CN103553992B - One group of 2-rubigan-3-methylbutyryl compound - Google Patents
One group of 2-rubigan-3-methylbutyryl compound Download PDFInfo
- Publication number
- CN103553992B CN103553992B CN201310526284.3A CN201310526284A CN103553992B CN 103553992 B CN103553992 B CN 103553992B CN 201310526284 A CN201310526284 A CN 201310526284A CN 103553992 B CN103553992 B CN 103553992B
- Authority
- CN
- China
- Prior art keywords
- compound
- rubigan
- methylbutyryl
- group
- agricultural
- 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
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides one group of 2-rubigan-3-methylbutyryl compound, this compound formula is
wherein R
1for 2-methyl-2-methylthiopropionaldehyde oximido, ethylamino-, N-nitro imido imidazolyl alkane base, 3-methyl-4-nitro-imine-1,3,5-oxadiazine base, 2-cyanoimino-1,3-thiazoles alkyl; The invention discloses these compounds structure and to agricultural insect management effect, also disclose the application of these compounds as sterilant.
Description
(1) technical field
The invention belongs to pesticide field, technical scheme relates to one group of 2-rubigan-3-methylbutyryl compound and preparation method thereof and using it as the application of pesticide active ingredient.
(2) background technology
2-rubigan-3-methylbutyryl ester compound often has good insecticidal action, as fenvalerate etc.We splice principle according to active group; one group of 2-rubigan-3-methylbutyryl compound has been prepared in design, and indoor biological determination of activity result shows, new compound has certain insecticidal activity; and compare environmental protection when producing as sterilant, be beneficial to industrialization and Serve " Agriculture.
(3) summary of the invention
The object of this invention is to provide one group of 2-rubigan-3-methylbutyryl compound and preparation method thereof.
It is agricultural insecticide application that another object of the present invention is to provide described 2-rubigan-3-methylbutyryl compound.
3rd object of the present invention is to provide a kind of agricultural composition as the application in agricultural insecticide, and this agricultural composition comprises acceptable carrier and/or vehicle in 0.1 ~ 99.9 % by weight 2-rubigan-3-methylbutyryl compound of the present invention and Pesticide Science.
The chemical structural formula of 2-rubigan-3-methylbutyryl compound provided by the invention, as shown in general formula I:
Wherein, R
1for any one in 2-methyl-2-methylthiopropionaldehyde oximido, ethylamino-, N-nitro imido imidazolyl alkane base, 3-methyl-4-nitro-imine-1,3,5-oxadiazine base, 2-cyanoimino-1,3-thiazoles alkyl.
Concrete, 2-rubigan-3-methylbutyryl compound (I formula) structural formula provided by the invention is as shown in table 1.
Table 1 2-rubigan provided by the invention-3-methylbutyryl compound
The preparation method of 2-rubigan-3-methylbutyryl compound provided by the invention is as follows:
Reaction equation:
Concrete operation step: in reaction flask, add appropriate inert solvent as reaction solvent, HR and acid binding agent, under low temperature (0 ± 5 DEG C), stirring, slowly drip the inert solvent solution of 2-rubigan-3-Methylbutanoyl chloride, then stirring reaction certain hour under low temperature (0 ± 5 DEG C), to reacting end.Use 5% sodium hydrogen carbonate solution, water respectively washs once; Organic addition anhydrous magnesium sulfate drying, filter, precipitation obtains target compound or its crude product, and target compound crude product recrystallization obtains target compound sterling.
Concrete, reaction solvent can be chloroform, acetonitrile or toluene.
Concrete, acid binding agent can be pyridine, triethylamine or K
2cO
3.
Concrete, the ratio of the amount of substance (mole number) of 2-rubigan-3-Methylbutanoyl chloride, HR, acid binding agent is 1: 1: 1.
Concrete, described HR be selected from 2-methyl-2-methylthio propionaldoxime, ethamine, N-nitro imido imidazolyl alkane, 3-methyl-4-nitro-imine-1,3,5-oxadiazine, 2-cyanoimino-1,3-thiazoles alkane any one, concrete structure is in table 2.
HR needed for 2-rubigan-3-methylbutyryl compound of the present invention prepared by table 2
The insecticidal activity screening method of 2-rubigan-3-methylbutyryl compound provided by the invention is as follows:
To the Toxicity Determination of beet armyworm
Toxicity Determination adopts leaf dipping method to carry out.According to pilot study scheme, reagent agent is diluted to 100.0mg/L.By removing, the blade of surface wax layer is cleaned, the punch tool drying rear bore identical with 12 orifice plate internal diameters is broken into disk, floods 10 seconds, again dry, put into 12 orifice plates, 2, every hole after taking-up in liquid, 3 instar larvaes of access neat and consistent.Compare with the space management not containing medicament (containing solvent and emulsifying agent).Often process repetition 4 times, totally 48 examination worms, be placed in the incubator of temperature (27 ± 0.5) DEG C, humidity (70 ± 10) %, illumination 16L: 8D.48h checks dead larvae quantity, touches the motionless person of polypide larva for death with tweezers.
After the medicine of this test, 48h blank group mortality ratio is less than 10%, and meeting raw survey requirement, is efficiency test.
To the Toxicity Determination of small cabbage moth
Dip method process is adopted with reference to NY/T1154.6-2006, examination worm is inserted in leaching worm cage, flooded for 8 seconds in different agents solution, then the upper unnecessary liquid of polypide is sucked with filter paper, being transferred to by examination worm is placed with in the plastics insect box of fresh cabbage leaves again, be 28.0 ± 1.0 DEG C in temperature, relative humidity remains on 80 ± 5%, raises in the illumination box that the photoperiod (L/D) is 16h/8h.24h checks dead larvae quantity, touches the motionless person of polypide larva for death with tweezers.
After the medicine of this test, 48h blank group mortality ratio is less than 10%, and meeting raw survey requirement, is efficiency test.
To the Toxicity Determination of apple yellow aphid
With deionized water, the mother liquor prepared in advance is diluted by set concentration, spray with little watering can, if solvent control, parent solution solvents+emulsifier tween 80, solvent (2%)+tween 80 (0.1%).To spray the young aphid of front removal, parasitic aphid and alatae.Want during spraying evenly, prevent aphid from being swept away by liquid or be drowned.After having sprayed a kind of compound, carefully scrub little watering can with liquid detergent, and rinse twice with clear water, prevent cross interference from affecting.
To the Toxicity Determination of Bemisia tabaci
Before test period is selected in morning 8 or after at 5 in afternoon, now Bemisia tabaci torpescence, is beneficial to and checks aleyrodid number.First check adult whitefly number on wild cabbage, cover with gauze after inspection, surrounding clip fixes.Open gauze one osculum during spraying, with little watering can at gauze internal spraying, sprayed rear timely sealing, prevented Bemisia tabaci from flying out.With deionized water, the mother liquor prepared in advance is diluted by set concentration, be placed in little watering can respectively and spray, if solvent control, parent solution solvents+emulsifier tween 80, solvent (2%)+tween 80 (0.1%).After having sprayed a kind of compound, carefully scrub little watering can with liquid detergent, and rinse twice with clear water, prevent cross interference from affecting.
The invention has the beneficial effects as follows: 2-rubigan-3-methylbutyryl compound provided by the invention can obtain good effect for preventing and treating Agricultural pests.
2-rubigan-3-methylbutyryl compound provided by the invention is one of key characters of the present invention for preventing and treating Agricultural pests.
The present invention is by specific preparation and the biological activity determination embodiment more specifically preparation of bright 2-rubigan-3-methylbutyryl compound provided by the invention and biological activity, and described embodiment is unrestricted the present invention for specific description the present invention only.
