CN104650064B - A kind of aminothiazole carboxylic acid derivates and its production and use - Google Patents
A kind of aminothiazole carboxylic acid derivates and its production and use Download PDFInfo
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- CN104650064B CN104650064B CN201410809128.2A CN201410809128A CN104650064B CN 104650064 B CN104650064 B CN 104650064B CN 201410809128 A CN201410809128 A CN 201410809128A CN 104650064 B CN104650064 B CN 104650064B
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Abstract
The invention provides a kind of aminothiazole carboxylic acid derivates 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 IV.
Description
Technical field
Technical scheme is related to the heterocyclic compound containing S containing N, and in particular to 1,3-thiazoles class compound, i.e. 2-
Amino -1,3-thiazoles carboxylic acid derivates.
Background technology
Heterocyclic compound occupies critical role in novel super-high imitates pesticides discovery, novel living with biology finding structure
During the lead compound of property, design and synthesize that various Hete rocyclic derivatives are extremely important (Hu Deyu, waits the conjunction of thiazole series bactericidal agents
Into and bioactivity research progress synthesis chemistry, 2006,14 (4)：319-328.).Thiazole is a kind of important nitrogenous, sulfur-bearing
Five yuan of heteroaromatics, its special structure cause thiazole compound the fields such as chemistry, pharmacy, biology and material science have
Have broad application prospects and (Cui Shengfeng, wait thiazole compound application study new development .2012,42 (8)：1105-1131.).
Thiazole compound is due to being that (Liu's length makes world pesticides complete works of to the important guide structure of agricultural chemicals with excellent bioactivity：
Bactericide volume Beijing：Chemical Industry Press, 2006：73.), the kind of viable commercial product has：Insecticides thiamethoxam
(thiamethoxam), nematicide fluorine thiophene worm sulfone (fluensulfone), bactericide Guardian (ethaboxam) (Yan Fan
Bravely, the new type bactericide Guardian agricultural chemicals of preventing and treating oomycetes diseases, 2003,42 (4) are waited：46-47.), thiophene fluorine bacterium amine
(thifluzamide) (the firm fluorinated aromatics bactericide thiophene fluorine bacterium amine world pesticides of Pan Li, 2000,22 (5)：55-57.), thiophene
Bacterium spirit (thiabendazole), herbicide-safener solution grass amine (flurazole) and thiazole compound.
In order to find and find it is more efficiently, wide spectrum, low toxicities, low ecological risk and with existing bactericide no interactions resistance
Novel pesticide guide, present invention design have synthesized a kind of aminothiazole carboxylic acid derivates, while carried out the bioactivity of system
Screening and evaluation, to provide high activity candidate compounds for New pesticides discovery research.
The content of the invention
The technical problems to be solved by the invention are：The synthetic method of a kind of new aminothiazole carboxylic acid derivates is provided,
This kind of compound modulates agricultural, gardening and health and the bioactivity and its survey of forestry plant insect and the phytopathy original are provided
Determine method, while application of these compounds in agriculture field, horticultural field, field of forestry and health field is provided.
Technical scheme is used by the present invention solves the technical problem：With agriculture field, horticultural field, forestry and
The aminothiazole carboxylic acid that health field insecticidal activity, bactericidal activity, anti-phytoviral activity, induction plant produce anti-disease activity spreads out
The chemical structure of general formula of biology is shown in formula IV：
Wherein, X is selected from O, NH；R1Selected from 3- trifluoromethyl -5- methylpyrazole -1- methylene, the bromo- 1- of 3- (3- chloropyridines -
2- yls) -1H- pyrazoles -5- bases, tert-butoxy；R2It is 2,3,4- naphthane -1- bases, the fluoro ethyls of 2,2- bis-, different selected from ethyl, hydrogen, 1
Propyl group, propargyl, to Trifluoromethoxyphen-l, cyclopropyl, 2,2,2- trifluoroethyls, cyclohexyl, 5- methylthiazol -2- bases, 2-
Pyridine methylene.
The aminothiazole carboxylic acid derivates IV of present invention synthetic method is as follows：
Wherein, X is selected from O, NH；R1Selected from 3- trifluoromethyl -5- methylpyrazole -1- methylene, the bromo- 1- of 3- (3- chloropyridines -
2- yls) -1H- pyrazoles -5- bases, tert-butoxy；R2It is 2,3,4- naphthane -1- bases, the fluoro ethyls of 2,2- bis-, different selected from ethyl, hydrogen, 1
Propyl group, propargyl, to Trifluoromethoxyphen-l, cyclopropyl, 2,2,2- trifluoroethyls, cyclohexyl, 5- methylthiazol -2- bases, 2-
Pyridine methylene.
As above shown in reaction equation, compound II can use acid and amine according to the difference of the reaction raw materials of carbonyl containing compound
Condensation；It is prepared by acyl chlorides or acid anhydrides and the method for amine reaction.
The synthesis of target compound of the present invention and the specific method of biological activity determination are divided into following steps：
A. compound II preparation method one：
7.78 grams, i.e. 45.18 mMs of thiazolamine -5- formic acid are sequentially added in 250 milliliters of two mouthfuls of round-bottomed flasks
Ethyl ester I, 10 milligrams of DMAPs, 100 milliliters of dichloromethane steamed again, nitrogen protection, are stirred under condition of ice bath, to anti-
Answer and 9.86 grams are gradually added dropwise in system, be i.e. 45.18 mMs of di-tert-butyl dicarbonates, be abbreviated as Boc2O, drop, which finishes, removes ice bath,
It is stirred overnight at room temperature, is diluted with water after reaction completely, isolate organic layer, water layer is stripped twice with dichloromethane, is merged organic
Layer, organic layer are washed one time with saturated sodium-chloride water solution, and anhydrous magnesium sulfate is dried, and are filtered, removal of solvent under reduced pressure, residue warp
200~300 mesh silica gel column chromatographies purify to obtain 11.50 grams of light yellow solid 2- (tertiary fourth oxygen acylamino-) thiazole -5- Ethyl formate II,
Eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1, yield 93.55%；Prepared by compound II
Amount and the volume of reaction vessel are expanded or shunk by corresponding proportion.
B. part of compounds II preparation method two：
2.05 mMs of 3- trifluoromethyl -5- methylpyrazole -1- acetic acid are sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks
Or the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formic acid, 0.45 gram, i.e. 2.34 mMs of 1- (3- dimethylaminos third
Base) -3- ethyl-carbodiimide hydrochlorides, EDCI, 0.28 gram, i.e. 2.05 mMs of I-hydroxybenzotriazoles are abbreviated as, is abbreviated as
HOBT, vacuumize, nitrogen protection adds 30 milliliters of dichloromethane steamed again under ice bath into reaction system, and ice bath stirs 5 points
Ice bath is removed in clock recession, is stirred at room temperature 1 hour, is added under ice bath stirring into reaction system and is dissolved in 10 milliliters of dry methylene chlorides
In 0.12 gram, i.e., 1.95 mMs of 2- amino-thiazolyl -5- Ethyl formate I, finally be added dropwise 0.24 gram, i.e., 2.34 mMs
Triethylamine, remove ice bath after all adding and be stirred overnight at room temperature, after reaction terminates, added into reaction solution enough
Water, organic layer is isolated, water layer is stripped twice with dichloromethane, and the organic layer after merging uses saturated sodium bicarbonate and saturation respectively
Sodium chloride is respectively washed one time, and anhydrous magnesium sulfate is dried, and is filtered, removal of solvent under reduced pressure, residue is through 200~300 mesh silica gel column chromatographies
Purifying obtains white solid II respectively, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 4: 1, yield
20-45%；Amount and the volume of reaction vessel prepared by compound II is expanded or shunk by corresponding proportion.
C. part of compounds II preparation method three：
6.61 mMs of 3- trifluoromethyl -5- methylpyrazole -1- acetic acid or 3- are added in 100 milliliters of two mouthfuls of round-bottomed flasks
Bromo- 1- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formic acid, dissolved with 20 milliliters of dry dichloromethane, nitrogen protection, cryosel
Bath stirring, 1.26 grams of the addition into reaction, i.e. 9.92 mMs of oxalyl chlorides, then a drop N, N- diformazans are added dropwise into reactant mixture
Base formamide, solution is become by muddiness to be clarified, and is stirred at room temperature 2 hours, is directly concentrated reaction solution after having reacted, and what is concentrated is mixed
Compound is directly dissolved with 20 milliliters of dry dichloromethane, ice salt bath stirring, nitrogen protection, dissolving is added dropwise into reactant mixture
1.14 grams in 10 milliliters of dichloromethane, i.e. 6.61 mMs of thiazolamine -5- Ethyl formate I, it is small that reaction 2 is stirred at room temperature
When, directly reaction solution is concentrated after having reacted, residue is dissolved with 10 milliliters of ethyl acetate, and organic layer is successively with 1 mol/L salt
Acid, saturated sodium bicarbonate, saturated aqueous common salt are respectively washed one time, anhydrous sodium sulfate drying, are filtered, and rotary evaporation removes solvent, remaining
Thing purifies to obtain white solid II through 200~300 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: acetic acid second
Ester, volume ratio 2: 1, with gained sterling calculated yield, yield 30-45%；Amount and the body of reaction vessel prepared by compound II
Product is expanded or shunk by corresponding proportion.
