CN100471846C - Cyanoacrylate compounds and their application in pesticide - Google Patents
Cyanoacrylate compounds and their application in pesticide Download PDFInfo
- Publication number
- CN100471846C CN100471846C CNB2007100569351A CN200710056935A CN100471846C CN 100471846 C CN100471846 C CN 100471846C CN B2007100569351 A CNB2007100569351 A CN B2007100569351A CN 200710056935 A CN200710056935 A CN 200710056935A CN 100471846 C CN100471846 C CN 100471846C
- Authority
- CN
- China
- Prior art keywords
- add
- activity
- methyl
- pyridazine
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to cyanoacrylate compounds and their application in farm chemicals. The cyanoacrylate compounds of the present invention have excellent herbicidal activity for weeding broad leaved weeds and gramineous weeds, bactericidal activity, plant growth regulator activity and plant virus resisting activity, so that they may be used as herbicide, bactericide, plant growth regulator plant virus resisting agent.
Description
Technical field
The present invention relates to cyanoacrylate compound and the application on agricultural chemicals.
Background technology
Cyanoacrylate compound is class photosynthesis photosystem II (PSII) electron transfer inhibitor as weedicide, patent CN 1246474A discloses cyanoacrylate compound and the biological activity that contains sulfenyl pyridyl-methanamine base, after finding that phenyl ring becomes pyridine ring in the alpha-cyanoacrylate ester molecule, its weeding activity improves greatly.Patent CN 1483320A discloses a kind of heterocycle methylamino cyanoacrylate compound and weeding activity of containing, and biological activity determination is the result show: this compounds has very high weeding activity to broadleaf weeds and gramineous weeds.Patent CN 1594294A discloses the cyanoacrylate compound and the biological activity of fluorinated pyridine methylamino, finds that this compounds has very high Hill reactive behavior and weeding activity.Patent CN1603307A discloses cyanacrylate derivant and preparation method and biological activity, and the compound of report has antitumor and anti-phytoviral activity.Patent CN1760176A discloses the synthetic and weeding activity of Z-2-cyano group-3-(N-(S)-Alpha-Methyl p-fluorin benzyl amine group)-2-pentenoic acid ethoxy ethyl ester, and indoor and field efficacy shows: this compound can be prevented and kill off broadleaf weeds behind the corn field seedling.
Summary of the invention
The purpose of this invention is to provide cyanoacrylate compound (A) and the application on agricultural chemicals.The invention provides many new chemical structures and new compound.Biological activity determination is the result show: compd A not only has very high weeding activity, but also has sterilization, plant growth regulating and anti-phytoviral activity.
The present invention is following general formula (A) compound:
Wherein, R
1: pyridine, thiazole, pyrimidine, pyridazine, furans, tetrahydrofuran (THF), or on the above-mentioned heterocycle by fluorine, chlorine, bromine, C
1-C
6Alkoxyl group or C
1-C
6Alkylamino radical replaces; R
2: C
1-C
3Alkyl, methylthio group.
The synthetic route of The compounds of this invention (A) is as follows:
Synthesizing of furans, tetrahydrofuran methyl amine:
Synthesizing of substituted pyridines methylamine:
Synthesizing of substituted thiazole methylamine:
Replace the synthetic of pyridazine methylamine:
Synthesizing of substituted pyrimidines methylamine:
Cyanoacrylate target compound A's is synthetic:
Synthetic route of the present invention is described below: 2-cyano group-3-methoxyl group-2-olefin(e) acid ethoxy ethyl ester or 2-cyano group-3,3-diformazan sulfenyl vinylformic acid ethoxy ethyl ester and various heterocyclic methyl amine, mol ratio is respectively 1:1, mix stirring down with dehydrated alcohol, refluxed 3 hours, precipitation, column chromatography for separation gets target compound.
The application of cyanoacrylate compound (A) on agricultural chemicals is as weedicide, sterilant, plant-growth regulator and anti-plant virus agent.Cyanoacrylate compound (A) shows good weeding activity, is used for the weeding of broadleaf weeds and gramineous weeds, and cauline leaf is handled active in soil treatment; Activity to the broad-leaved rape is higher than Gramineae barnyard grass grass.Cyanoacrylate compound (A) also has fungicidal activity and plant growth regulating activity and anti-phytoviral activity.
Substantial characteristics of the present invention can be embodied from following embodiment, but it should not to be considered as be that the present invention is imposed any restrictions.
