CN102225928A - Cis-nitenpyram compound containing tetrahydropyridone ring, its preparation method and application - Google Patents
Cis-nitenpyram compound containing tetrahydropyridone ring, its preparation method and application Download PDFInfo
- Publication number
- CN102225928A CN102225928A CN2011101067912A CN201110106791A CN102225928A CN 102225928 A CN102225928 A CN 102225928A CN 2011101067912 A CN2011101067912 A CN 2011101067912A CN 201110106791 A CN201110106791 A CN 201110106791A CN 102225928 A CN102225928 A CN 102225928A
- Authority
- CN
- China
- Prior art keywords
- cis
- tetrahydropyridone
- ring
- preparation
- compounds
- 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.)
- Pending
Links
Abstract
The invention relates to a nitenpyram pesticide, in particular to a cis-nitenpyram compound containing tetrahydropyridone ring, its preparation method and application. The structural similarity of nitenpyram pesticides in prior art causes cross resistance problem between pesticides, so that the application of the pesticides is limited. The cis-nitenpyram compound containing tetrahydropyridone ring disclosed in the invention is represented by the general formula (I). The preparation method comprises the following steps: adding nitenpyram, aromatic aldehyde and meldrums acid in alcohol or acetonitrile, adding piperidine as catalyst, and carrying out a microwave reaction. The compound has insecticidal activity. The invention has the advantages of easy preparation method, simple technology, small investment, high insecticidal activity, good insecticidal effect, no residue in food and plant, and is safe for human and animal.
Description
Technical field
The present invention relates to the Ti304 insecticides, specifically a kind of cis Ti304 compounds that contains the tetrahydropyridone ring and preparation method thereof and as the application of sterilant.
Background technology
The discovery of neonicotine sterilant can be considered to a milestone in the agrochemicals research in 30 years in the past.Anabasine insecticide be after organic phosphates, amino formate, pyrethroid insecticides the 4th generation sterilant.The anabasine material is as nAChR (nAChRs) agonist, neural system (nAChRs) to insect optionally works, it has not only shown high-affinity to (nAChRs), but also has shown unionized and medium physics-chem characteristic such as water-soluble.Because it has the unique insecticidal mechanism and the performance of high-efficiency low-toxicity, become the higher effective and lower toxic pesticide new variety that modern agriculture needs rapidly.
Because the comparatively serious resistance problem that the excessive frequent use of neonicotine sterilant causes, and because the cross resistance between the neonicotine sterilant that structural similarity is brought, limit such application of compound to a certain extent, become the major issue of this compounds development of restriction.The present invention has improved the compound light stability by introduce a tetrahydropyridone ring on the Ti304 structure.The present invention also has the improvement effect to the resistance problem that a large amount of uses owing to various agricultural chemicals cause.
The present invention is that raw material has synthesized a series of cis Ti304 compounds that contain the tetrahydropyridone ring with Michaelis acid, aromatic aldehyde and Ti304 first, and has measured the efficient insecticide activity of this sterilant.
Summary of the invention
The purpose of this invention is to provide a kind of cis Ti304 compounds that contains the tetrahydropyridone ring.
Second purpose of the present invention provides the preparation method of the cis Ti304 compounds that contains the tetrahydropyridone ring.
The 3rd purpose of the present invention provides cis Ti304 compounds that general formula (I) contains the tetrahydropyridone ring as sterilant, kills the application of crop pests.
Purpose of the present invention is achieved through the following technical solutions:
A kind of cis Ti304 compounds that contains the tetrahydropyridone ring, represent with general formula (I):
Wherein: R=alkyl, cycloalkyl, aryl, substituted aryl, benzyl or heterocyclic substituent.
