CN104650060B - A kind of piperidines thiazole and its production and use - Google Patents
A kind of piperidines thiazole and its production and use Download PDFInfo
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- CN104650060B CN104650060B CN201410809130.XA CN201410809130A CN104650060B CN 104650060 B CN104650060 B CN 104650060B CN 201410809130 A CN201410809130 A CN 201410809130A CN 104650060 B CN104650060 B CN 104650060B
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- 0 CC(C1CCNCC1)SC=C(C(**)=O)N Chemical compound CC(C1CCNCC1)SC=C(C(**)=O)N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N C1OCCOC1 Chemical compound C1OCCOC1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- 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
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- 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 piperidines thiazole 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 II.
Description
Technical field
Technical scheme is related to thiazole containing piperidines, and in particular to piperidines thiazole.
Background technology
One of an important factor for plant pathogeny virus, fungi, bacterium are influence modern agricultural productions, is drawn by these pathogens
The various diseases risen have a strong impact on the yield and quality of agricultural product.Chemical bactericide is to ensure that reducing disease ensures agricultural product production
One of important means of rate and quality, but the extensive and unreasonable use of bactericide so that the pathogen in China farmland is to existing
Conventional sterilants have generated obvious resistance and (Jia Junchao, have waited pathogens to Strobilurin series bactericidal agent resistance mechanisms
Progress Pesticide Science journals, 2008,10 (1)：1-9.).Methoxy acrylic bactericide is made in China farmland
With one of most commonly used bactericide, also generate obvious resistance in China farmland at present and (Zhao Ping, wait methoxy acrylic acids
The exploitation of esters bactericide and resistance development present situation agricultural chemicals, 2011,50 (8)：547-542.), development structure is more novel, simple
Bactericide that is single, having different mechanism of action is one of effective way for solving resistance.
Thiazole derivative has extensive bioactivity, according to the literature, thiazole derivative have antibacterial, analgesia,
Anti-inflammatory, anticonvulsion, cardiac stimulant, anticancer, treating tuberculosis and expelling parasite isoreactivity (Sharshiral, E.M., et al.Synthesis,
characterization and antimicrobial activities of some thiazole
Derivatives.J.Org.Chem., 2012,2 (3)：69-73.).In addition, also such as killed with extensive pesticide activity
Worm, sterilization, weeding, plant growth regulating, antiviral etc. (Chen Caijun, the progress agricultural chemicals of thiazole insecticides is waited,
2005,44 (2)：53-55.).Piperidine derivatives have extensive bioactivity, and piperidine alkaloid is distributed widely in plant
Boundary, and show multiple biological activities (Richerson, G.B., et al.Dnymaic euqilibrium of
Neurotransmitters not just for reup-take anymore.J.Neurophysiol., 2003,90：
1363-1374.).Piperidine derivatives also show extensive bioactivity in terms of agricultural chemicals, such as bactericide fenpropidin, weeding
Agent dimepiperate, plant growth regulator first piperazine etc. all have preferable bioactivity (Jiang Zhigan, et
Al.Design, synthesis and antifungal activity of novel triazole derivatives
The piperidine side chains.Eur.J.Med.Chem of containing substituted 1,2,3-triazole-,
2014,82：490-497).Active substructure unit thiazole ring and piperidine ring are combined and carry out studying existing patent literature
(Black, Janice.Novel herbicides, WO2007071900A1；Pasteris, et al.Fungicidal
Amides, WO2008091580 A2).
Piperidines group is introduced into thiazole compound by the present invention using the principle of pesticide molecule design, and design has synthesized one
Thiazoles noval chemical compound of the class containing piperidine ring, and the bioactivity screening of system has been carried out, to be provided for the initiative of novel pesticide
More efficient candidate compounds.
The content of the invention
The technical problems to be solved by the invention are：There is provided the synthetic method of new piperidines thiazole, there is provided this kind of
Compound modulates agricultural, gardening and health and the bioactivity and its assay method of forestry plant insect and the phytopathy original,
There is provided middle application of these compounds in agriculture field, horticultural field, field of forestry and health field simultaneously.
Technical scheme is used by the present invention solves the technical problem：With agriculture field, horticultural field, forestry and
The piperidines thiazole that health field insecticidal activity, bactericidal activity, anti-phytoviral activity, induction plant produce anti-disease activity derives
The chemical structure of general formula of thing is shown in Formula II：
Wherein, R is selected from H, HHCl, 2- (5H) furanone -4- bases, 2- chloropyridine -5- methylene, propargyl, fluoroform
Sulfonyl orR2Selected from methyl, ethyoxyl, tertbutyloxycarbonyl, trifluoromethyl, phendioxin, 2,3- thiadiazoles -7- bases, 3,
Chloroisothiazole -5- the bases of 4- bis-, 3- trifluoromethyl -5- methylpyrazole -1- methylene, the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrroles
Azoles -5- bases, 1H- indoles -3- methylene, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases, cyclohexyl, cyclopropyl, 2- methyl -4- three
Methyl fluoride thiazole -5- bases, 2- chloropyridine -5- bases；X is selected from O, NH, R1Selected from the fluoro ethyls of 2,2- bis-, isopropyl, propargyl, ring
Hexyl, 5- methyl isophthalic acids, 2,3- thiadiazoles -4- methylene, cyclopropyl, the chlorallyls of 1,1- bis-, 5- bromopyridine -2- bases, 1,2,3,
4- naphthane -1- bases.
The piperidines thiazole II of present invention synthetic method is as follows：
Wherein, R is selected from H, HHCl, 2- (5H) furanone -4- bases, 2- chloropyridine -5- methylene, propargyl, fluoroform
Sulfonyl orR2Selected from methyl, ethyoxyl, tertbutyloxycarbonyl, trifluoromethyl, phendioxin, 2,3- thiadiazoles -7- bases, 3,
Chloroisothiazole -5- the bases of 4- bis-, 3- trifluoromethyl -5- methylpyrazole -1- methylene, the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrroles
Azoles -5- bases, 1H- indoles -3- methylene, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases, cyclohexyl, cyclopropyl, 2- methyl -4- three
Methyl fluoride thiazole -5- bases, 2- chloropyridine -5- bases；X is selected from O, NH, R1Selected from the fluoro ethyls of 2,2- bis-, isopropyl, propargyl, ring
Hexyl, 5- methyl isophthalic acids, 2,3- thiadiazoles -4- methylene, cyclopropyl, the chlorallyls of 1,1- bis-, 5- bromopyridine -2- bases, 1,2,3,
4- naphthane -1- bases；Y is selected from OH, Br, Cl.
Due to group R and Y difference, there are a variety of different synthetic methods when synthesizing compound II by compound VIII,
Specifically include following several synthetic methods：
When R isAnd Y, when being hydroxyl, the method that compound II is synthesized by compound VIII is as follows：
Wherein：R2Selected from methyl, ethyoxyl, tertbutyloxycarbonyl, trifluoromethyl, phendioxin, 2,3- thiadiazoles -7- bases, 3,
Chloroisothiazole -5- the bases of 4- bis-, 3- trifluoromethyl -5- methylpyrazole -1- methylene, the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H-
Pyrazoles -5- bases, 1H- indoles -3- methylene, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases, cyclohexyl, cyclopropyl, 2- methyl -4-
Trifluoromethyl thiazole -5- bases, 2- chloropyridine -5- bases；X is selected from O, NH, R1Selected from the fluoro ethyls of 2,2- bis-, isopropyl, propargyl,
Cyclohexyl, 5- methyl isophthalic acids, 2,3- thiadiazoles -4- methylene, cyclopropyl, the chlorallyls of 1,1- bis-, 5- bromopyridine -2- bases, 1,2,
3,4- naphthane -1- bases.
When R be propargyl,And Y, when being chlorine atom, the method that compound II is synthesized by compound VIII is as follows：
Wherein R1Selected from the fluoro ethyls of 2,2- bis-, isopropyl；R2For ethyoxyl；X is NH；
When R is 2 (5H) furanone -4- bases and Y is hydroxyl, the method that compound II is synthesized by compound VIII is as follows：
Wherein：R1For the fluoro ethyls of 2,2- bis-, X NH；
When R is 2-vhloro-5-chloromethylpyridine base and Y is Cl, the method that compound II is synthesized by compound VIII is as follows：
Wherein：R1For the fluoro ethyls of 2,2- bis-, X NH；
When R is trifyl and Y is chlorine atom, the method that compound II is synthesized by compound VIII is as follows：
Wherein R1For isopropyl, X NH；
When R is HHCl, the method for synthesizing the corresponding hydrochloride of the compound is as follows：
Wherein R1For isopropyl；X is NH；
The synthetic route of synthetizing thiazolium class compound II intermediate compound I is in the present invention：
It is specifically divided into following steps：
A. the preparation of intermediate compound IV：
10 mMs of III is placed in 100 milliliters of two mouthfuls of round-bottomed flasks, adds 26 mMs of triethylamine, 20 millis
Dichloromethane, nitrogen protection are risen, ice bath stirs, and being added dropwise 13 mMs into reaction system is dissolved in 20 milliliters of dichloromethane
Di-tert-butyl dicarbonate, i.e. Boc2O, be stirred overnight at room temperature after being added dropwise, reacted be added dropwise in backward reaction system 1 mole/
The hydrochloric acid risen, regulation pH value to 5 or so, isolates organic layer, and inorganic layer is washed one time with dichloromethane, merges organic layer and divides
Do not washed one time with water, saturated sodium bicarbonate, saturated sodium-chloride, merge organic phase anhydrous sodium sulfate drying, filtered, rotation is steamed
Hair removes solvent, obtains white crude IV, is stirred at room temperature after 50 milliliters of n-hexane is added into the crude product of gained, stirring is very
Filtered again after clock, naturally dry obtains white solid IV with n-hexane filter wash cake twice, with gained sterling calculated yield, yield
92%；Amount and the volume of reaction vessel prepared by intermediate compound IV is expanded or shunk by corresponding proportion.
B. intermediate V preparation：
Sequentially add 10 mMs of intermediate compound IV in 100 milliliters of round-bottomed flasks, 5.05 mMs of lawesson reagent, 25
Milliliter glycol dimethyl ether, 10 milliliters of dichloromethane, is stirred overnight at room temperature, and is concentrated under reduced pressure after having reacted and removes solvent, residue
Diluted with appropriate ethyl acetate, organic layer successively with saturated potassium carbonate wash twice, saturated common salt wash one time, anhydrous slufuric acid
Sodium is dried, and is filtered, and rotary evaporation removes solvent and obtains yellow solid V, yield 100%；Amount and reaction vessel prepared by intermediate V
Volume expanded or shunk by corresponding proportion.
C. intermediate VI preparation：
10 mMs of intermediate V is added in 100 milliliters of single necked round bottom flask, 20 milliliters of tetrahydrofurans, is stirred at room temperature,
11 mMs of ethyl bromide acetone is added dropwise into reaction system, back flow reaction is changed to after being added dropwise 2 hours, reacted
Directly reaction solution is concentrated backward and removes solvent, residue is dissolved with appropriate ethyl acetate, and organic layer is successively with 1 mol/L hydrogen
Sodium oxide molybdena is washed twice, and saturated common salt is washed one time, anhydrous sodium sulfate drying, is filtered, and rotary evaporation removes solvent, residue warp
200~300 mesh silica gel column chromatographies purify to obtain intermediate VI, and eluant, eluent volume ratio is ethyl acetate/60~90 degree Celsius cut
Petroleum ether=1/3；With gained sterling calculated yield, yield 70-90%；Amount and the volume of reaction vessel prepared by intermediate VI
Expanded or shunk by corresponding proportion.
D. the preparation of intermediate compound I
10 mMs of intermediate VI, 15 milliliters of tetrahydrofurans, 15 milliliters of nothings are added in 100 milliliters of single necked round bottom flask
Water methanol, it is stirred at room temperature, 20 mMs of sodium hydroxide is added in backward reaction bulb, 3 milliliters of water, it is small that reaction 3 is stirred at room temperature
When, directly reaction solution is concentrated after having reacted and removes organic solvent, residue is dissolved with appropriate ethyl acetate, adds 8 milliliters
Water, water layer is separated, water layer adjusts pH to 1 with the concentrated hydrochloric acid of 12 mol/Ls, now there is white solid precipitation, and decompression filters, filter cake
It is washed with water once, naturally dry obtains white solid I, yield 93%；Amount and the volume of reaction vessel prepared by intermediate compound I presses phase
Ratio is answered to expand or shrink.