D. compound III preparation：
42.27 mMs of compound II, 100 milliliters of tetrahydrofurans, 100 millis are added in 500 milliliters of single necked round bottom flask
Methanol, 10 milliliters of water are risen, 84.53 mMs of sodium hydroxides is eventually adding, is stirred at room temperature 4 hours, are reacted reaction solution after terminating
Concentration, residue are diluted with ethyl acetate, are added a small amount of water and are all dissolved solid, separate water-yielding stratum, aqueous layer with ethyl acetate
To wash one time, combined ethyl acetate layer is simultaneously stripped one time with water, water layer after the merging concentrated hydrochloric acid tune pH value of 12 mol/Ls to 1,
There is white solid precipitation, stirring is depressurized after 10 minutes and filters to obtain white solid III, yield 60-95%；Prepared by compound III
Amount and the volume of reaction vessel are expanded or shunk by corresponding proportion；Compound III chemical constitution and physical and chemical parameter is shown in Table 1.
E. compound IV preparation：
Sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks 2.05 mMs of different compound III, 0.45 gram, i.e.,
2.34 mMs of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, be abbreviated as EDCI, 0.28 gram, i.e., 2.05 milli
Mole I-hydroxybenzotriazole, is abbreviated as HOBT, vacuumizes, nitrogen protection, ice bath, and add 30 milliliters into reaction system steams again
Dichloromethane, ice bath stir 5 minutes recession removes ice bath, be stirred at room temperature 1 hour, continue ice bath stirring, into reaction system plus
Enter to be dissolved in 1.95 mMs of R in 10 milliliters of dry methylene chlorides2NH2Or R2OH, 0.24 gram is finally added dropwise, i.e. 2.34 mmoles
That triethylamine, remove ice bath after all adding and be stirred overnight at room temperature, after reaction terminates, added enough into reaction solution
Water, organic layer is isolated, water layer is stripped twice with dichloromethane, is merged organic layer and is used saturated sodium bicarbonate, saturated common salt respectively
Washing one time, anhydrous magnesium sulfate are dried, and are filtered, and removal of solvent under reduced pressure, residue purifies through 200~300 mesh silica gel column chromatographies
Compound IV, eluant, eluent are 60~90 degrees Celsius of petroleum ether: ethyl acetate, according to the difference of product, volume ratio 4: 1 to 1:
1, yield 50-95%；Amount and the volume of reaction vessel prepared by compound IV is expanded or shunk by corresponding proportion；Compound IV's
Chemical constitution and physical and chemical parameter are shown in Table 1.
F. aminothiazole carboxylic acid derivates IV of the invention bactericidal activity measure：
The aminothiazole carboxylic acid derivates IV of present invention sterilization or bacteriostatic activity use thalli growth rate determination method, specifically
Step is：Take 1.8 milligrams of samples to be dissolved in 2 drop DMFs, then use and contain a certain amount of polysorbas20 emulsifying agent
The aqueous solution be diluted to the medicaments of 500 mcg/mls, reagent agent is aseptically respectively drawn to 1 milliliter in culture dish,
9 milliliters of PDA culture mediums are separately added into again, 50 mcg/ml drug containing flat boards are made after shaking up, with the flat of 1 milliliter of aqua sterilisa of addition
Plate does blank control, cuts bacterium disk along mycelia outer rim with 4 millimeters of card punch of diameter, moves on drug containing flat board, in equilateral triangle
Shape is put, and 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, and its code name and title are such as
Under：AS：Tomato early blight bacterium, its Latin are entitled：Alternariasolani、BC：Botrytis cinerea pers, its Latin are entitled：
Botrytis cinerea、CA：Peanut Cercospora bacteria, its Latin are entitled：Cercospora arachidicola、GZ：Wheat is red
Mildew bacterium, 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：Physalosporapiricola、PS：Water
Rhizoctonia solani Kuhn, its Latin are entitled：Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin are entitled：
Rhizoctonia cerealis、SS：Sclerotinia sclerotiorum, its Latin are entitled：Sclerotinia sclerotiorum.
G. aminothiazole carboxylic acid derivates IV of the invention inducing anti-disease activity measure：
The aminothiazole carboxylic acid derivates IV of present invention evoking tobacco resisting tobacco mosaic virus, active screening technique is such as
Under, tobacco mosaic virus (TMV) is abbreviated as TMV：
(1) positive controls activating plants agent：It is positive control to select tiadinil of the quality purity purity more than 99.5%
Activating plants agent；Tiadinil is abbreviated as TDL；
(2) screening technique of the anti-TMV activity of aminothiazoles carboxylic acid derivates IV evoking tobacco：It is in vitro directly antiviral
The measure of activity is carried out using half leaf method；Live body induction is that 3 basins are one group, 7 before inoculation by the consistent common cigarette of seedling age
The tobacco seedlings of its pre-treatment, processing mode include：Spray test compounds solution 2 to 3 times, 10 milliliters every time, or soil treatment,
10 milliliters every time, measure concentration is 100 mcg/mls, in frictional inoculation TMV on the tobacco leaf newly grown, tobacco seedlings is placed within the 7th day
After being cultivated 3 days under its 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 controlling for the aminothiazole carboxylic acid derivates anti-TMV of IV is carried out
Treat the measure of activity, passivation activity and protection activity.
H. the measure of aminothiazole carboxylic acid derivates IV of the invention to diamondback moth insecticidal activity：
The aminothiazole carboxylic acid derivates IV of the present invention uses blade medicine embrane method to the screening technique of diamondback moth insecticidal activity：
Sample to be tested is configured to the solution of 200 mcg/mls, takes active compound sample first with a small amount of acetone solution, then with 0.5 ‰
The Triton-100 aqueous solution dilutes, and the 0.5 ‰ Triton-100 aqueous solution are control, and each 3 repetitions of concentration are each to reprocess
10 test worms；Fresh free of contamination cabbage leaves are taken, is soaked 10 seconds in decoction, after drying about 2 hours in interior, is put into diameter
In 9 centimetres of culture dish, the basically identical instar larvae of diamondback moth 2 of size is respectively connected to, diamondback moth is placed in after being tightened with rubber band
In constant temperature insectary, 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；With
Cyanogen insect amide is positive control.
I. the measure of aminothiazole carboxylic acid derivates IV of the invention to mythimna separata insecticidal activity：
Screenings of the aminothiazole carboxylic acid derivates IV of the present invention to mythimna separata insecticidal activity uses leaf dipping method：In assay balance
On weigh 2 milligrams of medicine samples in 10 milliliters of penicillin vials, add 10 milliliters of acetone, into the mother liquor of 200 mcg/mls, cover
Plug vibration dissolving, 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；Processing paper is successively placed on by sample flag sequence
On, it is put into after decoction is dry in the culture dish of markd 10 centimetres of tool, mythimna separata children at the beginning of accessing for 10 first 3 ages with elbow ophthalmology tweezers
Worm, test process is placed in constant temperature standard insectary to inspection result after cultivating 72 hours, larva is touched with small writing brush or tweezers
Body, it is completely motionless for death standard with larva；Maize leaves with acetone soln proofing are blank control.
J. the measure of aminothiazole carboxylic acid derivates IV of the invention to aphid cytotoxicity：
The aminothiazole carboxylic acid derivates IV of the present invention is determined as follows to aphid cytotoxicity：Using infusion process, broad bean
Aphid, its latin name are Aphis laburni Kaltenbach (ALK), the normal population of indoor feeding；Weigh for examination chemical combination
2.5 milligrams of thing is added dropwise 1 drop DMF, is i.e. DMF, adds 5 milliliters of acetone vibration dissolving samples, then add in beaker
Enter to have the water of Tween 80 to be configured to the solution to be measured of 200 mcg/mls；By the confession examination bean plant with least 60 black bean aphids
Cut from basin, impregnated 5 seconds in each decoction to be measured, unnecessary decoction is gently got rid of in taking-up, is inserted in water saturated
Moisturizing on sponge, escaped after decoction is dry with cloche cover, the opening of cloche upper end is sealed with gauze to prevent aphid, raising
Aphid death state is checked after placing 48 hours, standard is：It can be creeped or can stood or six Tiao Tuineng strenuous exercises with test worm
It is worm living；Using clear water as control, imidacloprid is positive control, calculates corrected mortality.
K. the measure of aminothiazole carboxylic acid derivates IV of the invention to Tetranychus cinnabarinus into mite acaricidal activity：
The aminothiazole carboxylic acid derivates IV acaricidal activities of the present invention are determined using infusion process, and detailed process is：To be measuredization
Compound is configured to mother liquor with dimethylformamide, and 200 μ g/mL solution 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, the blade with Tetranychus cinnabarinus into mite, its Latin
Entitled Tetranychus cinnabarinus, blade are cut into about 2 square centimeters of small pieces, and the one side for having mite is placed on tool two upward
On the blade of piece true leaf, under greenhouse natural light irradiation, after two hours, new leaf back is can be transferred into mite；Select every plant of mite amount
The new field planting plant of 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
Shake, remove unnecessary decoction, then move into water planting cylinder be placed in 25 DEG C of thermostatic chambers cultivate 48 hours after examined under binocular
Life or death borer population is looked into, calculates the death rate；Death standard：Mite is gently touched into dissecting needle, limbs, which move but are unable to scrambler, to be considered as extremely
Die；Clear water is blank control.
