CN102633740A - Anabasine compound, preparation method and application of nabasine compound - Google Patents
Anabasine compound, preparation method and application of nabasine compound Download PDFInfo
- Publication number
- CN102633740A CN102633740A CN2012100491748A CN201210049174A CN102633740A CN 102633740 A CN102633740 A CN 102633740A CN 2012100491748 A CN2012100491748 A CN 2012100491748A CN 201210049174 A CN201210049174 A CN 201210049174A CN 102633740 A CN102633740 A CN 102633740A
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- anabasine
- preparation
- anabasine 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.)
- Pending
Links
- 0 CC(N(*)*C1SC(Cl)=NC1)=* Chemical compound CC(N(*)*C1SC(Cl)=NC1)=* 0.000 description 1
Images
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention discloses an anabasine compound, a preparation method and the application of the nabasine compound. The preparation method of the anabasine compound comprises the steps of: carrying out a reaction on 2-chlorine-5-methylthiazole and NH2R1; and then, carrying out a reaction on the obtained product, NH2R2 and 1,1-dichloro-nitro-ethylene or 1,1,1-trichloro-nitroethane under the condition that alkali exists to obtain the anabasine compound, wherein R1 is C1-10 alkyl group, C2-4 cyano-group, C2-4 alkenyl or C3-6 naphthenic base; and R2 is C1-10 alkoxy, C2-4 alkenyl, C3-6 naphthenic base or C3-6 heterocyclic ring. The anabasine compound has the advantages of high insecticidal activity, low toxicity, wide insecticidal spectrum and the like, and has obvious effect of killing insects such as plant hoppers, stem borers, aphids and the like.
Description
Technical field
The present invention relates to a kind of organic cpds, be specifically related to a kind of anabasine compound.
Background technology
The first-generation anabasine insecticide that with the Provado is representative has been used nearly 20 years, has produced resistance, and insecticidal activity is not high; On the other hand, the Provado insecticidal spectrum is narrower, does not all have insecticidal activity for snout moth's larva and aphid etc., and using has certain limitation.
Mainly still adopt the high malicious sterilant of organic phosphates and prevent and treat snout moth's larva at present, like triazophos, Chlorpyrifos 94 etc., these sterilants all have certain hazardness for environment and people.
Summary of the invention
One of the object of the invention is to provide the anabasine compound that a kind of insecticidal activity is higher, toxicity is lower, particularly snout moth's larva is had the better prevention effect.
Two of the object of the invention is to provide the preparation method of above-mentioned anabasine compound.
Three of the object of the invention is to provide the application of above-mentioned anabasine compound.
The technical scheme that realizes one of the object of the invention is: a kind of anabasine compound has following logical formula I:
（Ⅰ）
In the formula I: R
1Be C
1-10Alkyl, C
2-4Cyanic acid, C
2-4Thiazolinyl or C
3-6Naphthenic base; R
2Be C
1-10Alkoxyl group, C
2-4Thiazolinyl, C
3-6Naphthenic base or C
3-6Heterocycle.
Two the technical scheme that realizes the object of the invention is: the preparation method of above-mentioned anabasine compound has following steps:
1. generate the compound of formula II by the compound reaction of 2-chloro-5-methylthiazol and formula III;
2. by 1,1-dichloro nitroethylene or 1,1, the compound of 1-three chloronitroethanes and formula IV and the compound of the formula II that 1. step obtains react the anabasine compound that obtains formula I in the presence of alkali;
The compound of said formula II is
;
The compound of said formula III is NH
2R
1R wherein
1Be C
1-10Alkyl, C
2-4Cyanic acid, C
2-4Thiazolinyl or C
3-6Naphthenic base;
The compound of said formula IV is NH
2R
2R wherein
2Be C
1-10Alkoxyl group, C
2-4Thiazolinyl, C
3-6Naphthenic base or C
3-6Heterocycle.
Above-mentioned steps temperature of reaction 1. is 0 ℃～100 ℃, preferred 0 ℃～60 ℃.
The mol ratio of the compound of 1. middle 2-chloro-5-methylthiazol of above-mentioned steps and formula III is 1: 1～1: 5, preferred 1: 3.
Above-mentioned steps reaction 1. can also be carried out in the presence of phase-transfer catalyst; Phase-transfer catalyst is a kind of in Tetrabutyl amonium bromide, triethyl benzyl ammonia chloride, triethyl benzyl brometo de amonio, palmityl trimethyl ammonium chloride or the cetyl trimethylammonium bromide, preferred Tetrabutyl amonium bromide.
Above-mentioned steps temperature of reaction 2. is 0 ℃～100 ℃, preferred 0 ℃～60 ℃.
Above-mentioned steps 2. in 1,1-dichloro nitroethylene or 1,1, the mol ratio of the compound of 1-three chloronitroethanes and formula IV and the compound of formula II is (1.1～1.3): (1.2～1.5): 1, preferred 1.1: 1.25: 1.
The alkali of above-mentioned steps described in 2. is Pottasium Hydroxide, sodium hydroxide, salt of wormwood, yellow soda ash, triethylamine, N, accelerine or pyridine, preferred salt of wormwood or triethylamine.
Three the technical scheme that realizes the object of the invention is: the application of above-mentioned anabasine compound on the preparation sterilant.
Above-mentioned anabasine compound is for preparing sterilant separately or being mixed with sterilant with pyrethrin, carbamate chemicals for agriculture, organophosphorus insecticide or Avermectins agricultural chemicals; When being mixed with sterilant, the weight percent of said anabasine compound is 0.1%～99.9%.
Prepared sterilant is used for preventing and treating cotten aphid, cigarette aphid, rice lice, thrips, leaf moth and the snout moth's larva of farm crop; Said farm crop are cotton, corn, wheat, paddy rice, fruit tree, flowers or vegetables.
The positively effect that the present invention has: (1) anabasine compound of the present invention has advantages such as the high and low poison of insecticidal activity, insecticidal spectrum be wide.(2) anabasine compound of the present invention all has obvious insecticidal effect for plant hopper, snout moth's larva and aphid etc.
Description of drawings
The nmr spectrum of (E)-N-that Fig. 1 makes for embodiment 1 [(2-chloro-thiazole) methyl]-N-ethyl-N '-methoxyl group-2-nitro vinylidene diamines.
Embodiment
(embodiment 1)
The anabasine compound of present embodiment is (E)-N-[(2-chloro-thiazole) methyl]-N-ethyl-N '-methoxyl group-2-nitro vinylidene diamines.Its structural formula is following:
The preparation method of this anabasine compound has following steps:
1. in the four-hole bottle of 500mL, add the 2-chloro-5-5-chloromethyl thiazole (0.2mol) of 33.6g and the chloroform of 100mL; Add the Tetrabutyl amonium bromide of 0.5g～1.0g and the ethylamine solution (0.6mol) that 38.6g concentration is 70wt% then, be warming up to back flow reaction 4h～5h under stirring.Sampling gas chromatographic analysis to 2-chloro-5-5-chloromethyl thiazole all transforms, and is cooled to 20 ℃, adds the water of 100mL; Stir 20min, leave standstill, divide oil-yielding stratum; Water layer merges oil reservoir with chloroform extraction 3 times, and washing is to neutral; Obtain N-(the 2-chloro-5-thiazole) methyl-N-ethamine of 33.45g behind the precipitation, content is 95%, and yield is 90%.
2. in the four-hole bottle of 500mL, add 1 of 31.24g; The methylene dichloride of 1-dichloro nitroethylene (0.22mol) and 100ml; Be cooled to the dichloromethane solution that drips N-(the 2-chloro-5-thiazole) methyl-N-ethamine (0.2mol) that contains 35.3g when reacting liquid temperature is 0～10 ℃; Adding continued Dropwise 5 4g concentration under this temperature is the 40wt% wet chemical, adds the back in 10 ℃ of insulation 2h.Sampling liquid-phase chromatographic analysis to N-(2-chloro-5-thiazole) methyl-N-ethamine transformation efficiency reaches more than 98%, and continuation adds the back at 15～25 ℃ of reaction 5h～6h at the methoxamine hydrochloride aqueous solution (0.25mol) that 5～10 ℃ of Dropwise 5 3g concentration are 40wt%; Leave standstill, divide oil-yielding stratum, water layer is with dichloromethane extraction 3 times; Merge oil reservoir, drying, precipitation; In the raffinate that obtains, add the ethyl acetate/petroleum ether mixed solvent (volume ratio of ETHYLE ACETATE and sherwood oil is 1: 3) of 50mL, fully stir, be cooled to 5 ℃ of crystallization 2h; Filter out crystal; Obtain (E)-N-[(2-chloro-thiazole) methyl]-N-ethyl-N '-methoxyl group-2-nitro vinylidene diamines of 40.3g, content is 96%, and yield is 70%.
The nmr spectrum of (E)-N-that present embodiment makes [(2-chloro-thiazole) methyl]-N-ethyl-N '-methoxyl group-2-nitro vinylidene diamines is seen Fig. 1.
(embodiment 2)
Present embodiment and embodiment 1 are basic identical; Difference is: 2. step adopts triethylamine to replace salt of wormwood; The result obtains 41.05g's (E)-N-[(2-chloro-thiazole) methyl]-N-ethyl-N '-methoxyl group-2-nitro vinylidene diamines, and content is 97%, and yield is 72%.
(embodiment 3)
The step of present embodiment is 1. identical with embodiment 1, and 2. step is:
In the four-hole bottle of 500mL, add 1 of 39.3g; 1; The trichloromethane of 1-three chloronitroethanes (0.22mol) and 100mL, be cooled to reacting liquid temperature when being 0～5 ℃ Dropwise 35 .5g concentration be the wet chemical of 40wt%, add the back and stir 2h; Under this temperature, drip the dichloromethane solution of N-(the 2-chloro-5-thiazole) methyl-N-ethamine (0.2mol) that contains 35.3g then, add the back and stir 3h in 10 ℃.The sampling liquid-phase chromatographic analysis all transforms to N-(2-chloro-5-thiazole) methyl-N-ethamine, and Dropwise 5 3g concentration is the methoxamine hydrochloride aqueous solution (0.25mol) of 40wt% under this temperature, and using concentration to be neutralized to pH as the KOH solution of 30wt% then is 9; And under this temperature, reacting 1h, (15～25 ℃) reaction 4h leaves standstill again at ambient temperature; Divide oil-yielding stratum, water layer is with dichloromethane extraction 3 times, merging oil reservoir; Using diluted acid that oil reservoir is transferred to the pH value is 6～7, drying, precipitation; In the raffinate that obtains, add the ethyl acetate/petroleum ether mixed solvent (volume ratio of ETHYLE ACETATE and sherwood oil is 1: 3) of 50mL, fully stir, be cooled to 5 ℃ of crystallization 2h; Filter out crystal; Obtain (E)-N-[(2-chloro-thiazole) methyl]-N-ethyl-N '-methoxyl group-2-nitro vinylidene diamines of 39.58g, content is 95%, and yield is 68%.
(application examples)
Use anabasine compound that embodiment 1 makes as sterilant, and carry out indoor biological activity determination, the result is following:
(1) brown paddy plant hopper indoor measurement result is shown: when the concentration of this anabasine compound was 1mg/L, killing rate was 100%.
(2) striped rice borer indoor measurement result is shown: when the concentration of this anabasine compound was 200mg/L, killing rate was 77%.
(contrast Application example)
Use Provado as sterilant, and carry out indoor biological activity determination, the result is following:
(1) brown paddy plant hopper indoor measurement result is shown: when the concentration of Provado during up to 10mg/L, killing rate is merely 80%.
(2) striped rice borer indoor measurement result is shown: when the concentration of Provado was similarly 200mg/L, killing rate was 0, explained that Provado does not have insecticidal activity to striped rice borer.
Claims (10)
1. anabasine compound is characterized in that having following logical formula I:
（Ⅰ）
In the formula I: R
1Be C
1-10Alkyl, C
2-4Cyanic acid, C
2-4Thiazolinyl or C
3-6Naphthenic base; R
2Be C
1-10Alkoxyl group, C
2-4Thiazolinyl, C
3-6Naphthenic base or C
3-6Heterocycle.
2. the preparation method of the described anabasine compound of claim 1 is characterized in that having following steps:
1. generate the compound of formula II by the compound reaction of 2-chloro-5-methylthiazol and formula III;
2. by 1,1-dichloro nitroethylene or 1,1, the compound of 1-three chloronitroethanes and formula IV and the compound of the formula II that 1. step obtains react the anabasine compound that obtains formula I in the presence of alkali;
The compound of said formula II is
;
The compound of said formula III is NH
2R
1R wherein
1Be C
1-10Alkyl, C
2-4Cyanic acid, C
2-4Thiazolinyl or C
3-6Naphthenic base;
The compound of said formula IV is NH
2R
2R wherein
2Be C
1-10Alkoxyl group, C
2-4Thiazolinyl, C
3-6Naphthenic base or C
3-6Heterocycle.
3. the preparation method of anabasine compound according to claim 2, it is characterized in that: step temperature of reaction 1. is 0 ℃～100 ℃.
4. the preparation method of anabasine compound according to claim 2 is characterized in that: step 1. in the mol ratio of compound of 2-chloro-5-methylthiazol and formula III be 1: 1～1: 5.
5. the preparation method of anabasine compound according to claim 2, it is characterized in that: step temperature of reaction 2. is 0 ℃～100 ℃.
6. the preparation method of anabasine compound according to claim 2; It is characterized in that: step 2. in 1; 1-dichloro nitroethylene or 1; 1, the mol ratio of the compound of 1-three chloronitroethanes and formula IV and the compound of formula II is (1.1～1.3): (1.2～1.5): 1.
7. the preparation method of anabasine compound according to claim 2 is characterized in that: the alkali of step described in 2. is Pottasium Hydroxide, sodium hydroxide, salt of wormwood, yellow soda ash, triethylamine, N, accelerine or pyridine.
8. the application of the described anabasine compound of claim 1 on the preparation sterilant.
9. application according to claim 8; It is characterized in that: said anabasine compound is for preparing sterilant separately or being mixed with sterilant with pyrethrin, carbamate chemicals for agriculture, organophosphorus insecticide or Avermectins agricultural chemicals; When being mixed with sterilant, the weight percent of said anabasine compound is 0.1%～99.9%.
10. according to Claim 8 or 9 described application, it is characterized in that: prepared sterilant is used for preventing and treating cotten aphid, cigarette aphid, rice lice, thrips, leaf moth and the snout moth's larva of farm crop; Said farm crop are cotton, corn, wheat, paddy rice, fruit tree, flowers or vegetables.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100491748A CN102633740A (en) | 2012-02-29 | 2012-02-29 | Anabasine compound, preparation method and application of nabasine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100491748A CN102633740A (en) | 2012-02-29 | 2012-02-29 | Anabasine compound, preparation method and application of nabasine compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102633740A true CN102633740A (en) | 2012-08-15 |
Family
ID=46618335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100491748A Pending CN102633740A (en) | 2012-02-29 | 2012-02-29 | Anabasine compound, preparation method and application of nabasine compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102633740A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103004773A (en) * | 2012-12-25 | 2013-04-03 | 江苏省农用激素工程技术研究中心有限公司 | Insecticidal composition |
| CN107474022A (en) * | 2017-09-07 | 2017-12-15 | 连云港立本作物科技有限公司 | Thiazolyl anabasine compound and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031079A (en) * | 1987-08-01 | 1989-02-15 | 武田药品工业株式会社 | α-unsaturated amine, its production method and application thereof |
-
2012
- 2012-02-29 CN CN2012100491748A patent/CN102633740A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031079A (en) * | 1987-08-01 | 1989-02-15 | 武田药品工业株式会社 | α-unsaturated amine, its production method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103004773A (en) * | 2012-12-25 | 2013-04-03 | 江苏省农用激素工程技术研究中心有限公司 | Insecticidal composition |
| CN107474022A (en) * | 2017-09-07 | 2017-12-15 | 连云港立本作物科技有限公司 | Thiazolyl anabasine compound and its preparation method and application |
| CN107474022B (en) * | 2017-09-07 | 2020-06-26 | 连云港立本作物科技有限公司 | Thiazolyl neonicotine compound and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103068814B (en) | Anthranilic acid derivative | |
| CN103119034B (en) | Heterocyclic compound as pest control agent | |
| JP6867299B2 (en) | Fertilizer pesticide preparation | |
| CN102090412B (en) | Ferulic acid and ferulic acid derivative anti-phytoviral agents | |
| CN103221397B (en) | For preventing and treating novel composition and the method for nematode pests | |
| CN104557709A (en) | Pyrazole amide compound containing diphenyl ether, and application and pesticide composition of pyrazole amide compound | |
| EA028392B1 (en) | Compositions and methods for controlling nematodes | |
| RO116548B1 (en) | 5-amino-4-ethyl sulphinylpyrrazole derivatives, process for preparing the same, intermediate and pesticide composition | |
| CN105101800A (en) | Heterocyclic compounds as pesticides | |
| CN103265527A (en) | Anthranilamide compound as well as preparation method and application thereof | |
| CN105517995A (en) | Six-membered c-n-linked aryl sulfide derivatives and aryl sulfoxide derivatives as pest control agents | |
| CN103214461B (en) | Quinoline derivative and application thereof | |
| CN109503562B (en) | 2- [4- (2-thienyl) ] pyrimidyl urea derivative and preparation method and application thereof | |
| CN102633740A (en) | Anabasine compound, preparation method and application of nabasine compound | |
| CN101723943A (en) | 1,3,4-thiadiazole fluorouracil compound as well as preparation method and application thereof | |
| CN102229600B (en) | Cis-neonicotinoid compound containing 1, 4-dihydropyridine ring and its preparation method and application | |
| CN104488900B (en) | A kind of complex composition of the azoles of bacterium containing methylsulfonyl and anabasine insecticide | |
| KR20000076074A (en) | Pesticidal 1-arylpyrazoles | |
| BR102013027162B1 (en) | METAL AND NARINGIN AND NARINGENIN COMPLEXES AND INSETICATED COMPOSITIONS FOR THE CONTROL OF URBAN PEST INSECTS, AGRICULTURE AND FORESTRY FIELD OF THE INVENTION | |
| CN1199563C (en) | 5-acylanilino-2,4-di(trifluoride) thiazole and use for preventing and controlling rice blast | |
| CN103283768B (en) | A kind of pesticide composition containing triticonazole | |
| BR102012031380A2 (en) | METHOD FOR PREPARATION OF HESPERIDINE AND HESPERITIN METAL COMPLEXES, METAL COMPLEXES AND INSECTICATED COMPOSITIONS FOR THE CONTROL OF URBAN PEST INSECTS, AGRICULTURE AND FORESTRY | |
| CN105820668A (en) | HZSN.J absorption-resistant film agent for preventing and controlling rice planthoppers and preparation method thereof | |
| CN106748979B (en) | A kind of 2,4,6- trichlorophenyl pyridine ethyl ether plant growth regulator | |
| CN105254625A (en) | Compound containing chloro-thiazolyl benzamide 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 | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120815 |