E. intermediate VII preparation
10.5 mMs of intermediate compound I, 12 mMs of 1- (3- bis- are sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks
Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides, i.e. EDCI, 10.5 mMs of I-hydroxybenzotriazole, i.e. HOBT, take out
Vacuum, nitrogen protection, 20 milliliters of dry dichloromethane are added into reaction system, ice bath is changed to after being stirred at room temperature 1 hour and stirs
Mix, 10 mMs of a variety of amine or alcohol that are dissolved in 10 milliliters of dichloromethane are added dropwise into reaction, 12 millis are finally added dropwise
Mole triethylamine, all add after be stirred overnight at room temperature, reaction solution is washed with water twice successively after having reacted, saturation
Sodium acid carbonate and saturated aqueous common salt are respectively washed one time, anhydrous sodium sulfate drying, are filtered, and rotary evaporation removes solvent, residue warp
200~300 mesh silica gel column chromatographies purify to obtain intermediate VII, and eluant, eluent is the oil of ethyl acetate/60~90 degree Celsius cut
Ether, volume ratio 1: 5 to 3: 1 different according to product；With gained sterling calculated yield, yield 33-95%；Intermediate VII systems
Standby amount and the volume of reaction vessel are expanded or shunk by corresponding proportion.
F. intermediate VIII preparation
10 mMs of intermediate VII is placed in 100 milliliters of two-mouth bottles, dissolved with 20 milliliters of dry dichloromethane,
Nitrogen is protected, ice bath stirring, and 4 milliliters of trifluoroacetic acid is added dropwise into reaction system, it is small to be stirred at room temperature 1 after being all added dropwise
When, the sodium hydroxide that 1 mol/L is added dropwise in backward reaction solution has been reacted, has adjusted pH value to separate organic layer, organic layer to 10 or so
With saturated common salt washing once, anhydrous sodium sulfate drying, filter, rotary evaporation removes solvent, and residue is through 200~300 mesh silicon
Gel column chromatography eluting to obtain intermediate VIII, eluant, eluent is methylene chloride/methanol, different according to product, volume ratio 50: 1 to 6:
1；With gained sterling calculated yield, yield 75-93%；Amount and the volume of reaction vessel prepared by intermediate VIII is by corresponding ratio
Example is expanded or shunk.
G. piperidines thiazole II preparation：
When R isAnd Y, when being hydroxyl, compound II preparation method is as follows：
10.5 mMs of intermediate compound I, 12 mMs of 1- (3- bis- are sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks
Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides, i.e. EDCI, 10.5 mMs of I-hydroxybenzotriazole, i.e. HOBT, take out
Vacuum, nitrogen protection, 20 milliliters of dry dichloromethane are added into reaction system, ice bath is changed to after being stirred at room temperature 1 hour and stirs
Mix, 10 mMs of a variety of amine or alcohol that are dissolved in 10 milliliters of dichloromethane are added dropwise into reaction, 12 millis are finally added dropwise
Mole triethylamine, all add after be stirred overnight at room temperature, reaction solution is washed with water twice successively after having reacted, saturation
Sodium acid carbonate and saturated aqueous common salt are respectively washed one time, anhydrous sodium sulfate drying, are filtered, and rotary evaporation removes solvent, residue warp
200~300 mesh silica gel column chromatographies purify to obtain compound II, and eluant, eluent is the oil that people's degree cut is taken the photograph in ethyl acetate/60~90
Ether, it is different according to product, it is 1: 5 to 3: 1 to volume ratio；With gained sterling calculated yield, yield 24-98%；Compound II systems
Standby amount and the volume of reaction vessel are expanded or shunk by corresponding proportion.Compound II chemical constitution and physical and chemical parameter is shown in Table 1.
When R be propargyl,And Y, when being chlorine atom, compound II preparation method is as follows：
10 mMs of compound VIII, 20 mMs of potassium carbonate, with 10 are added in 100 milliliters of two mouthfuls of round-bottomed flasks
Milliliter DMF dissolving, ice bath stirring, the propargyl bromide or chloro-carbonic acid second of 15 mMs of dropwise addition into reaction
Ester, it is stirred at room temperature after being added dropwise 4 hours, decompression, which filters, after having reacted removes insoluble solid, and filtrate is dilute with enough water
Release, add appropriate ethyl acetate, separate organic layer, with saturated common salt washing once, anhydrous sodium sulfate drying, filter, rotation
Evaporation of solvent, residue purify to obtain compound II through 200~300 mesh silica gel column chromatographies, eluant, eluent be ethyl acetate/60~
The petroleum ether of 90 degrees Celsius of cuts, when R is propargyl, volume ratio is 1: 1, works as R2For ethyoxyl when, volume ratio 1: 2；With
Gained sterling calculated yield, yield 40-80%；Amount and the volume of reaction vessel prepared by compound II is expanded by corresponding proportion
Or reduce.Compound II chemical constitution and physical and chemical parameter is shown in Table 1.
When R is 2 (5H) furanone -4- bases and Y is hydroxyl, compound II preparation method is as follows：
The compound VIII of 0.73 mM of addition, 1.09 mMs of tetronic acids in 100 milliliters of round-bottomed flasks, 10 milligrams
P-methyl benzenesulfonic acid, add the appropriate molecular sieve dried through Muffle furnace, dissolved, be heated to reflux with 10 milliliters of dry toluenes
Reaction 6 hours, decompression, which filters, after reacting completely removes solid, filtrate concentration, and residue is pure through 200~300 mesh silica gel column chromatographies
Change to obtain compound II, eluant, eluent volume ratio is petroleum ether=1/1 of ethyl acetate/60~90 degree Celsius cut, with gained sterling
Calculated yield, yield 50%；Amount and the volume of reaction vessel prepared by compound II is expanded or shunk by corresponding proportion.Chemical combination
Thing II chemical constitution and physical and chemical parameter is shown in Table 1.
When R is the chloro- pyridine -5- methylene of 2- and Y is chlorine atom, compound II preparation method is as follows：
1.94 mMs of compound VIII is added in 100 milliliters of single necked round bottom flask, rear 0.97 mM of addition
Potassium carbonate, dissolved with 20 milliliters of acetonitriles, heating reflux reaction is overnight, and decompression, which filters, after reacting completely removes solid, and filtrate is dense
Contracting, residue are diluted with ethyl acetate, are washed one time with water, saturated sodium bicarbonate, saturated common salt respectively, anhydrous sodium sulfate is done
It is dry, filter, rotary evaporation remove solvent, residue through 200~300 mesh silica gel column chromatographies purify compound II, eluant, eluent are
Petroleum ether=1 of ethyl acetate/60~90 degree Celsius cut: 3, with gained sterling calculated yield, yield 51.55%；Compound
Amount and the volume of reaction vessel prepared by II is expanded or shunk by corresponding proportion；Compound II chemical constitution and physical and chemical parameter is shown in
Table 1.
When R is trifyl and Y is chlorine atom, compound II preparation method is as follows：
10 mMs of compound VIII is added in 100 milliliters of two mouthfuls of round-bottomed flasks, with 20 milliliters of dry dichloromethanes
Alkane is dissolved, and 20 mMs of diisopropylethylamine, 10 milligrams of 4-dimethylaminopyridine are added in backward reaction, and ice bath stirs
Mix, 15 mMs of trifluoromethanesulfchloride chloride is added dropwise into reaction, rear room temperature stirring reaction is added dropwise 5 hours, it is anti-after having reacted
Liquid is answered to use saturated sodium bicarbonate successively, saturated common salt is washed once, anhydrous sodium sulfate drying, is filtered, and rotary evaporation removes molten
Agent, residue purify to obtain compound II through 200~300 mesh silica gel column chromatographies, and eluant, eluent is ethyl acetate/60~90 degree Celsius
Petroleum ether=1 of cut: 2, with gained sterling calculated yield, yield 79.39%；Amount and reaction vessel prepared by compound II
Volume is expanded or shunk by corresponding proportion；Compound II chemical constitution and physical and chemical parameter is shown in Table 1.
When R is HHCl, the method for synthesizing the corresponding hydrochloride II of the compound is as follows：
1 mM of compound VII 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 into reaction, and room temperature continues stirring 3 hours, reaction
Reaction solution directly concentrates removing organic solvent after complete, and appropriate absolute ethyl alcohol is added into flask, continues concentration and removes on a small quantity
Water, finally obtain product as light yellow solid II, yield 100%；Amount and the volume of reaction vessel prepared by compound II is by corresponding ratio
Example is expanded or shunk；Compound II chemical constitution and physical and chemical parameter is shown in Table 1.
H. piperidines thiazole II of the invention bactericidal activity measure：
The piperidines thiazole II of present invention sterilization or bacteriostatic activity use thalli growth rate determination method, specific steps
For：Take 1.8 milligrams of samples to be dissolved in appropriate dimethylformamide, then use and contain a certain amount of polysorbas20 emulsifier aqueous solution
The medicament of 500 mcg/mls is diluted to, reagent agent is aseptically respectively drawn in 1 milliliter of injection culture dish, then is divided
Not Jia Ru 9 milliliters of PDA culture mediums, 50 mcg/ml drug containing flat boards are made after shaking up, with add 1 milliliter of aqua sterilisa flat board
Blank control is done, bacterium disk is cut along mycelia outer rim with 4 millimeters of card punch of diameter, moves on drug containing flat board, in equilateral triangle
Put, 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
Each processing bacterium disk extension diameter is investigated after opening up 2-3 centimetres, averages, relative bacteriostasis rate is calculated compared with blank control, is supplied
Examination strain is the kind of most of typical plant pathogen that field actually occurs in China's agricultural production, its code name and title
It is as follows：AS：Tomato early blight bacterium, its Latin are entitled：Alternaria solani、BC：Botrytis cinerea pers, its latin name
For：Botrytis cinerea、CA：Peanut Cercospora bacteria, its Latin are entitled：Cercospora arachidicola、 GZ：It is small
Wheat gibberellic hypha, its Latin are entitled：Gibberella zeae、PI：Phytophthora infestans, its Latin are entitled：
Phytophthora infestans(Mont.)de Bary、PP：Botryosphaeria berengeriana f. sp, its Latin are entitled：Physalospora
piricola、PS：Rhizoctonia solani Kuhn, its Latin are entitled：Pellicularia sasakii、RC：Rhizoctonia cerealis, it draws
Fourth is entitled：Rhizoctonia cerealis、SS：Sclerotinia sclerotiorum, its Latin are entitled：Sclerotinia
sclerotiorum。
I. piperidines thiazole II of the invention inducing anti-disease activity measure：
The screening technique of the piperidines thiazole II evoking tobacco activity of resisting tobacco mosaic virus of the present invention is as follows, tobacco
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 piperidines thiazole：In vitro directly antiviral activity
Measure is carried out using half leaf method；Live body induction is that 3 basins are one group, before inoculation before 7 days by the consistent common cigarette of seedling age
Treated tobacco seedlings, 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 50 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, comprehensive scab number is calculated as follows out for examination chemical combination
Induction antiviral effect of the thing 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 treatment for carrying out piperidines thiazole II anti-TMV is lived
Property, passivation activity and protection activity measure.
J. the measure of piperidines thiazole II of the invention to diamondback moth insecticidal activity：
The piperidines thiazole II of the present invention uses blade medicine embrane method to the screening technique of diamondback moth insecticidal activity：It is to be measured
Sample is configured to the solution of 100 mg/litres, takes active compound sample first with a small amount of acetone solution, then with 0.5 ‰ Triton-100
The aqueous solution dilutes, and the 0.5 ‰ Triton-100 aqueous solution are control, each 3 repetitions of concentration, each reprocess 10 test worms；
Fresh free of contamination cabbage leaves are taken, are soaked 10 seconds in decoction, after drying about 2 hours in interior, are put into 9 centimetres of diameter
In culture dish, the basically identical instar larvae of diamondback moth 2 of size is respectively connected to, diamondback moth constant temperature is placed in after being tightened with rubber band and is supported
In zooecium, inspection result after 72 hours, polypide is touched with small writing brush or tweezers, it is impossible to which the coordinated movement of various economic factors is as dead.
K. the measure of piperidines thiazole II of the invention to mythimna separata insecticidal activity：
Screenings of the piperidines thiazole II of the present invention to mythimna separata insecticidal activity uses leaf dipping method：Claim on assay balance
Take 2 milligrams of medicine samples to add 10 milliliters of acetone in 10 milliliters of penicillin vials, into the mother liquor of 100 mg/litres, cover plug and shake
Dissolving is swung, then decoction is diluted to the working solution of 5 mcg/mls with acetone, with straight peen ophthalmology tweezers soaking maize blade,
2~3 seconds time, get rid of extraction raffinate；1 tablet once, totally 8, each sample；It is successively placed on processing paper, treats by sample flag sequence
It is put into after decoction is dry in the culture dish of markd 10 centimetres of tool, armyworm larvae at the beginning of accessing for 10 first 3 ages with elbow ophthalmology tweezers,
Test process is placed in constant temperature standard insectary to inspection result after cultivating 72 hours, larva body is touched with small writing brush or tweezers,
It is completely motionless for death standard with larva；The maize leaves impregnated with acetone soln are blank control.