L. aminothiazole carboxylic acid derivates IV of the invention determines to the live body protection activity of pathogen：
Using the potted plant assay method of live body, by test compound sample a small amount of solvent acetone or methanol or N, N- dimethyl
Formyl amine solvent, solvent is selected according to its solvability to sample, the volume ratio of quantity of solvent and spouting liquid is equal to or less than
0.05, diluted with the water containing 0.1% Tween 80, be configured to required concentration prepare liquid；On crops sprayer, prepare liquid is sprayed
Impose on the host plant with pathogen, host plant is the standard Potted orchard cultivated in greenhouse, and cause of disease is inoculated with after 24 hours
Thing；The characteristics of according to disease, it would be desirable to be placed in phjytotron and train after the plant inoculating with pathogen of temperature control moisturizing culture
Support, after disease is completed to infect, move into hot-house culture, the plant with pathogen of moisturizing culture will not needed directly in greenhouse
It is inoculated with and cultivates；Compound protection effect assessment is carried out after fully morbidity is compareed, plant disease time is usually one week or so；
The live plant disease of test is as follows：Cucumber downy mildew, the entitled Pseudoperonospora cubensis (Berk.et of Latin
Curt.) Rostov, PCB, wheat powdery mildew is abbreviated as, entitled Blumeria graminis (DC.) Speer of Latin, is abbreviated as
BGS, corn rust, the entitled Puccinia sorghi Schw of Latin, are 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：Aminothiazole carboxylic acid derivates IV has carried out guide's optimization, and to newization of synthesis
Compound has carried out the screening of insecticidal activity and bacteriostatic activity and antiviral activity.
The present invention passes through specific preparation and the more specific explanation aminothiazole carboxylic acid derivates of biological activity determination embodiment
IV 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
Bioactivity is merely illustrative of, and unrestricted this patent, embodiment are as follows：
Embodiment 1
Compound II preparation method one：
7.78 grams, i.e. 45.18 mMs of 2- amino-thiazolyl -5- formic acid are sequentially added in 250 milliliters of two mouthfuls of round-bottomed flasks
Ethyl ester I, 10 milligrams of DMAPs, 100 milliliters of dichloromethane steamed again, nitrogen protection, are stirred under condition of ice bath, to anti-
Answer and 9.86 grams are gradually added dropwise in system, be i.e. 45.18 mMs of di-tert-butyl dicarbonates, be abbreviated as Boc2O, drop, which finishes, removes ice bath,
It is stirred overnight at room temperature, is diluted with water after reaction completely, isolate organic layer, water layer is stripped twice with dichloromethane, is merged organic
Layer, organic layer are washed one time with saturated sodium-chloride water solution, and anhydrous magnesium sulfate is dried, and are filtered, removal of solvent under reduced pressure, residue warp
200~300 mesh silica gel column chromatographies purify to obtain 11.50 grams of light yellow solid 2- (tertiary fourth oxygen acylamino-) thiazole -5- Ethyl formate II,
Eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1, yield 93.55%；1HNMR(CDCl3)：δ
7.79 (s, 1H), 4.37 (q, J=7.1Hz, 2H), 1.52 (s, 9H), 1.37 (t, J=7.1Hz, 3H).
Embodiment 2
Compound II preparation method two：
0.43 gram, i.e. 2.05 mMs of 3- trifluoromethyl -5- methyl pyrroles are sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks
Azoles -1- acetic acid or 0.62 gram, i.e. the 2.05 mMs of bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formic acid, 0.45 gram, i.e.,
2.34 mMs of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, be abbreviated as EDCI, 0.28 gram, i.e., 2.05 milli
Mole I-hydroxybenzotriazole, is abbreviated as HOBT, vacuumizes, nitrogen protection, ice bath, and add 30 milliliters into reaction system steams again
Dichloromethane a heatable brick bed, ice bath stir 5 minutes recession removes ice bath, be stirred at room temperature 1 hour, continue ice bath stirring, into reaction system plus
Enter to be dissolved in 0.12 gram in 10 milliliters of dry methylene chlorides, i.e. 1.95 mMs of 2- amino-thiazolyl -5- Ethyl formate I, finally drip
Add 0.24 gram, i.e. 2.34 mMs of triethylamines, removing ice bath after all adding is stirred overnight at room temperature, after reaction terminates, to
Enough water is added in reaction solution, isolates organic layer, water layer is stripped twice with dichloromethane, is merged organic layer and is used saturation respectively
Sodium acid carbonate and saturated sodium-chloride are washed one time, and anhydrous magnesium sulfate is dried, and are filtered, removal of solvent under reduced pressure, residue is through 200~300
The purifying of mesh silica gel column chromatography obtains white solid II respectively, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio
For 4: 1, yield 20-45%；When A is 3- trifluoromethyl -5- methylpyrazole -1- methylene, nuclear magnetic data is as follows：1HNMR
(CDCl3) δ 7.83 (s, 1H), 6.36 (s, 1H), 5.10 (s, 2H), 4.37 (q, J=6.8Hz, 2H), 2.33 (s, 3H) 1.35t,
J=6.9Hz, 3H).This step reaction was once attempted to use the DCC/DMAP condensing agents used in patent document WO2008091594 to enter
OK, but products therefrom1H NMR have DCC proton peak in δ=1-2ppm all the time, and product can not purify；By substantial amounts of condition
Grope, finally selected EDCI/HOBT is as condensing agent by the present invention, obtained product product1H NMR do not have any impurity peak to do
Disturb, this is the important innovations characteristic of the present invention.
Embodiment 3
Compound II preparation method three：
6.61 mMs of 3- trifluoromethyl -5- methylpyrazole -1- acetic acid or 3- are added in 100 milliliters of two mouthfuls of round-bottomed flasks
Bromo- 1- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formic acid, dissolved with 20 milliliters of dry dichloromethane, nitrogen protection, cryosel
Bath stirring, 1.26 grams of the addition into reaction, i.e. 9.92 mMs of oxalyl chlorides, then a drop N, N- dimethyl formyls are added dropwise into reaction
Amine, solution is become by muddiness to be clarified, and is stirred at room temperature 2 hours, and reaction solution is directly concentrated after having reacted, and the product concentrated is directly used
20 milliliters of dry dichloromethane dissolvings, ice salt bath stirring, nitrogen protection, are added dropwise into reaction and are dissolved in 10 milliliters of dichloromethane
In 1.14 grams, i.e. 6.61 mMs of thiazolamine -5- Ethyl formates, be stirred at room temperature reaction 2 hours.Directly will after having reacted
Reaction solution is concentrated, and residue is dissolved with appropriate ethyl acetate, and organic layer with 1 mol/L hydrochloric acid, saturated sodium bicarbonate, is satisfied successively
Respectively wash one time, anhydrous sodium sulfate drying, filter with saline solution, rotary evaporation removes solvent, and residue is through 200~300 mesh silica gel
Column chromatography purifies to obtain compound II, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 2: 1, with gained
Sterling calculated yield, yield 30-45%；Work as R1For 3- trifluoromethyl -5- methylpyrazole -1- methylene when, the core of the compound
Magnetic data is as follows：1HNMR(CDCl3) δ 7.83 (s, 1H), 6.36 (s, 1H), 5.10 (s, 2H), 4.37 (q, J=6.8Hz, 2H),
2.33 (s, 3H) 1.35 (t, J=6.9Hz, 3H).
Embodiment 4
Compound III preparation：
42.27 mMs of compound II, 100 milliliters of tetrahydrofurans, 100 millis are added in 500 milliliters of single necked round bottom flask
Methanol, 10 milliliters of water are risen, 84.53 mMs of sodium hydroxides is eventually adding, is stirred at room temperature 4 hours, are reacted reaction solution after terminating
Concentration, residue are diluted with ethyl acetate, are added a small amount of water and are all dissolved solid, separate water-yielding stratum, aqueous layer with ethyl acetate
Wash one time, combined ethyl acetate layer is stripped one time with water, and combining water layer adjusts pH value to have white to 1 with the concentrated hydrochloric acid of 12 mol/Ls
Solid is separated out, and stirring is depressurized after 3 minutes and filters to obtain white solid III, yield 70-95%；Its physical and chemical parameter and structural parameters are shown in
Table 1.
Embodiment 5
Compound IV preparation：
Sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks 2.05 mMs of different compound III, 0.45 gram, i.e.,
2.34 mMs of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, be abbreviated as EDCI, 0.28 gram, i.e., 2.05 milli
Mole I-hydroxybenzotriazole, is abbreviated as HOBT, vacuumizes, nitrogen protection, ice bath, and add 30 milliliters into reaction system steams again
Dichloromethane a heatable brick bed, ice bath stir 5 minutes recession removes ice bath, be stirred at room temperature 1 hour, continue ice bath stirring, into reaction system plus
Enter to be dissolved in 1.95 mMs of R in 10 milliliters of dry methylene chlorides2NH2Or R2OH, 0.24 gram is finally added dropwise, i.e. 2.34 mmoles
That triethylamine, remove ice bath after all adding and be stirred overnight at room temperature, after reaction terminates, added enough into reaction solution
Water, organic layer is isolated, water layer is stripped twice with dichloromethane, is merged organic layer and is used saturated sodium bicarbonate and saturated common salt respectively
Water is respectively washed one time, and anhydrous magnesium sulfate is dried, and is filtered, and removal of solvent under reduced pressure, residue purifies through 200~300 mesh silica gel column chromatographies
Compound IV, eluant, eluent are 60~90 degrees Celsius of petroleum ether: ethyl acetate, according to the difference of product, volume ratio 4: 1 to
1: 1, yield 50-95%；Its physical and chemical parameter and structural parameters are shown in Table 1.