Embodiment
The preparation of embodiment 1:2-furfuryl amine:
In 100ml four-hole round-bottomed bottle, add 9.61g furtural, 8.69g oxammonium hydrochloride and 15ml water, drip the mixed solution of 6.63g yellow soda ash and 25ml water, dripped complete reflux 1 hour.Cold filtration gets 2 furan carboxyaldehyde oxime solid 10.97g, productive rate 98.8%, mp:78-80 ℃.
Add 2.22g2-furtural oxime in the 100ml four-hole bottle, 20ml ethanol, 1g Raney Ni, normal pressure feeds hydrogen 12h.Filter, filtrate drying, filtration, concentrate faint yellow oily 2-furfuryl amine 27.5g, productive rate 60.0% is directly used in next step reaction.
Embodiment 2:(±) preparation of 3-tetrahydrofuran methyl amine:
Add 0.5g 3-furfuryl amine, 10ml ethanol and 0.2g palladium/carbon in the autoclave, feed 100atm hydrogen room temperature reaction 40h.Reacting liquid filtering, filtrate concentrate yellow oily (±) 3-tetrahydrofuran methyl amine, productive rate 77.5%.
1H?NMR(CDCl
3)δ1.53-1.64(m，2H)，1.99-2.10(m，1H)，2.23-2.37(m，1H)，2.71-2.73(m，1H)，3.48-3.53(m，1H)，3.71-3.79(m，1H)，3.83-3.91(m，2H)，4.83(s，2H)。
The preparation of embodiment 3:2-bromine-5-picolyl amine:
The preparation of 2-bromo-5-picoline: in the 250ml four-hole bottle, add 3.01g 2-amido-5-picoline, add the HBr of 15ml 40% under the room temperature, be cooled to-15 ℃ then, add 4ml liquid bromine, finish, stir 90min.Drip 7.5ml NaNO then
2Solution is warmed up to room temperature, and stirs 45min.Drip 100ml NaOH solution again.Finish room temperature reaction 1h again.The suction filtration after drying promptly obtains 2-bromo-5-picoline 3.56g, yield 80%, fusing point 38-40 ℃.
The preparation of 2-bromo-5-bromo methyl cycloheptapyridine: add 3.37g 2-bromo-5-picoline, 3.14g N-bromo-succinimide, 0.11g Diisopropyl azodicarboxylate and 100ml tetracol phenixin in the 250ml there-necked flask, stirring heating refluxed 2 hours.Reaction solution washing, dry, concentrated back column chromatography for separation obtain 2-bromo-5-monobromomethane pyridine 2.04g, yield 46.0%, fusing point 62-63 ℃.
The preparation of N-(2-bromo-5-picolyl) phthalic imidine: in 100ml single port bottle, add 1.92g2-bromo-5-monobromomethane pyridine, 10ml DMF adds the 1.42g potassium phthalimide under the induction stirring.Add cold water behind the reaction 3h, produce a large amount of white precipitates.Filter washing and drying, obtain white solid N-(2-bromo-5-picolyl) phthalic imidine 2.19g, yield 90.5%, fusing point 139-141 ℃.
The preparation of 2-bromine-5-picolyl amine: 2.19g N-(2-bromo-5-picolyl) phthalic imidine is joined in the 100ml there-necked flask, add 20ml ethanol again, the hydrazine hydrate of 0.53g 85%.Stirring and refluxing 5h.Add 10% hydrochloric acid then, 1h again refluxes.Filter filtrate hydro-oxidation sodium water solution.With 20ml dichloromethane extraction 3 times.Merge organic phase, drying, filtration, precipitation promptly obtain 2-bromine-5-picolyl amine 0.97g, yield 87.4%.
The preparation of embodiment 4:2-dimethylin-5-picolyl amine:
The preparation of 6-chloropyridine-3-methane amide: in 50ml single port bottle, add 2.0g chlordene nicotinic acid, 1.89g sulfur oxychloride, 20ml toluene, stirring and refluxing 3h.Water pump is taken excessive sulfur oxychloride away, and the toluene solution of the acyl chlorides that obtains splashes in the 20ml strong aqua, stirs 1h under the room temperature.Suction filtration, dry cake promptly obtains white solid 6-chloropyridine-3-methane amide 1.77g, yield 89%, fusing point 213-215 ℃.
6-dimethylin-3-pyridine carboxamide: in the 50ml there-necked flask, add the 1.74g 6-chloropyridine-3-methane amide for preparing, the 2.67ml diethylamine, 7ml DMF under the induction stirring, is heated to 130 ℃ of reaction 6h.With the reaction solution precipitation, add distilled water again, filter, filtration cakes torrefaction promptly is 6-dimethylin-3-pyridine carboxamide 0.89g, yield 34.2%, fusing point 231-232 ℃.