L. the measure of piperidines thiazole II of the invention to aphid cytotoxicity：
The piperidines thiazole II of the present invention is determined as follows to aphid cytotoxicity：Using infusion process, black bean aphid, draw
The entitled Aphis laburni Kaltenbach (ALK) of fourth, the normal population of indoor feeding；Weigh 2.5 milligrams of test compound
In beaker, 1 drop DMF is added dropwise, be i.e. DMF, adds 5 milliliters of acetone vibration dissolving samples, has added tween
80 water is configured to the solution to be measured of 100 mg/litres；The bean plant that supplies to try with least 60 black bean aphids is cut from basin
Under, impregnated 5 seconds in each decoction to be measured, unnecessary decoction is gently got rid of in taking-up, is inserted in and is protected on water saturated sponge
It is wet, escaped after decoction is dry with cloche cover, the opening of cloche upper end is sealed with gauze to prevent aphid, raising places 48
Aphid death state is checked after hour, standard is：It can be creeped or can stood or six Tiao Tuineng strenuous exercises are work with test worm
Worm；Using clear water as control, imidacloprid is positive control, calculates corrected mortality.
M. the measure of piperidines thiazole II of the invention to the full acaricidal activity of cinnabar leaf：
The piperidines thiazole II of present invention acaricidal activity is determined using infusion process, and detailed process is：Test compounds
Thing is configured to mother liquor with dimethylformamide, and the solution of 100 mg/litres is diluted to the water containing 0.1%-0.2% containing emulsifying agent
Stand-by, dimethylformamide is no more than 2%；Selection density is big, age is neat, entitled with Tetranychus cinnabarinus, Latin
Tetranychus cinnabarinus are cut into about 2 square centimeters of small pieces into the blade of mite, and the one side for having mite is placed on tool upward
On the blade of two panels true leaf, under greenhouse natural light irradiation, after two hours, new leaf back is can be transferred into mite；Select mite amount every
The new field planting plant of strain 50~80, cuts from basal part of stem, after blade is immersed into decoction taking-up in 5 seconds together with worm band seedling, gently
Light shake, removes unnecessary decoction, then move into water planting cylinder be placed on cultivated 48 hours in 25 DEG C of thermostatic chambers after under binocular
Life or death borer population is checked, calculates the death rate；Death standard is gently to touch into mite with Jie's dissecting needle, and limbs are dynamic but are unable to scrambler
It is considered as death；Clear water is blank.
N. piperidines thiazole II of the invention live body bactericidal activity measure：
Using the potted plant assay method of live body, i.e., test compound sample is dissolved with a small amount of solvent acetone or methanol or DMF,
Select solvent according to its solvability to sample, the volume ratio of quantity of solvent and spouting liquid is equal to or less than 0.05, with containing
The water dilution of 0.1% Tween 80, is configured to required concentration prepare liquid；On crops sprayer, prepare liquid is sprayed in band cause of disease
On the host plant of thing, host plant is the standard Potted orchard cultivated in greenhouse, and pathogen is inoculated with after 24 hours；According to disease
The characteristics of evil, it would be desirable to be placed in phjytotron and cultivate after the plant inoculating with pathogen of temperature control moisturizing culture, treat disease
After completion is infected, hot-house culture is moved into, the plant with pathogen for not needing moisturizing culture directly in warm indoor inoculation and is trained
Support；Compound protection effect assessment is carried out after fully morbidity is compareed, plant disease time is usually one week or so；Test
Live plant disease is：Cucumber downy mildew, the entitled Pseudoperonospora cubensis of Latin (Berk.et Curt.)
Rostov, PCB, wheat powdery mildew are abbreviated as, entitled Blumeria graminis (DC.) Speer of Latin, is abbreviated as BGS, jade
Rice rust, the entitled Puccinia sorghi Schw of Latin, is abbreviated as PSS, watermelon anthrax, Latin is entitled
Colletotrichum orbiculare (Berk.＆Ment.), are abbreviated as COB, and test concentrations are 400 mg/litres, rice rice
Seasonal febrile diseases, entitled Pyricularia grisea (Cooke) Sacc of Latin, are abbreviated as PGS, gray mold of cucumber, Latin is entitled
Botrytis cinerea are abbreviated as BC, and test concentrations are 25 mg/litres.
The beneficial effects of the invention are as follows：Guide's optimization has been carried out to piperidines thiazole II, and to the new chemical combination of synthesis
Thing has carried out the screening of insecticidal activity and bacteriostatic activity and antiviral activity.
The present invention illustrates piperidines thiazole II's by the way that specific preparation and biological activity determination embodiment are more specific
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 biological
Activity is merely illustrative of, and unrestricted this patent, embodiment are as follows：
Embodiment 1
The preparation of intermediate compound IV：
10 mMs of III is placed in 100 milliliters of two mouthfuls of round-bottomed flasks, adds 26 mMs of triethylamine, 20 millis
Dichloromethane, nitrogen protection are risen, ice bath stirs, and being added dropwise 13 mMs into reaction system is dissolved in 20 milliliters of dichloromethane
Di-tert-butyl dicarbonate, i.e. Boc2O, be stirred overnight at room temperature after being added dropwise, reacted be added dropwise in backward reaction system 1 mole/
The hydrochloric acid risen, regulation pH value isolate organic layer to 5 or so, and inorganic layer is washed one time with dichloromethane, organic layer respectively with water,
Saturated sodium bicarbonate, saturated sodium-chloride are respectively washed one time, merge organic phase anhydrous sodium sulfate drying, are filtered, and rotary evaporation removes
Solvent obtains white crude IV, is stirred at room temperature after adding 50 milliliters of n-hexanes into the crude product of gained, and stirring is taken out again after 10 minutes
Filter, naturally dry obtains white solid IV with n-hexane filter wash cake twice, with gained sterling calculated yield, yield 92%；1H
NMR(CDCl3)δ：5.92 (s, 1H), 5.68 (s, 1H), 4.24-4.04 (m, 2H), 2.84-2.68 (m, 2H), 2.34-2.27
(m, 1H), 1.89-1.80 (m, 2H), 1.67-1.57 (m, 2H), 1.46 (s, 9H).
Embodiment 2
Intermediate V preparation：
Sequentially add 10 mMs of intermediate compound IV in 100 milliliters of round-bottomed flasks, 5.05 mMs of lawesson reagent, 25
Milliliter glycol dimethyl ether, 10 milliliters of dichloromethane, is stirred overnight at room temperature, and is concentrated under reduced pressure after having reacted and removes solvent, residue
Diluted with appropriate ethyl acetate, organic layer is washed twice with saturated potassium carbonate successively, and saturated common salt is washed one time, anhydrous slufuric acid
Sodium is dried, and is filtered, and rotary evaporation removes solvent and obtains yellow solid V, yield 100%；1HNMR(CDCl3)δ：7.75 (s, 1H),
7.21 (s, 1H), 4.33-4.11 (m, 2H), 2.82-2.64 (m, 3H), 1.91-1.87 (m, 2H), 1.78-1.67 (m, 2H),
1.46 (s, 9H).
Embodiment 3
Intermediate VI preparation：
10 mMs of intermediate V is added in 100 milliliters of single necked round bottom flask, 20 milliliters of tetrahydrofurans, is stirred at room temperature,
11 mMs of ethyl bromide acetone is added dropwise into reaction system, back flow reaction is changed to after being added dropwise 2 hours, reacted
Directly reaction solution is concentrated backward and removes solvent, residue is dissolved with appropriate ethyl acetate, and organic layer is successively with 1 mol/L hydrogen
Sodium oxide molybdena is washed twice, and saturated common salt is washed one time, anhydrous sodium sulfate drying, is filtered, and rotary evaporation removes solvent, residue warp
200~300 mesh silica gel column chromatographies purify to obtain intermediate VI, and eluant, eluent volume ratio is ethyl acetate/60~90 degree Celsius cut
Petroleum ether=1/3, with gained sterling calculated yield, yield：70-90%；1HNMR(CDCl3)δ：8.07 (s, 1H), 4.40 (q, J
=7.1Hz, 2H), 4.22-4.20 (m, 2H), 3.27-3.20 (m, 1H), 2.83 (brd, 2H), 2.12-2.09 (m, 2H),
1.75-1.65 (m, 2H), 1.45 (s, 9H), 1.38 (t, J=7.1Hz, 3H).
Embodiment 4
The preparation of intermediate compound I：
10 mMs of intermediate VI, 15 milliliters of tetrahydrofurans, 15 milliliters of nothings are added in 100 milliliters of single necked round bottom flask
Water methanol, it is stirred at room temperature, 20 mMs of sodium hydroxide is added in backward reaction bulb, 3 milliliters of water, it is small that reaction 3 is stirred at room temperature
When, directly reaction solution is concentrated after having reacted and removes organic solvent, residue is dissolved with appropriate ethyl acetate, adds 8 milliliters
Water, water layer is separated, water layer adjusts pH to 1 with the concentrated hydrochloric acid of 12 mol/Ls, now there is white solid precipitation, and decompression filters, filter cake
It is washed with water once, naturally dry obtains white solid I, yield 93%；1HNMR(CDCl3)δ：9.09 (brd, 1H), 8.21 (s,
1H), 4.25-4.24 (m, 2H), 3.33-3.20 (m, 1H), 2.88 (brd, 2H), 2.15-2.12 (m, 2H), 1.80-1.48
(m, 2H), 1.48 (s, 9H).
Embodiment 5
Intermediate VII preparation：
10.5 mMs of intermediate compound I, 12 mMs of 1- (3- bis- are sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks
Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides, i.e. EDCI, 10.5 mMs of I-hydroxybenzotriazole, i.e. HOBT,
Vacuumize, nitrogen protection, 20 milliliters of dry dichloromethane are added into reaction system, ice bath is changed to after being stirred at room temperature 1 hour
Stirring, 10 mMs of a variety of amine or alcohol that are dissolved in 10 milliliters of dichloromethane are added dropwise into reaction, are finally added dropwise 12
MM triethylamine, all add after be stirred overnight at room temperature.Reaction solution is washed with water twice successively after having reacted, satisfied
Respectively wash one time, anhydrous sodium sulfate drying, filter with sodium acid carbonate and saturated aqueous common salt, rotary evaporation removes solvent, residue warp
200~300 mesh silica gel column chromatographies purify to obtain intermediate VII, and eluant, eluent is the oil of ethyl acetate/60~90 degree Celsius cut
Ether, according to the difference of product, volume ratio 1: 5 to 3: 1；With gained sterling calculated yield, yield 80-95%.
Embodiment 6
Intermediate VIII preparation：
10 mMs of intermediate VII is placed in 100 milliliters of two-mouth bottles, dissolved with 20 milliliters of dry dichloromethane,
Nitrogen is protected, ice bath stirring, and 4 milliliters of trifluoroacetic acid is added dropwise into reaction system, it is small to be stirred at room temperature 1 after being all added dropwise
When, the sodium hydroxide that 1 mol/L is added dropwise in backward reaction solution has been reacted, tune pH value to 10 or so, has separated organic layer, it is organic
Layer once, anhydrous sodium sulfate drying, is filtered, rotary evaporation removes solvent, and residue is through 200~300 mesh with saturated common salt washing
Silica gel column chromatography purifies to obtain intermediate VIII, and eluant, eluent is methylene chloride/methanol, according to the difference of product, volume ratio 50: 1
To 6: 1；With gained sterling calculated yield, yield 75-93%.
Embodiment 7
When R isAnd Y, when being hydroxyl, compound II preparation method is as follows：
10.5 mMs of intermediate compound I, 12 mMs of 1- (3- bis- are sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks
Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides, i.e. EDCI, 10.5 mMs of I-hydroxybenzotriazole, i.e. HOBT,
Vacuumize, nitrogen protection, 20 milliliters of dry dichloromethane are added into reaction system, ice bath is changed to after being stirred at room temperature 1 hour
Stirring, 10 mMs of a variety of amine or alcohol that are dissolved in 10 milliliters of dichloromethane are added dropwise into reaction, are finally added dropwise 12
MM triethylamine, be stirred overnight at room temperature after all adding, reaction solution be washed with water twice successively after react, it is full
Respectively wash one time, anhydrous sodium sulfate drying, filter with sodium acid carbonate and saturated aqueous common salt, rotary evaporation removes solvent, residue warp
200~300 mesh silica gel column chromatographies purify to obtain compound II, and eluant, eluent is the oil of ethyl acetate/60~90 degree Celsius cut
Ether, volume ratio 1: 5 to 3: 1 different according to product；With gained sterling calculated yield, yield 80-95%；Compound II change
Learn structure and physical and chemical parameter is shown in Table 1.
Embodiment 8
When R be propargyl,And Y, when being chlorine atom, compound II preparation method is as follows：
10 mMs of compound VIII, 20 mMs of potassium carbonate, with 10 are added in 100 milliliters of two mouthfuls of round-bottomed flasks
Milliliter DMF dissolving, ice bath stirring, the propargyl bromide or chloro-carbonic acid second of 15 mMs of dropwise addition into reaction
Ester, it is stirred at room temperature after being added dropwise 4 hours, decompression, which filters, after having reacted removes insoluble solid, and filtrate is dilute with enough water
Release, add appropriate ethyl acetate, separate organic layer, with saturated common salt washing once, anhydrous sodium sulfate drying, filter, rotation
Evaporation of solvent, residue purify to obtain compound II through 200~300 mesh silica gel column chromatographies, eluant, eluent be ethyl acetate/60~
The petroleum ether of 90 degrees Celsius of cuts, when R is propargyl, volume ratio is 1: 1, works as R2For ethyoxyl when, volume ratio 1: 2；With
Gained sterling calculated yield, yield 40-80%；Compound II chemical constitution and physical and chemical parameter is shown in Table 1.