Embodiment 6
The aminothiazole carboxylic acid derivates IV of present invention Antibacterial Activity result：
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：Apple
Fruit Target spot pathogen, its Latin are entitled：Physalospora piricola、PS：Rhizoctonia solani Kuhn, its Latin are entitled：
Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin are entitled：Rhizoctonia cerealis、SS：Sclerotina Sclerotiorum in Winter Rape
Core germ, its Latin are entitled：Sclerotinia sclerotiorum, these strains have representativeness well, can represented
The kind for most of pathogen that field occurs in agricultural production.Thalli growth rate method measurement result is shown in Table 2, and table 2 shows, 50
During mcg/ml, all compounds that the present invention synthesizes have different degrees of bactericidal activity.Compound lfy005-25,
Lfy005-28, lfy005-47, lfy006-25, lfy006-27, lfy006-32, lfy006-42, lfy006-43 are early to tomato
The inhibitory activity of epidemic disease bacterium more than 40%, wherein compound lfy005-25, lfy005-28, lfy005-47, lfy006-25,
Lfy006-27, lfy006-42 inhibitory activity are more than 50%, higher than comparison medicament Fluoxastrobin.To the activity of peanut Cercospora asparagagas
As a result show, compound lfy005-28, lfy006-27, lfy006-33, lfy006-34, lfy006-36, lfy006-37,
Lfy006-42, lfy006-44, lfy006-48 activity be higher than 40%, wherein compound lfy006-34, lfy006-36,
Lfy006-37, lfy006-42, lfy006-44, lfy006-48 inhibitory activity are more than 60%, higher than the phonetic bacterium of comparison medicament
The activity of ester, wherein lfy006-42 is optimal, up to 100%.The active testing result of fusarium graminearum is shown, compound
Lfy005-13, lfy006-33, lfy006-32, lfy006-34, lfy006-36, lfy006-43, lfy006-38 activity exist
More than 40%, wherein lfy005-13 activity is 75.86%, and activity is slightly above comparison medicament Fluoxastrobin.Except compound
Beyond lfy005-28, lfy006-43, all compounds of the present invention are higher than 40%, wherein chemical combination to Botryosphaeria berengeriana f. sp inhibiting rate
Thing lfy006-25, lfy006-33, lfy006-42 activity are more than 95%, higher than comparison medicament Fluoxastrobin.To cucumber grey mold
The active testing of germ shows, compound lfy005-8, lfy005-13, lfy005-34, lfy006-33, lfy006-32,
Lfy006-35, lfy006-36, lfy006-37, lfy006-38, lfy006-42, lfy006-44's is active more than 40%,
Wherein lfy005-8, lfy006-36 activity are more than 71%, higher than comparison medicament Fluoxastrobin.Work to Sclerotinia sclerotiorum
Property test show, compound lfy005-13, lfy006-25, lfy006-32, lfy006-34, lfy006-35, lfy006-36,
Lfy006-37, lfy006-38, lfy006-42, lfy006-43, lfy006-44, lfy006-48's is active more than 90%,
Activity is close to comparison medicament Fluoxastrobin.The active testing of Rhizoctonia cerealis is shown, all compounds activity more than 40%,
Wherein compound lfy005-47 activity is higher than 80%, close to comparison medicament Fluoxastrobin.To the active testing of Rhizoctonia solani Kuhn
Show, compound lfy005-13, lfy005-47, lfy006-33, lfy006-32, lfy006-35, lfy006-36,
Lfy006-37, lfy006-38, lfy006-43, lfy006-44, lfy006-48 activity are more than 40%, wherein lfy005-
13rd, lfy005-47, lfy006-32, lfy006-36, lfy006-38 activity are more than 50%, higher than the phonetic bacterium of comparison medicament
Ester.The active testing of Phytophthora infestans shows that compound lfy006-32, lfy006-34, lfy006-37 activity exist
More than 40%, wherein lfy006-34 activity are more than 80%, higher than comparison medicament Fluoxastrobin.Above-mentionedization that the present invention synthesizes
Compound has good bactericidal activity.
Embodiment 7
The aminothiazole carboxylic acid derivates IV of the present invention anti-TMV activity：
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 lfy005-25, lfy006-33, lfy006-35, lfy006-36, lfy006-37, lfy006-38,
Lfy006-43, lfy006-44, lfy006-48 inhibiting rate are higher than 45%, higher than comparison medicament Ningnanmycin, wherein, chemical combination
Thing lfy006-43 inhibiting rate is higher than 60%, higher than comparison medicament BTH.Under passivation pattern, compound lfy005-13,
Lfy005-34, lfy006-27, lfy006-33, lfy006-35, lfy006-38, lfy006-43, lfy006-48 inhibiting rate
Higher than 60%, higher than comparison medicament SZG-7, wherein, compound lfy005-34 and lfy006-27 inhibiting rate are higher than 70%.
Under protected mode, compound lfy005-13, lfy005-28, lfy006-44, lfy006-37, lfy006-35 inhibiting rate are high
In 80%, higher than comparison medicament SZG-7 and Ningnanmycin, wherein, compound lfy005-28 inhibiting rate is higher than comparison medicament
BTH.Under induction pattern, compound lfy005-25, lfy005-34, lfy006-35, lfy006-36, lfy006-37,
Lfy006-44 inhibiting rate is higher than 80%, higher than comparison medicament TDL, BTH, SZG-7 and Ningnanmycin.It can be seen that ammonia of the invention
Base thiazole carboxylic acid's derivative I V has anti-TMV activity well.
Embodiment 8
The aminothiazole carboxylic acid derivates IV of present invention insecticidal activity：
Aminothiazole carboxylic acid derivates IV insecticidal activity assay the results are shown in Table 4, and table 4 is visible：It is in reagent agent concentration
During 100 mg/litre, after observation acts on 72 hours, poisoning of the part of compounds to diamondback moth, mythimna separata, Tetranychus cinnabarinus and aphid is made
With weaker, wherein compound lfy006-33, lfy006-35, lfy006-36 is higher than to Tetranychus cinnabarinus into the acaricidal activity of mite
10%；Compound lfy005-8 to kill aphid activity stronger, reached 100%.
Embodiment 9
Live body protection activities of the aminothiazole carboxylic acid derivates IV of the present invention to pathogen：
The aminothiazole carboxylic acid derivates IV live body protection activity measurement result to pathogen is shown in Table 5, and table 5 is visible：Greatly
Part of compounds is weaker to BGS, PSS, COB, PGS and BC protection activity, but compound lfy006-33 is to PSS inhibiting rate
Up to 50.00%, compound lfy005-47 is to PGS inhibiting rate up to 80.00%；The compound of the present invention has preferable suppression to PCB
Rate processed, wherein：Compound lfy005-13, lfy005-25, lfy005-28, lfy005-47, lfy006-25, lfy005-34,
Lfy006-27 and lfy006-35 inhibiting rate is higher than 70%.Therefore, IV pairs of part aminothiazole carboxylic acid derivates of the invention
Pathogen has good live body protection activity.