6-dimethylin-3-picolyl amine: add the 1.50g lithium aluminum hydride in the 100ml four-hole bottle, 50ml THF, cryosel bathe 6-dimethylin-3-pyridine carboxamide that cooling adds the preparation of 1.36g previous step down.Room temperature reaction 4h then.Add NaOH solution and remove unreacted lithium aluminum hydride, filtrate is used CHCl
3Extraction merges organic liquor, and precipitation promptly obtains 2-dimethylin-5-picolyl amine 1.02g, yield 60%.
The preparation of embodiment 5:2-trifluoro ethoxy-5-picolyl amine:
In the 100ml there-necked flask, add 10ml trifluoroethanol and 0.23g sodium Metal 99.5, after reaction finishes, add 0.5g 2-chlorine-5-picolyl amine, be back to reaction and finish.Add 20ml water, chloroform extraction merges organic layer, and precipitation gets faint yellow solid 0.56g, yield 78%.
The preparation of embodiment 6:2-bromine-5-thiazole methyl amine:
The preparation of 2-bromo-5-methylthiazol: the 250ml there-necked flask, add Hydrogen bromide 61g, add 17.13g2-amino-5-methylthiazol under the mechanical stirring, drip the solution of 13.78g Sodium Nitrite then, behind reinforced the finishing, keep reaction 2h, temperature reaction 1h then under the low temperature.Filtering reacting liquid, merging filtrate is used dichloromethane extraction, concentrates, and rapid column chromatography gets light yellow oily 2-bromo-5-methylthiazol 16.03g, yield 63.0%.
The preparation of 2-bromo-5-thiazole methyl bromine: 100ml single port bottle adds 8.90g 2-bromo-5-methylthiazol, the 60ml tetracol phenixin, 8.90g NBS, 0.05g benzoyl peroxide, induction stirring, heating reflux reaction 6 hours, filter, use the saturated aqueous common salt wash filtrate, the anhydrous sodium sulfate drying organic phase concentrates, rapid column chromatography gets yellow oily 2-bromo-5-thiazole methyl bromine 9.38g, yield 73.0%.
The preparation of N-(2-bromo-5-thiazole methyl) phthalic imidine: the 100ml there-necked flask, add 6.42g 2-bromo-5-thiazole methyl bromine, exsiccant DMF 40ml, induction stirring adds the 4.63g potassium phthalimide, room temperature reaction 5 hours.Add 45ml water in the reaction flask, filtering reacting liquid is collected filter cake, and the anhydrous methanol recrystallization gets pale yellow crystals N-(2-bromo-5-thiazole methyl) phthalic imidine 6.30g, yield 78%.
The preparation of 2-bromo-5-thiazole methylamine: 50ml single port bottle, add 0.97g N-(2-bromo-5-thiazole methyl) phthalic imidine, the 20ml dehydrated alcohol, 0.5g hydrazine hydrate, reflux reaction in 2 hours finishes filtering reacting liquid, merging filtrate, concentrate, quantitatively obtain crude product 2-bromo-5-thiazole methylamine, be light yellow oil.
The preparation of embodiment 7:2-oxyethyl group-5-thiazole methyl amine:
50ml single port bottle adds the 25ml dehydrated alcohol, the 0.25g sodium Metal 99.5, and sodium reaction finishing back adds 1.16g 2-bromo-5-thiazole methylamine, and heating reflux reaction reaction in 8 hours finishes.Under the ice-water bath, add entry 10ml in reaction solution, with the chloroform extraction reaction solution, merge organic phase, anhydrous sodium sulfate drying concentrates, and gets yellow oily product 0.56g, yield 58.9%.
The preparation of embodiment 8:3-chlorine-6-pyridazine methylamine:
The preparation of 4,5-dihydro-6-methyl pyridazine-3 (2H) ketone: in the 50ml flask, add the hydrazine hydrate of 14.4g ethyl levulinate, 9.0g 85%, reflux 1 hour, placement is spent the night.Filter 4,5-dihydro-6-methyl pyridazine-3 (2H) ketone 12.0g, fusing point is 85-86 ℃, yield 92%.
The preparation of 6-methyl pyridazine-3 (2H) ketone: in the 50ml there-necked flask, add 3.0g 4,5-dihydro-6-methyl pyridazine-3 (2H) ketone, 8.0ml acetic acid.Add 2.3ml liquid bromine.Be heated to 70 ℃, the bromine water color fade.After the cooling, separate out solid.The solid that obtains is dissolved in the boiling water, slowly adds NaOH and regulate PH=6-7.Crystal is separated out in cooling, obtains the 2.8g product altogether, yield 81%.