Embodiment 9
When R is 2 (5H) furanone -4- bases and Y is hydroxyl, compound II preparation method is as follows：
The compound VIII of 0.73 mM of addition, 1.09 mMs of tetronic acids in 100 milliliters of round-bottomed flasks, 10 milligrams
P-methyl benzenesulfonic acid, add the appropriate molecular sieve dried through Muffle furnace, dissolved, be heated to reflux with 10 milliliters of dry toluenes
Reaction 6 hours, decompression, which filters, after reacting completely removes solid, filtrate concentration, and residue is pure through 200~300 mesh silica gel column chromatographies
Change to obtain compound II, eluant, eluent volume ratio is petroleum ether=1/1 of ethyl acetate/60~90 degree Celsius cut, with gained sterling
Calculated yield, yield 50%；Compound II chemical constitution and physical and chemical parameter is shown in Table 1.
Embodiment 10
When R is the chloro- pyridine -5- methylene of 2- and Y is chlorine atom, compound II preparation method is as follows：
1.94 mMs of compound VIII is added in 100 milliliters of single necked round bottom flask, rear 0.97 mM of addition
Potassium carbonate, dissolved with 20 milliliters of acetonitriles, heating reflux reaction is overnight, and decompression, which filters, after reacting completely removes solid, and filtrate is dense
Contracting, residue are diluted with ethyl acetate, are washed one time with water, saturated sodium bicarbonate, saturated common salt respectively, anhydrous sodium sulfate is done
It is dry, filter, rotary evaporation remove solvent, residue through 200~300 mesh silica gel column chromatographies purify compound II, eluant, eluent are
Petroleum ether=1 of ethyl acetate/60~90 degree Celsius cut: 3, with gained sterling calculated yield, yield 51.55%；Compound
II chemical constitution and physical and chemical parameter is shown in Table 1.
Embodiment 11
When R is trifyl and Y is chlorine atom, compound II preparation method is as follows：
10 mMs of compound VIII is added in 100 milliliters of two mouthfuls of round-bottomed flasks, with 20 milliliters of dry dichloromethanes
Alkane is dissolved, and 20 mMs of diisopropylethylamine, 10 milligrams of 4-dimethylaminopyridine are added in backward reaction, and ice bath stirs
Mix, 15 mMs of trifluoromethanesulfchloride chloride is added dropwise into reaction, rear room temperature stirring reaction is added dropwise 5 hours, it is anti-after having reacted
Liquid is answered to use saturated sodium bicarbonate successively, saturated common salt is washed once, anhydrous sodium sulfate drying, is filtered, and rotary evaporation removes molten
Agent, residue purify to obtain compound II through 200~300 mesh silica gel column chromatographies, and eluant, eluent is ethyl acetate/60~90 degree Celsius
Petroleum ether=1 of cut: 2, with gained sterling calculated yield, yield 79.39%；Compound II chemical constitution and physical and chemical parameter
It is shown in Table 1.
Embodiment 12
When R is HHCl, the method for synthesizing the corresponding hydrochloride II of the compound is as follows：
1 mM of compound VII 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 into reaction, are stirred at room temperature 3 hours, after having reacted
Reaction solution directly concentrates removing organic solvent, and appropriate absolute ethyl alcohol is added into flask, continues concentration and removes a small amount of water,
Finally obtain product as light yellow solid II, yield 100%；Compound II chemical constitution and physical and chemical parameter is shown in Table 1.
Embodiment 13
The piperidines thiazole II 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, its latin name
For： Alternaria solani、BC：Botrytis cinerea pers, its Latin are entitled：Botrytis cinerea、CA：Peanut foxiness
Germ, its Latin are entitled：Cercospora arachidicola、GZ：Fusarium graminearum, its Latin are entitled：
Gibberella zeae、 PI：Phytophthora infestans, its Latin are entitled：Phytophthora infestans(Mont.)de
Bary、PP：Botryosphaeria berengeriana f. sp, its Latin are entitled：Physalospora piricola、PS：Rhizoctonia solani Kuhn, its Latin
It is entitled：Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin are entitled：Rhizoctonia cerealis、SS：Oil
Dish hyphal cluster germ, its Latin are entitled：Sclerotinia sclerotiorum, these strains have representativeness well, can
Represent the kind of most of pathogen that field occurs in agricultural production.It is worth noting that compound lfy006- in the present invention
5 and lfy006-39 is the known compound for the high activity reported in patent document WO2008091594, in order to more of the invention
The bioactivity of the noval chemical compound of synthesis, this 2 structures have been synthesized closest to target compound of the present invention and patent in of the invention
Document report its active highest similar compound lfy006-5, lfy006-39.Thalli growth rate method measurement result is shown in Table 2,
Table 2 shows, in 50 mcg/ml, all compounds that the present invention synthesizes have different degrees of bactericidal activity.To tomato
For early epidemic germ, compound lfy006-3, lfy005-23, lfy005-22, lfy004-35, lfy004-36, lfy004-
6、lfy004-16、lfy005-21、 lfy006-19、lfy006-24、lfy6-16、lfy005-17、lfy005-10、
lfy006-12、lfy007-1、lfy007-16、lfy004-43、 lfy005-6、lfy006-6、lfy006-9、lfy005-32
Inhibitory activity more than 48%, the bactericidal activity of above-claimed cpd is higher than lfy006-5, lfy006-39 and Fluoxastrobin, and living
Property be higher by structure is similar, document report active best compound lfy006-5 and lfy006-39 more than 10%, chemical combination
Thing lfy005-22, lfy006-6, lfy006-9 activity are higher than 70%, wherein lfy006-9 active highest, reach
85.71%.The Activity Results of peanut Cercospora asparagagas are shown, compound lfy004-36, lfy004-30, lfy006-6,
Lfy006-24, lfy007-16, lfy005-22, lfy004-6, lfy005-6 bacteriostatic activity are more than 50%, above-mentioned chemical combination
The bactericidal activity of thing is higher than lfy006-5, lfy006-39, wherein, compound lfy005-22, lfy004-6, lfy005-6's
Bacteriostatic activity is more than 60%, and activity is higher than comparison medicament Fluoxastrobin, and activity is higher by that structure is similar, document report is active most
Good compound lfy006-5 and lfy006-39 compound lfy005-6 active highest, reaches more than 10%
74.19%.The active testing result of fusarium graminearum is shown, compound lfy004-36, lfy004-39, lfy004-30,
Lfy006-6, lfy005-32, lfy006-16, lfy005-10, lfy008-4-1 bacteriostatic activity are more than 50%, above-mentionedization
The bactericidal activity of compound is higher than lfy006-5, lfy006-39, wherein, compound lfy005-32, lfy006-9, lfy004-
39th, lfy008-4-1 bacteriostatic activity is more than 60%, and activity is higher by that structure is similar, the active best compound of document report
Lfy006-5 and lfy006-39 is more than 10%, compound lfy004-39 active highest, be 75.86%, slightly above pair
According to medicament Fluoxastrobin.Compound shows Botryosphaeria berengeriana f. sp inhibitory activity result, compound lfy004-35, lfy004-47,
lfy004-36、 lfy004-16、lfy005-15、lfy005-21、lfy006-3、lfy005-10、lfy006-12、lfy006-
29th, lfy007-1, lfy004-43, lfy004-30, lfy006-18, lfy004-39, lfy004-23 bacteriostatic activity exist
More than 63%, the bactericidal activity of above-claimed cpd is higher than lfy006-5, lfy006-39, wherein, compound lfy006-3,
Lfy005-10, lfy007-1, lfy004-35, lfy004-36, lfy004-16, lfy005-15, lfy004-47 antibacterial work
Property be higher than 73%, activity is higher by that structure is similar, document report active best compound lfy006-5 and lfy006-39 exist
More than 10%, compound lfy006-3 activity are 96.15%, higher than comparison medicament Fluoxastrobin.Work to botrytis cinerea pers
Property test show, compound lfy004-4, lfy005-8, lfy004-36, lfy004-16, lfy004-6, lfy005-21,
Lfy005-32, lfy006-16, lfy005-10, lfy004-32, lfy004-43, lfy005-6 bacteriostatic activity 65% with
On, the bactericidal activity of above-claimed cpd is higher than lfy006-5, lfy006-39, wherein, compound lfy004-4, lfy004-16,
Lfy004-6, lfy005-21, lfy005-10 bacteriostatic activity are more than 75%, and higher than comparison medicament Fluoxastrobin, activity is higher by
Structure is similar, document report active best compound lfy006-5 and lfy006-39 are more than 10%.To rape sclerotium
The active testing of germ shows, compound lfy006-18, lfy005-22, lfy004-47, lfy004-36, lfy004-6,
lfy005-15、lfy005-21、lfy006-6、lfy005-17、 lfy005-23、lfy006-3、lfy005-32、lfy006-
24th, lfy005-10, lfy006-29, lfy007-1, lfy007-16, lfy007-17, lfy004-43, lfy007-8's is antibacterial
Activity is more than 50%, and the bactericidal activity of above-claimed cpd is similar higher than structure, the active best compound of document report
Lfy006-5, lfy006-39, wherein, compound lfy006-18, lfy005-22, lfy004-47, lfy004-36,
lfy004-6、lfy005-15、lfy005-21、lfy006-6、lfy005-17、lfy005-23、lfy006-3、 lfy005-
32nd, lfy006-24, lfy006-29, lfy007-1, lfy007-16, lfy004-43 bacteriostatic activity are higher than 60%, and activity is high
Go out structure is similar, document report active best compound lfy006-5 and lfy006-39 more than 10%, compound
lfy006-18、lfy005-22、lfy004-47、lfy004-36、lfy005-15、lfy005-21、lfy005-17、lfy006-
3rd, lfy006-24 bacteriostatic activity is all higher than 90%.The active testing of Rhizoctonia cerealis is shown, compound lfy006-18,
lfy005-22、lfy004-35、lfy004-47、lfy004-36、lfy004-16、lfy004-6、lfy004-39、lfy005-
15、 lfy005-21、lfy004-30、lfy005-17、lfy006-9、lfy005-10、lfy006-12、lfy004-43、
For lfy005-6 bacteriostatic activity more than 75%, the bactericidal activity of above-claimed cpd is higher than lfy006-5, lfy006-39, its
In, compound lfy004-47, lfy004-39, lfy005-15, lfy005-2l, lfy006-9, lfy005-10, lfy005-
22nd, lfy004-35, lfy004-36, lfy004-16, lfy004-30, lfy004-43 bacteriostatic activity are higher than 80%, activity
Be higher by structure is similar, document report active best compound lfy006-5 and lfy006-39 more than 10%, compound
Lfy004-35, lfy004-36, lfy004-16, lfy005-21, lfy004-43 activity are more than 90%, higher than comparison medicine
Agent Fluoxastrobin.The active testing of Rhizoctonia solani Kuhn is shown, compound lfy004-36, lfy004-16, lfy004-6,
Lfy004-39, lfy005-15, lfy005-21, lfy004-43, lfy005-10, lfy006-12 bacteriostatic activity 70% with
On, the bactericidal activity of above-claimed cpd is higher than lfy006-5, lfy006-39, wherein, compound lfy004-36, lfy004-
16th, lfy004-6, lfy005-21, lfy004-43, lfy006-12 bacteriostatic activity are higher than 80%, and activity is higher by structure class
Like, document report activity best compound lfy006-5 and lfy006-39 more than 10%, compound lfy004-36,
Lfy004-16, lfy004-6, lfy005-21 activity are more than 90%, higher than comparison medicament Fluoxastrobin.To potato late blight
The active testing of germ shows, compound lfy004-35, lfy004-36, lfy005-21, lfy006-9, lfy007-16,
lfy007-33、lfy008-17、lfy004-43、lfy006-29、 lfy007-17、lfy005-10、lfy005-17、
Lfy004-14 bacteriostatic activity is higher than 30%, wherein, compound lfy004-35, lfy004-36, lfy005-21, lfy006-
9th, lfy007-16, lfy007-33, lfy008-17 bacteriostatic activity is more than 40%, and activity is higher by that structure is similar, document report
Road activity best compound lfy006-5 and lfy006-39 are less than comparison medicament Fluoxastrobin more than 10%.Therefore,
Difference of the noval chemical compound of present invention design synthesis due to introducing substituent, the bactericidal activity and patent document of target compound
The similar compound of the high activity of middle report compares, and bactericidal activity has obtained significant raising, and this is the invention difference
In the place invented.
