CN101402606A - Nitrogen heterocyclic ring substituted arylpropenone compounds, preparation method and application thereof - Google Patents
Nitrogen heterocyclic ring substituted arylpropenone compounds, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nitrogen heterocyclic ring substituted aryl propenone compound (formula I), a preparation method and application thereof. The structural formula of the compound is shown in the formula I, wherein in the formula I, R in X (shown as formula on the right) is H, F, Cl, Br, CH3O, C2H5O, 2, 4-dichloro, NO2 and CH3; and in the formula I, Y is 2-nitroiminoimidazolidine, 2-cyanoimino-1, 3-thiazolidine, thiazolidine and other nitrogen heterocyclic rings. The compound has excellent chemical killing activity to aphid, tetranychus cinnabarinus, diamondback moth and other harmful pests, and biological activity of partial compound is equivalent to that of control insecticides. Furthermore, compared with effective constituents of natural Stellera chamaejasma L, the compound has the advantages that the compound has simple structure and easy acquisition, and can be actually applied to agricultural production.
Description
Technical field
The present invention relates to a kind of nitrogenous heterocyclic substituted aryl acrylketone compounds and preparation method thereof, and the application of this compounds in the control harmful organism.
Background technology
Along with continuing to bring out of new heterocyclic pesticide in recent years, and the progress in field such as plant insecticide, for the research and development of novel agrochemical provide new thinking; Because the chemical structure of plant-sourced active substance is extremely various, development along with modern separation technology and spectral configuration authenticate technology, from natural active matter, seek novel chemical structure, as the guide, designing and developing the novel pesticide with unique effect mode and good environment consistency has become a kind of effective way.
Stellera chamaejasme L. (Stellera chamaejasme L.) is a thymelaeceae stellera plant, long ago people find that promptly the root of Stellera chamaejasme L. can be used for making biological pesticide-vegetable insecticide, have tag, stomach toxicity, effect such as stifling, can effectively prevent and treat cabbage caterpillar, aphid, eating-core bean worm, two-spotted spider mite, agrotis, loose high and steep moth, pine moth, pine sawfoy etc., but, and mainly concentrate on research to ethanol extraction to activeconstituents and indeterminate.Calendar year 2001 waits people such as peace and uses the normal hexane extraction Daphnetin first, isolates two kinds to the activated compound of aphid from Stellera chamaejasme L.: 1, and 5-phenylbenzene-1-pentanone (1) and 1,5-phenylbenzene-2-pentenone (2).The indoor biometrics test shows that two compounds have stronger tagging and the food refusal effect to cotten aphid and green bugs (Schizaphis gram inum).Tag in the test, compound behind the 24h (1) and (2) are to the LC of green bugs
50Be respectively 440 and 195mg/L, to the LC of cotten aphid
50Value is respectively 470 and 230mg/L; In the food refusal test, (1) and (2) food refusal rate to two kinds of aphids when 1000mg/L is respectively 50% and 70% behind the 48h.Because these two compound sources are limited, and are difficult for synthesizing, and limited their practical applications in anti-eliminating aphis, and therefore the activeconstituents in the Stellera chamaejasme L. carried out structure of modification and modification, are expected to find to have the compound of practical value.
Structure of modification about Stellera chamaejasme L. effective constituent (1) and (2), only there is one piece of document openly to report up to now, promptly 2007 (Synthesis and structure-activity study ofbotanical aphicides 1 such as Hou taiping, 5-diphenyl-1-pentanone analogues.Pesticide Biochemistryand Physiology, 2007,89:60～64) article, though the document has related to 1, the preparation of 5-phenylbenzene-1-pentanone (1) analogue, but mainly be confined to transformation to carbon chain lengths, do not introduce heterocycle, and only tested biological activity aphid; In order to adapt to the requirement of PCO under the new situation, need exploitation how simple in structure, be easy to the analogue that synthetic has obvious biological activity, with the synthetic difficulty that reduces medicine and the pollution of environment.
Summary of the invention
One of purpose of the present invention is to disclose the nitrogenous heterocyclic substituted aryl acrylketone of class compounds and preparation method thereof, and anti-eliminate aphis, application in the harmful organisms such as carmine spider mite, small cabbage moth.
Two of purpose of the present invention is the preparation methods that disclose above-mentioned analogue.
Three of the object of the invention be to disclose the above-mentioned compound of a class as directly anti-ly eliminate aphis, the application of carmine spider mite, small cabbage moth.
Provided by the present invention is nitrogenous heterocyclic substituted aryl acrylketone compounds, and its structural formula is formula I,
(formula I)
Wherein, among the formula I, X is
Wherein R is H, F, Cl, Br, CH
3O, C
2H
5O, 2,4-Cl
2, NO
2, CH
3Among the formula I, Y is:
Compound provided by the present invention can be prepared as follows:
Preparation method: furans acrylate chloride, thiophene acrylate chloride, substituted-phenyl acrylate chloride and the compound of structural formula shown in Y in the presence of basic cpd, are carried out condensation reaction in organic solvent, obtain the compound shown in the formula I.
Its reaction equation is:
In the described method, be substituted aryl acrylate chloride and structural formula 10-50% suc as formula the compound total mass shown in the Y as the consumption of the basic cpd of catalyzer.
In the described method, the compound of structural formula shown in Y is marketable material.
In the described method, described organic solvent comprises hydrocarbon or its halogenated product of aliphatics, alicyclic or aromatics: such as, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin etc.; Ethers: as ether, diisopropyl ether, tetrahydrofuran (THF) or glycol dimethyl ether or ethylene glycol diethyl ether etc.; Ketone: as acetone, butanone or mibk etc.; Nitrile: as acetonitrile, propionitrile or butyronitrile etc.; Amides: as N, dinethylformamide, N,N-dimethylacetamide, N-methyl-formylaniline, N-Methyl pyrrolidone or HMPA etc.; Ester class: as methyl acetate or ethyl acetate etc.; Sulfoxide class: as dimethyl sulfoxide (DMSO); Alcohols: as methyl alcohol, ethanol, just-or Virahol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether etc. in one or more arbitrary combination.Described organic solvent is preferably toluene, benzene, second eyeball, sherwood oil and N, one or more arbitrary combination in the dinethylformamide.
Described basic cpd is organic bases or mineral alkali, is preferably one or more arbitrary combination in piperidines, sodium hydroxide, salt of wormwood, pyridine, triethylamine, yellow soda ash, sodium methylate and the sodium hydride etc.
Above-mentioned reaction can be carried out in wide relatively temperature range, and temperature of reaction can be-10 ℃ to 120 ℃, is preferably 20 ℃ to 100 ℃.
In the described method, also comprise reaction product is carried out chromatography purification.
With the The compounds of this invention be that activeconstituents anti-eliminates aphis, the medicine of carmine spider mite, small cabbage moth also belongs to protection scope of the present invention.
In needs, can also add acceptable carrier in one or more pesticide preparation in described medicine, described carrier comprises thinner conventional in the pesticide preparation, vehicle, weighting agent, tackiness agent, wetting agent, absorption enhancer, tensio-active agent, lubricant, stablizer etc.The formulation of the medicine of making also is various, can be pulvis, emulsion, aqua, granule etc.
Compound of the present invention is on the basis of using for reference Stellera chamaejasme L. effective active composition active structure, introducing has the nitrogen heterocyclic ring active group that fine chemistry kills the anabasine pesticide such as Provado, thiophene worm quinoline of aphid effect, the gained compound has good chemistry to aphid, carmine spider mite, small cabbage moth and kills activity, and compare with Stellera chamaejasme L. effective active composition, range of application is wider, chemical structure is simple, and is active good, has more practical value in agriculture production.
Experiment showed, that compound of the present invention has tangible biological activity, aphid, carmine spider mite, small cabbage moth are had direct chemical prevention effect, can be prepared as corresponding control agent.
The method for preparing compound of the present invention, simple to operate, cost is low, and the product purification method is fairly simple.
Embodiment
The present invention can be described further with following examples, but the present invention is not limited in these embodiment, and the method among the following embodiment if no special instructions, is ordinary method.
The preparation of embodiment 1, (2E)-3-(4-fluorophenyl)-1-(2-cyanoimino-thiazolidine-3-yl)-acrylketone (A12)
In the there-necked flask of 100mL, drop into 1.27g 2-cyanoimino-thiazolidine, 1.5g piperidines and 30mL acetonitrile stir, and to the acetonitrile solution that wherein adds 2.0g 4-fluoro-phenylacrylyl chloride, dropwise, in 40 ℃ of reaction 5h again.Reaction solution is cooled to room temperature, and solvent is sloughed in decompression, obtains red liquid.The direct silicagel column of crossing of product that to slough then behind the solvent carries out chromatographic separation, elutriant is the mixed solution (V: V=1: 10) of ethyl acetate and sherwood oil, the decompression precipitation, obtain white solid 2.3g, be (2E)-3-(4-fluorophenyl)-1-(2-cyanoimino-thiazolidine-3-yl)-acrylketone (A12), productive rate 85.0%.Its
1H NMR spectrum data see Table 1.
Make the substituted aryl acrylketone compounds that other contains thiazolidine with method.
The preparation of embodiment 2, (2E)-3-(4-fluorophenyl)-1-(2-nitro imino--imidazolidine-1-yl)-acrylketone (A1)
According to embodiment 1 preparation method preparation, wherein, be that reaction raw materials substitutes 2-cyanoimino-1,3-thiazoles alkane with the 2-nitro imido imidazolyl alkane, solvent for use is DMF, substitutes piperidines with pyridine, and temperature of reaction is 80 ℃, and the reaction times is 8h.Remaining operation step is with embodiment 1.
According to embodiment 1 described purification process the reaction after product is carried out purifying, obtain white solid product 1.9g, be (2E)-3-(4-fluorophenyl)-1-(2-nitro imino--imidazolidine-1-yl)-acrylketone (A1), weight yield is 75%.Its
1H NMR spectrum sees Table 1.
Make the substituted aryl acrylketone compounds that other contains imidazolidine with method.
The preparation of embodiment 3, (2E)-3-(4-fluorophenyl)-piperidino acrylketone (A23)
According to embodiment 1 preparation method preparation, wherein, be that reaction raw materials substitutes 2-cyanoimino-1,3-thiazoles alkane with the piperidines, solvent for use is a toluene, and used alkaline matter is a sodium hydroxide, and temperature of reaction is 100 ℃, and the reaction times is 6h.
According to embodiment 1 described purification process the reaction after product is carried out purifying, obtain needle-like solid product 2.3g, be (2E)-3-(4-fluorophenyl)-piperidino acrylketone (A23), productive rate is 92.0%.Its
1H NMR spectrum the results are shown in Table 1.
Make the substituted aryl acrylketone compounds that other contains piperidines with method.
Listed formula I compound structure, fusing point and hydrogen spectrum data below in the table-1, they all are according to being similar to the prepared in various methods shown in the previous embodiment.
Table-1 formula I structural formula of compound and hydrogen spectrum data
The killing aphis activity of embodiment 4, The compounds of this invention
Use ten thousand/balance to take by weighing 12mg (folding hundred) compound sample respectively former medicine of positive control medicament Provado (providing) and embodiment 1-3 gained compound sample by the long Longhua worker in Jiangsu limited liability company in the 20ml weighing bottle, get 2ml acetone/methanol (1: 1) mixed solvent with 1～5ml liquid-transfering gun again and add weighing bottle, after treating that it fully dissolves, adding 18ml contains the aqueous solution of 0.1% tween-80, abundant mixing, the mensuration liquid of 600 μ g/mL.Select tape aphid Leaf of Shrubalthea stays 3 ages in days if aphid will be with the aphid blade to flood 5s in soup, dries back record borer population and puts into the culture dish that is added with the filter paper of preserving moisture, and puts into (25 ± 1) ℃ illumination box after adding a cover.Each chemicals treatment is more than 30.Check result after 48 hours.Dead judging criterion is: touch polypide, the insect individuality that can not normally creep is considered as dead calculation correction mortality ratio.The result is shown in table-2, the result shows that under test concentrations, compound of the present invention has tangible lethal effect to aphid, part of compounds has significant lethal effect to aphid, judges that tentatively this compounds is the novel aphid control agent with applications well prospect.
Table-2 formula I compounds are to the insecticidal activity of cotten aphid
The acaricidal activity of embodiment 5, The compounds of this invention detects
Use ten thousand/balance to take by weighing 12mg (folding hundred) compound sample respectively positive control medicament pyridaben (providing) and embodiment 1-3 gained compound sample by medicine inspecting institute of the Ministry of Agriculture in the 20ml weighing bottle, get 2ml acetone/methanol (1: 1) mixed solvent with 1～5ml liquid-transfering gun again and add weighing bottle, after treating that it fully dissolves, adding 18ml contains the aqueous solution of 0.1% tween-80, abundant mixing, the mensuration liquid of 600 μ g/mL.With method join pyridaben 50 μ g/mL.The beans leaf of the carmine spider mite of having transferred is flooded 5s in soup, dry back record borer population and put into the culture dish that is added with the filter paper of preserving moisture, petiole is preserved moisture with the cotton of preserving moisture, and puts into (25 ± 1) ℃ illumination box after adding a cover.Each chemicals treatment is more than 20.Check result after 48 hours.Dead judging criterion is: touch polypide, the insect individuality that can not normally creep is considered as death.The result is shown in table-3, and the result shows that under test concentrations, part of compounds of the present invention has tangible lethal effect to carmine spider mite, judges that tentatively this compounds is the novel acarid control agent with applications well prospect.
Table-3 formula I compounds are to the insecticidal activity of carmine spider mite
Embodiment 6, The compounds of this invention are to the biological activity assay of small cabbage moth
With positive control medicament 90.4% pleocidin (providing) and embodiment 1-3 gained compound sample by the farming of Tao Shi benefit respectively with taking by weighing 12mg (rolling over hundred) compound sample in the 20ml weighing bottle with ten thousand/balance, get 2mL acetone/methanol (1: 1) mixed solvent with 1～5mL liquid-transfering gun again and add weighing bottle, after treating that it fully dissolves, adding 18ml contains the aqueous solution of 0.1% tween-80, abundant mixing, the mensuration liquid of 600 μ g/mL.With method join pleocidin 10 μ g/mL.With the punch tool device clean cabbage leaves is broken into diameter 2cm leaf dish, in soup, flood 5s, dry posterior lobe and put into the diameter 6cm culture dish that is added with the filter paper of preserving moisture on dorsad, insert 10 of small cabbage moth 2 instar larvaes, put into (27 ± 1) ℃ illumination box after adding a cover.Check result after 72 hours.Dead judging criterion is: touch polypide, the insect individuality that can not normally creep is considered as death.The result is shown in table-4, and the result shows that under test concentrations, part of compounds of the present invention has tangible lethal effect to small cabbage moth, judges that tentatively this compounds has a good application prospect to small cabbage moth.
Table-4 formula I compounds are to the insecticidal activity of small cabbage moth
Claims (10)
1, structural formula is the nitrogenous heterocyclic substituted aryl acrylketone compounds of formula I,
Wherein, among the formula I, X is
2, the preparation method of the described compound of claim 1 is in the presence of basic cpd, in that the compound shown in Y carries out condensation reaction by substituted aryl acrylate chloride and structural formula in the organic solvent, obtains the described compound of formula I;
3, method according to claim 2 is characterized in that: described alkaline matter is selected from one or more arbitrary combination in piperidines, sodium hydroxide, salt of wormwood, pyridine, triethylamine, yellow soda ash, sodium methylate or the sodium hydride; Described organic solvent is selected from benzene, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin, ether, diisopropyl ether, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, acetone, butanone, mibk, acetonitrile, propionitrile or butyronitrile, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N-methyl-formylaniline, N-Methyl pyrrolidone or HMPA, methyl acetate, ethyl acetate, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, just-propyl alcohol, Virahol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, one or more arbitrary combination in the diethylene glycol monoethyl ether, be preferably toluene, butanone, benzene, N, dinethylformamide, acetonitrile or sherwood oil; Described organic solvents in particular is preferably toluene, N, dinethylformamide, acetonitrile, butanone.
4, method according to claim 3 is characterized in that: the temperature of described condensation reaction is-10 ℃-120 ℃; Be preferably 20 ℃-100 ℃.
5, method according to claim 4 is characterized in that: in the described method, also comprise reaction product is carried out chromatography purification.
6, the application of the described compound of claim 1 in control of aphids.
7, the application of the described compound of claim 1 in the carmine spider mite control.
8, the application of the described compound of claim 1 in the small cabbage moth control.
9, be the medicine of activeconstituents with the described compound of claim 1.
10, medicine according to claim 9 is characterized in that: described medicine be used for anti-eliminating aphis, the medicine of carmine spider mite, small cabbage moth.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163008A (en) * | 2017-04-25 | 2017-09-15 | 西华大学 | The oxoethanol ramification of carboxylic esters of 2 { [(3 heterocyclic radical) acryloyl group] phenyl } amino 2 and its application |
| CN114394922A (en) * | 2022-01-26 | 2022-04-26 | 河南农业大学 | Preparation method of N-substituted pyrrolyl aryl propenone compound |
-
2008
- 2008-11-25 CN CNA2008102272382A patent/CN101402606A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163008A (en) * | 2017-04-25 | 2017-09-15 | 西华大学 | The oxoethanol ramification of carboxylic esters of 2 { [(3 heterocyclic radical) acryloyl group] phenyl } amino 2 and its application |
| CN107311966A (en) * | 2017-04-25 | 2017-11-03 | 西华大学 | Hydroxyl acetamide analog derivative of N [(3 heterocyclic radical) acryloyl group] phenyl 2 and its preparation method and application |
| CN107311965A (en) * | 2017-04-25 | 2017-11-03 | 西华大学 | Alkoxypropionamide derivative of N [(3 heterocyclic radical) acryloyl group] phenyl 3 and its preparation method and application |
| CN107311966B (en) * | 2017-04-25 | 2019-04-09 | 西华大学 | N- [ (3-heterocyclic group) acryloyl ] phenyl-2-hydroxyacetamide derivative and preparation method and application thereof |
| CN107311965B (en) * | 2017-04-25 | 2019-05-21 | 西华大学 | N- [ (3-heterocyclic group) acryloyl ] phenyl-3-alkoxy propionamide derivative and preparation method and application thereof |
| CN114394922A (en) * | 2022-01-26 | 2022-04-26 | 河南农业大学 | Preparation method of N-substituted pyrrolyl aryl propenone compound |
| CN114394922B (en) * | 2022-01-26 | 2024-06-11 | 河南农业大学 | Preparation method of N-substituted pyrrolyl aryl propenone compound |
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