Synthesizing of 3-chlorine-6-methyl pyridazine: in the single port bottle of 50ml, add 4.0g 6-methyl pyridazine-3 (2H) ketone, 20ml phosphorus oxychloride, stir and make the solid dissolving.Reacted 3 hours.Reaction is removed excessive phosphorus oxychloride after finishing.Use saturated NaHCO
3The aqueous solution transfers to 7-8 with the pH value of reaction system, ethyl acetate extraction, organic phase anhydrous Na
2SO
4Drying, precipitation, column chromatography is purified, and gets 3.6g 3-chlorine-6-methyl pyridazine, yield 78%.Fusing point 56-57 ℃.
Synthesizing of 3-chlorine-6-chloromethyl pyridazine: in 50ml single port bottle, add 4.10g 3-chlorine-6-methyl pyridazine, 4.30g N-chlorosuccinimide, 0.30g Benzoyl Peroxide, 20ml tetracol phenixin, reflux 11 hours, with the washing of 20ml salt solution, anhydrous sodium sulfate drying, precipitation.Column chromatography for separation gets brown liquid 3-chlorine-6-chloromethyl pyridazine 1.62g, yield 31%.
Synthesizing of N-(3-chlorine-6-pyridazine methyl) phthalic imidine: in 25ml single port bottle, add 0.63g 3-chlorine-6-chloromethyl pyridazine, 0.72g potassium phthalimide, 10ml DMF, stirred 2 hours under the room temperature.Reaction solution is poured in the 50ml water, separates out white solid.Filtration, drying get 0.84g N-(3-chlorine-6-pyridazine methyl) phthalic imidine, yield 79%, fusing point 202-203 ℃.
Synthesizing of 3-chlorine-6-pyridazine methylamine: in 50ml single port bottle, add 0.84g compound N-(3-chlorine-6-pyridazine methyl) phthalic imidine, 0.54g hydrazine hydrate, 15ml ethanol, reflux 2 hours.After reaction stops, adding 6M hydrochloric acid to PH＜2, filter to system.Filtrate decompression is removed ethanol, the solid that is dissolved in water and obtains.To alkalescence, use CHCl with NaOH solution regulator solution
3Extraction.Organic phase merges with behind the anhydrous sodium sulfate drying, concentrates, and gets 0.41g 3-chlorine-6-pyridazine methylamine, yield 93%, fusing point 97-98 ℃.
The preparation of embodiment 9:3-oxyethyl group-6-pyridazine methylamine:
In 50ml single port bottle, add 15ml ethanol, 0.25g sodium Metal 99.5, after having reacted, add 0.30g 3-chloro-6-pyridazine methylamine, refluxed two hours.Add water, use CH
2Cl
2Extraction.Organic phase with anhydrous sodium sulfate drying after, concentrate, 0.25g oily 3-oxyethyl group-6-pyridazine methylamine, yield 60%.
Synthesizing of embodiment 10:3-(N-morpholinyl)-6-pyridazine methylamine:
Add 0.45g 3-chloro-6-pyridazine methylamine, 10ml morpholine in 25ml single port bottle, reflux 1 hour is to reacting completely.Be dissolved in water, use CH
2Cl
2Extraction.Organic phase with anhydrous sodium sulfate drying after, concentrate 0.43g brown oily 3-(N-morpholinyl)-6-pyridazine methylamine, yield 72%.
The preparation of embodiment 11:2-chlorine-5-pyrimidine methylamine:
Synthesizing of 5-methylpyrimidine-2 (1H)-ketone: in the 500ml four-hole bottle, add 30ml 1, the 2-ethylene dichloride, 18.2g DMF drips the 31.2g oxalyl chloride, behind the continuation stirring 20min, drips 13.6g propionic aldehyde diethyl acetal after dropwising.Be warming up to 70 ℃, reaction 4h.Drip wet chemical, adjust pH is to 9-10.Add about 150ml distilled water, tell organic phase, drying.Slough low boiling point solvent, obtain the thick product of red-brown.In the 100ml single port bottle, add the 1.8g urea, 3ml hydrochloric acid adds the above-mentioned crude product of 3.3g, reflux 3.5h.Add wet chemical, adjust pH is neutral.Filter, the filtrate precipitation gets 5-methylpyrimidine-2 (1H)-ketone crude product.Silica gel column chromatography gets light yellow solid 1.77g, two step yields 38.8%.
