosethyl-Al, sulphur, Bordeaux
Liquid, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, spiral shell
Ring bacterium amine, tricyclazole, triforine, more fruit pyridines, the pungent salt of biguanides, iminoctadine, botran, benzene flusulfamide, toluene flusulfamide, indoles
Ester, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium, enemy's line ester, dazomet, nemamort, thiazole
Phosphorus, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, isazofos, fosthietan, oxamyl, Aldicarb, gram
Budweiser, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole；The thiazole aldoxime ether compound of the present invention is answered in gained
It is 1%-90% with total weight/mass percentage composition in bactericide, thiazole aldoxime ether compound of the invention kills with the commodity
The ratio of microbial inoculum is mass percent 1%: 99% to 99%: 1%；The applicable formulation of the composite bactericide is selected from following dosage forms
In 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, 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, 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,
It is solid harl agent, solid/mixing dress agent, medicine paint, seed treatment liquor, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, bold and vigorous
Pour 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 applicable plant choosing of the composite bactericide
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 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 the composite bactericide 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 rot, 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 blue or green
Rot, Diplodia gossypina, peanut root rot, the cercospora brown spot of peanut, Peanut Web Blotch Disease, activity of peanuts disease, Peanut Scab, tobacco are blue or green
Rot, 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 bar 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 lug 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 rot, grape grey mould, grapevine anthracnose, black rot of grape, the big room rot 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 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, 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, peach gummosis, peach wood rot, peach do
Rot, 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 thiazole aldoxime ether compound 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 isophthalic acids, 2,3- thiophenes two
Azoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 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 isophthalic acids, 2,3- thiadiazoles, 4,4- dibromo methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid second
Ester, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- Ethyl formates of 3,4- bis-,
DL- beta-aminobutyric acids, virazole, antofine, Ningnanmycin, first thiophene lure amine, salicylic acid, cytosintetidemycin, dichloro-isonicotinic acid, allyl
Isothiazole, well ridge azanol, jinggangmeisu；The thiazole aldoxime ether compound of the present invention compounds anti-plant virus agent, plant in gained
Total weight/mass percentage composition in thing activator is 1%-90%, and thiazole aldoxime ether compound 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
Formulation 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, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, oil
Bag aqueous emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, 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
Solid agent, solid/mixing dress agent, medicine paint, seed treatment liquor, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, bold and vigorous pour
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 applicable plant of toxic agent, activating plants agent 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 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 virus disease of the compounding anti-plant virus agent, activating plants agent is selected from
Rice dwarf virus disease, BYDV, 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 thiazole aldoxime ether compound of the present invention with agriculturally acceptable auxiliary agent and with following commodity acaricide
Any one or more combination preparing Compositional acaricide and its preventing and treating 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, AVM,
Doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin,
Rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, Hexythiazox, Envidor, fluacrypyrim, chlorfenizon, propargite,
Pyridaben；Total weight/mass percentage composition of the thiazole aldoxime ether compound of the present invention in gained Compositional acaricide in the composition
It is 1%-90%, thiazole aldoxime ether compound of the invention and the acaricidal ratio of the commodity are mass percent 1%:
99% to 99%: 1%；The formulation 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, block 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 rod, 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, sheet poison bait, dense jelly, sprinkle pour agent, liniment, suspended emulsion, film forming finish, soluble powder, seed
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 applicable plant of the Compositional acaricide 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 tube, 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；The applicable mite evil of the Compositional acaricide selected from Tetranychidae,
Tenuipalpidae, furan line mite, Eriophyidae, tetranychus telarius category, the evil mite of Eriophyidae, these evil mites are worldwide Agricultural Mites, forestry evil
Mite, gardening evil mite and hygienic evil mite.