Embodiment 10
The aminothiazole carboxylic acid derivates of the present invention kill with agriculturally acceptable auxiliary agent and following one or more commodity
The purposes in compounded pesticides are prepared is combined in worm agent：
The commodity insecticide is selected from：Chlopyrifos, sub- Nong, Acetamiprid, emamectin benzoate, milbemectin, AVM hereinafter
Rhzomorph, pleocidin, fenvalerate, esfenvalerate, cypermethrin, effective cypermethrin, Cyhalothrin, bromine cyanogen chrysanthemum
Ester, Fenpropathrin, Beta- cyfloxylates, cyfloxylate, Lambda- Cyhalothrins, Permanone, benzyl chloride
Chrysanthemum ester, allethrin, cyhalothrin, Biphenthrin, Permethrin, ethofenprox, flumethrin, fluvalinate, pyrrole worm
Quinoline, Acetamiprid, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, go out
Young urea, Teflubenzuron, deinsectization are grand, HEXAFLUMURON, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron are more
Fluorine urea, its CAS 121451-02-3, flucycloxuron, Novaluron are Rimon, chlorfluazuron, Bay sir 6874 i.e. { 1-
[(3.5- bis- chloro- 4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzenes)-urea }, Bay SIR-8514 be [1- (4- trifluoromethoxies
Phenyl) -3- (2- chlorobenzenes)-urea], piperazine worm urea, Bistrifluron be bistrifluron, furan tebufenozide, tebufenozide, chlorine worm acyl
Hydrazine, methoxyfenozide, ring tebufenozide, Rogor, flolimat, DDVP, orthene, Hostathion, quinalphos, pyridazine sulphur
Phosphorus, isazofos, isoprocarb, sevin, Aphox, MTMC, Mobucin, cartap, Bassa, leaf disperse, carbaryl, rosickyite
Carbofuran, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, third
Carbosulfan, pymetrozine, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, phonamiphos, fluorine worm
Nitrile, Cupric sulfate, dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromine worm
Nitrile, pyrazinones, etoxazole, tebufenpyrad, rattle away young ketone, Nylar, emaricin；The aminothiazole carboxylic acid derivates of the present invention are in institute
The total weight/mass percentage composition obtained in compounded pesticides is 1%-90%, aminothiazole carboxylic acid derivates of the invention and the business
The ratio of product insecticide is mass percent 1%: 99% to 99%: 1%；The applicable formulation of the compounded pesticides is selected from seed
Handle emulsion, aqueous emulsion, big granula, microemulsion, suspension emulsion, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain,
Aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, Waterless Seed Dressing pulvis, missible oil, electrostatic spray
Agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, seed treatment suspending agent, cigarette
Mist piece, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, solid-liquid mix dress agent, liquid liquid mixing fills agent,
Solid harl agent, solid/mixing dress agent, medicine paint, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, it is bold and vigorous pour agent,
Seed coat agent, liniment, fritter poison bait, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, super-low capacity
Measure any one in suspending agent, tracking pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water-dispersible powder；It is described
The applicable plant of compounded pesticides be selected from paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean,
Garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, can
Can, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet,
Rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, wild vegetables, bamboo shoots, hops, pepper,
Banana, papaya, orchid, potted landscape；The insect pest of compounded pesticides preventing and treating be selected from Asiatic migrotory locust, reading room management, Chinese rice grasshopper,
Patanga japonica (l.Bol.), single thorn mole cricket, Oriental burmeister, rice thripses, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipes thrips, greenhouse
Trialeurodes vaporariorum, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, sugarcane are flat
Angle plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, pears circle
A red-spotted lizard, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, rice spider edge
Stinkbug, niphe elongata, scotinophora lurida, green rice bug, green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth,
Casemaking clothes moth, oriental moth, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, diamondback moth, small heart-eating peach worm, the soybean food heart
Worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, corn borer,
Yellow rice borer, Oeobia undalis, rice leaf roller, bar snout moth's larva, Notarchaderogata, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, the small bridging of cotton
Worm, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point spark, black cutworm, big cutworm, yellow cutworm, steal poison moth, gypsymoth,
Palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, cabbage butterfly, pyrameis indica, ramie
A Chinese ephedra a kind of butterfly harmful to crop plants, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, casting skin
It is moth, the small buprestid beetle of citrus, golden edge buprestid beetle, yellow meal worm, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, black dull
Cockchafer, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, Huang are kept
Melon, phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm
White star ichneumon wasp, corn earworm hang the yellow suction of cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, wheat
Starch worm, pachydiplosis oryzae, citrus fruit fly, melonfly, the latent fly of wheat leaf ash, Americal rice leaf miner, Soybean stem borer, frit fly, Hylemyia Platura Meigen, green onion
Fly, radish fly, full skirt Exorista civilis, corn borer are strict to post fly, armyworm.
Embodiment 11
In the aminothiazole carboxylic acid derivates of the present invention and agriculturally acceptable auxiliary agent and following commodity bactericide
Purposes of any one or more combination in composite bactericide is prepared：
The commodity bactericide is selected from diazosulfide, tiadinil, first thiophene and lures amine, 4- methyl isophthalic acids, 2,3- thiadiazoles -5-
Formic acid, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, 4- bromomethyl -1,
2,3- thiadiazoles -5- Ethyl formates, 4- iodomethyls -1,2,3- thiadiazoles -5- Ethyl formates, 4- bromomethyl -5- methyl isophthalic acids, 2,3-
Thiadiazoles, 4- iodomethyl -5- methyl isophthalic acids, 2,3- thiadiazoles, 4,4- dibromo methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, 3,4-
Two chloroisothiazole -5- formic acid, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- Ethyl formates of 3,4- bis-, DL- beta-aminos
Butyric acid, isotianil, virazole, antofine, Ningnanmycin, first thiophene lure amine, salicylic acid, cytosintetidemycin, dichloro-isonicotinic acid, allyl
Isothiazole, cymoxanil, thiram, ziram, Mancozeb, aliette, thiophanate-methyl, Bravo, enemy can pine, procymidone,
Fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, salicylic acid, flumorph, dimethomorph, mefenoxam, efficient benzene frost
Spirit, double chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, ring acyl
Bacterium amine, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, second
Bacterium profit, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, azoles bacterium amine
Ester, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, Cyproconazole, Difenoconazole, olefin conversion, efficient alkene azoles
Alcohol, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, hexaconazole, glyoxalin, kind bacterium azoles, metconazole, nitrile bacterium azoles, penta bacterium
Azoles, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Triadimenol, triticonazole, bitertanol, probenazole, wheat
Fringe is peaceful, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, Evil imidazoles, pefurazoate, famoxadones,
The spirit of SYP-Z048, hymexazo, Evil frosts, Guardian, Grandox fumigant, octhilinone, benthiozole, dodemorph, butadiene morpholine, ten
Morpholine, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, Boscalid, fluopicolide, pyridine bacterium amine, phonetic collarium
Amine, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, Fenarimol, nuarimol, chinomethionat, dithianon, ethoxyquin
Quinoline, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos,
Different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, well ridge are mould
Element, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, carbendazim, benomyl, thiophanate-methyl, triazolone,
Bupirimate, dimethirimol, ethirimol, difoltan, captan, folpet, vinclozolin, fluoromide, sclerotium
Only, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, Mancozeb, Propineb, phosethyl-Al, sulphur, Bordeaux mixture,
Copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, loop coil bacterium
Amine, tricyclazole, triforine, more fruit pyridines, the pungent salt of biguanides, iminoctadine, botran, benzene flusulfamide, toluene flusulfamide, K-281,
Fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium, enemy's line ester, dazomet, nemamort, lythidathion,
Cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, isazofos, fosthietan, oxamyl, Aldicarb, grams hundred
Prestige, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole；The aminothiazole carboxylic acid derivates of the present invention compound in gained
Total weight/mass percentage composition in bactericide is 1%-90%, and aminothiazole carboxylic acid derivates of the invention are sterilized with the commodity
The ratio of agent is mass percent 1%: 99% to 99%: 1%；The applicable formulation of the composite bactericide is in following dosage forms
Any one：Wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment breast
Agent, aqueous emulsion, big granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, moisture
Dissipate property granula, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray
Agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, seed treatment suspending agent, cigarette
Mist piece, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, solid-liquid mix dress agent, liquid liquid mixing fills agent,
It is solid harl agent, solid/mixing dress agent, medicine paint, seed treatment liquor, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, bold and vigorous
Pour agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, chase after
Track pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water-dispersible powder；The applicable plant choosing of the composite bactericide
From paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean,
Red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut,
Oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon,
"Hami" melon, pawpaw, apple, citrus, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape；
The applicable controlling disease of the composite bactericide is selected from：It is wheat rust, wheat scab, wheat powdery mildew, wheat virus disease, small
The compacted spore leaf spot of the mould leaf blights of Mai Xue, wheat, flag smut of wheat, take-all, wheat sharp eyespot, wheat downy mildew, Ma Ling
Potato late blight, wart of potatoes, potato scab, target, bacterial ring rot o potato, potato bacterial wilt, horse
Bell potato balck shank, Potyvirus and viroid disease, bacterial soft rot of potato, dry rot of potato, potato verticillium wilt, Ma Ling
Potato tar spot, potato bacterial wilt, bacterial ring rot o potato, blakleg of potato, bacterial soft rot of potato, cotton wilt, cotton
Verticillium wilt, angular leaf spot of cotton, red leaf blight, cotton seedling blight, cotton samping off, cotton anthracnose, cotton spoting verticillium wilt, cotton