The cis Ti304 compounds preparation method who contains the tetrahydropyridone ring is as follows:
(1) in ethanol or acetonitrile, adds Ti304, aromatic aldehyde and Michaelis acid, add the catalyzer piperidines; Preferably, Ti304, aromatic aldehyde and Michaelis acid mol ratio are 1: 1.5: 1.5;
(2) with mixed solution at 75~80 ℃ of following microwave reactions 20~40 minutes, microwave power 1000-1050W; Be preferably under 78 ℃ of temperature and reacted 30 minutes.
Reaction formula is:
The cis alkene pyridine insects compound that contains the tetrahydropyridone ring has insecticidal activity, can be made into emulsion, aqueous suspension and water emulsion pesticide sterilant, has widespread use aspect the crop pests killing.
The inventive method is utilized the sound response activity of Michaelis acid, introduces the tetrahydropyridone structure first in Ti304, adopts microwave heating method to improve productive rate and has also greatly shortened the reaction times.Prior art adopted the heating reflux method reaction needed 12 hours, and the present invention adopts microwave heating method only to need 30 minutes.
The cis Ti304 compounds that contains the tetrahydropyridone ring with insecticidal activity with general formula (I) expression has good insecticidal activity, the effective active composition of useful as pesticides, make the various pesticide formulation according to the method for producing agricultural of prior art, example emulsion, aqueous suspension and aqueous emulsion etc., use killing on the crop pests, have the efficient insecticide effect.
The present invention is that raw material has synthesized a series of cis Ti304 compounds that contain the tetrahydropyridone ring with insecticidal activity with Ti304, aromatic aldehyde, Michaelis acid first; The present invention has measured the efficient insecticide activity of this sterilant, has significant practicality in modern agriculture production.
Advantage of the present invention is:
1, the preparation method is easy, technology is simple, facility investment is few.
2, insecticidal activity height, good disinsection effect.
3, noresidue in food and plant materials; The person poultry safety.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with specific embodiment.
The embodiment that contains tetrahydropyridone ring cis Ti304 compounds that the present invention's preparation has insecticidal activity is:
(Ia), cis-1-methyl-4-phenyl-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone;
(Ib), cis-1-methyl-4-(4-p-methoxy-phenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone;
(Ic), cis-1-methyl-4-(3-chloro phenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone;
(Id), cis-1-methyl-4-(4-cyano-phenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone;
(Ie), cis-1-methyl-4-(4-chloro-phenyl-)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone;
(If), cis-1-methyl-4-(4-bromophenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone;
Embodiment 1
Preparation cis-1-methyl-4-phenyl-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone.
In the 250mL three-necked bottle, add the 30mL dehydrated alcohol, add the acid of 15mmol Michaelis, 15mmol phenyl aldehyde, 10mmol Ti304 more successively, add 0.3 milliliter of piperidines again as catalyzer.The three-necked round bottom flask that above-mentioned solution is housed is put into 1000-1050W, 78 ℃ of temperature, microwave reaction 30 minutes, dehydrated alcohol is removed in decompression, adds the 10mL water dissolution and divides three extractions with the 60mL ethyl acetate.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: sherwood oil=column chromatography got faint yellow solid in 1: 1, cis-1-methyl-4-phenyl-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone is made, productive rate 85.5%.
Ultimate analysis: measured value C%59.90 H%5.25 N%13.95
Calculated value C%59.92 H%5.28 N%13.98
IR(KBr,cm
-1)v
max?2946,1681,1648,1485,1413,1097,879.
1H?NMR(CDCl
3,400MHz)δ8.23(s,1H,Pyridine),7.40(s,1H),7.19-7.28(m,4H),6.99(s,2H),4.68(t,J=3.8Hz,1H,CH),4.39(d,J=14.7Hz,1H),4.18(d,J=14.7Hz,1H),3.13-3.15(m,2H),3.09(d,J=4.0Hz,2H),3.04(s,3H),1.29(t,J=6.9Hz,3H,NCH
2CH
3)。
Embodiment 2
Preparation cis-1-methyl-4-(4-p-methoxy-phenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone.
In the 250mL three-necked bottle, add the 30mL dehydrated alcohol, add 0.3 milliliter of piperidines as catalyzer.Add the acid of 15mmol Michaelis, 15mmol aubepine, 10mmol Ti304 more successively, the three-necked round bottom flask that above-mentioned solution is housed is put into the 1000-1050W microwave reactor, 78 ℃ of controlled temperature, microwave reaction 30 minutes, dehydrated alcohol is removed in decompression, adds the 10mL water dissolution and divides three extractions with the 60mL ethyl acetate.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: sherwood oil=column chromatography got faint yellow solid in 1: 1, cis-1-methyl-4-(4-p-methoxy-phenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone is made, productive rate 87.5%.
Ultimate analysis: measured value C%58.58 H%5.34 N%13.02
Calculated value C%58.54 H%5.38 N%13.00
IR(KBr,cm
-1)V
max2998,1684,1649,1488,1412,1228,1097,882.
1H?NMR(CDCl
3,400MHz)δ8.24(s,1H,Pyri?dine),7.20-7.42(m,2H),6.76-6.86(m,4H),4.60(s,1H,CH),4.39(d,J=14.6Hz,1H),4.19(d,J=14.6Hz,1H),3.79(s,3H,OCH
3),3.10-3.14(m,2H),3.05(s,5H),1.29(t,J=6.4Hz,3H,NCH
2CH
3)。
Embodiment 3
Preparation cis-1-methyl-4-(3-chloro phenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone.
In the 250mL three-necked bottle, add the 30mL dehydrated alcohol, add the 3mL piperidines as catalyzer.Add the acid of 15mmol Michaelis, 15mmol m chlorobenzaldehyde, 10mmol Ti304 more successively.The three-necked round bottom flask that above-mentioned solution is housed is put into the 1000-1050W microwave reactor, and controlled temperature is about 78 ℃, and microwave reaction 35 minutes reduces pressure and removes dehydrated alcohol, adds the 10mL water dissolution and divides three extractions with the 60mL ethyl acetate.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: sherwood oil=column chromatography got faint yellow solid in 1: 1, cis-1-methyl-4-(3-chloro phenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone is made, productive rate 81.8%.
Ultimate analysis: measured value C%55.17 H%4.67 N%12.88
Calculated value C%55.18 H%4.63 N%12.87
IR(KBr,cm
-1)V
max2947,1663,1628,1445,1413,1097,889.
1H?NMR(CDCl
3,400MHz)δ8.25(s,1H,Pyridine),7.45(s,1H),7.18-7.26(m,3H),7.10(s,1H),6.84(s,1H),4.66-4.67(m,1H),4.41(d,J=14.7Hz,1H),4.16(d,J=14.7Hz,1H),3.13-3.14(m,2H),3.02-3.11(m,5H),1.30(t,J=7.5Hz,3H,NCH
2CH
3)。
Embodiment 4
Preparation cis-1-methyl-4-(4-cyano-phenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone.
In the 250mL three-necked bottle, add the 30mL dehydrated alcohol, add the 3mL piperidines as catalyzer.Add the acid of 15mmol Michaelis, 15mmol more successively to cyanobenzaldehyde, 10mmol Ti304.The three-necked round bottom flask that above-mentioned solution is housed is put into the 1000-1050W microwave reactor, and controlled temperature is at 78 ℃, and microwave reaction 30 minutes reduces pressure and removes dehydrated alcohol, adds the 10mL water dissolution and divides three extractions with the 60mL ethyl acetate.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: sherwood oil=column chromatography got faint yellow solid in 1: 1, made cis-1-methyl-4-(4-cyano-phenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone, productive rate 79.8%.
Ultimate analysis: measured value C%59.26 H%4.72 N%11.25
Calculated value C%59.23 H%4.73 N%11.27
IR(KBr,cm
-1)V
max2911,1690,1650,1480,1400,1221,1096,881.
1H?NMR(CDCl
3,400MHz)δ8.18(s,1H,Pyridine),7.35-7.56(m,3H),7.07-7.19(m,3H),4.70(s,1H),4.37(d,J=14.6Hz,1H),4.23(d,J=14.6Hz,1H),3.16-3.20(m,2H),3.09-3.12(m,5H),1.31(t,J=6.5Hz,3H,NCH
2CH
3)。
Embodiment 5
Preparation cis-1-methyl-4-(4-chloro-phenyl-)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone.
With the phenyl aldehyde among the 4-chlorobenzaldehyde replacement embodiment 1, other raw material and working method equally obtain faint yellow solid cis-1-methyl-4-(4-chloro-phenyl-)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone, productive rate are 72.3%.
Ultimate analysis: measured value C%55.16 H%4.60 N%12.87
Calculated value C%55.18 H%4.63 N%12.87
IR(KBr,cm
-1)v
max2907,1687,1670,1480,1413,1648,1557,1226,1097,880.
1H?NMR(CDCl
3,400MHz)δ8.25(s,1H,Pyridine),7.45(s,1H),7.18-7.26(m,3H),7.10(s,1H),6.84(s,1H),4.66-4.67(m,1H),4.41(d,J=14.7Hz,1H),4.16(d,J=14.7Hz,1H),3.13-3.14(m,2H),3.02-3.11(m,5H),1.30(t,J=7.5Hz,3H,NCH
2CH
3)。
Embodiment 6
Preparation cis-1-methyl-4-(4-bromophenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone.
With the phenyl aldehyde among the 4-bromobenzaldehyde replacement embodiment 1, other raw material and working method equally obtain faint yellow solid cis-1-methyl-4-(4-bromophenyl)-6-[N-(6-chloro-3 picolyls)-N-ethyl] amino-5-nitro-1,2,3,4-tetrahydropyridine-2-ketone, productive rate are 72.3%.
Ultimate analysis: measured value C%50.06 H%4.20 N%11.67
Calculated value C%50.07 H%4.20 N%11.68
IR(KBr,cm
-1)v
max2987,1683,1648,1485,1413,1648,1557,1226,1097,889.
1H?NMR(CDCl
3,400MHz)δ8.25(s,1H,Pyridine),7.45(s,1H),7.18-7.26(m,3H),7.10(s,1H),6.84(s,1H),4.66-4.67(m,1H),4.41(d,J=14.7Hz,1H),4.16(d,J=14.7Hz,1H),3.13-3.14(m,2H),3.02-3.11(m,5H),1.30(t,J=7.5Hz,3H,NCH
2CH
3)。
The test of embodiment 7 insecticidal activities
1. test target
Planthopper (Nilaparvata legen), aphis craccivora (Aphis medicagini).
2. plant and instrument
Culture dish, electronic analytical balance, Potter spray tower, liquid-transfering gun, writing brush etc.
3. chemicals treatment
Take by weighing the medicament of a certain amount of target compound with analytical balance (0.0001g), add the solvent that contains 0.1% tween-80, be mixed with 1~5% preparation.Take by weighing the preparation of certain mass, the adding distil water dilution is mixed with the soup of measuring desired concn.General sieve concentration is generally 500mg/L.
4. test method
A. paddy rice brown paddy plant hopper screening---the quantitative spray method of culture dish seedling worm:
The paddy rice seedling is fixed in the culture dish with white quartz sand; Use CO
2Anaesthetize 3 mid-term in age nymph, place under the POTTER spray tower spraying.The spraying back covers with the transparent plastics cup, is put in the observation ward behind the mark.Check result behind the 72h.
B. aphis craccivora screening---the quantitative spray method of bamboo tower
If the broad bean blade is cut off two ends, and the back side is placed on the fritter cotton up, places in the plastic culture dish, adds less water, connects aphis craccivora and becomes aphid to produce aphid.Remove into aphid behind the 24h, continue behind the cultivation 2d blade behind the abundant 5s of infiltration, to be placed on the cotton in soup again, dry naturally.Check result behind the 24h.
Test statistics and advance the sieve standard:
Add up the dead borer population of each processing and the borer population of living, the calculating mortality ratio (Abbott ' the s formula).
Embodiment Compound I a~Ij desinsection test result:
Target compound Ia~Ij is to planthopper (Nilaparvata legen), aphis craccivora (Aphis medicagini) insecticidal activity, and (nitenpyram) does contrast with Ti304, and activity data sees Table 1.
Table 1
The foregoing description only is a preference of the present invention, is not used for limiting the present invention.All within principle of the present invention, any modifications and variations of being done are all within protection scope of the present invention.
Claims (6)
2. the described preparation method who contains the cis Ti304 compounds of tetrahydropyridone ring of claim 1 is characterized in that, comprises the steps:
(1) in ethanol or acetonitrile, adds Ti304, aromatic aldehyde and Michaelis acid, add the catalyzer piperidines;
(2) with mixed solution at 75~80 ℃ of following microwave reactions 20~40 minutes, microwave power 1000-1050W.
3. the described preparation method who contains the cis Ti304 compounds of tetrahydropyridone ring of claim 2 is characterized in that step (2) temperature of reaction is 78 ℃, 30 minutes reaction times.
4. the described preparation method who contains the cis Ti304 compounds of tetrahydropyridone ring of claim 2 is characterized in that, Ti304, aromatic aldehyde and Michaelis acid mol ratio are 1: 1.5: 1.5.
5. the described application of cis Ti304 compounds aspect the preparation sterilant that contains the tetrahydropyridone ring of claim 1.
6. a sterilant is characterized in that, contains the described cis Ti304 compounds that contains the tetrahydropyridone ring of claim 1, and formulation is emulsion, aqueous suspension or aqueous emulsion.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011101067912A CN102225928A (en) | 2011-01-14 | 2011-04-15 | Cis-nitenpyram compound containing tetrahydropyridone ring, its preparation method and application |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201110008279.4 | 2011-01-14 | ||
CN201110008279 | 2011-01-14 | ||
CN2011101067912A CN102225928A (en) | 2011-01-14 | 2011-04-15 | Cis-nitenpyram compound containing tetrahydropyridone ring, its preparation method and application |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102225928A true CN102225928A (en) | 2011-10-26 |
Family
ID=44806935
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2011101067912A Pending CN102225928A (en) | 2011-01-14 | 2011-04-15 | Cis-nitenpyram compound containing tetrahydropyridone ring, its preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102225928A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104761601A (en) * | 2015-03-09 | 2015-07-08 | 江苏师范大学 | Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrasulfo-D-glucopyranose hydrosulfate |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101070321A (en) * | 2006-05-08 | 2007-11-14 | 中国科学院化学研究所 | Tetrahydropyridone-1,3-diazacyclo compound and preparing method |
CN101558758A (en) * | 2009-05-26 | 2009-10-21 | 上海师范大学 | L-alpha-amino acid ester contained Z-configuration anabasine pesticide and preparation method thereof |
CN101906096A (en) * | 2009-06-05 | 2010-12-08 | 华东理工大学 | 3,4-dihydropyridine-2-ketone heterocyclic compound and application thereof |
-
2011
- 2011-04-15 CN CN2011101067912A patent/CN102225928A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101070321A (en) * | 2006-05-08 | 2007-11-14 | 中国科学院化学研究所 | Tetrahydropyridone-1,3-diazacyclo compound and preparing method |
CN101558758A (en) * | 2009-05-26 | 2009-10-21 | 上海师范大学 | L-alpha-amino acid ester contained Z-configuration anabasine pesticide and preparation method thereof |
CN101906096A (en) * | 2009-06-05 | 2010-12-08 | 华东理工大学 | 3,4-dihydropyridine-2-ketone heterocyclic compound and application thereof |
Non-Patent Citations (2)
Title |
---|
杨定荣: "(Z)型硝基亚甲基四氢嘧啶新烟碱类化合物的合成及杀虫活性研究", 《工程科技Ⅰ辑》 * |
纪顺俊等: "《现代有机合成新技术》", 30 September 2009, 化学工业出版社 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104761601A (en) * | 2015-03-09 | 2015-07-08 | 江苏师范大学 | Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrasulfo-D-glucopyranose hydrosulfate |
CN104761601B (en) * | 2015-03-09 | 2017-07-07 | 江苏师范大学 | The synthesis of the tetrasulfonic acid base D glucopyranose sulfur hydrogen salts of 1 imidazoles of β 2,3,4,6 and purposes |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101558758B (en) | L-alpha-amino acid ester contained Z-configuration anabasine pesticide and preparation method thereof | |
CN104892591A (en) | Preparation method of pyrazole oxime compound containing 3-aryl-1,2,4-oxdiazole heterocycle structure and application thereof | |
CN104193727A (en) | Preparation and application of pyrazole oxime ether compound containing trifluoro methyl pyridine | |
CN104557710B (en) | The preparation and application of the pyrazoles oxime compound of the pyrrazole structure containing multi-substituent | |
CN109689644B (en) | Pyridazinone compound and application thereof | |
CN104119316A (en) | Pyridine phenyl ether compound as well as preparation and application of pyridine phenyl ether compound | |
CN102229600B (en) | Cis-neonicotinoid compound containing 1, 4-dihydropyridine ring and its preparation method and application | |
CN102225928A (en) | Cis-nitenpyram compound containing tetrahydropyridone ring, its preparation method and application | |
CN102229560B (en) | Cis-nitenpyram compound including 1,3-dicarbonyl, preparation method and use | |
CN102267991B (en) | Neonicotinoid clothianidin compound, preparation method and application thereof | |
CN102229599A (en) | 1,4- dihydropyridine ring-containing cis-nitenpyram compound, preparation method and application thereof | |
CN101965841A (en) | Application of 4-tertiary butyl-5-(1,2,4-triazole-1-base)-2-benzyliminothiazole in preparation of insecticide | |
CN102241676A (en) | Tetrahydropyridone 1,3-diazacyclo cis-neonicotine compounds as well as preparation method and applications thereof | |
CN103319343A (en) | Pyrethroid compound, and preparation method and applications thereof | |
CN108794461B (en) | Fluorine-containing phenyl oxadiazole pyrazole insecticidal bactericide | |
CN102225931B (en) | Amino acid ester-containing bivalent cis-neonicotinoid compound and its preparation method and application | |
CN102304122A (en) | Cis-nitenpyram compound containing amino-acid ester as well as preparation method and application thereof | |
CN102344446B (en) | Cis-nitenpyram analog containing carboxylic acid-substituted methyl ester and preparation method and application thereof | |
CN100369911C (en) | Valienamine A-4,7,4',7'-diacetal or ketone compound, and its preparation and use | |
CN106279040B (en) | Pyrimidine compound containing oximino and application thereof | |
CN102718755B (en) | Cis nitenpyram compound with amide flexible bond and preparation method and application thereof | |
CN103288798B (en) | Cis-nitenpyram analog containing tetrahydro-pyrimidine ring and preparation method and application thereof | |
CN102838587B (en) | Containing cis-nitenpyram analogue and the Synthesis and applications thereof of peptide bond | |
CN104761499A (en) | 1, 1-dichloropropene ether compound containing N-substituent-3-methylpyrazole oxime unit structure, preparation method and application thereof | |
CN102321152B (en) | Cis-nitenpyram analogue containing glycylglycine, its preparation method and its application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C12 | Rejection of a patent application after its publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111026 |