The chemical constitution and physical and chemical parameter of the thiazole aldoxime ether compound of the present invention of table 1
The bacteriostatic activity (suppression/% of 50 mcg/mls) of the ether compound of aldoxime containing thiazole of the present invention of table 2
| Numbering | Compound | AS | CA | GZ | PP | SS | BC | PI | RC | PS |
| 1 | zyj002-3 | 35.29 | 63.64 | 30.77 | 61.36 | 82.35 | 66.67 | 26.32 | 43.90 | 10.53 |
| 2 | zyj002-15 | 5.88 | 0 | 34.62 | 34.09 | 58.82 | 19.05 | 10.53 | 48.78 | 5.26 |
| 3 | zyj002-10 | 17.65 | 0 | 26.92 | 27.27 | 64.71 | 9.52 | 5.26 | 51.22 | 15.79 |
| 4 | zyj002-32 | 11.76 | 18.18 | 46.15 | 34.09 | 47.06 | 23.81 | 15.79 | 48.78 | 15.79 |
| 5 | zyj002-33 | 23.53 | 18.18 | 15.38 | 20.45 | 52.94 | 38.10 | 15.79 | 65.85 | 21.05 |
| 6 | zyj002-41 | 59.09 | 57.14 | 62.07 | 55.56 | 30.51 | 38.71 | 23.81 | 46.15 | 11.11 |
| 7 | zyj002-47 | 63.64 | 52.38 | 34.48 | 41.67 | 54.24 | 48.39 | 38.10 | 84.62 | 22.22 |
| 8 | zyj002-42 | 72.73 | 57.14 | 34.48 | 47.22 | 22.03 | 51.61 | 23.81 | 30.77 | 27.78 |
| 9 | zyj004-4 | 31.25 | 12.50 | 65.22 | 100 | 69.44 | 88.89 | 47.62 | 76.19 | 12.50 |
| 10 | zyj002-38 | 15.79 | 45.45 | 11.76 | 28.57 | 23.08 | 18.18 | 47.06 | 80.49 | 15.79 |
| 11 | zyj002-43 | 27.27 | 57.14 | 62.07 | 41.67 | 55.93 | 41.94 | 9.52 | 73.08 | 16.67 |
| 12 | zyj002-44 | 27.27 | 66.67 | 27.59 | 63.89 | 22.03 | 80.65 | 47.62 | 19.23 | 27.78 |
| 13 | zyj002-40 | 36.36 | 47.62 | 20.69 | 52.78 | 38.98 | 64.52 | 23.81 | 42.31 | 27.78 |
| 14 | zyj003-2 | 56.25 | 31.25 | 30.43 | 0 | 0 | 55.56 | 57.14 | 23.81 | 62.50 |
| 15 | zyj003-9 | 31.25 | 12.50 | 43.48 | 47.62 | 80.56 | 41.67 | 47.62 | 23.81 | 31.25 |
| 16 | zyj003-10 | 43.75 | 62.50 | 30.43 | 19.05 | 77.78 | 100 | 47.62 | 47.62 | 31.25 |
| 17 | lfy006-39 | 10.00 | 11.11 | 33.33 | 61.40 | 44.83 | 42.25 | 31.58 | 67.50 | 68.29 |
| 18 | Fluoxastrobin | 46.88 | 55.56 | 75.00 | 91.18 | 71.43 | 100 | 88.10 | 84.06 | 80.77 |
Activity (the 100 μ g/mL suppression of the resisting tobacco mosaic virus of the thiazole aldoxime ether compound of the present invention of table 3
Rate/%)
| Numbering | Compound | Treatment | Passivation | Induction |
| 1 | zyj002-3 | 45.07±2.08 | 35.60±2.56 | 70.53±2.76 |
| 2 | zyj002-15 | 65.35±2.25 | 45.78±0.25 | 66.69±0.53 |
| 3 | zyj002-10 | 23.47±3.47 | 50.23±0.78 | 55.73±1.28 |
| 4 | zyj002-32 | 36.03±4.02 | 66.80±3.03 | 45.89±2.27 |
| 5 | zyj002-33 | 42.50±3.15 | 28.90±4.21 | 69.23±3.45 |
| 6 | zyj002-41 | 27.08±0.24 | 57.86±3.57 | 58.98±5.67 |
| 7 | zyj002-47 | 70.83±3.03 | 45.78±2.15 | 47.23±7.71 |
| 8 | zyj002-42 | 30.45±1.23 | 47.23±2.67 | 68.92±3.45 |
| 9 | zyj004-4 | 35.60±0.54 | 35.65±2.78 | 80.95±3.30 |
| 10 | zyj002-38 | 57.28±2.50 | 70.89±3.85 | 65.23±1.25 |
| 11 | zyj002-43 | 52.35±1.78 | 38.88±4.26 | 77.50±1.46 |
| 12 | zyj002-44 | 45.07±0.34 | 66.95±0.45 | 60.38±2.38 |
| 13 | zyj00240 | 66.23±4.07 | 33.73±2.55 | 80.51±3.75 |
| 14 | zyj003-2 | 37.89±2.57 | 44.28±5.06 | 77.40±3.67 |
| 15 | zyj003-9 | 50.20±3.35 | 30.75±0.05 | 50.28±2.50 |
| 16 | zyj003-10 | 68.05±4.01 | 45.37±2.78 | 45.73±1.23 |
| 17 | lfy006-39 | 40.22±5.65 | 15.33±0.67 | 65.00±5.00 |
| 18 | Ningnanmycin | 65.03±3.09 | 45.64±2.35 | 28.36±2.99 |
| 19 | TDL | 28.17±4.08 | 89.33±2.67 | 66.67±6.66 |
| 20 | BTH | 50.78±2.00 | 35.33±2.00 | 77.50±2.50 |
| 21 | SZG-7 | 30.89±2.59 | 60.26±3.85 | 48.75±1.25 |
| 22 | Virazole | 50.12±2.94 | 65.64±3.87 | 57.08±4.39 |
Insecticidal activity (death rate, %, 100 mg/litres) of the thiazole aldoxime ether compound of the present invention of table 4 to aphid
| Numbering | Compound | Death rate % | Numbering | Compound | Death rate % |
| 1 | zyj002-3 | 4.72 | 10 | zyj002-38 | 12.61 |
| 2 | zyj002-15 | 18.13 | 11 | zyj002-43 | 18.78 |
| 3 | zyj002-10 | 15.31 | 12 | zyj002-44 | 8.15 |
| 4 | zyj002-32 | 16.43 | 13 | zyj002-40 | 23.48 |
| 5 | zyj002-33 | 10.74 | 14 | zyj003-2 | 10.58 |
| 6 | zyj002-41 | 15.79 | 15 | zyj003-9 | 11.14 |
| 7 | zyj002-47 | - | 16 | zyj003-10 | 9.23 |
| 8 | zyj002-42 | 17.38 | 17 | lfy006-39 | 4.94 |
| 9 | zyj004-4 | - | 18 |
Claims (6)
1. a kind of thiazole aldoxime ether compound, it is characterised in that there is following test code number and chemical constitution：
Boc in above-mentioned chemical constitution is tertbutyloxycarbonyl.
2. the synthetic method of the thiazole aldoxime ether compound described in claim 1, specific synthetic route are as follows：
According to the difference of R group, the particular chemical for the compound that above-mentioned VI and VII are represented is as defined in claim 1；
The specific method of the synthesis of target compound described in claim 1 is divided into following steps：
A. compound III preparation：
7.47 grams are added into 250 milliliters of round-bottomed flasks, be i.e. 21.95 mMs of compound II, is then added into reaction bulb
The mixed solution of 110 milliliters of tetrahydrofurans and methanol, tetrahydrofuran: the volume ratio of methanol is 4: 1, after stirring 3 minutes, in ice bath
Under the conditions of 1.66 grams, i.e. 43.89 mMs of sodium borohydrides are added portionwise into reaction bulb, after addition, ice bath stir 30 points
Clock, finally heated backflow 1 hour；After reaction completely, reaction solution is first concentrated, 25 milliliters of dichloromethanes are then added into reaction bulb
Alkane and 25 milliliters of saturated ammonium chloride solutions, extraction, dichloromethane layer being separated, dichloromethane is mutually washed one time with saturated sodium-chloride again,
After anhydrous magnesium sulfate is dried, filter, concentration, removal of solvent under reduced pressure, residue purifies through 200~300 mesh silica gel column chromatographies
5.11 grams of white powder compound III, eluant, eluent are 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1,
Yield 78.5%；
B. compound IV preparation：
3 grams, i.e. 10.05 mMs of compound III are sequentially added into 100 milliliters of round-bottomed flasks, then add 30 milliliters of dichloros
Methane, 4.7 grams, i.e., 11.06 mMs are worn this Martin's oxidant, are stirred overnight at room temperature；After reaction completely, filter, be removed under reduced pressure
Solvent, residue purify to obtain 2.8 grams of compound as white solid IV through 200~300 mesh silica gel column chromatographies, and eluant, eluent is taken the photograph for 60~90
The petroleum ether of family name's degree: ethyl acetate, volume ratio 2: 1, yield 94%；
C. compound V preparation：
0.7 gram, i.e. 2.36 mMs of compound IV, 0.33 gram, i.e., 4.72 mMs are sequentially added into 100 milliliters of round-bottomed flasks
Hydroxylamine hydrochloride, 0.24 gram, i.e., 2.36 mMs of triethylamine, be stirred at room temperature 2 hours；After reaction completely, first concentrate, Ran Houjia
Enter appropriate water and ethyl acetate extraction, separate ethyl acetate layer, organic layer washes one time with saturated sodium-chloride again, anhydrous magnesium sulfate
To dry, concentration filters, and removal of solvent under reduced pressure, residue purifies to obtain 0.56 gram of white solid V through 200~300 mesh silica gel column chromatographies,
Eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1, yield 80.5%；
D. compound VI preparation：
Sequentially add 0.3 gram into 100 milliliters of round-bottomed flasks, i.e. corresponding to 0.96 mM of compound V, 1.45 mMs of R
Different chloros or bromo-derivative, 30 milliliters of acetonitrile solutions are then added into bottle, then add 0.68 mmoles into reaction bulb successively
That cesium carbonate, 0.01 gram of KI, two drop N are finally added dropwise, N-2- NMFs, i.e. DMF are anti-in 65-80 degrees Centigrades
It should stay overnight；Reaction completely after, first concentrate, then into residue add 20 milliliters saturated sodium bicarbonate solution and 20 milliliter two
Chloromethanes, dichloromethane layer is separated, dichloromethane is mutually washed with saturated sodium-chloride again, and anhydrous magnesium sulfate is dried, and is filtered, and concentration, is subtracted
Pressure removes solvent, and residue purifies through 200~300 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: acetic acid
Ethyl ester, according to the difference of product, volume ratio 2: 1-1: 1, yield 50-90%；
E. compound VII preparation：
0.18 mM of compound VI is added in 100 milliliters of two mouthfuls of round-bottomed flasks, 25 milliliters are then added into reaction bulb smokes
Dichloromethane after steaming, 5 milliliters of trifluoroacetic acid is slowly added dropwise under condition of ice bath into reaction bulb, is stirred at room temperature after being added dropwise
1 hour, after reaction completely, it was 8-9 that reaction solution adjusts pH value with the sodium hydroxide solution of 1 mol/L, then separates dichloromethane
Layer, dichloromethane are mutually washed one time with saturated sodium-chloride again, and anhydrous magnesium sulfate is dried, and are filtered, concentration, and removal of solvent under reduced pressure is remaining
Thing purifies through 200~300 mesh silica gel column chromatographies, and eluant, eluent is dichloromethane: methanol, according to the difference of product, volume ratio 40:
1-30: 1, yield 50-80%.
3. purposes of the thiazole aldoxime ether compound in insecticide is prepared described in claim 1.
4. purposes of the thiazole aldoxime ether compound in fungicide is prepared described in claim 1.
5. purposes of the thiazole aldoxime ether compound in resisting tobacco mosaic virus agent is prepared described in claim 1.
6. purposes of the thiazole aldoxime ether compound in activating plants agent is prepared described in claim 1.
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| CN103153992A (en) * | 2010-08-11 | 2013-06-12 | 拜耳知识产权有限责任公司 | Heteroarylpiperidine and -piperazine derivatives as fungicides |
| CN103180317A (en) * | 2010-08-25 | 2013-06-26 | 拜耳知识产权有限责任公司 | Heteroarylpiperidine and -piperazine derivatives as fungicides |
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| CN102292334A (en) * | 2008-12-11 | 2011-12-21 | 拜尔农作物科学股份公司 | Thiazolyl oxime ether and hydrazones asl plant protection agent |
| CN103153992A (en) * | 2010-08-11 | 2013-06-12 | 拜耳知识产权有限责任公司 | Heteroarylpiperidine and -piperazine derivatives as fungicides |
| CN103180317A (en) * | 2010-08-25 | 2013-06-26 | 拜耳知识产权有限责任公司 | Heteroarylpiperidine and -piperazine derivatives as fungicides |
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