Anthracnose, cotton spoting verticillium wilt, rice blast, rice sheath blight disease, water rice brown spot, small round sclerotial disease of rice, rice
Bakanae disease, downymildewofrice, rice green smut, rice leaf sheath rot, bacterial blight of rice, bacterial leaf streak of rice, water
Rice bacterial Footrot, stripe disease, black streaked dwarf virus of rice, rice rice black sclerotium stalk rot, the leaf blight of corn,
Corn southern leaf blight, Helminthosporium carbonum, maize brown spot, maize sheath blight, corn rust, maize head smut, Corn Stalk Rot,
Corn smut, corn dry rot, maize virus disease and corn stalk rot disease, sclerotinia sclerotiorum, Rape virus disease, rape downy mildew
It is disease, white rust of colza, root rot, soybean sclerotinia crown rot, grey speck of soybean, soybean Mosaic, soy bean cyst roundworm, big
Beans root-knot nematode, soybean rust, soybean anthracnose, bacterial pustule of soybean, soybean spot blight, downy mildew, peanut are blue or green
Rot, Diplodia gossypina, peanut root rot, the cercospora brown spot of peanut, Peanut Web Blotch Disease, activity of peanuts disease, Peanut Scab, tobacco are blue or green
Rot, wildfire, tobacco hollw stalk, Tobacco Angular Leaf Spot Disease, tobacco black shank, Alternaria alternate, frog-eye leaf spot of tobacco, tobacco charcoal
Subcutaneous ulcer disease, black root of tobacco, fusarium tabacinum root rot, Tobacco seedling diseases, tobacco damping-off, tobacco junk leaf spot, tobacco
Powdery mildew, tobacco southern blight, tobacco black spot, tobacco mosaic disease, cucumber mosaic virus, etch virus of tobacco, Chinese cabbage downy mildew, Chinese cabbage
Soft rot, Chinese cabbage Tipburn Disease, Chinese cabbage virosis, Cabbage Leaf Spot, Seed detection, Chinese cabbage anthracnose, cabbage clubroot, kind
Eggplant bacterial speck, tomato late blight, tomato blossom-end rot, tomato powdery mildew, tomato samping off, tomato fish pelargonium mosaic disease,
Tomato bacterial speck, tomato yellow leaf curl virus, leaf muld of tomato, tomato virus disease, tomato late blight, tomato samping off
With damping-off, tomato deformation fruit, tomato perforation fruit, tomato black ring virus disease, tomato rot stem nematodes disease, tamato fruit buphthalmos
Disease, tomato stain root rot, tomato stain root rot, tomato branch spore fruit rot, tomato heartrot, tomato Rhizopus fruit rot, kind
Eggplant low temperature obstacle, tomato bolter, tomato physiological leaf curl, tomato samping off, tomato fruit drop disease, tomato bud are withered
Disease, Tomato soft rot, tomato stem rot, tomato seedling damping-off, tomato sun burn, tomato shot hole, tomato rouge and powder disease, tomato virus
Disease, tomato cracked fruit, canker of tomato, tomato navel corruption fruit, tomato sesame pinta bacterium, bacterial spot of tomato, tomato are fainted leaf
Virosis, tomato yellow leaf curl virus disease, eggplant cotton disease, eggplant sclerotiniose, eggplant bacterial wilt, eggplant Phomopisis vexans, eggplant are yellow
Wither disease, eggplant leaf spot, eggplant early blight, eggplant virosis, eggplant leaf spot disease, eggplant leaf mold, eggplant powdery mildew, eggplant spot
Select disease, eggplant coal spot disease, cercospora leaf spot of egg plant, helminthosporium leaf blight and fruit rot of egg plant, eggplant epidemic disease, eggplant anthracnose, eggplant head mold soft rot,
Wilt of eggplant, grey mould of egg plant, eggplant base rot disease, capsicum green pepper virosis, capsicum early blight, capsicum Leucoplakia, capsicum
White star, capsicum leaf spot, capsicum Scald, capsicum sooty mold, capsicum wilt, capsicum sclerotiniose, capsicum sunscald, capsicum
Virosis, capsicum malformed fruit, capsicum blossom-end rot, capsicum soft rot, bacterial spot of pepper, capsicum bar virus scab, capsicum pythium rot,
Macrosporium leaf spot of red pepper, capsicum spot blight, capsicum black spot, capsicum verticillium wilt, pepper bacterial leaf spot, capsicum brown rot, capsicum
Root rot, capsicum damping-off, pepper anthracnose, capsicum brown spot, capsicum downy mildew, Botrytis cinerea, capsicum leaf blight, capsicum
Leaf mold, capsicum samping off, capsicum epidemic disease, downy mildew of garpe, uncinula necator, brown spot of grape, grapevine leafroll disease, grape fan
Leaf disease, grape rust, grape ring spot, grape leaf spot, the small brown spot of grape, grape zonate spot, grape graywall, grape are new
The golden yellow disease of tip wasting disease, grape mosaic disease, grape wasting disease, grape stripe disease, grape, grape infectivity necrosis disease, grape are yellow
Select disease, grape lug disease, the downright bad disease of grape vein, Grapevine fleck virus disease, the starlike mosaic disease of grape, grape Pearls, Portugal
Grape white rot, bitter rot or anthracnose of grape, grape room rot, grape grey mould, grapevine anthracnose, black rot of grape, the big room rot of grape,
Grape coal selects that disease, grape are brown to select the mould dirty disease of disease, grape, grape bitter rot, grape branch spore rot, grape penicilliosis, grape
Alternaria rot, apple tree canker, dry rot of apple, ring rot of apple, apple branch canker, apple blister canker,
Pink Disease of Apple, apple die back disease, apple branch-rot, apple anthracnose, Apple Mould Core, rust of apple (Gymnosporangium yamadai), apple blossom rot, apple
Fruit brown rot, black fruit rot of apple, apple phytophthora rot, Apple Sooty, sick apple marssonina leaf spot, alternaria leaf spot of apple, apple wheel
Pinta, apple graywall, apple mildew, scab of apple, silver leaf of apple, apple infectivity root rot, armillariella root rot of apple,
Apple Root―rot disease, apple southern blight, apple violet root rot, rosellinia trunk rot of apple, Apple crown gall, apple decline disease, apple rust
Fruit disease, apple mosaic, apple green wrinkle fruit disease, apple fruit-shrink disease, Apple little leaf, apple chlorosis, apple bitter pit, apple
Water core, apple superficial scald, carbuncle apple scab, Gold Delicious apple fruit russeting, green mold of apple, apple soft rot, apple pulp
Powder silk floss disease, apple pulp brown stain disease, apple brown heart, pear scab, black rot of pear, Fungus of Pear Canker Disease, pears southern blight, pear tree wood
Maize ear rot, pears die back disease, rust of pear, Pear black spot, pears graywall, pears brown spot, pears Socty Blotch And Greasy Blotch, pears top rot, pears fruit-shrink disease, pears
Yellowtop, anthracnose of peach, peach reality maize ear rot, peach fruit rot, peach soft rot, peach canker, peach powdery mildew, peach brown rot, peach sore
The abnormal fruit disease of scall, peach, peach sooty mould, peach leaf-curl, peach fungoid shothole disease, peach Bacterial septicaemia syndrome, peach leaves
Pinta, peach leaf rust, peach mosaic disease, peach red-leaf disease, peach rot, peach gummosis, peach wood rot, peach do
Rot, Peach crown gall, peach root rot, peach root knot nematode disease, Citrus Huanglongbing pathogen, exocortis, the broken leaf disease of citrus, mandarin orange
Tangerine decline disease, Satsuma dwarf virus, citrus bacterial canker disease, citrus scab, citrus anthracnose, citrus foot rot, citrus resin
Disease, citrus bleeding disease, Citrus fuliginous, citrus powdery mildew, citrus fat select maculopathy, citrus intends fat and selects the red clothing of maculopathy, citrus
Disease, citrus felt fungus, citrus seedling blight, citrus seedling epidemic disease, banana bunchy top disease, Banana Mosaic Disease, banana sickle-like bacteria
Droop, Cercospora musae bacterium leaf spot, the banana secretly mould leaf spot of double spores, the mould leaf spots of the small Dou Shi of banana, banana freckle, banana
Leaf seasonal febrile diseases, banana anthracnose, banana crown rot, wild cabbage bacterial black rot, cottony rot of cabbage, cabbage black rot, wild cabbage blackspot
Disease, wild cabbage brown spot, wild cabbage blastomere disease, wild cabbage virosis, wild cabbage soft rot, wild cabbage bolting disease, cabbage downy mildew, wild cabbage in advance
Anthracnose, black leg of cabbage, sugarcane pineapple disease, smut of sugarcane, sugarcane ratoon stunting disease, sugarcane brown streak, sugarcane rust, height
Beam smut, jowar leaf spot, jowar anthracnose, jowar leaf blight, jowar virosis.
Embodiment 12
The aminothiazole carboxylic acid derivates of the present invention with agriculturally acceptable auxiliary agent and with following commodity antivirotic
In any one or more combination preparing compounding anti-plant virus agent, the purposes in activating plants agent：
The commodity antivirotic is selected from：Diazosulfide, tiadinil, first thiophene lure amine, 4- methyl isophthalic acids, 2,3- thiophenes two
Azoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, 4- bromine first
Base -1,2,3- thiadiazoles -5- Ethyl formates, 4- iodomethyls -1,2,3- thiadiazoles -5- Ethyl formates, 4- bromomethyl -5- methyl -
1,2,3- thiadiazoles, 4- iodomethyl -5- methyl isophthalic acids, 2,3- thiadiazoles, 4,4- dibromo methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid second
Ester, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- Ethyl formates of 3,4- bis-,
DL- beta-aminobutyric acids, virazole, antofine, Ningnanmycin, first thiophene lure amine, salicylic acid, cytosintetidemycin, dichloro-isonicotinic acid, allyl
Isothiazole, well ridge azanol, jinggangmeisu；The aminothiazole carboxylic acid derivates of the present invention compound anti-plant virus agent, plant in gained
Total weight/mass percentage composition in thing activator is 1%-90%, and aminothiazole carboxylic acid derivates of the invention resist with the commodity
The ratio of viral agent is mass percent 1%: 99% to 99%: 1%；The compounding anti-plant virus agent, activating plants agent
Formulation is selected from wettable powder, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, water
Emulsion, big granula, microemulsion, oil-suspending agent, with the seed of coated pesticidal, water-soluble granule, soluble thick agent, water dispersible grain
Agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, oil
Bag aqueous emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, seed treatment suspending agent, smog piece,
Smog ball, granular poison bait, foaming agent, drift pulvis, ointment, thermal fog, the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, harl
Solid agent, solid/mixing dress agent, medicine paint, seed treatment liquor, fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, bold and vigorous pour
Agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, tracking
Any one in pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water-dispersible powder；The anti-phytopathy of compounding
The applicable plant of toxic agent, activating plants agent be selected from paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava,
Soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee
Coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube,
Beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, wild vegetables, bamboo shoots, hops,
Pepper, banana, papaya, orchid, potted landscape；The applicable virus disease of the compounding anti-plant virus agent, activating plants agent is selected from
Rice dwarf virus disease, BYDV, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease, tobacco veinal necrosis virus disease,
Any one of maize dwarf mosaic, cauliflower mosaic virus, citrus virosis, cymbidium mosaic virus, cybidium ring spot virus.
Embodiment 13
The aminothiazole carboxylic acid derivates of the present invention with agriculturally acceptable auxiliary agent and with following commodity acaricide
Any one or more combination preparing Compositional acaricide and its preventing and treating plant mites evil in purposes：
The commodity acaricide is selected from azacyclotin, plictran, fenbutatin oxide, three phosphor tins, chlorfenviphos, dimethylvinphos, bar poison
Phosphorus, DDVP, heptenophos, Menite, Azodrin, 2-dichloroethylk dimethyl phosphate, chlopyrifos, Diothyl, imino-formyl chloride sulphur phosphorus, omethoate, enemy kill
Phosphorus, Ethodan, malathion, methacrifos, Phosalone, phoxim, methylpyrimidine sulphur phosphorus, quinalphos, sulfotep, Hostathion,
Kilval, isocarbophos, acephatemet, propetamphos, dialifos, phosmet, acrinathrin, Biphenthrin, chlorine fluorine cyanogen chrysanthemum
Ester, smart gamma cyhalothrin, Fenpropathrin, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, biphenyl hydrazine
Ester, fenothiocarb, Aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, benomyl, sok, carbofuran, fourth sulphur gram hundred
Prestige, MTMC, promacyl, Carzol, single carbonamidine, medimeform, Amitraz, Spanon, Ergol, fenisobromolate, fourth fluorine mite
Ester, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, AVM,
Doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin,
Rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, Hexythiazox, Envidor, fluacrypyrim, chlorfenizon, propargite,
Pyridaben；Total weight/mass percentage composition of the aminothiazole carboxylic acid derivates of the present invention in gained Compositional acaricide in the composition
It is 1%-90%, aminothiazole carboxylic acid derivates of the invention and the acaricidal ratio of the commodity are mass percent 1%:
99% to 99%: 1%；The formulation of the Compositional acaricide is selected from wettable powder, micro-capsule suspension, dispersible system
Agent, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, big granula, microemulsion, oil-suspending agent, the kind with coated pesticidal
Son, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule
Granula, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, cigarette
Mist cylinder, smog rod, seed treatment suspending agent, smog piece, smog ball, granular poison bait, foaming agent, drift pulvis, ointment, hot mist
Solid agent, the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, harl agent, solid/mixing fill agent, medicine paint, seed treatment liquor, fine granule,
Oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle pour agent, liniment, suspended emulsion, film forming finish, soluble powder, seed
Treatment of water-soluble pulvis, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, steam releasing agent, wet-mixing kind water dispersible
Any one in pulvis；The applicable plant of the Compositional acaricide is selected from paddy, wheat, barley, oat, corn, sorghum, sweet
Potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Xiang
Certain herbaceous plants with big flowers, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber,
Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, hill
Dish, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape；The applicable mite evil of the Compositional acaricide selected from Tetranychidae,
Tenuipalpidae, furan line mite, Eriophyidae, tetranychus telarius category, the evil mite of Eriophyidae, these evil mites are worldwide Agricultural Mites, forestry evil
Mite, gardening evil mite and hygienic evil mite.
The aminothiazole carboxylic acid derivates IV of the present invention of table 1 chemical constitution and physical and chemical parameter
The aminothiazole carboxylic acid derivates IV of the present invention of table 2 bacteriostatic activity (inhibiting rate/% of 50 mcg/mls)
| Sequence number | Compound | AS | CA | GZ | PP | BC | SS | RC | PS | PI |
| 1 | lfy005-8 | 25.00 | 20.00 | 23.33 | 42.86 | 76.67 | 21.13 | 52.27 | 24.24 | 7.41 |
| 2 | lfy005-13 | 33.33 | 0 | 75.86 | 42.25 | 63.16 | 91.23 | 76.25 | 51.22 | 5.00 |
| 3 | lfy005-25 | 60.00 | 16.13 | 11.11 | 48.08 | 28.57 | 32.14 | 58.82 | 10.42 | 7.69 |
| 4 | lfy005-28 | 51.43 | 48.39 | 38.89 | 34.62 | 0 | 42.86 | 54.41 | 0 | 19.23 |
| 5 | lfy005-47 | 54.29 | 32.26 | 16.67 | 53.85 | 4.76 | 50.00 | 82.35 | 67.71 | 26.92 |
| 6 | lfy006-25 | 68.57 | 35.48 | 22.22 | 96.15 | 23.81 | 92.86 | 54.41 | 10.42 | 38.46 |
| 7 | lfy005-34 | 30.00 | 24.00 | 6.67 | 42.86 | 43.33 | 21.13 | 52.27 | 21.21 | 3.70 |
| 8 | lfy006-27 | 57.14 | 41.94 | 33.33 | 46.15 | 28.57 | 25.00 | 61.76 | 10.42 | 15.38 |
| 9 | lfy006-33 | 38.89 | 54.55 | 63.64 | 100 | 46.43 | 30.77 | 54.39 | 46.51 | 33.33 |
| 10 | lfy006-32 | 44.44 | 0 | 54.55 | 51.22 | 50.00 | 96.15 | 66.67 | 55.81 | 45.83 |
| 11 | lfy006-34 | 16.67 | 81.82 | 54.55 | 65.85 | 35.71 | 100 | 68.42 | 34.88 | 87.50 |
| 12 | lfy006-35 | 38.89 | 9.09 | 27.27 | 68.29 | 64.29 | 96.15 | 73.68 | 46.51 | 37.50 |
| 13 | lfy006-36 | 22.22 | 72.73 | 54.55 | 60.98 | 75.00 | 100 | 63.16 | 51.16 | 33.33 |
| 14 | lfy006-37 | 22.22 | 63.64 | 9.09 | 60.98 | 42.86 | 100 | 63.16 | 46.51 | 45.83 |
| 15 | lfy006-38 | 38.89 | 9.09 | 45.45 | 41.46 | 53.57 | 100 | 43.86 | 53.49 | 33.33 |
| 16 | lfy006-42 | 66.67 | 100 | 36.36 | 95.12 | 46.43 | 96.15 | 57.89 | 39.53 | 33.33 |
| 17 | lfy006-43 | 44.44 | 0 | 54.55 | 26.83 | 0 | 96.15 | 64.91 | 46.51 | 29.17 |
| 18 | lfy006-44 | 11.11 | 63.64 | 27.27 | 65.85 | 50.00 | 100 | 66.67 | 46.51 | 33.33 |
| 19 | lfy006-48 | 27.78 | 63.64 | 36.36 | 60.98 | 39.29 | 92.31 | 54.39 | 58.14 | 29.17 |
| 20 | Fluoxastrobin | 46.88 | 55.56 | 75.00 | 91.18 | 71.43 | 100 | 88.10 | 84.06 | 80.77 |
Activity (the suppression of 100 mcg/mls of the aminothiazole carboxylic acid derivates IV resisting tobacco mosaic virus of the present invention of table 3
Rate/% processed)
| Sequence number | Compound | Treatment | Passivation | Induction | Protection |
| 1 | lfy005-8 | 27.50±0.83 | 53.85±2.57 | 33.00±3.00 | 20.00±5.71 |
| 2 | lfy005-13 | 45.00±4.41 | 68.38±5.42 | 56.00±2.00 | 84.29±1.43 |
| 3 | lfy005-25 | 56.11±2.76 | 12.82±2.56 | 89.33±3.65 | 47.14±4.29 |
| 4 | lfy005-28 | 35.00±1.67 | 25.65±2.57 | 54.00±6.00 | 90.48±3.88 |
| 5 | lfy005-47 | 28.33±1.67 | 53.85±6.08 | 25.00±1.00 | 77.14±1.91 |
| 6 | lfy006-25 | 33.33±3.33 | 53.85±5.13 | 62.00±4.00 | 77.14±8.20 |
| 7 | lfy005-34 | 30.83±2.50 | 76.92±6.98 | 80.00±7.68 | 67.14±1.43 |
| 8 | lfy006-27 | 30.56±5.29 | 76.92±2.21 | 78.00±4.00 | 30.00±1.43 |
| 9 | lfy006-33 | 49.17±0.83 | 69.23±2.56 | 71.00±5.00 | 14.29±5.72 |
| 10 | lfy006-32 | 41.50±8.17 | 28.21±2.56 | 61.00±7.00 | 62.86±2.86 |
| 11 | lfy006-34 | 31.67±6.44 | 29.49±1.28 | 79.33±6.87 | 60.95±7.54 |
| 12 | lfy006-35 | 49.17±4.17 | 60.68±8.76 | 83.33±3.13 | 89.52±4.15 |
| 13 | lfy006-36 | 47.50±2.50 | 33.33±2.57 | 81.00±3.00 | 68.57±2.86 |
| 14 | lfy006-37 | 55.83±2.50 | 53.85±5.13 | 88.00±2.00 | 87.62±6.83 |
| 15 | lfy006-38 | 47.50±2.50 | 62.39±7.06 | 78.00±4.00 | 58.57±4.29 |
| 16 | lfy006-42 | 29.17±0.83 | 54.70±5.25 | 60.00±2.00 | 41.43±4.29 |
| 17 | lfy006-43 | 63.33±3.33 | 66.67±2.56 | 38.00±6.00 | 47.14±1.43 |
| 18 | lfy006-44 | 55.00±5.00 | 26.92±3.85 | 86.00±2.00 | 82.86±2.86 |
| 19 | lfy006-48 | 53.33±5.00 | 63.25±5.49 | 36.67±3.23 | 74.29±2.86 |
| 20 | Ningnanmycin | 45.00±4.84 | 45.64±2.35 | 28.36±2.99 | 43.19±3.54 |
| 21 | TDL | 29.17±4.17 | 26.15±3.08 | 63.00±3.00 | 26.76±5.07 |
| 22 | BTH | 59.17±4.17 | - | 79.00±1.00 | 90.00±1.43 |
| 23 | SZG-7 | 33.33±3.33 | 60.26±3.85 | 78.00±3.27 | 70.00±1.43 |
The aminothiazole carboxylic acid derivates IV of the present invention of table 4 desinsection, acaricidal activity (death rate/%, 100 mg/litres；
Black bean aphid 48 hours, other 72 hours)
| Numbering | Compound | Diamondback moth | Mythimna separata | Aphid | Tetranychus cinnabarinus |
| 1 | lfy005-8 | 0 | 0 | 100 | 0 |
| 2 | lfy005-13 | 0 | 0 | 0 | 0 |
| 3 | lfy005-25 | 0 | 0 | 0 | 0 |
| 4 | lfy005-28 | 0 | 0 | 0 | 0 |
| 5 | lfy005-47 | 0 | 0 | 0 | 0 |
| 6 | lfy006-25 | 0 | 0 | 0 | 0 |
| 7 | lfy005-34 | 0 | 0 | 0 | 0 |
| 8 | lfy006-27 | 0 | 0 | 0 | 0 |
| 9 | lfy006-33 | 0 | 0 | 0 | 27.70 |
| 10 | lfy006-32 | - | - | 0 | - |
| 11 | lfy006-34 | 0 | 0 | 0 | 0 |
| 12 | lfy006-35 | 0 | 0 | 0 | 13.30 |
| 13 | lfy006-36 | 0 | 0 | 0 | 23.30 |
| 14 | lfy006-37 | 0 | 0 | 0 | 0 |
| 15 | lfy006-38 | - | - | 2.00 | - |
| 16 | lfy006-42 | 0 | 0 | 0 | 0 |
| 17 | lfy006-43 | - | - | 5.56 | - |
| 18 | lfy006-44 | - | - | 4.25 | - |
| 19 | lfy006-48 | - | - | 6.63 | - |
The aminothiazole carboxylic acid derivates IV of the present invention of table 5 sterilization live body protection activity
Claims (6)
1. a kind of aminothiazole carboxylic acid derivates, it is characterised in that：With the general structure as shown in formula IV：
Wherein, X NH；
Work as R1During selected from 3- trifluoromethyl -5- methylpyrazole -1- methylene；R2Selected from H, 1,2,3,4- naphthane -1- bases, 2,2-
Two fluoro ethyls, isopropyl；
Work as R1During selected from the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- bases；R2Selected from H, the fluoro ethyls of 2,2- bis-；
Work as R1During selected from tert-butoxy；R2Selected from isopropyl, the fluoro ethyls of 2,2- bis-, cyclopropyl, 1,2,3,4- naphthane -1- bases, ring
Hexyl, 5- methylthiazol -2- bases, propargyl.
2. the synthetic method of the aminothiazole carboxylic acid derivates described in claim 1, specific synthetic route are as follows：
Wherein, X NH；
Work as R1During selected from 3- trifluoromethyl -5- methylpyrazole -1- methylene；R2Selected from H, 1,2,3,4- naphthane -1- bases, 2,2-
Two fluoro ethyls, isopropyl；
Work as R1During selected from the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- bases；R2Selected from H, the fluoro ethyls of 2,2- bis-；
Work as R1During selected from tert-butoxy；R2Selected from isopropyl, the fluoro ethyls of 2,2- bis-, cyclopropyl, 1,2,3,4- naphthane -1- bases, ring
Hexyl, 5- methylthiazol -2- bases, propargyl.
3. the synthetic method of the aminothiazole carboxylic acid derivates described in claim 2, it is concretely comprised the following steps：
A. compound III preparation：
42.27 mMs of compound II, 100 milliliters of tetrahydrofurans, 100 milliliters of first are added in 500 milliliters of single necked round bottom flask
Alcohol, 10 milliliters of water, are eventually adding 84.53 mMs of sodium hydroxides, are stirred at room temperature 4 hours, and reaction concentrates reaction solution after terminating,
Residue is diluted with ethyl acetate, is added a small amount of water and is all dissolved solid, separates water-yielding stratum, aqueous layer with ethyl acetate washes one
Time, combined ethyl acetate layer is simultaneously stripped one time with water, and the water layer after merging adjusts pH value to have white to 1 with the concentrated hydrochloric acid of 12 mol/Ls
Color solid is separated out, and stirring is depressurized after 10 minutes and filters to obtain white solid III, yield 60-95%；
B. compound IV preparation：
Sequentially added in 100 milliliters of two mouthfuls of round-bottomed flasks 2.05 mMs of different compound III, 0.45 gram, i.e., 2.34 milli
Mole 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, are abbreviated as EDCI, 0.28 gram, i.e. 2.05 mMs of 1-
Hydroxybenzotriazole, HOBT is abbreviated as, vacuumized, nitrogen protection, ice bath, 30 milliliters of dichloros steamed again are added into reaction system
Methane, ice bath stir recession in 5 minutes and remove ice bath, be stirred at room temperature 1 hour, continue ice bath stirring, add and be dissolved in into reaction system
1.95 mMs of R in 10 milliliters of dry methylene chlorides2NH2, 0.24 gram is finally added dropwise, i.e. 2.34 mMs of triethylamines are whole
Ice bath is removed after addition to be stirred overnight at room temperature, and after reaction terminates, enough water is added into reaction solution, is isolated organic
Layer, water layer are stripped twice with dichloromethane, are merged organic layer and are used saturated sodium bicarbonate respectively, saturated common salt is washed one time, anhydrous
Magnesium sulfate is dried, and is filtered, and removal of solvent under reduced pressure, residue purifies to obtain compound IV through 200~300 mesh silica gel column chromatographies, is eluted
Agent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, according to the difference of product, volume ratio 4: 1 to 1: 1, yield 50-
95%.
4. purposes of the aminothiazole carboxylic acid derivates in bactericide is prepared described in claim 1.
5. purposes of the aminothiazole carboxylic acid derivates in resisting tobacco mosaic virus agent is prepared described in claim 1.
6. purposes of the aminothiazole carboxylic acid derivates in activating plants agent is prepared described in claim 1.
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| CN106856955A (en) * | 2017-03-24 | 2017-06-20 | 新疆农业科学院粮食作物研究所 | A kind of jujube-wheat integrated cultivation method |
| CN107041222A (en) * | 2017-03-24 | 2017-08-15 | 新疆农业科学院粮食作物研究所 | A kind of walnut-wheat integrated cultivation method |
| CN108640887B (en) * | 2018-04-12 | 2019-12-24 | 南开大学 | Heterocyclic morpholine derivatives, and preparation method and application thereof |
| CN109535154B (en) * | 2018-12-14 | 2021-09-10 | 南通大学 | Pyrazole amide compound containing 4-arylthiazole structure and preparation method and application thereof |
| CN110272413B (en) * | 2019-07-01 | 2023-04-07 | 长沙理工大学 | N-thiazolyl-1-pyridyl-5-pyrazolecarboxamide derivatives and application thereof |
| CN113880762B (en) * | 2020-07-02 | 2023-02-21 | 河北农业大学 | Triacylamine derivatives containing 1,8-naphthalimide as well as preparation method and application thereof |
| CN111903411B (en) * | 2020-07-10 | 2022-04-01 | 浙江锦珩健康科技有限责任公司 | Comprehensive control method for Raspberry wilt |
| CN112166734A (en) * | 2020-09-18 | 2021-01-05 | 海南富友种苗有限公司 | Method for soaking and sterilizing seeds of Hami melons |
| CN113408849B (en) * | 2021-05-13 | 2023-03-24 | 柳州东风容泰化工股份有限公司 | Method and system for evaluating mixed pesticide effect of fenpyroximate and pesticide |
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| JP2007119416A (en) * | 2005-10-31 | 2007-05-17 | Bayer Cropscience Ag | Insecticidal 2-acylaminothiazole-4-carboxamides |
| WO2010066353A1 (en) * | 2008-12-11 | 2010-06-17 | Bayer Cropscience Ag | Thiazolyl oxime ether and hydrazones asl plant protection agent |
| AU2011256730B2 (en) * | 2010-05-20 | 2015-07-09 | E. I. Du Pont De Nemours And Company | Fungicidal oximes and hydrazones |
| CN102942565B (en) * | 2012-11-06 | 2016-01-27 | 江西天人生态股份有限公司 | One class 3,4-dichloro Isothizole derivatives and its production and use |
| CN103483287B (en) * | 2013-10-12 | 2015-07-08 | 南开大学 | 3,4-dichloroisothiazole containing bisamide compounds as well as preparation method and application thereof |
| CN103497182B (en) * | 2013-10-25 | 2016-05-11 | 南开大学 | One class contains 3 of 4,5-thiazoline carboxylic ester, 4-dichloro Isothizole derivatives and its production and use |
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