CN101130525A - [inverse]-beta- farnesene analogue, preparing method and application of the same - Google Patents
[inverse]-beta- farnesene analogue, preparing method and application of the same Download PDFInfo
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- CN101130525A CN101130525A CNA2007101213344A CN200710121334A CN101130525A CN 101130525 A CN101130525 A CN 101130525A CN A2007101213344 A CNA2007101213344 A CN A2007101213344A CN 200710121334 A CN200710121334 A CN 200710121334A CN 101130525 A CN101130525 A CN 101130525A
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Abstract
The invention discloses a preparing method of inverse-beta-fanihene analogue and application, which is characterized by the following: possessing compound with structural formula as formula 1; setting Y as O or S; setting Z as O, S or NCN; possessing good chemical activity for aphid. This compound possesses big molecular weight and good stability, which can get actual utility in agricultural production.
Description
Technical field
The present invention relates to [instead]-β-farnesene analogue and preparation method thereof and using particularly a kind of [instead] of nitrogenous five-membered ring-β-farnesene analogue and preparation method thereof and this compound application in preventing eliminating aphis.
Background technology
Aphid is a class important pests of harm agricultural and forestry production in the world wide, have of a great variety, breed characteristics rapidly.It is mainly by directly getting food, propagating the plant virus dual mode farm crop of causing harm, at present known have at least 159 kinds of aphids can pass the band plant virus, occupy first of world's infection insect, control of aphids is exactly one of focus of agriculture field prevention and control of plant diseases, pest control research all the time.Particularly in the world environmental quality requirement is improved gradually in recent years and the conventional pesticides problem becomes increasingly conspicuous, make the research of aphid control agent enter a new period, based on ecology, make full use of have adjusting function, material such as aphid self excretory pheromone, become the Critical policies of the novel aphid control agent of initiative.Under this strategy instruction, owing to be based on aphid self excretory pheromone class material, advantage environmentally friendly, that be beneficial to benign ecological cycles that such control agent very likely has, simultaneously have chemical classes sterilant effect characteristics rapidly again, good application and development prospect will be arranged in the control of aphids field in future.
The aphid alarm pheromones is the volatile liquid that aphid secretes out from cornical when being subjected to external interference, it is (instead)-β-farnesene ((E)-β-farnesene that people in 1972 separate, identify its main component first, be called for short EBF), and carried out complete synthesis, this pheromone can be to the individual warning effect that produces of the same race, it is fled the scene rapidly, thereby stop infringement crop.Up-to-date result of study shows that EBF has the multi-biological activity, and except well-known warning activity, EBF also has the function that is similar to neotonin III to some insect, influences insectean metamorphosis and grows; Find further that subsequently EBF has obvious toxic action to aphid when 100ng/ aphid dosage, simultaneously trialeurodes vaporariorum is also had toxic action; In addition, EBF also has the adjusting function to the ratio of alatae and wingless aphid among the aphid offspring.But owing to have conjugated double bond in the EBF molecule, because of easy oxidation poor stability, be unfavorable for its effective utilization in actual control of aphids, therefore many scholars carry out structure of modification and modification to the EBF molecule, in the hope of finding the active compound that gets both with stability.
Existing [instead]-β-farnesene analogue was disclosed in the following document: as (Structure-activity relationships of analogs of the aphid alarm pheromone such as Bowers in 1977, (E)-β-farnesene J.Insect.Physiol.1977,23:697-701), 1986 (Somefluorine-containing pheromone analogues Pestic.Sci.1986.17:441-448) such as Briggs, (the chemical journal 1987 of insect pheromone research (intending the plain research of aphid warning) such as Li Zhengming in 1987,45 (11): 1124-1128), (the aphid alarm pheromones analogue insect journals 1988 of several biologically actives such as Zhang Zhongning in 1988,31 (4): 435-438), (Structure-activity studies on aphid alarmpheromone derivatives and their fields ude against transmission of BarleyYellow Dwarf Virus.Pestic.Sci. such as Dawson, 1988,22; 17-30), nineteen ninety-five yellow rose-tinted clouds etc. (aphid is guarded against the synthetic of plain analogue, applied chemistry 1995,12 (3): 82-84), though these documents have related to the preparation of aphid alarm pheromones [instead]-β-farnesene analogue, mainly be confined to transformation to the two keys of EBF, do not introduce heterocycle; (design of [instead]-β-farnesene analogue, synthetic and bioactivity research SCI 2004,25 (9): 1657～1661 such as the inventor in 2004; Chinese invention patent CN1544421) document and 2005 the inventor (Chinese invention patent CN1631883) document in introduced 5-member heterocyclic ring containing nitrogen imidazolidine and Liu Yuan oxadiazine ring respectively, but still need simple in structure, easily synthetic has the compound of obvious toxic action to aphid, to improve the synthetic cost of medicine, reduce the pollution of environment.
Summary of the invention
The purpose of this invention is to provide [instead]-β-farnesene analogue and preparation method thereof and the application in anti-eliminating aphis thereof.
[instead] provided by the present invention-β-farnesene analogue is the compound that contains five-membered ring, and its structural formula is formula I,
Wherein, among the formula I, Y is heteroatomss such as O or S, and Z is substituted radicals such as O, S or NCN.
Compound provided by the present invention can be prepared according to following several method:
First method: with 1-chloro-3,7-dimethyl-2,6-octadiene and structural formula in the presence of basic cpd, carry out condensation reaction suc as formula the compound shown in the II in organic solvent, obtain the compound shown in the formula I.
Wherein, among the formula II, Y is heteroatomss such as O or S, and Z is substituted radicals such as O, S or NCN.
Its reaction equation is:
(formula II) (formula I)
In the described method, the consumption of described basic cpd is a 1-chloro-3,7-dimethyl-2, and 6-octadiene and structural formula are suc as formula the 10-50% of the compound total mass shown in the II.
Second method: when the Y in the compound shown in the formula I is S, Z when being NCN, can adopt the method preparation that comprises the steps:
1) with 1-chloro-3,7-dimethyl-2,6-octadiene and mercaptoethylamine carry out condensation reaction in organic solvent in the presence of basic cpd, obtain N-(3,7-dimethyl-2,6-octadienyl) sulfur alcohol;
2) with N-(3,7-dimethyl-2,6-octadienyl) sulfur alcohol and N-cyanoimino thiocarbonic acid SOH dimethyl ester in organic solvent, carrying out condensation reaction in the presence of basic cpd, to obtain Y be that S, Z are the compound shown in the formula I of NCN.
Its reaction equation is:
In the described method, the consumption of basic cpd described in the step 1) is a reaction substrate 1-chloro-3,7-dimethyl 2, the 10-50% of 6-octadiene and mercaptoethylamine total mass; The consumption of basic cpd step 2) is the 10-50% of reaction substrate N-(3,7-dimethyl-2,6-octadienyl) sulfur alcohol and N-cyanoimino thiocarbonic acid SOH dimethyl ester total mass.
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 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.
The anti-medicine that eliminates aphis that with the The compounds of this invention is activeconstituents 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 etc.
Compound of the present invention is on the active skeleton structure of the warning that keeps aphid alarm pheromones [instead]-β-farnesene basis, introducing has five Yuans nitrogen heterocyclic ring active structures that fine chemistry kills the aphid effect, the gained compound has good chemistry to aphid and kills activity, and compare with EBF, molecular weight is big, good stability can be used in agriculture production.
Experiment showed, that compound of the present invention has tangible chemical killing aphis activity, aphid is had direct chemical prevention effect, can be prepared as the control of aphids 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
Method among the following embodiment if no special instructions, is ordinary method.
The preparation of embodiment 1, [instead]-β-farnesene analog compounds 3-(3,7-dimethyl-2,6-octadienyl)-2-carbonyl-1,3 oxazolidine
In the there-necked flask of 100mL, drop into 4.3g 2-carbonyl-1, the 3 oxazolidine (compound shown in the formula II, wherein Y is 0, and Z is 0, and the big chemical industry instrument of easypro uncle limited liability company provides by Beijing, article No. 09409-100G), 1.5g sodium hydroxide (basic cpd) and 30mL acetonitrile stir, and contain 8.3g 1-chloro-3 to wherein dripping 7mL, 7-dimethyl-2, the acetonitrile solution of 6-octadiene dropwises, in 40 ℃ of reaction 5h.Reaction solution is cooled to room temperature, with diameter is the B filtration of 10cm, washs solid with acetonitrile, after filtrate merges, solvent is sloughed in decompression, obtain red liquid, will slough the direct silicagel column of crossing of product behind the solvent then and carry out chromatographic separation (this column length is 30cm, diameter 2cm, filling silica gel is the thin layer silica gel G, produced by Qingdao Marine Chemical Co., Ltd., lot number is 0020269), be 1: 10 the ethyl acetate and the mixed solution wash-out of sherwood oil with volume ratio, the decompression precipitation is removed elutriant, obtain light yellow liquid 3.4g, be 3-(3,7-dimethyl-2, the 6-octadienyl)-2-carbonyl-1,3 oxazolidines (Y is 0 among the formula I, and Z is 0), productive rate 34%.
Through ultimate analysis, the result is: C69.87, H9.47, N6.23; Theoretical value: C69.92, H9.48, N6.27.
Its
1HNMR spectrum result is δ: 1.57-1.76 (m, 9H, 3CH
3-C=C), 2.04-2.13 (m, 4H, CH
2-CH
2-C=C), 3.34-3.85 (m, 4H, N-CH
2-CH
2-O), 4.03-4.05 (d, J=7.25Hz, 2H, C=C-CH
2-N), and 5.02-5.17 (m, 2H, 2CH=C).
Ultimate analysis and its structural formula of hydrogen spectrum digital proof are shown in formula III.
The preparation of embodiment 2, [instead]-β-farnesene analog compounds 3-(3,7-dimethyl-2,6-octadienyl)-2-thiazole thione
Prepare 3-(3,7-dimethyl-2,6-octadienyl)-2-thiazole thione according to embodiment 1 preparation method, wherein, with the 2-thiazole thione (compound shown in the formula II, wherein Y is S, Z is S, available from Beijing big chemical industry instrument of easypro uncle limited liability company, article No. M6204-100G) be that reaction raw materials substitutes 2-carbonyl-1,3 oxazolidine, solvent for use is a toluene, use the sodium hydride replace sodium hydroxide, temperature of reaction is 80 ℃, and the reaction times is 8h.
According to embodiment 1 described purification process the reaction after product is carried out purifying, obtain light yellow liquid product 5.6g, be 3-(3,7-dimethyl-2,6-octadienyl)-2-thiazole thione (Y is s among the formula I, and Z is s), productive rate is 45%.
Through ultimate analysis, the result is C61.32, H8.23, N5.45, theoretical value: C61.12, H8.29, N5.48;
Its
1HNMR spectrum result is δ: 1.61-1.76 (m, 9H, 3CH
3-C=C), 2.05-2.13 (m, 4H, CH
2-CH
2-C=C), 3.45-3.51 (m, 2H, N-CH
2), 3.84-3.88 (m, 2H, C=C-CH
2-N), 4.19-4.32 (m, 2H, CH
2-S), and 5.05-5.19 (m, 2H, 2CH=C).
Ultimate analysis and its structural formula of hydrogen spectrum digital proof are suc as formula shown in the IV.
The preparation of embodiment 3, [instead]-β-farnesene analog compounds 3-(3,7-dimethyl-2,6-octadienyl)-2-cyanoimino-1,3 thiazolidine (compound shown in the formula V)
Prepare 3-(3,7-dimethyl-2,6-octadienyl)-2-thiazole thione according to embodiment 1 preparation method, wherein, with 2-cyanoimino-1, the 3 thiazolidine (compound shown in the formula II, wherein Y is S, and Z is NCN, available from Yixing, Jiangsu chemical industry company limited, article No. 26363-65-8) for reaction raw materials substitutes 2-carbonyl-1,3 oxazolidine, solvent for use is N, dinethylformamide, used alkaline matter is a pyridine, 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 light yellow liquid product 13g, be 3-(3,7-dimethyl-2,6-octadienyl)-2-cyanoimino-1,3 thiazolidine (Y is s among the formula I, and Z is NCN), productive rate is 52.0%.
Through ultimate analysis, the result is: C63.78, H8.23, N15.89; Theoretical value: C63.84, H8.04, N15.95;
(formula V)
Its
1HNMR spectrum result is δ: δ: 1.57-1.71 (m, 9H, 3CH
3-C=C), 2.04-2.11 (m, 4H, CH
2-CH
2-C=C), 3.34-3.83 (m, 4H, N-CH
2-CH
2-S), 4.02-4.05 (d, J=7.23Hz, 2H, C=C-CH
2-N), and 5.02-5.17 (m, 2H, 2CH=C).
Ultimate analysis and its structural formula of hydrogen spectrum digital proof are suc as formula shown in the V.
The preparation of embodiment 4, [instead]-β-farnesene analog compounds 3-(3,7-dimethyl-2,6-octadienyl)-2-cyanoimino-1,3 thiazolidine (compound shown in the formula V)
In the there-necked flask of 100mL, drop into 7.8g 2-aminoothyl mercaptan, 50ml butanone and 13.0g salt of wormwood, stir, be warming up to 80 ℃, contain 17.5g 1-chloro-3,7-dimethyl-2 to wherein dripping, the 10ml butanone solution of 6-octadiene dropwises insulation reaction 4h.Reaction solution is cooled to room temperature, add N-cyanoimino thiocarbonic acid SOH dimethyl ester down at 20 ℃, room temperature reaction 3h, decompression is sloughed solvent and is obtained brown liquid, and (this column length is 30cm, diameter 2cm then the direct silicagel column excessively of this brown liquid to be carried out column chromatography for separation, filling silica gel is the thin layer silica gel G, produced by Qingdao Marine Chemical Co., Ltd., lot number is 0020269), be 1: 10 the ethyl acetate and the mixed solution wash-out of sherwood oil with volume ratio, the decompression precipitation is removed elutriant, yellow liquid 6.8g, be 3-(3,7-dimethyl-2, the 6-octadienyl)-2-cyanoimino-1,3 thiazolidines (Y is S among the formula I, and Z is NCN), weight yield is 26%.
Its
1The result is with embodiment 3 for the HNMR spectrum.
Nuclear magnetic resonance spectrum proves that its structural formula is suc as formula shown in the V.
The killing aphis of embodiment 5, The compounds of this invention is active to be detected
With the former medicine of positive control medicament thiophene worm quinoline (available from permanent field, Xi'an Chemical Industry Science Co., Ltd, lot number 20040615) and embodiment 1-3 gained compound sample be mixed with 5 concentration to be measured (1000 μ g/ml with acetone respectively, 500 μ g/ml, 250 μ g/ml, 125 μ g/ml, 62.5 μ g/ml), be that the hand-held micro-dropper of 0.0307 μ l drips to the turnip aphid back with the soup point with the drop amount, each concentration is handled 20 of aphids.Make blank with the acetone drop.Aphid after the processing is with light synthetic glass test box (the diameter 5cm that moves into fresh clean rape leave of writing brush, high 1cm) in, add preservative film, add a cover, tighten with bungee, preserve under 22 ℃ of room temperatures, reexamine death toll after 48 hours, calculate inhibiting rate (inhibiting rate=(the dead number-blank of aphid)/aphid is handled a number)
The result is as shown in table 1, and the result shows that compound of the present invention has significant lethal effect to aphid, and especially when lower concentration, the killing aphis activity of The compounds of this invention is better than contrasting medicament thiophene worm quinoline.
The compounds of this invention is to the activity test result of turnip aphid under table 1. different concns
| Compound | Inhibiting rate (%) | ||||
| 1000(μg/ml) | 500(μg/ml) | 250(μg/ml) | 125(μg/ml) | 62.5(μg/ml) | |
| The former medicine of thiophene worm quinoline | 68.3 | 56.7 | 41.7 | 25.0 | 15.2 |
| Embodiment 1 | 57.9 | 46.7 | 37.7 | 31.7 | 21.7 |
| Embodiment 2 | 60.0 | 55.9 | 50.0 | 44.8 | 41.7 |
| Embodiment 3 | 18.9 | 20.3 | 16.7 | 15.5 | 27.3 |
Claims (9)
1. structural formula is the compound of formula I,
Wherein, among the formula I, Y is O or S, and Z is O, S or NCN.
2. the preparation method of the described compound of claim 1 is in the presence of basic cpd, in organic solvent by 1-chloro-3,7-dimethyl-2,6-octadiene and structural formula carry out condensation reaction suc as formula the compound shown in the II, obtain the described compound of formula I;
Wherein, among the formula II, Y is O or S, and Z is O, S or NCN.
3. Y is the method for the compound shown in S, the Z formula I when being NCN in the preparation claim 1, comprises the steps:
1) in the presence of alkaline matter, in anhydrous organic solvent by 1-chloro-3,7-dimethyl-2,6-octadiene and mercaptoethylamine carry out condensation reaction, obtain N-(3,7-dimethyl-2,6-octadienyl) sulfur alcohol;
2) by N-(3,7-dimethyl-2,6-octadienyl) sulfur alcohol and N-cyanoimino thiocarbonic acid SOH dimethyl ester in organic solvent, in the presence of alkaline matter, carry out condensation reaction and obtain described compound.
4. according to claim 2 or 3 described methods, it is characterized in that: described alkaline matter is selected from one or more arbitrary combination in 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, butyronitrile, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N-methyl-formylaniline, N-Methyl pyrrolidone, HMPA, methyl acetate, ethyl acetate, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, just-propyl alcohol, Virahol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, one or more arbitrary combination in diethylene glycol monomethyl ether and the diethylene glycol monoethyl ether, be preferably toluene, butanone, benzene, N, dinethylformamide, one or more arbitrary combination in acetonitrile and the sherwood oil; Described organic solvents in particular is preferably toluene, N, one or more arbitrary combination in dinethylformamide, acetonitrile and the butanone.
5. method according to claim 4 is characterized in that: the temperature of described condensation reaction is-10 ℃-120 ℃; Be preferably 20 ℃-100 ℃.
6. method according to claim 5 is characterized in that: in the described method, also comprise reaction product is carried out chromatography purification.
7. the application of the described compound of claim 1 in control of aphids.
8. be the medicine of activeconstituents with the described compound of claim 1.
9. medicine according to claim 8 is characterized in that: described medicine is to be used for the anti-medicine that eliminates aphis.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103254171A (en) * | 2013-04-16 | 2013-08-21 | 中国农业大学 | Aromatic heterocyclic triazine (trans)-delta-farnesene analogue and application thereof |
| CN103858869A (en) * | 2014-03-10 | 2014-06-18 | 中国计量学院 | Method for luring Chrysopa sinica Tjeder to restrict Toxoptera aurantii Boyer by pheromones |
| JP2014525422A (en) * | 2011-09-02 | 2014-09-29 | バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー | Process for producing [3-[(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] cyanamide |
| CN104829555A (en) * | 2015-04-28 | 2015-08-12 | 中国农业大学 | (cis)-beta-farnesene analog containing 1,2,3-thiadiazole group, preparation method, and applications thereof |
| CN111233747A (en) * | 2020-02-18 | 2020-06-05 | 中国农业大学 | (trans) - β -farnesene analogue containing hydroxypiperidine, preparation and application thereof |
-
2007
- 2007-09-04 CN CNB2007101213344A patent/CN100567274C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014525422A (en) * | 2011-09-02 | 2014-09-29 | バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー | Process for producing [3-[(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] cyanamide |
| CN103254171A (en) * | 2013-04-16 | 2013-08-21 | 中国农业大学 | Aromatic heterocyclic triazine (trans)-delta-farnesene analogue and application thereof |
| CN103858869A (en) * | 2014-03-10 | 2014-06-18 | 中国计量学院 | Method for luring Chrysopa sinica Tjeder to restrict Toxoptera aurantii Boyer by pheromones |
| CN104829555A (en) * | 2015-04-28 | 2015-08-12 | 中国农业大学 | (cis)-beta-farnesene analog containing 1,2,3-thiadiazole group, preparation method, and applications thereof |
| CN111233747A (en) * | 2020-02-18 | 2020-06-05 | 中国农业大学 | (trans) - β -farnesene analogue containing hydroxypiperidine, preparation and application thereof |
| CN111233747B (en) * | 2020-02-18 | 2021-06-15 | 中国农业大学 | (trans) -beta-farnesene analogue containing hydroxypiperidine, preparation and application thereof |
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|---|---|
| CN100567274C (en) | 2009-12-09 |
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Granted publication date: 20091209 Termination date: 20160904 |