Embodiment 14
The piperidines thiazole II of the present invention anti-TMV Activity Results：
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 lfy004-4, lfy003-47, lfy005-22, lfy004-39, lfy005-21, lfy005-17, lfy006-
3、 lfy006-19、lfy006-24、lfy005-10、lfy006-29、lfy007-1、lfy007-8、lfy007-33、
Lfy008-4-1, lfy008-12, lfy008-17, lfy005-10, lfy004-30, lfy005-15 inhibiting rate are higher than
40%, activity be higher by structure is similar, document report active best compound lfy006-5 and lfy006-39 10% with
On, wherein, compound lfy004-4, lfy005-22, lfy006-29, lfy007-1, lfy007-8, lfy004-39,
Lfy005-17 inhibiting rate is higher than 60%, higher than comparison medicament Ningnanmycin, BTH.Under passivation pattern, compound
lfy004-44、lfy004-17、lfy004-21、 lfy004-20、lfy004-35、lfy004-36、lfy004-6、lfy006-
9、lfy005-32、lfy007-16、lfy007-33、 lfy008-12、lfy008-23、lfy004-32、lfy005-6、
Lfy004-24, lfy008-17, lfy008-4-1, lfy004-39 inhibiting rate are higher than 40%, and activity is higher than known compound
Lfy006-5 and lfy006-39, wherein, compound lfy004-44, lfy004-17, lfy004-21, lfy004-20,
lfy004-35、lfy004-36、lfy004-6、lfy006-9、lfy005-32、 lfy007-16、lfy007-33、lfy008-
12nd, lfy008-23, lfy004-32, lfy005-6 inhibiting rate are more than 50%, and activity is higher by that structure is similar, document report is lived
Property best compound lfy006-5 and lfy006-39 more than 10%, compound lfy004-44, lfy004-17,
Lfy004-20, lfy004-35, lfy004-36, lfy004-6, lfy005-32, lfy004-32, lfy005-6 inhibiting rate
Higher than 60%, higher than comparison medicament SZG-7.In protected mode, compound lfy004-47, lfy004-16, lfy005-17,
lfy005-23、lfy006-19、lfy006-16、lfy005-10、lfy007-8、lfy007-16、lfy007-17、 lfy007-
33rd, lfy008-4-1, lfy008-12, lfy008-17, lfy008-23, lfy005-6 inhibiting rate are more than 75%, and activity is high
In comparison medicament SZG-7, activity is higher by that structure is similar, document report active best compound lfy006-5 and lfy006-39
More than 10%, compound lfy006-19 and lfy006-16 activity are equal to or higher than 90%, with comparison medicament BTH's
It is active suitable.Under induction pattern, compound lfy004-14, lfy004-23, lfy004-47, lfy005-15, lfy005-
21、lfy005-10、lfy004-16、lfy008-12、lfy008-17、lfy007-l、lfy007-8、lfy006-18、
lfy007-33、lfy003-47、lfy004-6、lfy004-24、lfy004-30、lfy006-29、lfy004-4、lfy004-
32nd, lfy005-6, lfy008-4-1, lfy004-44 inhibiting rate are higher than 45%, and activity is higher than known compound lfy006-5
And lfy006-39, wherein, compound lfy004-14, lfy004-23, lfy004-47, lfy005-15, lfy005-21,
lfy005-10、lfy004-16、 lfy008-12、lfy008-17、lfy007-1、lfy007-8、lfy006-18、lfy007-
33rd, lfy003-47, lfy004-24, lfy004-30, lfy006-29, lfy004-4, lfy005-6 inhibiting rate are more than
55%, activity be higher by structure is similar, document report active best compound lfy006-5 and lfy006-39 10% with
On, compound lfy004-23, lfy004-16, lfy005-10, lfy006-29, lfy001-1, lfy008-12 inhibiting rate
More than 80%, higher than comparison medicament TDL, BTH and SZG-7.It can be seen that piperidines thiazole II of the invention has preferably
Anti- TMV activity.
Embodiment 15
The piperidines thiazole II of present invention insecticidal activity result：
Piperidines thiazole II insecticidal activity assay the results are shown in Table 4, and table 4 is visible：It is 100 millis in reagent agent concentration
G/l when, observation act on 72 hours after, it is known that compound lfy006-5 and lfy006-39 is to diamondback moth, mythimna separata, aphid and Zhu
Sand tetranychid does not all have toxic action, and the compound having in the present invention has certain poisoning to make to mythimna separata, aphid and Tetranychus cinnabarinus
With, if compound lfy004-47 is 74.60% to the cytotoxicity of aphid, poisonings of the compound lfy004-35 to Tetranychus cinnabarinus
Activity is 95.20%, and compound lfy006-19 is 40.00% to the cytotoxicity of mythimna separata.
Embodiment 16
The piperidines thiazole II of present invention live body bactericidal activity result：
Piperidines thiazole II live body protection activity measurement result is shown in Table 5, and table 5 is visible：Known compound lfy006-
5 and lfy006-39 does not have inhibitory activity to BGS, PSS, COB, PGS and BC substantially, compound of the invention to BGS, PSS and
BC does not have inhibitory activity yet, but the part of compounds of the present invention has preferable inhibitory activity to COB and PGS, for PCB, changes
Compound lfy004-23, lfy005-21, lfy006-19, lfy005-32, lfy004-17, lfy004-36, lfy004-6,
Lfy004-4 and lfy004-32 inhibitory activity is higher than 60%, compound lfy006-9, lfy005-17 and lfy004-21 couple
PGS inhibiting rate is respectively 100%, 50% and 100%.The compound of the present invention has preferable inhibiting rate to PCB, wherein, change
Compound lfy005-13, lfy005-25, lfy005-28, lfy005-47, lfy006-25, lfy005-34, lfy006-27 and
Lfy006-35 inhibiting rate is higher than 70%.
Embodiment 16
The piperidines thiazole of the present invention and agriculturally acceptable auxiliary agent and following one or more commodity insecticides
Combine the purposes in compounded pesticides are prepared：
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
Permethrin, allethrin, cyhalothrin, Biphenthrin, Permethrin, ethofenprox, flumethrin, fluvalinate, pyrrole
Worm quinoline, Acetamiprid, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, deinsectization
Urea, d ichlorbenzuron, Teflubenzuron, deinsectization are grand, HEXAFLUMURON, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron,
Noviflumuron is noviflumuron, its CAS 121451-02-3, flucycloxuron, Novaluron be Rimon, chlorfluazuron,
Bay sir 6874 are { 1- [(3.5- bis- chloro- 4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzenes)-urea }, Bay SIR-8514
I.e. [1- (4- Trifluoromethoxyphen-ls) -3- (2- chlorobenzenes)-urea], piperazine worm urea, Bistrifluron are bistrifluron, furans
Tebufenozide, tebufenozide, chlorine tebufenozide, methoxyfenozide, ring tebufenozide, Rogor, flolimat, DDVP, orthene,
Hostathion, quinalphos, pyridaphethione, isazofos, isoprocarb, sevin, Aphox, MTMC, Mobucin, cartap, Zhong Ding
Prestige, leaf disperse, carbaryl, Benfuracard micro, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, four
Mite piperazine, propargite, diafenthiuron, Benfuracard micro, pymetrozine, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, triazole
Tin, Buprofezin, phonamiphos, ethiprole, Cupric sulfate, dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide,
Tolfenpyrad, tebufenpyrad, chlorfenapyr, pyrazinones, etoxazole, tebufenpyrad, rattle away young ketone, Nylar, emaricin；The present invention's
Total weight/mass percentage composition of the piperidines thiazole in gained compounded pesticides is 1%-90%, piperidines thiophene of the invention
The ratio of Zole derivatives and the commodity insecticide is mass percent 1%: 99% to 99%: 1%；The compounded pesticides
Applicable formulation is selected from seed treatment emulsion, aqueous emulsion, big granula, microemulsion, suspension emulsion, water-soluble granule, soluble thick
It is agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, dry
Dress seed pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge,
Smog rod, seed treatment suspending agent, smog piece, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, it is solid/
Gu the agent of liquid mixing dress, the agent of liquid liquid mixing dress, harl agent, solid/mixing dress agent, medicine paint, fine granule, oil suspending agent, oil-dispersing property powder
Agent, sheet poison bait, dense jelly, sprinkle pour agent, seed coat agent, liniment, fritter poison bait, suspended emulsion, film forming finish, soluble powder
Agent, seed treatment water solube powder, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind
Any one in water-dispersible powder；The applicable plant of the compounded pesticides is selected from paddy, wheat, barley, oat, jade
Rice, sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, oil
Dish, 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, mandarin orange
Tangerine, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape；The compounded pesticides preventing and treating
Insect pest be selected from Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, Oriental burmeister, rice thripses, cigarette
Thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipes thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, cotton leaf
Cicada, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle plant hopper of sugarcane, cotten aphid, green bugs, grain aphid, black peach aphid,
Kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug,
Banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, green rice bug, green plant bug, clover
Fleahopper, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, brown slug moth, thosea siensis, gelechiid, cotton
Pink bollworm, brachmia triannuella, diamondback moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown band
Long 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, lap
Leaf open country snout moth's larva, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point Buddha's warrior attendant
Brill, black cutworm, big cutworm, yellow cutworm, steal poison moth, be gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, laid
Paddy is hesperided, Papilio xuthus, Common Mormon, cabbage butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans blister beetle, Venus ground beetle, wrinkle sheath step
The small buprestid beetle of first, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, citrus, golden edge buprestid beetle, bloom
Worm, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, star day
Ox, nadezhdiella cantori, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea weevil, silkworm
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, bollworm tooth
Lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, 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, onion fly, radish fly, full skirt Exorista civilis, corn borer are strict
Post fly, armyworm.
Embodiment 17
The piperidines thiazole of the present invention and appointing in agriculturally acceptable auxiliary agent and following commodity bactericide
Purposes of the one or more combinations of meaning 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- bis- chloroisothiazole -5- formic acid, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- Ethyl formates of 3,4- bis-, DL-
Beta-aminobutyric acid, isotianil, virazole, antofine, Ningnanmycin, first thiophene lure the different cigarette of amine, salicylic acid, cytosintetidemycin, dichloro
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,
Benalaxyl-M, double chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, ring fluorine
Bacterium amine, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, first furan acyl
Amine, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, pyridine
Oxygen bacterium ester, pyraclostrobin, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, Cyproconazole, Difenoconazole,
Olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, hexaconazole, glyoxalin, kind bacterium azoles, leaf
Bacterium azoles, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Triadimenol, triticonazole, biphenyl
Triadimenol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, Evil imidazoles,
The white spirit of pefurazoate, famoxadones, SYP-Z048, hymexazo, Evil, Guardian, Grandox fumigant, octhilinone, benthiozole, 12
Cyclomorpholine, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, Boscalid, fluorine pyridine
Acyl bacterium amine, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, Fenarimol, nuarimol,
Chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, iprovalicarb, benzene thiophene bacterium
Amine, Propamocarb, methasulfocarb, edifenphos, different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin,
Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, carbendazim,
Benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, ethirimol, difoltan, captan, folpet,
It is vinclozolin, fluoromide, dimethachlon, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, Mancozeb, third gloomy
Zinc, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, penta bacterium
Grand, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, more fruit pyridines, the pungent salt of biguanides, iminoctadine, chlorine
Nitramine, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, prestige hundred
Mu, enemy's line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion,
Isazofos, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole；
Total weight/mass percentage composition of the piperidines thiazole of the present invention in gained composite bactericide is 1%-90%, the present invention
Piperidines thiazole and the ratio of the commodity bactericide be mass percent 1%: 99% to 99%: 1%；It is described multiple
Any one in following dosage forms of formulation being applicable with bactericide：Wettable powder, micro-capsule suspension, dispersible
Body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, big granula, microemulsion, oil-suspending agent, use coated pesticidal
Seed, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison
Bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis,
Smoke candle, smoke cartridge, smog rod, seed treatment suspending agent, smog piece, smog ball, granular poison bait, foaming agent, drift pulvis,
Gu the agent of ointment, thermal fog, solid-liquid mixing dress, the agent of liquid liquid mixing dress, harl agent, solid/mixing dress agent, medicine paint, seed treatment liquid
Agent, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and pour agent, liniment, suspended emulsion, film forming finish, solvable
Property pulvis, seed treatment water solube powder, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, steam releasing agent, wet
Seed dressing water-dispersible powder；The applicable plant of the composite bactericide 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, to
Day certain herbaceous plants with big flowers, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, Huang
Melon, 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 choosing of the composite bactericide
From：Wheat rust, wheat scab, wheat powdery mildew, wheat virus disease, wheat avenge mould leaf blight, the compacted spore leaf spot of wheat,
Flag smut of wheat, take-all, wheat sharp eyespot, wheat downy mildew, the late blight of potato, wart of potatoes, potato
Shot hole, target, bacterial ring rot o potato, potato bacterial wilt, blakleg of potato, Potyvirus and class disease
Virus disease, bacterial soft rot of potato, dry rot of potato, potato verticillium wilt, black scurf of potato, potato bacterial wilt, Ma Ling
Potato ring rot, blakleg of potato, bacterial soft rot of potato, cotton wilt, cotton verticillium wilt, angular leaf spot of cotton, red autumnal leaves stem are withered
Disease, cotton seedling blight, cotton samping off, cotton anthracnose, cotton spoting verticillium wilt, cotton anthracnose, cotton spoting verticillium wilt, water
Rice rice blast, rice sheath blight disease, water rice brown spot, small round sclerotial disease of rice, bakanae disease of rice, downymildewofrice, rice
False smut, rice leaf sheath rot, bacterial blight of rice, bacterial leaf streak of rice, Characters of Erwinia chrysanthemi pv. zeae, rice bar
Line leaf blight, black streaked dwarf virus of rice, rice rice black sclerotium stalk rot, the leaf blight of corn, corn southern leaf blight, corn round spot
Disease, maize brown spot, maize sheath blight, corn rust, maize head smut, Corn Stalk Rot, corn smut, corn are done
Maize ear rot, maize virus disease and corn stalk rot disease, sclerotinia sclerotiorum, Rape virus disease, oilseed rape downy mildew, white rust of colza, soybean
Root rot, soybean sclerotinia crown rot, grey speck of soybean, soybean Mosaic, soy bean cyst roundworm, root-knot nematode, soybean rust
Disease, soybean anthracnose, bacterial pustule of soybean, soybean spot blight, downy mildew, bacterial wilt of peanut, Diplodia gossypina,
Peanut root rot, the cercospora brown spot of peanut, Peanut Web Blotch Disease, activity of peanuts disease, Peanut Scab, tobacco bacterial wilt, tobacco prairie fire
Disease, tobacco hollw stalk, Tobacco Angular Leaf Spot Disease, tobacco black shank, Alternaria alternate, frog-eye leaf spot of tobacco, anthracnose of tobacco, Tobacco Root
Black rot, fusarium tabacinum root rot, Tobacco seedling diseases, tobacco damping-off, tobacco junk leaf spot, Powdery Mildew in Tobacco, tobacco
It is southern blight, tobacco black spot, tobacco mosaic disease, cucumber mosaic virus, etch virus of tobacco, Chinese cabbage downy mildew, soft rot of cabbage, white
Dish Tipburn Disease, Chinese cabbage virosis, Cabbage Leaf Spot, Seed detection, Chinese cabbage anthracnose, cabbage clubroot, tomato bacterial
Spot disease, tomato late blight, tomato blossom-end rot, tomato powdery mildew, tomato samping off, tomato fish pelargonium mosaic disease, tomato bacterium
Property macula disease, tomato yellow leaf curl virus, leaf muld of tomato, tomato virus disease, tomato late blight, tomato samping off with it is vertical withered
Disease, 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, tomato low temperature
Obstacle, tomato bolter, tomato physiological leaf curl, tomato samping off, tomato fruit drop disease, tomato bud blight, tomato
Soft rot, tomato stem rot, tomato seedling damping-off, tomato sun burn, tomato shot hole, tomato rouge and powder disease, tomato virus disease, kind
Eggplant cracked fruit, canker of tomato, tomato navel corruption fruit, tomato sesame pinta bacterium, bacterial spot of tomato, tomato rot leaf poison
Disease, tomato yellow leaf curl virus disease, eggplant cotton disease, eggplant sclerotiniose, eggplant bacterial wilt, eggplant Phomopisis vexans, eggplant Huang 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, the soft corruption of eggplant head mold
Disease, wilt of eggplant, grey mould of egg plant, eggplant base rot disease, capsicum green pepper virosis, capsicum early blight, capsicum Leucoplakia,
Pepper white star disease, capsicum leaf spot, capsicum Scald, capsicum sooty mold, capsicum wilt, capsicum sclerotiniose, capsicum day burn
It is disease, pepper virus disease, capsicum malformed fruit, capsicum blossom-end rot, capsicum soft rot, bacterial spot of pepper, capsicum bar virus scab, peppery
Green pepper pythium rot, macrosporium leaf spot of red pepper, capsicum spot blight, capsicum black spot, capsicum verticillium wilt, pepper bacterial leaf spot, capsicum are brown
Maize ear rot, Fusarium solani, capsicum damping-off, pepper anthracnose, capsicum brown spot, capsicum downy mildew, Botrytis cinerea, capsicum
Leaf blight, pepper leaf mold, capsicum samping off, capsicum epidemic disease, downy mildew of garpe, uncinula necator, brown spot of grape, grape
Leaf curl, Grapevine Fan Leaf Virus Disease, grape rust, grape ring spot, grape leaf spot, the small brown spot of grape, grape zonate spot, Portugal
The golden yellow disease of grape graywall, grape young sprout wasting disease, grape mosaic disease, grape wasting disease, grape stripe disease, grape, grape infect
Property necrosis disease, grape it is yellow select sick disease, grape lug, grape vein necrosis disease, Grapevine fleck virus disease, the starlike mosaic disease of grape,
Grape Pearls, fruit white rot of grape, bitter rot or anthracnose of grape, grape room rot, grape grey mould, grapevine anthracnose, vine black are rotten
Disease, the big room rot of grape, grape coal select disease, grape, and brown to select the mould dirty disease of disease, grape, grape bitter rot, grape branch spore mould rotten
Disease, grape penicilliosis, grape Alternaria rot, apple tree canker, dry rot of apple, ring rot of apple, apple branch ulcer
Disease, apple blister canker, Pink Disease of Apple, apple die back disease, apple branch-rot, apple anthracnose, Apple Mould Core, apple
Fruit russeting disease, apple blossom rot, apple brown rot, black fruit rot of apple, apple phytophthora rot, Apple Sooty, sick apple marssonina leaf spot,
Alternaria leaf spot of apple, Glomerella cingulata, apple graywall, apple mildew, scab of apple, silver leaf of apple, apple are invaded
Metachromia root rot, armillariella root rot of apple, apple Root―rot disease, apple southern blight, apple violet root rot, rosellinia trunk rot of apple, apple root
Carninomatosis, apple decline disease, apple rough skin disease, apple mosaic, apple green wrinkle fruit disease, apple fruit-shrink disease, Apple little leaf, apple
Fruit yellowtop, apple bitter pit, apple water core, apple superficial scald, carbuncle apple scab, Gold Delicious apple fruit russeting, apple are blue or green
The continuous disease of mildew, apple soft rot, Apples digested tankage, apple pulp brown stain disease, apple brown heart, pear scab, black rot of pear,
Fungus of Pear Canker Disease, pears southern blight, pear tree wood rot, pears die back disease, rust of pear, Pear black spot, pears graywall, pears brown spot, pears
Socty Blotch And Greasy Blotch, pears top rot, pears fruit-shrink disease, pears yellowtop, anthracnose of peach, peach reality maize ear rot, peach fruit rot, peach soft rot, peach ulcer
Disease, peach powdery mildew, peach brown rot, peach scab, the abnormal fruit disease of peach, peach sooty mould, peach leaf-curl, peach fungoid are worn
Hole disease, peach Bacterial septicaemia syndrome, peach leaves pinta, peach leaf rust, peach mosaic disease, peach red-leaf disease, peach are rotted
Disease, peach gummosis, peach wood rot, peach die back disease, Peach crown gall, peach root rot, peach root knot nematode disease, mandarin orange
The broken leaf disease of tangerine yellow twig, exocortis, citrus, citrus decline, Satsuma dwarf virus, citrus bacterial canker disease, citrus scab
Disease, 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 disease of maculopathy, citrus, citrus felt fungus, citrus seedling blight, citrus seedling epidemic disease, perfume (or spice)
Any of several broadleaf plants bunchy top, Banana Mosaic Disease, research of fusarium wilt disesase of banana, Cercospora musae bacterium leaf spot, the banana secretly mould tikka of double spores
Disease, 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 are bacillary
It is black spot, cottony rot of cabbage, cabbage black rot, black spot of cabbage, wild cabbage brown spot, wild cabbage blastomere disease, wild cabbage virosis, sweet
Blue soft rot, wild cabbage bolting disease, cabbage downy mildew, wild cabbage anthracnose, black leg of cabbage, sugarcane pineapple disease, sugarcane dust-brand in advance
Disease, sugarcane ratoon stunting disease, sugarcane brown streak, sugarcane rust, sorghum smut, sorghum leaf spot, anthracnose of sorghum, sorghum
Leaf blight, sorghum virosis.Embodiment 18
The piperidines thiazole of the present invention with agriculturally acceptable auxiliary agent and with following commodity antivirotic
Purposes of any one or more combination in compounding anti-plant virus agent, activating plants agent is prepared：
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, alkene
Third isothiazole, well ridge azanol, jinggangmeisu；The piperidines thiazole of the present invention compounds anti-plant virus agent, plant in gained
Total weight/mass percentage composition in activator is 1%-90%, and piperidines thiazole of the invention and the commodity are antiviral
The ratio of agent is mass percent 1%: 99% to 99%: 1%；The compounding anti-plant virus agent, the formulation of activating plants agent
Selected from wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, water and milk
Agent, 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, solid-liquid mix dress agent, liquid liquid mixing fills agent,
Solid harl agent, solid/mixing fill agent, medicine paint, seed treatment liquor, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly,
Sprinkle and pour agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension
Agent, tracking pulvis, ultra low volume liquids, steam releasing agent, any one in wet-mixing kind water-dispersible powder；The compounding
The applicable plant of anti-plant virus agent, activating plants agent is selected from paddy, wheat, barley, oat, corn, sorghum, sweet potato, Ma Ling
Potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, sweet tea
It is dish, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, white
Dish, 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 compounding anti-plant virus agent, activating plants agent are fitted
Virus disease be 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, maize dwarf mosaic, cauliflower mosaic virus, citrus virosis, cymbidium mosaic virus, sword-leaved cymbidium ring
Any one of pinta poison.
Embodiment 19
The piperidines thiazole of the present invention with agriculturally acceptable auxiliary agent and with appointing in following commodity acaricide
The one or more combinations of meaning are preparing Compositional acaricide and its purposes in preventing and treating plant mites evil：
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
Budweiser, 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
Element, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, print
Chinaberry element, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, Hexythiazox, Envidor, fluacrypyrim, chlorfenizon,
Propargite, pyridaben；Total quality percentage of the piperidines thiazole of the present invention in gained Compositional acaricide in the composition
Content is 1%-90%, and piperidines thiazole 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, glue
Capsule granula, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smog
Candle, smoke cartridge, smog rod, seed treatment suspending agent, smog piece, smog ball, granular poison bait, foaming agent, drift pulvis, ointment,
Solid thermal fog, solid-liquid mixing dress agent, the agent of liquid liquid mixing dress, harl agent, solid/mixing fill agent, medicine paint, seed treatment liquor, micro-
Granula, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle pour agent, liniment, suspended emulsion, film forming finish, soluble powder
Agent, seed treatment water solube powder, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind
Any one in water-dispersible powder；The applicable plant of the Compositional acaricide is selected from paddy, wheat, barley, oat, jade
Rice, sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, oil
Dish, 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, mandarin orange
Tangerine, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape；The Compositional acaricide is applicable
Mite evil selected from Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae, tetranychus telarius category, the evil mite of Eriophyidae, these evil mites are the world
Property Agricultural Mites, forestry harmful mites, gardening evil mite and hygienic evil mite.
The bacteriostatic activity (inhibiting rate/% of 50 mcg/mls) of the piperidines thiazole of the present invention of table 2
Activity (the suppression of 100 mcg/mls of the piperidines thiazole II of the present invention of table 3 resisting tobacco mosaic virus
Rate/%)
| Sequence number | Compound | Treatment | Passivation | Induction | Protection |
| 1 | lfy004-44 | 27.50±2.50 | 64.96±4.96 | 46.00±2.00 | 31.43±5.71 |
| 2 | lfy004-19 | 33.89±3.69 | 12.82±2.84 | 30.00±4.80 | 42.86±2.86 |
| 3 | lfy004-21 | 34.17±2.50 | 53.85±2.56 | 27.00±3.00 | 58.57±1.43 |
| 4 | lfy004-14 | 37.50±4.17 | 21.79±6.41 | 74.00±2.46 | 52.86±4.29 |
| 5 | lfy004-23 | 28.33±6.27 | 14.10±3.85 | 81.00±3.00 | 64.29±1.43 |
| 6 | lfy004-47 | 25.00±5.00 | 30.77±5.13 | 75.00±5.00 | 76.19±5.44 |
| 7 | lfy004-39 | 60.00±1.67 | 42.74±5.92 | 17.00±7.00 | 30.00±1.43 |
| 8 | lfy005-15 | 45.00±1.67 | 6.41±3.85 | 71.33±8.56 | 55.71±7.14 |
| 9 | lfy005-21 | 50.00±6.67 | 34.62±3.85 | 72.00±6.00 | 70.00±7.14 |
| 10 | lfy005-17 | 78.33±4.70 | 11.97±3.74 | 10.00±3.32 | 89.52±2.11 |
| 11 | lfy006-9 | 23.33±3.34 | 58.97±5.13 | 25.00±1.00 | 14.29±2.86 |
| 12 | lfy006-19 | 56.67±5.00 | 2.57±2.57 | 36.00±2.00 | 90.48±3.07 |
| 13 | lfy005-32 | 19.17±2.50 | 65.38±7.61 | 6.00±3.74 | 20.00±5.71 |
| 14 | lfy006-24 | 50.00±3.33 | 3.85±1.29 | 39.00±3.00 | 52.86±7.14 |
| 15 | lfy005-10 | 51.67±1.67 | 3.85±1.29 | 81.33±7.48 | 78.10±3.81 |
| 16 | lfy004-17 | 36.67±1.67 | 85.90±4.70 | 22.00±7.39 | 32.86±4.29 |
| 17 | lfy004-20 | 30.00±1.67 | 73.50±4.15 | 38.00±4.00 | 27.14±1.43 |
| 18 | lfy005-22 | 60.00±3.33 | 21.79±1.28 | 35.33±7.07 | 41.43±1.43 |
| 19 | 1fy004-35 | 35.00±1.67 | 64.10±5.13 | 37.00±3.00 | 20.95±3.38 |
| 20 | lfy004-36 | 19.17±2.50 | 62.82±1.28 | 9.00±1.00 | 32.86±1.43 |
| 21 | lfy004-16 | 21.11±4.50 | 11.11±5.21 | 85.00±1.00 | 78.57±1.43 |
| 22 | lfy005-23 | 29.17±4.17 | 30.77±7.56 | 9.00±5.00 | 79.05±4.62 |
| 23 | lfy008-4-1 | 50.00±6.59 | 40.17±7.05 | 46.00±8.00 | 75.24±6.18 |
| 24 | lfy008-12 | 59.44±1.06 | 57.26±7.95 | 83.33±5.45 | 84.29±1.43 |
| 25 | lfy008-17 | 55.83±5.83 | 47.44±6.41 | 70.00±6.00 | 89.52±1.68 |
| 26 | lfy008-23 | 39.17±2.50 | 53.85±3.27 | 42.00±4.00 | 82.86±8.57 |
| 27 | lfy007-1 | 66.67±3.33 | 15.38±7.37 | 86.00±4.00 | 50.00±4.29 |
| 28 | lfy007-8 | 73.33±3.33 | 13.68±8.31 | 60.00±2.00 | 86.67±5.24 |
| 39 | lfy007-16 | 39.17±5.83 | 58.97±2.56 | 27.00±1.00 | 86.67±4.31 |
| 30 | lfy007-17 | 35.00±1.67 | 16.67±1.29 | 17.00±3.00 | 79.05±9.51 |
| 31 | lfy006-18 | 15.00±5.00 | 32.05±3.85 | 69.00±3.00 | 31.43±2.86 |
| 32 | lfy007-33 | 59.17±0.83 | 57.69±6.41 | 72.00±2.00 | 90.00±1.43 |
| 33 | lfy003-47 | 47.50±0.83 | 11.97±1.86 | 78.67±4.12 | 64.29±4.29 |
| 34 | lfy004-6 | 25.00±3.15 | 74.36±5.13 | 53.33±6.29 | 4.29±4.29 |
| 35 | lfy004-24 | 25.00±3.33 | 45.30±2.53 | 71.00±3.00 | 35.71±7.14 |
| 36 | lfy004-30 | 45.00±8.33 | 33.33±2.56 | 75.33±5.52 | 38.57±7.14 |
| 37 | lfy006-29 | 62.78±2.18 | 6.84±6.79 | 81.33±3.79 | 65.71±2.86 |
| 38 | lfy004-4 | 61.67±5.00 | 12.82±4.62 | 67.00±3.00 | 62.86±7.79 |
| 39 | lfy006-6 | - | - | - | - |
| 40 | lfy006-12 | - | - | - | - |
| 41 | lfy004-32 | 27.50±7.50 | 67.52±6.54 | 54.00±2.00 | 18.57±1.43 |
| 42 | lfy004-43 | - | - | - | - |
| 43 | lfy005-6 | 54.44±3.68 | 73.50±5.34 | 71.00±1.00 | 81.43±4.29 |
| 44 | lfy006-3 | 49.44±4.51 | 33.33±2.56 | 19.00±7.00 | 32.73±2.86 |
| 45 | lfy006-16 | 10.83±2.50 | 24.36±1.28 | 36.00±2.00 | 90.48±2.30 |
| 46 | lfy006-5 | 25.56±5.46 | 20.51±7.69 | 39.33±2.41 | 15.71±4.29 |
| 47 | lfy006-39 | 29.17±4.17 | 35.04±9.98 | 43.00±1.00 | 65.71±5.71 |
| 48 | Ningnanmycin | 45.00±4.84 | 45.64±2.35 | 28.36±2.99 | 43.19±3.54 |
| 49 | TDL | 29.17±4.17 | 26.15±3.08 | 63.00±3.00 | 26.76±5.07 |
| 50 | BTH | 59.17±4.17 | - | 79.00±1.00 | 90.00±1.43 |
| 51 | SZG-7 | 33.33±3.33 | 60.26±3.85 | 78.00±3.27 | 70.00±1.43 |
The piperidines thiazole II of the present invention of table 4 insecticidal activity (the target death rate/%, 100 mg/litres；Aphid
48 hours, other 72 hours)
| Numbering | Compound | Diamondback moth | Mythimna separata | Aphid | Tetranychus cinnabarinus |
| 1 | lfy004-44 | 0 | 0 | 26.70 | 0 |
| 2 | lfy004-19 | 0 | 0 | 0 | 0 |
| 3 | lfy004-21 | 0 | 0 | 0 | 0 |
| 4 | lfy004-14 | 0 | 0 | 0 | 39.50 |
| 5 | lfy004-23 | 0 | 0 | 0 | 0 |
| 6 | lfy004-47 | 0 | 0 | 74.60 | 0 |
| 7 | lfy004-39 | 0 | 0 | 0 | 0 |
| 8 | lfy005-15 | 0 | 0 | 0 | 0 |
| 9 | lfy005-21 | 0 | 0 | 0 | 0 |
| 10 | lfy005-17 | 0 | 0 | 0 | 0 |
| 11 | lfy006-9 | 0 | 0 | 0 | 0 |
| 12 | lfy006-19 | 0 | 40.00 | 0 | 0 |
| 13 | lfy005-32 | 0 | 0 | 0 | 0 |
| 14 | lfy006-24 | 0 | 0 | 0 | 0 |
| 15 | lfy005-10 | 0 | 0 | 0 | 25.00 |
| 16 | lfy004-17 | 0 | 0 | 0 | 28.20 |
| 17 | lfy004-20 | - | - | - | - |
| 18 | lfy005-22 | 0 | 0 | 0 | 0 |
| 19 | lfy004-35 | 0 | 0 | 31.60 | 95.20 |
| 20 | lfy004-36 | 0 | 0 | 0.0 | 22.40 |
| 21 | lfy004-16 | 0 | 0 | 0 | 22.20 |
| 22 | lfy005-23 | 0 | 0 | 0 | 0 |
| 23 | lfy008-4-1 | - | - | - | - |
| 24 | lfy008-12 | - | - | - | - |
| 25 | lfy008-17 | - | - | 2.63 | - |
| 26 | lfy008-23 | - | - | - | - |
| 27 | lfy007-1 | - | - | 1.67 | - |
| 28 | lfy007-8 | - | - | 12.94 | - |
| 39 | lfy007-16 | - | - | 8.33 | - |
| 30 | lfy007-17 | - | - | 2-50 | - |
| 31 | lfy006-18 | 0 | 0 | 0 | 0 |
| 32 | lfy007-33 | - | - | 2.63 | - |
| 33 | lf003-47 | 0 | 0 | 0 | 0 |
| 34 | lfy004-6 | 0 | 0 | 0 | 0 |
| 35 | lfy004-24 | 0 | 0 | 0 | 0 |
| 36 | lfy004-30 | 0 | 0 | 0 | 0 |
| 37 | lfy006-29 | - | - | 8.78 | - |
| 38 | lfy004-4 | 0 | 0 | 0 | 0 |
| 39 | lfy006-6 | 0 | 0 | 33.30 | 0 |
| 40 | lfy006-12 | - | - | - | - |
| 41 | lfy004-32 | 0 | 0 | 0 | 0 |
| 42 | lfy004-43 | 0 | 0 | 0 | 0 |
| 43 | lfy005-6 | - | - | - | - |
| 44 | lfy006-3 | 0 | 0 | 0 | 0 |
| 45 | lfy006-16 | 0 | 0 | 0 | 0 |
| 46 | lfy006-5 | 0 | 0 | 0 | 0 |
| 47 | lfy006-39 | 0 | 0 | 0 | 0 |
The piperidines thiazole compound II of the present invention of table 5 live body bactericidal activity
Claims (6)
1. a kind of piperidines thiazole, it is characterised in that：With the general structure as shown in Formula II：
Wherein, R is selected from H, HHCl, 2- (5H) furanone -4- bases, 2- chloropyridine -5- methylene, propargyl, trifluoro methylsulfonyl
Base orR2Selected from methyl, ethyoxyl, tertbutyloxycarbonyl, trifluoromethyl, phendioxin, 2,3- thiadiazoles -7- bases, 3,4- dichloros
Isothiazole -5- bases, the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- bases, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases, hexamethylene
Base, cyclopropyl, 2- methyl -4- trifluoromethyl thiazole -5- bases, 2- chloropyridine -5- bases；X is selected from O, NH；R1Selected from 2,2- difluoro second
Base, isopropyl, propargyl, cyclohexyl, cyclopropyl, the chlorallyls of 1,1- bis-, 5- bromopyridine -2- bases, 1,2,3,4- naphthane -1-
Base.
2. the synthetic method of the piperidines thiazole described in claim 1, specific synthetic route are as follows：
Wherein, R is selected from H, HHCl, 2- (5H) furanone -4- bases, 2- chloropyridine -5- methylene, propargyl, trifluoro methylsulfonyl
Base orR2Selected from methyl, ethyoxyl, tertbutyloxycarbonyl, trifluoromethyl, phendioxin, 2,3- thiadiazoles -7- bases, 3,4- dichloros
Isothiazole -5- bases, the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- bases, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases, hexamethylene
Base, cyclopropyl, 2- methyl -4- trifluoromethyl thiazole -5- bases, 2- chloropyridine -5- bases；X is selected from O, NH, R1Selected from 2,2- difluoro second
Base, isopropyl, propargyl, cyclohexyl, cyclopropyl, the chlorallyls of 1,1- bis-, 5- bromopyridine -2- bases, 1,2,3,4- naphthane -1-
Base；
Due to group R and Y difference, there are a variety of different synthetic methods when synthesizing compound II by compound VIII, specifically
Including following several synthetic methods：
When R isAnd Y, when being hydroxyl, the method that compound II is synthesized by compound VIII is as follows：
Wherein：R2Selected from methyl, ethyoxyl, tertbutyloxycarbonyl, trifluoromethyl, phendioxin, 2,3- thiadiazoles -7- bases, 3,4- dichloros
Isothiazole -5- bases, the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- bases, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases, hexamethylene
Base, cyclopropyl, 2- methyl -4- trifluoromethyl thiazole -5- bases, 2- chloropyridine -5- bases；X is selected from O, NH；R1Selected from 2,2- difluoro second
Base, isopropyl, propargyl, cyclohexyl, cyclopropyl, the chlorallyls of 1,1- bis-, 5- bromopyridine -2- bases, 1,2,3,4- naphthane -1-
Base；
When R be propargyl,And Y, when being chlorine atom, the method that compound II is synthesized by compound VIII is as follows：
Wherein R1Selected from the fluoro ethyls of 2,2- bis-, isopropyl；R2For ethyoxyl；
When R is 2 (5H) furanone -4- bases and Y is hydroxyl, the method that compound II is synthesized by compound VIII is as follows：
Wherein：R1For the fluoro ethyls of 2,2- bis-, X NH；
When R is 2- chloropyridine -5- methylene and Y is Cl, the method that compound II is synthesized by compound VIII is as follows：
Wherein：R1For the fluoro ethyls of 2,2- bis-, X NH；
When R is trifyl and Y is chlorine atom, the method that compound II is synthesized by compound VIII is as follows：
Wherein R1For isopropyl, X NH；
When R is HHCl, the method for synthesizing the corresponding hydrochloride of the compound is as follows：
Wherein R1For isopropyl；X is NH；
The synthetic route of intermediate compound I is：
The specific method of the synthesis of compound is divided into following steps：
A. the preparation of intermediate compound IV：
10 mMs of III is placed in 100 milliliters of two mouthfuls of round-bottomed flasks, adds 26 mMs of triethylamine, 20 milliliter two
Chloromethanes, nitrogen protection, ice bath stirring, 13 mMs of two carbonic acid being dissolved in 20 milliliters of dichloromethane are added dropwise into reaction system
Di tert butyl carbonate, i.e. Boc2O, it is stirred overnight at room temperature after being added dropwise, has reacted the salt that 1 mol/L is added dropwise in backward reaction system
Acid, regulation pH value isolate organic layer to 5 or so, and inorganic layer is washed one time with dichloromethane, merge organic layer and respectively with water,
Saturated sodium bicarbonate, saturated sodium-chloride are washed one time, merge organic phase anhydrous sodium sulfate drying, are filtered, and rotary evaporation removes molten
Agent, white crude IV is obtained, be stirred at room temperature after 50 milliliters of n-hexane is added into the crude product of gained, stirring is taken out again after ten minutes
Filter, naturally dry obtains white solid IV with n-hexane filter wash cake twice, with gained sterling calculated yield, yield 92%；
B. intermediate V preparation：
Sequentially add 10 mMs of intermediate compound IV in 100 milliliters of round-bottomed flasks, 5.05 mMs of lawesson reagent, 25 milliliters
Glycol dimethyl ether, 10 milliliters of dichloromethane, is stirred overnight at room temperature, and is concentrated under reduced pressure after having reacted and removes solvent, and residue is used suitable
Amount ethyl acetate dilution, organic layer successively with saturated potassium carbonate wash twice, saturated common salt wash one time, anhydrous sodium sulfate is done
It is dry, filter, rotary evaporation removes solvent and obtains yellow solid V, yield 100%；
C. intermediate VI preparation：
10 mMs of intermediate V is added in 100 milliliters of single necked round bottom flask, 20 milliliters of tetrahydrofurans, is stirred at room temperature, to anti-
The ethyl bromide acetone of 11 mMs of dropwise addition in system is answered, back flow reaction is changed to after being added dropwise 2 hours, after having reacted directly
Reaction solution is concentrated and removes solvent, residue is dissolved with appropriate ethyl acetate, and organic layer is successively with 1 mol/L caustic washing
Twice, saturated common salt is washed one time, anhydrous sodium sulfate drying, is filtered, and rotary evaporation removes solvent, and residue is through 200~300 mesh
Silica gel column chromatography purifies to obtain intermediate VI, and eluant, eluent volume ratio is petroleum ether=1/ of ethyl acetate/60~90 degree Celsius cut
3；With gained sterling calculated yield, yield 70-90%；
D. the preparation of intermediate compound I：
10 mMs of intermediate VI is added in 100 milliliters of single necked round bottom flask, 15 milliliters of tetrahydrofurans, 15 milliliters without water beetle
Alcohol, it is stirred at room temperature, 20 mMs of sodium hydroxide is added into reaction bulb, 3 milliliters of water, reaction 3 hours is stirred at room temperature, has reacted
Directly reaction solution is concentrated afterwards and removes organic solvent, residue is dissolved with appropriate ethyl acetate, is added 8 milliliters of water, is separated water
Layer, water layer adjust pH to 1 with the concentrated hydrochloric acid of 12 mol/Ls, now there is white solid precipitation, and decompression filters, and filter cake is washed with water once,
Naturally dry obtains white solid I, yield 93%；
E. intermediate VII preparation：
10.5 mMs of intermediate compound I, 12 mMs of 1- (3- diformazan ammonia are sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks
Base propyl group) -3- ethyl-carbodiimide hydrochlorides, i.e. EDCI, 10.5 mMs of I-hydroxybenzotriazole, i.e. HOBT, vacuumize,
Nitrogen is protected, and 20 milliliters of dry dichloromethane are added into reaction system, and ice bath stirring is changed to after being stirred at room temperature 1 hour, to
10 mMs of a variety of amine or alcohol that are dissolved in 10 milliliters of dichloromethane are added dropwise in reaction, are finally added dropwise 12 mMs
Triethylamine, it is stirred overnight at room temperature, reaction solution is washed with water twice successively after having reacted, saturated sodium bicarbonate after all adding
Respectively wash one time, anhydrous sodium sulfate drying, filter with saturated aqueous common salt, rotary evaporation removes solvent, and residue is through 200~300 mesh
Silica gel column chromatography purifies to obtain intermediate VII, and eluant, eluent is the petroleum ether of ethyl acetate/60~90 degree Celsius cut, according to product
Difference, volume ratio 1: 5 to 3: 1；With gained sterling calculated yield, yield 33-95%；
F. intermediate VIII preparation：
10 mMs of intermediate VII is placed in 100 milliliters of two-mouth bottles, dissolved with 20 milliliters of dry dichloromethane, nitrogen
Protection, ice bath stirring, 4 milliliters of trifluoroacetic acid is added dropwise into reaction system, is stirred at room temperature 1 hour after being all added dropwise, instead
The sodium hydroxide that 1 mol/L is added dropwise in backward reaction solution has been answered, has adjusted pH value to separate organic layer, organic layer saturation to 10 or so
Salt is washed once, anhydrous sodium sulfate drying, is filtered, and rotary evaporation removes solvent, and residue is through 200~300 mesh silica gel column layers
Analysis purifies to obtain intermediate VIII, and eluant, eluent is methylene chloride/methanol, different according to product, volume ratio 50: 1-6: 1；
G. piperidines thiazole II preparation：
When R isAnd Y, when being hydroxyl, compound II preparation method is as follows：
10.5 mMs of intermediate VIII, 12 mMs of 1- (3- diformazans are sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks
Aminopropyl) -3- ethyl-carbodiimide hydrochlorides, i.e. EDCI, 10.5 mMs of I-hydroxybenzotriazole, i.e. HOBT, take out true
Sky, nitrogen protection, 20 milliliters of dry dichloromethane are added into reaction system, and ice bath stirring is changed to after being stirred at room temperature 1 hour,
10 mMs of a variety of amine or alcohol that are dissolved in 10 milliliters of dichloromethane are added dropwise into reaction, are finally added dropwise 12 mMs
Triethylamine, all add after be stirred overnight at room temperature, reaction solution is washed with water twice successively after having reacted, unsaturated carbonate hydrogen
Sodium and saturated aqueous common salt are respectively washed one time, anhydrous sodium sulfate drying, are filtered, and rotary evaporation removes solvent, and residue is through 200~300
Mesh silica gel column chromatography purifies to obtain compound II, and eluant, eluent is the petroleum ether of ethyl acetate/60~90 degree Celsius cut, according to product
Difference, volume ratio 1: 5 to 3: 1；With gained sterling calculated yield, yield 24-98%；
When R be propargyl,And Y, when being chlorine atom, compound II preparation method is as follows：
10 mMs of compound VIII, 20 mMs of potassium carbonate, with 10 milliliters are added in 100 milliliters of two mouthfuls of round-bottomed flasks
DMF dissolves, ice bath stirring, and 15 mMs of propargyl bromide or ethyl chloroformate are added dropwise into reaction, is added dropwise
After be stirred at room temperature 4 hours, decompression, which filters, after having reacted removes insoluble solid, and filtrate is diluted with enough water, is added and is fitted
The ethyl acetate of amount, separates organic layer, with saturated common salt washing once, anhydrous sodium sulfate drying, filters, rotary evaporation removes molten
Agent, residue purify to obtain compound II through 200~300 mesh silica gel column chromatographies, and eluant, eluent is that ethyl acetate/60~90 degree Celsius evaporate
The petroleum ether divided, when R is propargyl, volume ratio is 1: 1, works as R2For ethyoxyl when, volume ratio 1: 2；Calculated with gained sterling
Yield, yield 40-80%；
When R is 2 (5H) furanone -4- bases and Y is hydroxyl, compound II preparation method is as follows：
The compound VIII of 0.73 mM of addition, 1.09 mMs of tetronic acids, 10 milligrams of pair in 100 milliliters of round-bottomed flasks
Toluenesulfonic acid, the appropriate molecular sieve dried through Muffle furnace is added, dissolved with 10 milliliters of dry toluenes, heating reflux reaction 6
Hour, decompression, which filters, after reacting completely removes solid, and filtrate concentration, residue is purified and must changed through 200~300 mesh silica gel column chromatographies
Compound II, eluant, eluent volume ratio are petroleum ether=1/1 of ethyl acetate/60~90 degree Celsius cut, are calculated and received with gained sterling
Rate, yield 50%；
When R is the chloro- pyridine -5- methylene of 2- and Y is chlorine atom, compound II preparation method is as follows：
1.94 mMs of compound VIII is added in 100 milliliters of single necked round bottom flask, adds 0.97 mM of potassium carbonate,
Dissolved with 20 milliliters of acetonitriles, heating reflux reaction is overnight, and decompression, which filters, after reacting completely removes solid, filtrate concentration, residue
Diluted with ethyl acetate, washed one time, anhydrous sodium sulfate drying, filtered with water, saturated sodium bicarbonate, saturated common salt respectively, rotation
Turn evaporation of solvent, residue purifies to obtain compound II through 200~300 mesh silica gel column chromatographies, and eluant, eluent is ethyl acetate/60
Petroleum ether=1 of~90 degrees Celsius of cuts: 3, with gained sterling calculated yield, yield 51.55%；
When R is trifyl and Y is chlorine atom, compound II preparation method is as follows：
10 mMs of compound VIII is added in 100 milliliters of two mouthfuls of round-bottomed flasks, it is molten with 20 milliliters of dry dichloromethane
Solution, adds 20 mMs of diisopropylethylamine into reaction, 10 milligrams of 4-dimethylaminopyridine, ice bath stirring, to anti-
15 mMs of trifluoromethanesulfchloride chloride is added dropwise in answering, rear room temperature stirring reaction is added dropwise 5 hours, has reacted rear reaction solution successively
With saturated sodium bicarbonate, saturated common salt is washed once, anhydrous sodium sulfate drying, is filtered, and rotary evaporation removes solvent, residue warp
200~300 mesh silica gel column chromatographies purify to obtain compound II, and eluant, eluent is the petroleum ether of ethyl acetate/60~90 degree Celsius cut
=1: 2, with gained sterling calculated yield, yield 79.39%；
When R is HHCl, the method for synthesizing the corresponding hydrochloride II of the compound is as follows：
1 mM of compound VII is added in 50 milliliters of single necked round bottom flask, is dissolved with 5 milliliters of absolute methanols, room temperature is stirred
Mix, the hydrogen chloride dioxane solutions of 4 excessive mol/Ls are added into reaction, room temperature continues stirring 3 hours, after having reacted
Reaction solution directly concentrates removing organic solvent, and appropriate absolute ethyl alcohol is added into flask, continues concentration and removes a small amount of water, most
Product as light yellow solid II, yield 100% are obtained afterwards.
3. purposes of the piperidines thiazole in insecticide is prepared described in claim 1.
4. purposes of the piperidines thiazole in fungicide is prepared described in claim 1.
5. purposes of the piperidines thiazole in resisting tobacco mosaic virus agent is prepared described in claim 1.
6. purposes of the piperidines thiazole in activating plants agent is prepared described in claim 1.
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| CN107646855B (en) * | 2017-08-02 | 2020-07-07 | 浙江工业大学 | Application of thiazole compound containing piperidine in preparation of bactericide and preparation method thereof |
| CN108558857B (en) * | 2018-05-07 | 2021-07-02 | 南开大学 | Thiazole piperidine furanone derivatives and preparation method and application thereof |
| CN109239336B (en) * | 2018-09-19 | 2023-02-24 | 北京勤邦生物技术有限公司 | Test strip for detecting isoprocarb and application thereof |
| CN109354589B (en) * | 2018-10-30 | 2021-02-09 | 浙江工业大学 | Alpha-amino acid derivative containing piperidine thiazole heterocycle and preparation method and application thereof |
| CN109232552B (en) * | 2018-10-30 | 2021-02-09 | 浙江工业大学 | Piperidine thiazole derivative containing bisamide structure and preparation method and application thereof |
| CN111217767B (en) * | 2020-01-19 | 2021-10-12 | 广东药科大学 | Method for preparing functionalized thiazole heterocyclic compound through Cu (I) -catalyzed multi-component cyclization reaction and application |
| CN113004263B (en) * | 2021-03-11 | 2024-01-26 | 陕西大美化工科技有限公司 | 4-thiophene ring substituted pyridine derivative and application thereof in pesticides |
| CN114699705B (en) * | 2022-05-06 | 2022-12-16 | 广州大学 | Method for degrading imidaclothiz by adopting white rot fungi |
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| CN101228156A (en) * | 2005-07-26 | 2008-07-23 | 杜邦公司 | Fungicidal carboxamides |
| WO2008091594A2 (en) * | 2007-01-24 | 2008-07-31 | E. I. Du Pont De Nemours And Company | Fungicidal mixtures |
| 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 |
| CN102971314A (en) * | 2010-04-28 | 2013-03-13 | 拜尔农作物科学股份公司 | Ketoheteroarylpiperidine and ketoheteroarylpiperazine derivates as fungicides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101228156A (en) * | 2005-07-26 | 2008-07-23 | 杜邦公司 | Fungicidal carboxamides |
| WO2008091594A2 (en) * | 2007-01-24 | 2008-07-31 | E. I. Du Pont De Nemours And Company | Fungicidal mixtures |
| 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 |
| CN102971314A (en) * | 2010-04-28 | 2013-03-13 | 拜尔农作物科学股份公司 | Ketoheteroarylpiperidine and ketoheteroarylpiperazine derivates as fungicides |
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