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1 compound R 100826
The 5ml chloroformic solution of 3.08g (0.022mol) 95%2-methyl-2-methylthio propionaldoxime is loaded in 50ml there-necked flask, ice-water bath is cooled to 2 DEG C, slowly drips the 10ml chloroformic solution of 4.91g (0.022mol) 2-(4-chloro-phenyl-)-3-Methylbutanoyl chloride and the 5ml chloroformic solution of 1.74g (0.022mol) pyridine wherein.Drip process temperature to rise to some extent, control reacting liquid temperature 2 ~ 3 DEG C reaction 1h.Stopped reaction, uses 20ml5% sodium hydrogen carbonate solution, and 10ml water respectively washs once, adds anhydrous magnesium sulfate drying, and filter, precipitation obtains yellow transparent liquid, R100618, yield 87.6%.
The preparation of other 4 kinds of compounds in embodiment 2 ~ 5 table 1
Concrete operations are as table 3.
Table 3 embodiment 2 ~ 5 concrete operations
The physical and chemical parameter of compound prepared by embodiment 6 embodiment 1-5 measures and Identification of chemical structure
Measure the fusing point of compound prepared by embodiment 1-5,
1h-NMR and IR, its chemical structural formula and physical and chemical parameter are in table 4, table 5 and table 6.
2-rubigan-3-methylbutyryl compound physical chemical property prepared by table 4 embodiment 1-5 and yield
2-rubigan-3-methylbutyryl compound hydrogen nuclear magnetic resonance modal data prepared by table 5 embodiment 1-5
2-rubigan-3-methylbutyryl compound ir data prepared by table 6 embodiment 1-5
| Numbering | Infrared spectra (charateristic avsorption band) data (IR)/cm -1 |
| R100826 | IR(KBr)v：1765，1624cm -1 |
| R91006 | IR(KBr)v：3295，1635cm -1 |
| R100515 | IR(KBr)v：3448，1624，1561，1337,715cm -1 |
| R91209 | IR(KBr)v：1599，1337cm -1 |
| L090903 | IR(KBr)：max=2963(CH3),2191(CN)，1702(C＝O) |
From table 5 and table 6, the 2-rubigan-3-methylbutyryl compound prepared by embodiment 1-5
1h
-number and its structure of the NMR display chemical shift corresponding to its structure, H are identical, and corresponding skeleton absorption peak appears in IR.
2-rubigan-3-methylbutyryl compound prepared by embodiment 7 embodiment 1-5 is to the Toxicity Determination of beet armyworm, small cabbage moth, apple yellow aphid, Bemisia tabaci.
The results are shown in Table 7 (concentration is 100mg/L, and data are 48 hours corrected mortality %).
Wherein, bromothalonil is contrast agricultural chemicals.
2-rubigan-3-methylbutyryl compound Toxicity Determination result prepared by table 7 embodiment 1-5
| Beet armyworm | Small cabbage moth | Apple yellow aphid | Bemisia tabaci | |
| R100826 | 86.7 | 88.5 | 68.2 | 59.3 |
| R91006 | 34.6 | 41.5 | 23.4 | 33.5 |
| R100515 | 88.9 | 90.3 | 70.5 | 63.1 |
| R91209 | 74.2 | 65.3 | 44.2 | 38.9 |
| L090903 | 81.5 | 91.0 | 50.1 | 44.3 |
| Bromothalonil | 95.66 | 90.12 | 65.37 | 58.67 |
From table 7, data are found out, prepared by embodiment 1-5,2-rubigan-3-methylbutyryl compound is under 100mg/L concentration, and having beet armyworm, small cabbage moth, apple yellow aphid, Bemisia tabaci Agricultural pests must kill ratio; Wherein R100826, R100515 and L090903 have higher kill ratio to beet armyworm and small cabbage moth, and agricultural chemicals bromothalonil is close with contrasting; R100826 and R100515 to the kill ratio of apple yellow aphid and Bemisia tabaci higher than contrast agricultural chemicals bromothalonil.
Claims (4)
1. one group of 2-rubigan-3-methylbutyryl compound, described compound be selected from following table any one:
2. 2-rubigan-3-methylbutyryl compound is preparing the application in agricultural insecticide according to claim 1.