1H?NMR(CDCl
3)δ：8.12(s，2H)，2.15(s，3H)。
Synthesizing of 2-chloro-5-methylpyrimidine: in the 100ml single port bottle, add 8.55g 5-methylpyrimidine-2 (1H)-ketone, 45ml phosphorus oxychloride, reflux 6h.The pressure reducing and steaming phosphorus oxychloride adds wet chemical, and adjust pH is to 7-8, extracted with diethyl ether, anhydrous magnesium sulfate drying.Precipitation gets light yellow solid 5.9g, yield 59.1%.m.p.92-94℃。
1H?NMR(CDCl
3)δ：8.40(s，2H)，2.25(s，3H)
Synthesizing of N-(2-chloro-5-pyrimidine methyl) phthalic imidine: in the 250ml four-hole bottle, add the 100ml tetracol phenixin, 3.6g 2-chloro-5-methylpyrimidine, 4.99g N-bromo-succinimide, and 0.14g Diisopropyl azodicarboxylate, reflux 13h.Filter, the filtrate precipitation gets pale brown look transparent liquid 6.03g.Above-mentioned crude product and 15ml DMF are joined in the 100ml four-hole bottle, add the 5.18g potassium phthalimide, 10 ℃ are reacted 2h down then.Add entry, filter, get brown solid, recrystallizing methanol gets white solid 2.12g, two step yields 27.9%.m.p.183-185℃。
1H?NMR(CDCl
3)δ：8.75(s，2H)，7.91-7.85(m，2H)，7.79-7.73(m，2H)，4.84(s，2H)。
The preparation of 2-chlorine-5-pyrimidine methylamine: in the 50ml single port bottle, add 0.41g N-(2-chloro-5-pyrimidine methyl) phthalic imidine, 30ml ethanol, 0.22g hydrazine hydrate, reflux 3h.Filter, precipitation gets 2-chloro-5-pyrimetamine crude product.
The preparation of embodiment 12:2-alkoxyl group-5-pyrimidine methylamine:
Synthesizing of N-(2-methoxyl group-5-pyrimidine methyl) phthalic imidine: in the 50ml single port bottle, add 20ml methyl alcohol, the 0.21g sodium Metal 99.5 after sodium reacts completely, adds 0.89g N-(2-chloro-5-pyrimidine methyl) phthalic imidine, reflux 50min.Drip 1N hydrochloric acid, adjust pH filters to 7-8, gets white solid 0.69g, yield 77.5%.M.p.156-158 ℃,
1H NMR (CDCl
3) δ: 8.64 (s, 2H), 7.89-7.83 (m, 2H), 7.76-7.70 (m, 2H), 4.78 (s, 2H), 3.99 (s, 3H), ultimate analysis: calculated for C
14H
11N
3O
3: C, 62.45; H, 4.12; N, 15.61.found:C, 62.44; H, 3.89; N, 15.41.
The preparation of 2-methoxyl group-5-pyrimidine methylamine: in the 50ml single port bottle, add 0.4g N-(2-methoxyl group-5-pyrimidine methyl) phthalic imidine, 30ml ethanol, 0.22g hydrazine hydrate, reflux 3h.Filter, and use the ethanol thorough washing, merging filtrate, precipitation gets 2-methoxyl group-5-pyrimetamine crude product.
1H NMR (CDCl
3) δ: 8.51 (s, 2H), 4.00 (s, 3H), 3.87 (s, 2H) not purified, be directly used in the next step.
Synthesizing of embodiment 13:2-cyano group-3-(2-bromo-5-pyridyl-methanamine base)-3-methylthio group vinylformic acid ethoxy ethyl ester (21):
0.21g2-bromine-5-picolyl amine and 0.26g diformazan sulfenyl cyanoacrylate are joined in the 50ml single port bottle, add 20ml ethanol, heated and stirred backflow 1h concentrates the back column chromatography and promptly obtains desired product 0.24g, yield 60%.
Synthesizing of embodiment 14:2-cyano group-3-(2-dimethylin-5-pyridyl-methanamine base)-3-methylthio group vinylformic acid ethoxy ethyl ester (24):
0.59g2-dimethylin-5-pyridyl-methanamine and 0.64g diformazan sulfenyl cyanoacrylate are joined in the 50ml single port bottle, add 20ml ethanol, heated and stirred backflow 1h, concentrate the back column chromatography and promptly obtain 2-cyano group-3-(2-dimethylin-5-pyridyl-methanamine base)-3-methylthio group vinylformic acid ethoxy ethyl ester 0.43g, yield 44%.
Synthesizing of embodiment 15:2-cyano group-3-(2-trifluoro ethoxy-5-pyridyl-methanamine base)-3-methylthio group vinylformic acid ethoxy ethyl ester (26):
In the 50ml single port bottle, add 0.43g 2-trifluoro ethoxy-5-picolyl amine, 0.43g diformazan sulfenyl cyanoacrylate, 20ml ethanol, reflux 1.5h.Concentrate the back column chromatography and promptly obtain 2-cyano group-3-(2-trifluoro ethoxy-5-pyridyl-methanamine base)-3-methylthio group vinylformic acid ethoxy ethyl ester 0.62g, productive rate 94%, fusing point 54-56 ℃.
Synthesizing of embodiment 16:2-cyano group-3-(3-chloro-6-pyridazine methylamino)-4-methyl-2-pentenoic acid ethoxy ethyl ester (39):
Add 0.21g 3-chloro-6-pyridazine methylamine crude product, 0.34g 3-methoxyl group-4-methyl-2-pentenoic acid ethoxy ethyl ester, 15ml ethanol in 50ml single port bottle, reflux 2 hours is to reacting completely.Concentrate the back column chromatography for separation and get product 0.34g, yield 68%, fusing point 116-117 ℃.
Synthesizing of embodiment 17:2-cyano group-3-(2-methoxyl group-5-pyrimetamine base)-2-pentenoic acid ethoxy ethyl ester (44):
In 50ml single port bottle, add 0.21g 2-methoxyl group-5-pyrimidine methylamine crude product, 0.42g3-methoxyl group-2-pentenoic acid ethoxy ethyl ester, 15ml ethanol, reflux 2.5 hours is to reacting completely.Concentrate the back column chromatography for separation and get product 0.42g, yield 82.6%, fusing point 108-110 ℃ C.
With synthetic other target compounds (A) of similar approach.Concrete outcome sees Table 1.
The materialization data of table 1 target compound A
*-be oily matter.
Embodiment 18: the primary dcreening operation of weeding activity is measured:
Adopt pot-culture method to measure the live body weeding activity of target compound (A): put into a certain amount of soil in the plastics cuvette of diameter 8cm, add a certain amount of water, after planting cover certain thickness soil, cultivate in greenhouse, it is preceding with plastic covered to come up.Every day in addition quantitative clear water to keep normal growth.Cauline leaf (one heart stage of seedling one leaf) is handled.Test examination material: rape (Brassica napus), Amaranthus retroflexus (Amaranthus retroflexus), barnyard grass grass (Echinochloacrusgalli (L.) Beauv.) and lady's-grass (Digitaria sanguinalis (L.) Scop.).Handle 10 to 15 days " Invest, Then Investigate " results, measure the overground part fresh weight, suppress percentage ratio with fresh weight and represent drug effect.The results are shown in Table 2.
The weeding activity inhibiting rate (%) of table 2 target compound A (dosage 100 gram/mus)
The result shows: part of compounds A shows good weeding activity; Cauline leaf is handled active in soil treatment; Activity to the broad-leaved rape is higher than Gramineae barnyard grass grass.
Embodiment 19: the outstanding compound of activity is reduced dosage carry out multiple sieve mensuration:
Measuring method the results are shown in Table 3 with embodiment 18.
The weeding activity of table 3 part of compounds A sieves result (inhibiting rate %) again
The result shows: part of compounds still has good weeding activity under the dosage of 25 gram/mus.
Embodiment 20: to the plant growth regulating activity of compd A, and the test of fungicidal activity and antiviral activity:
Adopt the isolated cucumber cotyledon rooting method to measure the plant growth regulating activity of compound.Cucumber variety is No. 4, Tianjin section, behind the seed-soaking, be sowed at and fill in the 0.7% agar enamel tray with cover, after darkroom (26 ℃) cultivate 3d, selected cotyledon of the same size is stand-by. and the filter paper method in the phytohormone activity substance-measuring is all adopted in the sample preparation, sample determination concentration is 10mg/L, and sample all adopts the dimethyl formamide dissolving. specific practice is: get the 3mg sample, be dissolved in the 3mL dimethyl formamide, dilute 10 times, get 0.3mL again and evenly drip on the filter paper of 6cm diameter, treat that solvent is air-dry after, in the incubator of 6cm diameter, put into 1 of the filter paper that contains sample, distilled water 3mL, 10 of cotyledons are the sample preparation of 10mg/L, with distilled water is contrast, each is handled 2 times and repeats, and cotyledon is (26 ℃) cultivation 5d in the darkroom, measures the number of taking root of per 10 slice, thin piece petiole bases.The results are shown in Table 4.
Adopt the Plating (Disc paper method) that exsomatizes to measure the fungicidal activity of target compound to gibberella saubinetii (P.zeae), tomato epidemic disease (A.solani) morning, peanut foxiness (C.rachidicola), apple wheel line (P.piricola) and withered (C.cucumerinum) the five kinds of thalline of cucumber; Adopt biomass growth rate assay method (mycelium growth rate test), reagent agent is diluted to certain multiple under aseptic condition, respectively drawing 1mL (500ug/mL) soup then injects in the culture dish, add the 9mL substratum more respectively, make 50 μ g/mL pastille flat boards after shaking up, do blank with the flat board that adds the 1mL aqua sterilisa. the punch tool with diameter 4mm cuts the bacterium dish along the mycelia outer rim, move on the pastille flat board, every processing triplicate. culture dish is placed on the interior .72h of cultivation of (24 ± 1) ℃ constant incubator " Invest, Then Investigate " and handles bacterium dish expansion diameter, average, relatively calculate relative bacteriostasis rate with blank. relative inhibition (%)=(control group bacterium dish expansion mean diameter-treatment group bacterium dish expansion mean diameter)/control group bacterium dish expansion mean diameter.The results are shown in Table 4.
Adopt half leaf method to measure the activity of resisting tobacco mosaic virus of compound.Get the new fresh tobacco leaf in 5-6 leaf vegetative period, with juice leaf rubbing manipulation inoculation tobacco mosaic virus (TMV) (tobacco mosaic virus (TMV) concentration 5.88 * 10
-2Ug/ml) back along the main lobe arteries and veins in two.Two and half leaves immersed respectively in test soln and the redistilled water 20 minutes, and each handles triplicate to cultivate 72h. in 25 ℃ then.By relatively calculating relative inhibition with blank. relative inhibition (%)=(control group virus infection spot number-treatment group virus infection spot number)/control group virus infection spot number.The results are shown in Table 4.
The plant growth regulating activity (10mg/L) of table 4 part of compounds A, fungicidal activity (50mg/L) and antiviral activity (100mg/L) data.(inhibiting rate %)
The result shows: part of compounds A has fungicidal activity and plant growth regulating activity and anti-phytoviral activity.
Claims (8)
1, alpha-cyanoacrylate ester cpds is characterized in that it is that structure is the compound of (A):
2, alpha-cyanoacrylate ester cpds is characterized in that it is that structure is the compound of (B):
3, alpha-cyanoacrylate ester cpds is characterized in that it is that structure is the compound of (C):
4, alpha-cyanoacrylate ester cpds is characterized in that it is that structure is the compound of (D):
5, alpha-cyanoacrylate ester cpds is characterized in that it is that structure is the compound of (E):
6, alpha-cyanoacrylate ester cpds is characterized in that it is that structure is the compound of (F):
7, alpha-cyanoacrylate ester cpds is characterized in that it is that structure is the compound of (G):
8, as said these alpha-cyanoacrylate ester cpds application on agricultural chemicals of claim 1-7, it is characterized in that as weedicide, sterilant and plant-growth regulator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100569351A CN100471846C (en) | 2007-03-16 | 2007-03-16 | Cyanoacrylate compounds and their application in pesticide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100569351A CN100471846C (en) | 2007-03-16 | 2007-03-16 | Cyanoacrylate compounds and their application in pesticide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101020677A CN101020677A (en) | 2007-08-22 |
| CN100471846C true CN100471846C (en) | 2009-03-25 |
Family
ID=38708564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100569351A Expired - Fee Related CN100471846C (en) | 2007-03-16 | 2007-03-16 | Cyanoacrylate compounds and their application in pesticide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100471846C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304460B (en) * | 2013-07-10 | 2015-04-01 | 南开大学 | Bactericidal activity of cyano acrylamide compound containing aryloxy propan-2-amino structure |
| CN103304459A (en) * | 2013-07-10 | 2013-09-18 | 南开大学 | Bactericidal activity of cyanoacrylate compound containing aryloxy propan-2-amino structure |
| CN103408478A (en) * | 2013-07-10 | 2013-11-27 | 南开大学 | Bactericidal activity of 2-aryloxy alanyl structure-containing cyano acrylamide compound |
| CN103304458A (en) * | 2013-07-10 | 2013-09-18 | 南开大学 | Bactericidal activity of cyanoacrylate compound containing 2-aryloxy propylamino structure |
| CN103819410B (en) * | 2014-01-26 | 2015-09-30 | 江苏新瀚有限公司 | A kind of preparation method of 6-chlorine pyridazine-3-formic acid |
| CN110437174B (en) * | 2019-08-30 | 2021-10-26 | 南通大学 | Cyanoacrylate compound containing thiazole methylthio phenyl unit and preparation method and application thereof |
| CN111995583A (en) * | 2020-08-18 | 2020-11-27 | 上海毕得医药科技有限公司 | Synthesis method of 1, 5-dimethylpyrimidine-2 (1H) -ketone |
| CN114890953A (en) * | 2022-07-15 | 2022-08-12 | 济南宣正药业有限公司 | Preparation method of 2-aminomethyl pyrimidine hydrochloride |
| CN115057820A (en) * | 2022-08-04 | 2022-09-16 | 东莞理工学院 | Method for synthesizing 4,5-dihydro-6-methylpyridazin-3(2H) -one from levulinic acid |
-
2007
- 2007-03-16 CN CNB2007100569351A patent/CN100471846C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 2-氰基-3-(2-氟吡啶-5-基)甲氨基-3-甲硫基氰基丙烯酸酯类化合物的合成及除草活性. 邹小毛等.有机化学，第26卷第3期. 2006 |
| 2-氰基-3-(2-氟吡啶-5-基)甲氨基-3-甲硫基氰基丙烯酸酯类化合物的合成及除草活性. 邹小毛等.有机化学，第26卷第3期. 2006 * |
| 2-氰基丙烯酸酯的合成及其生物活性研究进展. 金林红等.合成化学，第13卷第2期. 2005 |
| 2-氰基丙烯酸酯的合成及其生物活性研究进展. 金林红等.合成化学，第13卷第2期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101020677A (en) | 2007-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100471846C (en) | Cyanoacrylate compounds and their application in pesticide | |
| CN101817799B (en) | Cyanoacrylate compound and application thereof in pesticide and medicine | |
| WO2015000392A1 (en) | N-(aryl alkyl) aryloxy phenoxy carboxylic acid amide compound and preparation method and application thereof | |
| CN112574128B (en) | Quinazoline diketone compound, preparation method and application thereof, and herbicide | |
| CN114573565B (en) | Pyrazole-quinazolinone compound, preparation method and application thereof, and herbicide | |
| WO2023088426A1 (en) | Oxobutan(-2-enoic acid) acid compound and preparation method therefor, herbicidal composition and use thereof, and herbicide | |
| CN110074124A (en) | Application of the phenanthridines class compound on pesticide | |
| CN110066286B (en) | Phenylpyrazoline compound with biological activity and preparation method and application thereof | |
| CN106632007B (en) | Pyridine-3-radical aryloxy phenoxy alkyl acid ester compound and application thereof | |
| CN110078673B (en) | Aryl uracil compound, preparation method thereof and pesticide composition | |
| CN100387582C (en) | N-carboxylic acid derivative substituted benzooxazine compounds with herbicidal activity | |
| CN112624973B (en) | Carboxylic acid ester compound and application thereof | |
| CN111662282B (en) | Aza-and pyridine compounds and intermediates thereof | |
| CN109553615B (en) | Pyrimidine salt compound and application thereof | |
| CN106699648B (en) | 2-(4- aryloxyphenoxy) alkanoic acid naphthalene ester compounds and its application | |
| CN103833670B (en) | 2-chlorine thiazolyl acrylonitrile compounds and application thereof | |
| CN117567446B (en) | Triazolinone compound containing heterocyclic structure, preparation method and application thereof | |
| CN114516841B (en) | N-aryloxy/thiobenzyl difluoromethyl pyrilamine compound, and preparation method and application thereof | |
| CN103833638B (en) | Phenylpyrazole base acrylonitrile compound and application thereof | |
| CN117069667A (en) | Triazolinone structure-containing compound, application thereof and herbicide | |
| JPH10512236A (en) | New pyrimidyloxy- and pyrimidinylamino-ethylphenyl-dioxolane derivatives | |
| CN110294751B (en) | Imidazo [4,5-b ] pyridine compound with biological activity and preparation method and application thereof | |
| CN115572282B (en) | Pyrazole amide compound containing aromatic heterocyclic structure, and preparation method and application thereof | |
| CN103833743B (en) | Thiazolyl pyrazolyl acrylonitrile compound and application thereof | |
| CN1927811B (en) | Compound of 4-benzoxybutenolate and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20070822 Assignee: SHANDONG BOYUAN PHARMACEUTICAL & CHEMICAL CO., LTD. Assignor: Nankai University Contract record no.: 2015370000043 Denomination of invention: Cyanoacrylate compounds and their application in pesticide Granted publication date: 20090325 License type: Exclusive License Record date: 20150319 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090325 Termination date: 20190316 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |