CN1317483A - 2-cyano-3-substituted phenylacrylate compounds, compositions and their preparing prcess and application as disinfectant of agricultural crops - Google Patents
2-cyano-3-substituted phenylacrylate compounds, compositions and their preparing prcess and application as disinfectant of agricultural crops Download PDFInfo
- Publication number
- CN1317483A CN1317483A CN 01115593 CN01115593A CN1317483A CN 1317483 A CN1317483 A CN 1317483A CN 01115593 CN01115593 CN 01115593 CN 01115593 A CN01115593 A CN 01115593A CN 1317483 A CN1317483 A CN 1317483A
- Authority
- CN
- China
- Prior art keywords
- compound
- calling
- following text
- substituted
- following
- 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.)
- Granted
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to 2-cyano-3-substituted phenylacrylate compounds and the composition containing them, which canbe used as agricultural disinfectant, and their preparing process. Its advantages are simple process and high disinfecting effect.
Description
The present invention relates to the new 2-cyano group-3-substituted phenylacrylate compounds as sterilant, contain these compound compositions, the method for control germ and prepare the method for these compounds.
At present, the sterilant that has good fungicidal activity and do not have other murder by poisoning is constantly studied in various places.These are active high because require this compounds to have, and selectivity is strong, and environmental pollution is low, and the fungicidal activity height of the germ of antagonism known biocides.
The compounds of this invention is fit to be used for the plantation plant, decorates tree control germ.
One of purpose of the present invention provides a kind of new compound and the compound compositions that contains these fungicidal activities.Another object of the present invention provides the method for Synthetic 2-cyano group-3-substituted phenyl acrylic acid ester.Another object of the present invention provides with the method for these new compounds as crop bactericide control germ.
Many 2-cyano group-3-substituted phenyl acrylic acid ester and their derivative have the 3-substituted-amino, and we find that a compounds has fungicidal activity in these compounds, in the compound that formula I is represented, some compound except not having, this is meant works as X=H, Y=H or X=H, Y=4-CH
3The time compound, these compounds have been seen bibliographical information [syntheticcommunications 26 (19) 3549-3557 (1996)], but these compounds do not report that it has fungicidal activity.Some other compound such as 2-cyano group-3-substituted anilinic ethyl propenoate report has fungicidal activity (EP885.45), but the structure of these compounds is different with compound structure of the present invention.
The invention provides compound with following formula:
Wherein, X, Y are respectively fluorine, chlorine, bromine, iodine or contain alkyl and alkoxyl group, nitro or the trifluoromethyl group of 1-3 carbon atom.
R1 is hydrogen, methyl, n-propyl or sec.-propyl.
R2 is hydrogen, methyl, ethyl, n-propyl, sec.-propyl, allyl group, cyclopropyl and various substituted alkyl.
R3 is methyl, ethyl, n-propyl and the alkyl that contains 1-6 carbon atom.
In the example of The compounds of this invention, X, Y are methyl, ethyl, and R1 is that hydrogen, R2 are methyl, ethyl, n-propyl, sec.-propyl, allyl group, and R3 is methyl, ethyl, propyl group, sec.-propyl.
Wherein, preferred compound, X, Y are methyl or ethyl, and R1 is a hydrogen, and R2 is ethyl, propyl group, and R3 is methyl, ethyl.
One of such examples of compounds, X is a hydrogen, and Y is the 2-methyl, and R1 is a hydrogen, and R2 is a n-propyl, R3 is an ethyl.
Its intermediate of sterilant of the present invention 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text) is by following two kinds of methods preparation.
One of preparation method
(1) preparation intermediate 2-cyano-3-hydroxy-3-substituted phenyl acrylic acid ester has following structural formula:
(calling compound ii in the following text) wherein, X, Y are respectively fluorine, chlorine, bromine, iodine or contain alkyl and alkoxyl group, nitro or the trifluoromethyl group of 1-3 carbon atom.R3 is methyl, ethyl, n-propyl and the alkyl that contains 1-6 carbon atom.Follow these steps to:
In the solution of glycol dimethyl ether of the magnesium ethylate of configuration, drip equimolar ethyl cyanoacetate down at 20 ℃, postcooling to 0 ℃, add equimolar substituted benzoyl chloride reaction, at room temperature stir, last acidifying gets solid product 2-cyano-3-hydroxy-3-substituted phenyl acrylic acid ester (calling compound ii in the following text), and chemical equation is as follows:
(calling compound ii in the following text)
(2) preparation intermediate 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text) has following structural formula:
(calling the compound III in the following text) wherein: X, Y, R3 and represented identical the following these steps to of compound ii:
With compound ii and phosphorus oxychloride is configured to the inert solvent methylene dichloride with 1: 1.1 mole or ethylene dichloride is a solvent, after dropping acid binding agent triethylamine stirring reaction is complete, neutralize with alkali, extraction, dry, distill resultant liquid 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text), chemical reaction is as follows:
Two (1) preparation 2-cyano group-3-substituted phenyl acrylic acid esters (calling the compound IV in the following text) of (calling the compound III in the following text) preparation method have following structural formula:
(calling the compound IV in the following text) follows these steps to:
With etc. the substituted benzaldehyde and the ethyl cyanoacetate of mole configuration be solvent with ethanol, send in the presence of the pyridine at catalyzer six hydrogen, after reflux to reaction was finished, partial solvent was sloughed in decompression, get solid 2-cyano group-3-substituted phenyl acrylic acid ester (calling the compound IV in the following text), chemical equation is as follows:
(calling the compound IV in the following text)
(2) preparation 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text) has following structural formula:
(calling the compound III in the following text)
Follow these steps to preparation:
In a certain amount of compound IV, add a small amount of pyridine hydrochloride as catalyzer, be heated to about 110 ℃ under stirring, feed chlorine, it is complete that the gas spectrum is followed the tracks of full response, decompression steams reaction product 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text), and chemical equation is as follows:
(calling the compound III in the following text)
Its intermediate of sterilant of the present invention 1-substituted azole-3-methyl substituted amido (calling the compound VII in the following text) is by following method preparation.
(4) preparation 1-replacement-5-oxygen pyrroles-3-methyl-formiate (calling the compound V in the following text) has following structural formula:
(calling the compound V in the following text) wherein R4 is hydrogen, methyl, ethyl and the alkyl that contains the 1-6 carbon atom and thiazolinyl, substituted-phenyl etc.
Follow these steps to
With a certain amount of furoate clothing dimethyl ester, be solvent: at a certain temperature, feed or add various replacement amine with methyl alcohol, stirring reaction, chromatogram tracking after react completely, the pressure reducing and steaming solvent, at last product 1-replacement-5-oxygen pyrroles-3-methyl-formiate (calling the compound V in the following text).Chemical equation is as follows:
(calling the compound V in the following text)
(5) preparation 1-replacement-5-oxygen pyrroles-3-formyl (replacement) amine (calling the compound VI in the following text) has following structural formula:
(calling the compound VI in the following text) wherein: R4 is with the compound V, and R5 is hydrogen, contains the alkyl of 1-6 carbon atom etc., follows these steps to:
Have in the methanol solution of a certain amount of 1-substituted azole-3-methyl-formiate at device, feeding at room temperature or adding are with the replacement amine of amount, at room temperature be stirred to and react completely, the decompression precipitation, get resultant of reaction 1-replacement-5-oxygen pyrroles-3-formyl (replacement) amine (calling the compound VI in the following text), chemical equation is as follows:
(calling the compound VI in the following text) (6) preparation 1-substituted azole-3-methyl (replacement) amine (calling the compound VII in the following text) has following structural formula:
(calling the compound VII in the following text) wherein: R4, R5 follow these steps to the compound VI:
A certain amount of aluminium lithium hydride is suspended in the tetrahydrofuran solvent, add a certain amount of 1-replacement-5-oxygen pyrroles-3-formyl (replacement) amine at a certain temperature in batches, add back room temperature reaction a few hours, filter, precipitation, get resultant 1-substituted azole-3-methyl (replacement) amine (calling the compound VII in the following text), chemical equation is as follows:
(calling the compound VII in the following text)
Fungicide compound I 2-cyano group of the present invention-3-substituted-amino-3-substituted phenyl acrylic acid ester has following structural formula by following method preparation:
(calling chemical compounds I in the following text)
Follow these steps to:
With inert solvent, methylene dichloride, ethylene dichloride or tetrahydrofuran (THF) are solvent with this compound III and various substituted-amino, and at pyridine or N, the accelerine acid binding agent exists down, at 0-70 ℃ of following stirring reaction, filter precipitation, washing gets the fungicide compound I, and chemical equation is as follows:
(calling chemical compounds I in the following text)
Show that according to the potted plant seedling experiment made on the living of contrast compound N O1 is better than being used at present prevent and treat unique medicament derosal of wheat scab to the prevention effect of wheat scab when the working concentration of 10 μ g/ml.Under this concentration, being 82.4% to the prevention effect of wheat scab, is 46.9% with the prevention effect of the derosal of concentration.This compound all is better than the derosal of corresponding concentration to the prevention effect of the fusarium graminearum of resisting carbendazim under 1000 μ g/ml, 100 μ g/ml, 10 μ g/ml isoconcentrations.
All cpds provided by the invention all has the different activity of degree to fusarium graminearum.The invention provides the compound of a kind of novel type of preventing and treating wheat scab, this compounds not only can prevented and treated wheat scab than under the low dosage, and can administer the resistance of the present fusarium graminearum that had occurred already to derosal.
Following example further specifies the present invention, but does not limit the present invention, and table 1 has been listed embodiments of the invention, has narrated the concrete preparation method of The compounds of this invention after table 1.
Table 1
The preparation of embodiment 1 2-cyano group-3-Tri N-Propyl Amine base-3-o-methyl-benzene ethyl propionate:
(a) preparation of 2-cyano-3-hydroxy-3-o-methyl-benzene ethyl propionate:
24.3 gram magnesium (1 mole) are placed 2 liters of there-necked flasks that contain 500 milliliters of dehydrated alcohols and 500 milliliters of glycol dimethyl ethers and 2 gram carbon tetrabromides, 90 ℃ of following stirring reactions 12 hours, after decompression steams ethanol and glycol dimethyl ether, add 500 milliliters of glycol dimethyl ethers again, be stirred in and be lower than 20 ℃ of droppings, 113 gram ethyl cyanoacetates (1 mole), solution is cooled to 0 ℃, drip 154.5 gram o-methyl-benzene formyl chlorides (1 mole), drip off afterreaction liquid stirring reaction 15 hours at room temperature, pressure reducing and steaming solvent, residue be with 325 milliliters of 5M hcl acidifyings, with 3 * 150 milliliters of chloroform extractions 3 times, merge organic layer, washing, anhydrous sodium sulfate drying, the pressure reducing and steaming solvent gets solid, the dehydrated alcohol recrystallization gets product 187 grams (Y=81%), M.P161.2-162.5 ℃.
(b) preparation of 2-cyano group-3-chloro-3-o-methyl-benzene ethyl propionate:
36.8 gram phosphorus oxychloride (0.24 mole) and 50.8 gram 2-cyano-3-hydroxy-3-o-methyl-benzene ethyl propionates (0.22 mole) are dissolved in 200 milliliters of methylene dichloride, stir and drip 48.5 gram triethylamines (0.48 mole) down, dripping off the afterreaction thing refluxed 15 hours, cooling drips 100 milliliters of 5M hydrochloric acid down, the pressure reducing and steaming solvent, residue is dissolved in the ether, use 100 milliliters of 5M hydrochloric acid respectively, sodium bicarbonate is washed to neutrality, the organic phase anhydrous sodium sulfate drying, behind the pressure reducing and steaming solvent, steam product 49.9 grams, yield is 91.1%, bp154.5-155.7 ℃ (5mmHg).
(c) 2-cyano group-3-Tri N-Propyl Amine base-3-o-methyl-benzene ethyl propionate (compound N O1) preparation
5.0 gram 2-cyano group-3-chloro-3-o-methyl-benzene ethyl propionates (0.02 mole) and 2.4 are restrained Tri N-Propyl Amines (0.04 mole) in 30 milliliters of tetrahydrofuran (THF)s, stir down and reacted 3 hours about 20 ℃, a broad layer chromatography tracks to and reacts completely, and filters, filtrate decompression boils off solvent, residue is dissolved in 30 milliliters of methylene dichloride, washing, anhydrous sodium sulfate drying, precipitation, the dehydrated alcohol recrystallization gets white crystal 4.9 grams (Y=92%), fusing point: 53.1-54.2 ℃.
Embodiment 2
2-cyano group-3-(1-methylpyrrole-3-methylamino)-3-o-methyl-benzene ethyl propionate
(a) preparation of 1-methyl-5-oxo pyrroles-3-methyl-formiate
In 500 milliliters of there-necked flasks that 158 gram furoate clothing dimethyl esters (1 mole) and 300 milliliters of anhydrous methanols are housed, be cooled under the 0-5 ℃ of stirring, feed 31 gram methylamine gas (1 mole), reaction mixture at room temperature stirred 24 hours, boil off solvent, steam product 139.7 grams (yield 89%) under the normal pressure, boiling point 160-161 ℃ of (18 mmhg) n
25 D1.4742.
(b) preparation of 1-methyl-5-oxo pyrrole-3-carboxamide
In the 300 ml methanol solution that 94.2 gram 1-methyl-5-oxo pyrroles-3-methyl-formiates (0.6 mole) are housed, be cooled to 0-10 ℃ of stirring feeding excessive ammonia down, reaction flask at room temperature stirred 24 hours, and is freezing, filter, get solid 80.9 gram (yields 95%) M.P141.1-142.3 ℃.
(c) preparation of 1-methylpyrrole-3-methylamine
In 1 liter of flask that 38 gram aluminium lithium hydrides (1.0 moles) and 650 milliliters of tetrahydrofuran (THF)s are housed, under 10-20 ℃, add 71 gram 1-methyl-5-oxo pyrrole-3-carboxamides in batches, add under the room temperature of back and react after 3 hours, reflux 4 hours is filtered, filter residue with absolute ethanol washing for several times, merge organic layer, precipitation, normal pressure steams product, weak yellow liquid 46.2 gram (yields 81%) boiling point 166-167 ℃, Nd1.4648.
(d) 2-cyano group-3-(1-methylpyrrole-3-methyl) amido-3-o-methyl-benzene ethyl propenoate
With 2.5 gram 2-cyano group-3-chloro-3-o-methyl-benzene ethyl propenoates (0.01 mole) and 0.57 gram 1-methylpyrrole-3-methylamine (0.01 mole) and 1.21 gram N, accelerine is mixed in the 30ml tetrahydrofuran (THF), 60 ℃ of left and right sides stirring reactions 5 hours, cooling is filtered, solvent decompression precipitation, residue is dissolved in 30 milliliters of chloroforms, washing, organic layer anhydrous sodium sulfate drying, precipitation get 3.0 gram (yield 93.0%) test examples one:
This compounds is to prevention effect (1) reagent of wheat scab:
Compound N o1, No2, No3, No4, No5, No6, No7, No8, No10, every compound takes by weighing 5mg, adds 0.5ml acetone, adds the tween 80 solution of 4.5ml 0.1% again, and fully vibration makes its dissolving standby.Is the contrast medicament with the carbendazim active compound, derosal is made into the mother liquor of 5000 μ g/ml, tween 80 solution dilution to the 1000 μ g/ml with 0.1% with 0.1NHCl.(2) test materials:
Wheat breed is raised wheat 158: seed soaked in water, is wrapped in 25 ℃ of vernalization after 24 hours, plant in the plastic tub alms bowl with wet towel, and 20 of every basin plantations, 25 ℃ of cultivations, it is stand-by during the phase to grow to 3 leaves.(3) subjects: fusarium graminearum, bacterial strain G01, dull and stereotyped last 28 ℃ of PDA
Last cultivation 3 days.(4) testing method: the soup that above-mentioned (1) is mixed with sprays in 3 leaf phase wheat childrens
On the seedling, every basin spraying liquid 2.5ml, every compound sprays 2 basins.The blank spray
Execute 0.1% tween 80 solution, every basin 2.5ml.Acupuncture in 24 hours is little behind the spray medicine
The wheat blade, inoculation mycelia piece was preserved moisture 3 days for 28 ℃, measured scab length, meter
Calculate the indoor control effect.
Prevention effect (%)=(1-chemicals treatment scab length/blank scab length)
* 100 (5) test-results: the result shows that compound N o1, No5, No15, No10 all show the different activity of degree at 1000 μ g/ml to wheat scab.Its prevention effect sees Table 2.5 compounds of table 2. are to the activity of wheat scab
Compound activity rank grade scale: A level: occurring degree and medicament contrast occurring degree are approaching; B: occurring degree is a little less than the medicament contrast but apparently higher than blank; The C level: occurring degree is starkly lower than medicament contrast but apparently higher than blank; The D level: occurring degree and blank are approaching.Test examples 2: compound N o1 takes by weighing 10mg to activity (1) the compound N o1 of the fusarium graminearum of resisting carbendazim, add 1ml acetone, the tween 80 solution that adds 9ml0.1% again, fully vibration makes its dissolving, and the tween 80 solution serial dilution with 0.1% becomes 5 kinds of concentration such as 500 μ g/ml, 100 μ g/ml, 50 μ g/ml, 10 μ g/ml; Is the contrast medicament with the carbendazim active compound, derosal is made into the mother liquor of 5000 μ g/ml, the tween 80 solution dilution to 1000 with 0.1%, 500 μ g/ml, 100 μ g/ml, 50 μ g/ml, 10 μ g/ml with 0.1NHCl.(2) test materials:
| Compound number | Active rank | Average scab length (mm) | Prevention effect (%) |
| The blank contrast of No1 No2 No3 No4 No5 No6 No7 No8 No10 carbendazim | ?A ?A ?B ?B ?B ?C ?B ?B ?B ?A ?D | ????2 ????2.2 ????2.8 ????3.1 ????4.5 ????13.2 ????5.1 ????5.6 ????5.6 ????0 ????24.5 | ?91.8 ?91.0 ?88.6 ?87.3 ?81.6 ?44.1 ?79.2 ?77.1 ?77.1 ?100 |
Wheat breed is raised wheat 158: seed soaked in water, is wrapped in 25 ℃ of vernalization after 24 hours, plant in the plastic tub alms bowl with wet towel, and 20 of every basin plantations, 25 ℃ of cultivations, it is stand-by during the phase to grow to 3 leaves.(3) subjects: fusarium graminearum resisting carbendazim bacterial strain, bacterial strain G03, PDA goes up cultivation 3 days for dull and stereotyped last 28 ℃.(4) testing method: the soup that above-mentioned (1) is mixed with sprays on 3 leaf phase wheat seedlings, every basin spraying liquid 2.5ml, and every compound sprays 2 basins.Blank sprays 0.1% tween 80 solution, every basin 2.5ml.24 hours acupuncture wheat leaf blades behind the spray medicine, inoculation mycelia piece was preserved moisture 3 days for 28 ℃, measured scab length, prevention effect in the counting chamber.
Prevention effect (%)=(1-chemicals treatment scab length/blank scab length)
* 100 (5) test-results: test-results (table 2) shows that compound N o1 has higher activity to the wheat scab bacterial strain of resisting carbendazim, and during 500 μ g/ml, the preventive effect of derosal is 32.3%, and the preventive effect of compound N o1 is 91.9%.Table 2. compound N o2 is to the biological activity of the fusarium graminearum of resisting carbendazim
Test examples 3 compound N o1 are to 1. experiment purposes that influence of gibberellic hypha mycelial growth: measure compound N o1 to the exsomatize influence of mycelial growth of gibberellic hypha, measure its influence to resisting carbendazim bacterial strain mycelial growth simultaneously.2. experimental technique: make the pastille flat board respectively with compound N o1 and derosal, move gibberellic hypha mycelia piece in flat board, cultivate for 28 ℃ and check the mycelial growth amount after 3 days.3. test-results: the plate test-results shows: the sensitive strain of compound N o1 fusarium graminearum still is that the mycelial growth of resistant strain all has good inhibitory effect, (0.25ppm) still can make mycelial growth sparse under lower concentration, the bobbles shape is got together at the mycelia top, the mycelial growth amount is lacked than the derosal with concentration, in this result and the live test, it is consistent that compound N o1 preventive effect under lower concentration is better than the result of derosal.Compound N o1 is to the influence of mycelial growth
411 compounds of test examples are to influence (1) test objective of fusarium graminearum mycelial growth: measure of the influence of each compound to the fusarium graminearum mycelial growth, thus its active difference relatively.(2) test method: compound is mixed with the pastille flat board of different concns, is the contrast medicament with the carbendazim active compound.The mycelia piece that moves the gibberellic hypha that meets diameter 5mm was cultivated 3 days for 25 ℃ on flat board, measured the colony growth diameter, relatively the mycelial growth amount.(3) test-results:
| Compound | Spraying medicine concentration | Average scab length | Prevention effect |
| No1 | ?1000 | ?2 | ?91.9 |
| ?500 | ?2 | ?91.9 | |
| ?100 | ?3.8 | ?84.7 | |
| ?50 | ?11 | ?55.7 | |
| ?10 | ?15.3 | ?38.3 | |
| Derosal | ?1000 | ?3.6 | ?85.5 |
| ?500 | ?16.8 | ?32.3 | |
| ?100 | ?15 | ?39.5 | |
| ?50 | ?27 | ?0 | |
| ?10 | ?26.8 | ?0 |
| Bacterial strain | Substratum contains concentration (ppm) | The average growth diameter of bacterium colony (mm) | The mycelial growth state | |
| Derosal | Sensitive organism | 100 | ?0 | Do not grow |
| 10 | ?1 | Substantially do not grow | ||
| 1 | ?34.8 | Mycelial growth is luxuriant | ||
| 0.5 | ?57.75 | Mycelial growth is luxuriant | ||
| 0.25 | ?55.75 | Mycelial growth is luxuriant | ||
| The resistance bacterium | 100 | ?14.25 | Mycelial growth is luxuriant | |
| 10 | ?46.5 | Mycelial growth is luxuriant | ||
| 1 | ?76.75 | Mycelial growth is luxuriant | ||
| 0.5 | ?76.5 | Mycelial growth is luxuriant | ||
| 0.25 | ?78.75 | Mycelial growth is luxuriant | ||
| Compound N o1 | Sensitive organism | 100 | ?8.5 | Mycelial growth is sparse, and the bobbles shape is got together at the top |
| 10 | ?26 | Mycelial growth is sparse, and the bobbles shape is got together at the top | ||
| 1 | ?56.25 | Mycelial growth is sparse, and the bobbles shape is got together at the top | ||
| 0.5 | ?53.5 | Mycelial growth is sparse, and the bobbles shape is got together at the top | ||
| 0.25 | ?55.5 | Mycelial growth is sparse, and the bobbles shape is got together at the top | ||
| The resistance bacterium | 100 | ?13.75 | Mycelial growth is sparse, and the bobbles shape is got together at the top | |
| 10 | ?33.5 | Mycelial growth is sparse, and the bobbles shape is got together at the top | ||
| 1 | ?54 | Mycelial growth is sparse, and the bobbles shape is got together at the top | ||
| 0.5 | ?71 | Mycelial growth is sparse, and the bobbles shape is got together at the top | ||
| 0.25 | ?76 | Mycelial growth is sparse, and the bobbles shape is got together at the top | ||
| CK | Sensitive organism | ?56 | Mycelial growth is luxuriant | |
| The resistance bacterium | ?75 | Mycelial growth is luxuriant | ||
Test-results shows, in 11 No1 series compounds, it is best that the mycelial growth of fusarium graminearum is pressed down effect, is No1 secondly.In the No2 series compound, fusarium graminearum is shown active compound, make the fusarium graminearum mycelia sparse in the plate, the mycelial growth amount obviously is less than the medicament contrast with the blank of colony diameter or derosal.Compound N O1 series compound is to the restraining effect of fusarium graminearum mycelial growth
| Compound | Fusarium graminearum mycelial growth diameter (mm) on each concentration (μ g/ml) pastille flat board | |||
| 0.5 | ?1 | ?10 | ?100 | |
| ?No1 | ?50 | ?50.5 | ?49 | ?31.1 |
| ?No4 | ?54.9 | ?54.8 | ?49.8 | ?35.8 |
| ?No5 | ?53.5 | ?53.4 | ?51.9 | ?54.5 |
| ?No1 | ?44.4 | ?42.1 | ?27.8 | ?15.3 |
| ?No14 | ?53.5 | ?54.9 | ?50.75 | ?48 |
| ?No11 | ?53.4 | ?56.8 | ?56.9 | ?36.5 |
| ?No12 | ?56.5 | ?57.6 | ?52 | ?26.3 |
| ?No13 | ?55.5 | ?56.1 | ?55 | ?40.1 |
| ?No6 | ?54.5 | ?57.9 | ?48.6 | ?40 |
| ?No3 | ?54.1 | ?58.4 | ?40.5 | ?15.5 |
| ?No11 | ?52.9 | ?51.4 | ?28.8 | ?16.3 |
| Derosal | 35.5 | ?19.5 | ?1 | ?0 |
| Blank | 59.5 | |||
Claims (5)
1, a kind of 2-cyano group-3-substituted phenylacrylate compounds, its chemical name is: 2-cyano group-3-substituted phenyl acrylic acid ester has the following chemical structure formula:
(calling chemical compounds I in the following text) wherein: X, Y are respectively fluorine, chlorine, bromine, iodine or contain the alkyl and the groups such as alkoxyl group, nitro or trifluoromethyl of 1-3 carbon atom; R1 is hydrogen, alkyl thiazolinyl etc.; R2 is hydrogen, various substituted alkyl, allyl group etc.; R3 is the alkyl that contains 1-6 carbon atom.
2, by the composition of the described 2-cyano group of claim 1-3-substituted phenylacrylate compounds, wherein said compound has following formula:
In the formula: X, Y are respectively fluorine, chlorine, bromine, iodine or methyl, ethyl, n-propyl or sec.-propyl;
R2 is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-.
3, by the composition of the described 2-cyano group of claim 2-3-substituted phenylacrylate compounds, wherein R2 is methyl, ethyl, n-propyl, sec.-propyl.
4, the preparation method of a kind of 2-cyano group-3-substituted phenylacrylate compounds, its step is as follows:
A. intermediate 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text) prepares by following two kinds of methods:
One of preparation method
(1) preparation intermediate 2-cyano-3-hydroxy-3-substituted phenyl acrylic acid ester has following structural formula:
(calling compound ii in the following text) wherein, X, Y are respectively fluorine, chlorine, bromine, iodine or contain alkyl and alkoxyl group, nitro or the trifluoromethyl group of 1-3 carbon atom; R3 is methyl, ethyl, n-propyl and the alkyl that contains 1-6 carbon atom;
In the solution of glycol dimethyl ether of the magnesium ethylate of configuration, drip equimolar ethyl cyanoacetate down at 20 ℃, postcooling to 0 ℃, add equimolar substituted benzoyl chloride reaction, at room temperature stir, last acidifying gets solid product 2-cyano-3-hydroxy-3-substituted phenyl acrylic acid ester (calling compound ii in the following text), and chemical equation is as follows:
(calling compound ii in the following text)
(2) preparation intermediate 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text) has following structural formula:
(calling the compound III in the following text) wherein: X, Y, R3 are represented identical with compound ii;
With compound ii and phosphorus oxychloride is configured to the inert solvent methylene dichloride with 1: 1.1 mole or ethylene dichloride is a solvent, after dropping acid binding agent triethylamine stirring reaction is complete, neutralize with alkali, extraction, dry, distill resultant liquid 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text), chemical reaction is as follows:
(calling the compound III in the following text)
Preparation method's two
(1) preparation 2-cyano group-3-substituted phenyl acrylic acid ester (calling the compound IV in the following text) has following structural formula:
(calling the compound IV in the following text)
With etc. the substituted benzaldehyde and the ethyl cyanoacetate of mole configuration be solvent with ethanol, send in the presence of the pyridine at catalyzer six hydrogen, after reflux to reaction was finished, partial solvent was sloughed in decompression, get solid 2-cyano group-3-substituted phenyl acrylic acid ester (calling the compound IV in the following text), chemical equation is as follows:
(calling the compound IV in the following text)
(2) preparation 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text) has following structural formula:
(calling the compound III in the following text)
In a certain amount of compound IV, add a small amount of pyridine hydrochloride as catalyzer, be heated to about 110 ℃ under stirring, feed chlorine, it is complete that the gas spectrum is followed the tracks of full response, decompression steams reaction product 2-cyano group-3-chloro-3-substituted phenyl acrylic acid ester (calling the compound III in the following text), and chemical equation is as follows:
(calling the compound III in the following text)
B. intermediate 1-substituted azole-3-methyl substituted amido (calling the compound VII in the following text) prepares by following method:
(1) preparation 1-replacement-5-oxygen pyrroles-3-methyl-formiate (calling the compound V in the following text) has following structural formula:
(calling the compound V in the following text) wherein R4 is hydrogen, methyl, ethyl and the alkyl that contains the 1-6 carbon atom and thiazolinyl, substituted-phenyl etc.;
With a certain amount of furoate clothing dimethyl ester, with methyl alcohol is solvent: at a certain temperature, feed or add various replacement amine, stirring reaction, chromatogram tracking is after react completely, the pressure reducing and steaming solvent gets product 1-replacement-5-oxygen pyrroles-3-methyl-formiate (calling the compound V in the following text) at last, and chemical equation is as follows:
(calling the compound V in the following text)
(2) preparation 1-replacement-5-oxygen pyrroles-3-formyl (replacement) amine (calling the compound VI in the following text) has following structural formula:
(calling the compound VI in the following text) wherein: R4 is with the compound V, and R5 is hydrogen, contain the alkyl of 1-6 carbon atom etc.;
Have in the methanol solution of a certain amount of 1-substituted azole-3-methyl-formiate at device, feeding at room temperature or adding are with the replacement amine of amount, at room temperature be stirred to and react completely, the decompression precipitation, get resultant of reaction 1-replacement-5-oxygen pyrroles-3-formyl (replacement) amine (calling the compound VI in the following text), chemical equation is as follows:
(calling the compound VI in the following text) (3) preparation 1-substituted azole-3-methyl (replacement) amine (calling the compound VII in the following text) has following structural formula:
(calling the compound VII in the following text) wherein: R4, R5 are with the compound VI;
A certain amount of aluminium lithium hydride is suspended in the tetrahydrofuran solvent, add a certain amount of 1-replacement-5-oxygen pyrroles-3-formyl (replacement) amine at a certain temperature in batches, add back room temperature reaction a few hours, filter, precipitation, get resultant 1-substituted azole-3-methyl (replacement) amine (calling the compound VII in the following text), chemical equation is as follows:
(calling the compound VII in the following text)
C. chemical compounds I 2-cyano group-3-substituted-amino-3-substituted phenyl acrylic acid ester has following structural formula by following method preparation:
(calling chemical compounds I in the following text)
With inert solvent, methylene dichloride, ethylene dichloride or tetrahydrofuran (THF) are solvent with this compound III and various substituted-amino, and at pyridine or N, the accelerine acid binding agent exists down, at 0-70 ℃ of following stirring reaction, filter precipitation, washing gets the fungicide compound I, and chemical equation is as follows:
(calling chemical compounds I in the following text)
5, a kind of 2-cyano group-3-substituted phenylacrylate compounds, the application of composition on crop bactericide, it is that acceptable carrier is formed crop bactericide on effective active composition and the agronomy with claim 1 or 2 or 3 described compounds, composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011155930A CN1160318C (en) | 2001-05-08 | 2001-05-08 | 2-cyano-3-substituted phenylacrylate compounds, compositions and their preparing prcess and application as disinfectant of agricultural crops |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011155930A CN1160318C (en) | 2001-05-08 | 2001-05-08 | 2-cyano-3-substituted phenylacrylate compounds, compositions and their preparing prcess and application as disinfectant of agricultural crops |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1317483A true CN1317483A (en) | 2001-10-17 |
| CN1160318C CN1160318C (en) | 2004-08-04 |
Family
ID=4662084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011155930A Expired - Lifetime CN1160318C (en) | 2001-05-08 | 2001-05-08 | 2-cyano-3-substituted phenylacrylate compounds, compositions and their preparing prcess and application as disinfectant of agricultural crops |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1160318C (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005012235A1 (en) * | 2003-07-29 | 2005-02-10 | Ciba Specialty Chemicals Holding Inc. | 3-aryl-2-cyano-3-hydroxy-acrylic acid derivatives |
| CN100435635C (en) * | 2004-02-18 | 2008-11-26 | 江苏省农药研究所有限公司 | Application of 2-cyano-3-amino-3-ethyl phenylacrylate for preventing agronomic crop disease |
| CN101671270A (en) * | 2008-09-11 | 2010-03-17 | 杭州澳赛诺化工有限公司 | Method for synthesizing cyanoacetylene derivatives |
| CN101258850B (en) * | 2008-04-18 | 2011-01-26 | 江苏中旗化工有限公司 | Application of 2-cyano-3-amino-3-phenylacrylate for preventing and controlling corps disease |
| CN101696193B (en) * | 2009-10-15 | 2011-07-27 | 沈阳化工学院 | 2-substituted methyl-3-phenyl-acrylic ester compounds with fungicidal activities and preparation method thereof |
| CN101544669B (en) * | 2009-05-06 | 2011-09-07 | 贵州大学 | Phenyl cyanoacrylate derivatives containing alpha-amino phosphonate ester and preparation method and application thereof |
| CN101584322B (en) * | 2009-04-01 | 2012-04-18 | 陕西蒲城县美邦农药有限责任公司 | 2-cyano-3-amino-3-phenylancryic acetate and hexaconazole-containing synergistic antiseptic composition |
| CN101584329B (en) * | 2009-04-01 | 2012-04-18 | 陕西蒲城县美邦农药有限责任公司 | 2-cyano-3-amino-3-phenylancryic acetate and propineb-containing synergistic antiseptic composition |
| CN101584324B (en) * | 2009-04-15 | 2012-06-27 | 陕西蒲城县美邦农药有限责任公司 | 2-cyano-3-amino-3-phenylancryic acetate and epoxiconazole-containing antiseptic composition |
| CN102715176A (en) * | 2012-05-22 | 2012-10-10 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Bactericidal composition containing 2-cyano-3-amino-3-ethyl phenylacrylate and clorine-nalidixic-methyl |
| EP2510787A1 (en) | 2011-04-15 | 2012-10-17 | Bayer Cropscience AG | Propenoates as fungicides |
| CN101417962B (en) * | 2008-12-04 | 2013-05-01 | 江苏省农药研究所股份有限公司 | Method for preparing 2-cyano-3-amino acrylic ester derivates |
| CN104068025A (en) * | 2014-05-26 | 2014-10-01 | 浙江大学 | Application of fungicidal composition to prevention and treatment of crop gibberellic diseases and gibberellic disease mycotoxin pollution |
| CN104094942A (en) * | 2014-06-30 | 2014-10-15 | 中国水稻研究所 | Pesticide composition containing 2-cyano-3-amino-3-phenylacrylic acetate and hymexazol |
| CN104430361A (en) * | 2014-10-29 | 2015-03-25 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Fungicidal composition containing JS399-19 and fluazinam |
| CN104542599A (en) * | 2015-01-23 | 2015-04-29 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Bactericidal composition containing JS399-19 and fluazinam |
| CN105815324A (en) * | 2015-01-09 | 2016-08-03 | 中化农化有限公司 | Bactericidal composition containing SYP-Z048 and JS399-19 |
| CN109776453A (en) * | 2019-03-15 | 2019-05-21 | 江苏省农药研究所股份有限公司 | A kind of preparation method of 3- amino -2- cyanoacrylate compound |
| CN109867623A (en) * | 2019-02-27 | 2019-06-11 | 江苏省农药研究所股份有限公司 | 3- pyridyl group -3- amino -2- cyanoacrylate compound and the preparation method and application thereof |
| CN109879834A (en) * | 2019-03-15 | 2019-06-14 | 江苏省农药研究所股份有限公司 | A kind of 3- amino -2- cyanoacrylate compound and its application |
| CN111194745A (en) * | 2018-11-19 | 2020-05-26 | 上海泰初化工技术有限公司 | Resonance isomer solid mixture for preventing and treating fusarium |
| CN113845443A (en) * | 2021-09-27 | 2021-12-28 | 江苏省农药研究所股份有限公司 | Preparation method and intermediate of 2-cyano-3-amino acrylate compound |
| CN113912519A (en) * | 2021-12-09 | 2022-01-11 | 江苏省农药研究所股份有限公司 | Crystal form B of 2-cyano-3-amino-3-ethyl phenylacrylate, preparation method and application |
| WO2022160466A1 (en) * | 2021-01-26 | 2022-08-04 | 浙江大学 | 2-cyanoacrylate compound, preparation method therefor and use thereof |
| CN115073544A (en) * | 2022-06-30 | 2022-09-20 | 上海应用技术大学 | PARP inhibitor pyrazoloquinine derivative and synthesis method thereof |
| WO2024007376A1 (en) * | 2022-07-05 | 2024-01-11 | 浙江省化工研究院有限公司 | Fungicidal compositions and uses thereof in prevention and treatment of fusarium diseases of crops |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393211C (en) * | 2004-10-27 | 2008-06-11 | 江苏省农药研究所有限公司 | Application of 2-cydno-3-amino-3-phenylethyl acrylate for preventing and treating patty rice bakanae disease |
| CN101381326A (en) * | 2008-10-15 | 2009-03-11 | 江苏中旗化工有限公司 | 2-cyano-3-(substituted) amidine-3-phenyl acrylates compounds, preparation method and use thereof |
-
2001
- 2001-05-08 CN CNB011155930A patent/CN1160318C/en not_active Expired - Lifetime
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005012235A1 (en) * | 2003-07-29 | 2005-02-10 | Ciba Specialty Chemicals Holding Inc. | 3-aryl-2-cyano-3-hydroxy-acrylic acid derivatives |
| CN100435635C (en) * | 2004-02-18 | 2008-11-26 | 江苏省农药研究所有限公司 | Application of 2-cyano-3-amino-3-ethyl phenylacrylate for preventing agronomic crop disease |
| CN101258850B (en) * | 2008-04-18 | 2011-01-26 | 江苏中旗化工有限公司 | Application of 2-cyano-3-amino-3-phenylacrylate for preventing and controlling corps disease |
| CN101671270A (en) * | 2008-09-11 | 2010-03-17 | 杭州澳赛诺化工有限公司 | Method for synthesizing cyanoacetylene derivatives |
| CN101671270B (en) * | 2008-09-11 | 2013-07-31 | 杭州澳赛诺化工有限公司 | Method for synthesizing cyanoacetylene derivatives |
| CN101417962B (en) * | 2008-12-04 | 2013-05-01 | 江苏省农药研究所股份有限公司 | Method for preparing 2-cyano-3-amino acrylic ester derivates |
| CN101584322B (en) * | 2009-04-01 | 2012-04-18 | 陕西蒲城县美邦农药有限责任公司 | 2-cyano-3-amino-3-phenylancryic acetate and hexaconazole-containing synergistic antiseptic composition |
| CN101584329B (en) * | 2009-04-01 | 2012-04-18 | 陕西蒲城县美邦农药有限责任公司 | 2-cyano-3-amino-3-phenylancryic acetate and propineb-containing synergistic antiseptic composition |
| CN101584324B (en) * | 2009-04-15 | 2012-06-27 | 陕西蒲城县美邦农药有限责任公司 | 2-cyano-3-amino-3-phenylancryic acetate and epoxiconazole-containing antiseptic composition |
| CN101544669B (en) * | 2009-05-06 | 2011-09-07 | 贵州大学 | Phenyl cyanoacrylate derivatives containing alpha-amino phosphonate ester and preparation method and application thereof |
| CN101696193B (en) * | 2009-10-15 | 2011-07-27 | 沈阳化工学院 | 2-substituted methyl-3-phenyl-acrylic ester compounds with fungicidal activities and preparation method thereof |
| EP2510787A1 (en) | 2011-04-15 | 2012-10-17 | Bayer Cropscience AG | Propenoates as fungicides |
| CN102715176A (en) * | 2012-05-22 | 2012-10-10 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Bactericidal composition containing 2-cyano-3-amino-3-ethyl phenylacrylate and clorine-nalidixic-methyl |
| CN104068025A (en) * | 2014-05-26 | 2014-10-01 | 浙江大学 | Application of fungicidal composition to prevention and treatment of crop gibberellic diseases and gibberellic disease mycotoxin pollution |
| CN104068025B (en) * | 2014-05-26 | 2016-09-07 | 浙江大学 | Bactericidal composition application in preventing and treating crops head blight and Scab pathotoxin are polluted |
| CN104094942A (en) * | 2014-06-30 | 2014-10-15 | 中国水稻研究所 | Pesticide composition containing 2-cyano-3-amino-3-phenylacrylic acetate and hymexazol |
| CN104094942B (en) * | 2014-06-30 | 2016-09-07 | 中国水稻研究所 | A kind of 2-cyano-3-amino-3-phenylancryic acetate-containing and hymexazol composition pesticide |
| CN104430361A (en) * | 2014-10-29 | 2015-03-25 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Fungicidal composition containing JS399-19 and fluazinam |
| CN104430361B (en) * | 2014-10-29 | 2017-04-05 | 安徽省农业科学院植物保护与农产品质量安全研究所 | A kind of bactericidal composition of 2-cyano-3-amino-3-phenylancryic acetate-containing and fluazinam |
| CN105815324B (en) * | 2015-01-09 | 2018-08-21 | 中化农化有限公司 | Bactericidal composition containing oxazole and 2-cyano-3-amino-3-phenylancryic acetate |
| CN105815324A (en) * | 2015-01-09 | 2016-08-03 | 中化农化有限公司 | Bactericidal composition containing SYP-Z048 and JS399-19 |
| CN104542599A (en) * | 2015-01-23 | 2015-04-29 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Bactericidal composition containing JS399-19 and fluazinam |
| CN111194745A (en) * | 2018-11-19 | 2020-05-26 | 上海泰初化工技术有限公司 | Resonance isomer solid mixture for preventing and treating fusarium |
| CN109867623A (en) * | 2019-02-27 | 2019-06-11 | 江苏省农药研究所股份有限公司 | 3- pyridyl group -3- amino -2- cyanoacrylate compound and the preparation method and application thereof |
| CN109776453A (en) * | 2019-03-15 | 2019-05-21 | 江苏省农药研究所股份有限公司 | A kind of preparation method of 3- amino -2- cyanoacrylate compound |
| CN109879834A (en) * | 2019-03-15 | 2019-06-14 | 江苏省农药研究所股份有限公司 | A kind of 3- amino -2- cyanoacrylate compound and its application |
| WO2022160466A1 (en) * | 2021-01-26 | 2022-08-04 | 浙江大学 | 2-cyanoacrylate compound, preparation method therefor and use thereof |
| CN113845443A (en) * | 2021-09-27 | 2021-12-28 | 江苏省农药研究所股份有限公司 | Preparation method and intermediate of 2-cyano-3-amino acrylate compound |
| CN113912519A (en) * | 2021-12-09 | 2022-01-11 | 江苏省农药研究所股份有限公司 | Crystal form B of 2-cyano-3-amino-3-ethyl phenylacrylate, preparation method and application |
| CN113912519B (en) * | 2021-12-09 | 2022-03-08 | 江苏省农药研究所股份有限公司 | Crystal form B of 2-cyano-3-amino-3-ethyl phenylacrylate, preparation method and application |
| WO2023103261A1 (en) * | 2021-12-09 | 2023-06-15 | 江苏省农药研究所股份有限公司 | Crystal form b of ethyl 2-cyano-3-amino-3-phenylacrylate, preparation method, and application |
| CN115073544A (en) * | 2022-06-30 | 2022-09-20 | 上海应用技术大学 | PARP inhibitor pyrazoloquinine derivative and synthesis method thereof |
| WO2024007376A1 (en) * | 2022-07-05 | 2024-01-11 | 浙江省化工研究院有限公司 | Fungicidal compositions and uses thereof in prevention and treatment of fusarium diseases of crops |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1160318C (en) | 2004-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1317483A (en) | 2-cyano-3-substituted phenylacrylate compounds, compositions and their preparing prcess and application as disinfectant of agricultural crops | |
| CN101268780B (en) | Methoxy group acrylic ester fungicide, preparation method and uses thereof | |
| CN101558758A (en) | L-alpha-amino acid ester contained Z-configuration anabasine pesticide and preparation method thereof | |
| CN109422744A (en) | Matrine derivative and its synthesis and the application in terms of preventing and treating plant pest | |
| CN104926725B (en) | Naphthalimide arylurea compound and use thereof | |
| CN114605298B (en) | Fluorine-containing benzoyl thiourea insecticide and acaricide | |
| CN103524417A (en) | 3-methyl-4-formyl pyrazol compounds | |
| CN108059613B (en) | Pyrazole amide compound and application thereof | |
| CN103275009A (en) | Chloropyrazole compound containing aryl methoxyl acrylate, preparation method and application | |
| CN101759649B (en) | Benzimidazole amide bactericide | |
| CN104003924B (en) | N-replaces-3-[3-(substituted-phenyl)-2-alkene-1-ketone]-4-hydroxypyrrole quinoline-2-ketone compounds and preparation method and application | |
| CN109666004B (en) | Trifluoromethyl-containing pyrazinamide compounds, preparation method and application thereof, and bactericide | |
| CN102002024A (en) | 3-aryl-4-arylamino-2 (5(i)H(/i))-furanone compounds as well as preparation method and application thereof | |
| CN101723923B (en) | N-2, 4-dichlorophenoxy acetyl (sulfur) carbamide weedicide and preparation method thereof | |
| CN103524407A (en) | 2-fluorine-3-pyridine formyl compounds | |
| CN111285815A (en) | Pyrazinamide compound and application thereof | |
| CN110183434B (en) | Oxadiazole compound and preparation method and application thereof | |
| CN114957113B (en) | 2-chloroquinoline-3-formaldehyde oxime-O- (N-p-fluorophenyl) carbamate and preparation method and application thereof | |
| JPH0254346B2 (en) | ||
| CN104351179A (en) | Agricultural bacteriostatic activity of 8-phenyl (isopropyl) cumarin | |
| CN104610142B (en) | 3-bishydrazide diphenylurea derivative, and preparation method and application of 3-bishydrazide diphenylurea derivative | |
| CN111285807A (en) | Pyrazole amide compound and application thereof | |
| CN1162401C (en) | 2,4-substituted phenoxypropanamide compounds and preparing process and application thereof | |
| CN1309303C (en) | Herbicide used in rape field, prepn. method and use thereof | |
| CN110981817B (en) | Quinazoline amide compound and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: JIANGSU PESTICIDE INST. CO., LTD. Free format text: FORMER NAME: JIANGSU PESTICIDE RESEARCH INSTITUTE |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 210036 screw Bridge No. 80, Jiangsu, Nanjing Patentee after: Jiangsu Pesticide Inst. Co., Ltd. Address before: 210036 screw Bridge No. 80, Jiangsu, Nanjing Patentee before: Jiangsu Prov. Inst. of Agricultural Chemicals |
|
| CX01 | Expiry of patent term |
Granted publication date: 20040804 |
|
| CX01 | Expiry of patent term |