3. an agricultural composition, it to comprise in the claim 1 of 0.1 ~ 99.9 % by weight acceptable carrier and/or vehicle in arbitrary described compound and Pesticide Science.
4. agricultural composition according to claim 3 is preparing the application in agricultural insecticide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310526284.3A CN103553992B (en) | 2013-10-31 | 2013-10-31 | One group of 2-rubigan-3-methylbutyryl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310526284.3A CN103553992B (en) | 2013-10-31 | 2013-10-31 | One group of 2-rubigan-3-methylbutyryl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103553992A CN103553992A (en) | 2014-02-05 |
| CN103553992B true CN103553992B (en) | 2015-09-30 |
Family
ID=50008400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310526284.3A Expired - Fee Related CN103553992B (en) | 2013-10-31 | 2013-10-31 | One group of 2-rubigan-3-methylbutyryl compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103553992B (en) |
-
2013
- 2013-10-31 CN CN201310526284.3A patent/CN103553992B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103553992A (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103524422B (en) | Benzimidazole derivative, and preparation method and purpose thereof | |
| DD144498A5 (en) | METHOD FOR REDUCING HERBICIDES | |
| CN103554176B (en) | One group of thiophosphoryl compound | |
| CN105037350A (en) | Harmine compound and applications of harmine compound in prevention and control of peronophthora litchi chen disease | |
| CN108341808B (en) | Oxadiazole pyrazole compound and application thereof | |
| CN103553992B (en) | One group of 2-rubigan-3-methylbutyryl compound | |
| CN102224825A (en) | Pesticide composition containing sulfoxaflor and nereistoxin compound | |
| CN103319343B (en) | Pyrethroid compound, and preparation method and applications thereof | |
| CN102960353A (en) | Insecticidal and acaricidal composition containing metaflumizone and flufenzine | |
| CN110143869A (en) | A kind of novel Biphenthrin derivative and its preparation method and application | |
| CN103539716A (en) | One group of 2-para chlorphenyl-4-substituted methyl-5- trifluoromethyl-3-cyanpyrrole compounds | |
| CN109320506B (en) | Difluorophenyl oxadiazole insecticide and acaricide | |
| CN109336879B (en) | 3-pyridyl-1, 2, 4-oxadiazole compound and application thereof | |
| CN103242196B (en) | Cyclopropane carboxylic ester compound, its preparation method and application thereof | |
| CN106366142A (en) | Macrolide benzoate compound, intermediate compound thereof, preparation method of the intermediate compound, and application of the macrolide benzoate compound | |
| CN102731363B (en) | Pyrrole pesticide compounds | |
| CN105646421A (en) | Sulfonate miticides containing spiro | |
| CN101205222A (en) | Total synthesis of Rocaglamide and uses thereof as insecticidal agent | |
| CN103570672A (en) | Benzoyl hydrazine compound containing thiophene ring, and preparation method and application of compound | |
| CN100567282C (en) | The preparation and the application of N-(2,3-dihydro-2,4-dimethyl benzofuran-5-acyl group)-N ＇-tertiary butyl-N ＇-(substituted benzoyl) hydrazine insecticides | |
| CN104610142B (en) | 3-bishydrazide diphenylurea derivative, and preparation method and application of 3-bishydrazide diphenylurea derivative | |
| CN105294598A (en) | Isolongifolene[1,2,3]thiadiazole compound and preparation method and application thereof | |
| CN101591295B (en) | Water-soluble benzopyrazolyl quaternary ammonium salt, preparation method thereof and application thereof | |
| CN103408482B (en) | Phenyl volution oxime ether enol ester compounds and uses thereof | |
| CN108264452A (en) | A kind of ethers Pesticidal compound with similar pyrethroid ester structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Sun Jialong Inventor after: Xue Changhui Inventor before: Sun Jialong |
|
| CB03 | Change of inventor or designer information | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150930 Termination date: 20191031 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |