CN101863828B - 3, 5, 6-three-halogenated pyridyl ethers compound and application thereof - Google Patents
3, 5, 6-three-halogenated pyridyl ethers compound and application thereof Download PDFInfo
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- CN101863828B CN101863828B CN2009100818584A CN200910081858A CN101863828B CN 101863828 B CN101863828 B CN 101863828B CN 2009100818584 A CN2009100818584 A CN 2009100818584A CN 200910081858 A CN200910081858 A CN 200910081858A CN 101863828 B CN101863828 B CN 101863828B
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Abstract
The invention discloses a 3, 5, 6-three-halogenated pyridyl ethers compound which is shown in general formula I, wherein R1, R2 and R3 are selected from F, Cl, Br or I; and n= 0, 1, 2, 3 or 4. The general formula I has excellent insecticidal activity and can be used for pest control.
Description
Technical field
The invention belongs to field of pesticides, be specifically related to a kind of 3,5,6-three haloperidid pyridyl ethers compound and application thereof.
Background technology
Because sterilant is in use for some time, insect can produce resistance to it, therefore, need constantly invention novel with compound and compsn improved tool insecticidal activity.Simultaneously, Along with people's also needs lower, the environment amenable new sterilant of use cost to growing needs such as agricultural and animal products with to the pay attention to day by day of environment protection always.
Some one or dihalo pyridyl ethers compounds and be disclosed as the application of sterilant, for example CN101337940A discloses following compounds (KC
1) preparation and insecticidal activity, under the concentration of 100ppm, be more than 90% to the mythimna separata preventive effect:
So far, in the prior art as shown in the present 3,5, the preparation of 6-three haloperidid pyridyl ethers compounds and insecticidal activity thereof are not seen open.
Summary of the invention
The object of the present invention is to provide 3,5 of a kind of novel structure, 6-three haloperidid pyridyl ethers compounds, it can be applicable to the control of insect pest on agricultural, forestry or the health.
Technical scheme of the present invention is following:
The invention provides a kind of 3,5,6-three haloperidid pyridyl ethers compounds, shown in general formula I:
In the formula:
R
1, R
2, R
3Can be identical or different, be selected from F, Cl, Br or I respectively;
N=0,1,2,3 or 4.
Further preferred compound does among the present invention, in the general formula I:
R
1, R
2, R
3Can be identical or different, be selected from F or Cl respectively;
N=0,1,2,3 or 4.
Take all factors into consideration factors such as synthetic easy, with low cost and environmental, further preferred compound does among the present invention, in the general formula I: R
1, R
2, R
3Be selected from Cl; N=1.Be the following compound of structural formula:
Compound of Formula I of the present invention can be by following method preparation, and reaction formula formula of II compounds X is selected from halogen, and other each group definition are the same.
General formula I I compound and compound of formula III in The suitable solvent, suitable alkali down, temperature is-10 ℃ and reacts under the boiling point and made target compound I in 0.5-48 hour.
The suitable solvent is selected from methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, ETHYLE ACETATE, acetonitrile, THF, dioxane, N, dinethylformamide or DMSO 99.8MIN. etc.
Suitable alkali comprises the hydrogenate such as the sodium hydride of basic metal such as lithium, sodium or potassium, and the oxyhydroxide of basic metal such as lithium, sodium or potassium such as sodium hydroxide can also be alkali-metal carbonate such as yellow soda ash, also can be organic bases such as triethylamine or sodium tert-butoxide etc.
The preparation method of compound of formula III is referring to CN101337940A (embodiment 1 and 4).
Table 1 has been listed the structure and the physical properties of part compound of Formula I.
The structure and the physical properties of table 1 part compound of Formula I
| Compound | R 1 | R 2 | R 3 | n | Outward appearance (fusing point (℃) |
| 1 | Cl | Cl | Cl | 0 | White solid (103-106) |
| 2 | Cl | Cl | Cl | 1 | Yellow oil |
| 3 | Cl | F | F | 1 | Yellow oil |
| 4 | Cl | Cl | Cl | 2 | Yellow oil |
Part of compounds
1H NMR (300MHz, CDCl
3) and
19F NMR (300MHz, CDCl
3) data are following:
Compound 1:
1H NMR 4.35-4.38 (m, 2H), 4.59 (d, 2H), 4.72-4.75 (m, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.74 (s, 1H).
Compound 2:
1H NMR 2.30-2.34 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.65 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.72 (s, 1H).
Compound 3:
1H NMR 2.27-2.35 (m, 2H), 4.13 (t, 2H), 4.58 (d, 2H), 4.63 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.50 (t, 1H).
19F?NMR-142.3(1F)，-78.6(1F)。
Compound 4:
1H NMR 1.98-2.11 (m, 4H), 4.03 (t, 2H), 4.58 (d, 2H), 4.65 (t, 2H), 6.12 (t, 1H), 6.83 (s, 2H), 7.70 (s, 1H).
Compare with known pair of haloperidid pyridyl ethers compound, three haloperidid pyridyl ethers compounds of the present invention have beyond thought high insecticidal activity.Therefore, the present invention comprises that also compound of Formula I is useful on the purposes of control insect pest.
The starting raw material of three chloro pyridyl ethers compounds of the present invention is a 4 chloro pyridine.4 chloro pyridine is the midbody of synthetic pesticide Chlorpyrifos 94, scale operation at present, and cost is significantly less than fluorinated pyridine.Therefore the synthetic cost of three chloro pyridyl ethers compounds of the present invention is more cheap.Thereby can realize with lower cost, reach the purpose of important disease and pest on control agricultural, forestry, the health.
The present invention also comprises with the insect-killing composition of compound of Formula I as active ingredient.The weight percentage of active ingredient is between 1-99% in this insect-killing composition.Also comprise acceptable carrier on agricultural, forestry, the health in this insect-killing composition.
Compsn of the present invention can preparation administered.Compound of Formula I is as solubilization of active ingredient or be scattered in the carrier or be mixed with preparation so that be easier to disperse when using as sterilant.For example: these chemicals can be made into wettable powder or missible oil.In these compsns, add a kind of liquid or solid carrier at least, and when needing, can add suitable tensio-active agent.
Technical scheme of the present invention also comprises the method for pest control: insect-killing composition of the present invention is imposed on described insect or its growth medium.Usually the comparatively suitable significant quantity of selecting is that per hectare 10 restrains 1000 grams, and preferred significant quantity is that per hectare 100 restrains 1000 grams.
Use for some, for example, can produce additional advantage and effect thus can in insect-killing composition of the present invention, adding one or more other sterilant, Insecticides (tech) & Herbicides (tech), plant-growth regulator or fertilizer etc. on the agricultural.
Should be clear and definite be in claim of the present invention institute restricted portion, can carry out various conversion and change.
Embodiment
Following synthetic instance, living test are tested the result and can be used to further specify the present invention, but do not mean that restriction the present invention.
Synthetic instance
The preparation of instance 1, compound 1
In reaction flask, add 5 milliliters of THFs and 2-(2,6-two chloro-4-(3,3-two chloro-allyloxys) phenoxy) ethanol (0.66 gram, 2 mmoles; Embodiment 1 and 4 among the compound method referenced patent CN101337940A), is stirred to dissolving under the room temperature, adds sodium hydride (0.17 gram, 4.2 mmoles); Stir after 2 hours, add 2,3,5; 6-4 chloro pyridine (0.43 gram, 2 mmoles) continues reaction after 3 hours, in reaction solution impouring 50 ml waters under the room temperature; With 3 * 50 milliliters of ethyl acetate extractions, organic layer is respectively with saturated sodium bicarbonate solution, saturated nacl aqueous solution washing, and anhydrous magnesium sulfate drying reduces pressure and steams solvent to the greatest extent.Resistates is through column chromatography purification (leacheate: ETHYLE ACETATE: sherwood oil=1: 40) obtain 0.66 gram white solid, yield 64%, fusing point: 103～106 ℃.
The preparation of instance 2, compound 2
In reaction flask, add 5 milliliters of THFs and 3-(2,6-two chloro-4-(3,3-two chloro-allyloxys) phenoxy) third-1-alcohol (0.35 gram, 1 mmole; Embodiment 1 and 4 among the compound method referenced patent CN101337940A), is stirred to dissolving under the room temperature, adds sodium hydride (0.08 gram, 2.1 mmoles); Stir after 2 hours, add 2,3,5; 6-4 chloro pyridine (0.22 gram, 1 mmole) continues reaction after 5 hours, in reaction solution impouring 50 ml waters under the room temperature; With 3 * 50 milliliters of ethyl acetate extractions, organic layer is respectively with saturated sodium bicarbonate solution, saturated nacl aqueous solution washing, and anhydrous magnesium sulfate drying reduces pressure and steams solvent to the greatest extent.Resistates is through column chromatography purification (leacheate: ETHYLE ACETATE: sherwood oil=1: 20) get 0.18 gram yellow oil, yield 35%.
The preparation of instance 3, compound 3
In reaction flask, add 5 milliliters of THFs and 3-(2,6-two chloro-4-(3,3-two chloro-allyloxys) phenoxy) third-1-alcohol (0.52 gram, 1.5 mmoles); Be stirred to dissolving under the room temperature, add sodium hydride (0.13 gram, 3.1 mmoles), stir after 2 hours; Add 3-chloro-2,5,6-trifluoromethyl pyridine (0.25 gram, 1.5 mmoles); Continue reaction under the room temperature after 5 hours, in reaction solution impouring 50 ml waters, with 3 * 50 milliliters of ethyl acetate extractions; Organic layer is respectively with saturated sodium bicarbonate solution, saturated nacl aqueous solution washing, and anhydrous magnesium sulfate drying reduces pressure and steams solvent to the greatest extent.Resistates is through column chromatography purification (leacheate: ETHYLE ACETATE: sherwood oil=1: 20) get 0.27 gram yellow oil, yield 36%.
The preparation of instance 4, compound 4
In reaction flask, add 5 milliliters of THFs and 4-(2,6-two chloro-4-(3,3-two chloro-allyloxys) phenoxy) fourth-1-alcohol (0.36 gram, 1 mmole; Embodiment 1 and 4 among the compound method referenced patent CN101337940A), is stirred to dissolving under the room temperature, adds sodium hydride (0.08 gram, 2.1 mmoles); Stir after 2 hours, add 2,3,5; 6-4 chloro pyridine (0.22 gram, 1 mmole) continues reaction and spends the night under the room temperature.In reaction solution impouring 50 ml waters, with 3 * 50 milliliters of ethyl acetate extractions, organic layer is respectively with saturated sodium bicarbonate solution, saturated nacl aqueous solution washing, and anhydrous magnesium sulfate drying reduces pressure and steams solvent to the greatest extent.Resistates is through column chromatography purification (leacheate: ETHYLE ACETATE: sherwood oil=1: 20) get 0.27 gram yellow oil, yield 50%.
Other compounds can be synthetic with reference to aforesaid method.
The biological activity determination instance
The mensuration of instance 5, insecticidal activity
According to the solvability of testing compound, the dissolving of former medicinal acetone or methyl-sulphoxide is mixed with 50 milliliters of the liquid to be measured of desired concn then with 1 ‰ tween 80 solution, and acetone or the methyl-sulphoxide content in total solution is no more than 10%.
(1), the active mensuration of killing beet noctuids
Cabbage leaves is broken into the leaf dish of 1 centimetre of diameter with punch tool, handle with the Airbrush spraying, certain density test compounds spray at every leaf dish pros and cons, and spouting liquid is 0.5 milliliter, and the every processing in back of drying in the shade inserts 8 examination worms (3 age), 3 repetitions of every processing.Put into 24 ℃, the indoor cultivation of relative humidity 60%～70%, unglazed photograph after the processing, 96 hours " Invest, Then Investigate " survival borer populations calculate mortality ratio.
Part supplies in the compound of examination, and following compounds control effect to beet armyworm when concentration is 10ppm is better, and mortality ratio is more than 85%: 1,2,3,4.
(2), kill the active mensuration of small cabbage moth
Cabbage leaves is broken into the leaf dish of 1 centimetre of diameter with punch tool, handle, carry out compound 2,3 and known compound KC under the 100ppm concentration with the Airbrush spraying
1(compound 19 among the CN101337940A) kills the active replicate(determination) of small cabbage moth.In every leaf dish pros and cons spraying, spouting liquid is 0.5 milliliter, and the every processing in back of drying in the shade inserts 8 examination worms (3 age), and every processing repeats for 3 times.Put into 24 ℃, the indoor cultivation of relative humidity 60%～70%, unglazed photograph after the processing, 48 and 72 hours " Invest, Then Investigate " survival borer populations calculate mortality ratio.Test-results is seen table 2.
Table 2: compound 2,3 and known compound KC
1Kill the active parallel comparison (spraying medicine concentration: 100ppm) of small cabbage moth
| Compound | Insecticidal activity (48 hours mortality ratio, %) | Insecticidal activity (72 hours mortality ratio, %) |
| 2 | 90 | 100 |
| 3 | 90 | 100 |
| KC 1 | 67 | 89 |
Claims (5)
1. one kind 3,5,6-three haloperidid pyridyl ethers compounds are shown in general formula I:
In the formula:
R
1Be selected from Cl; R
2, R
3Be selected from F or Cl respectively;
N=0,1 or 2.
2. according to the described compound of claim 1, it is characterized in that, in the general formula I:
R
1, R
2, R
3Be selected from Cl respectively;
n＝1。
3. purposes that is used for non-therapeutic purpose control insect pest according to the described compound of Formula I of claim 1.
4. insect-killing composition contains compound of Formula I as claimed in claim 1 and is acceptable carrier on active ingredient and agricultural, forestry or the health, and the weight percentage of active ingredient is 1-99% in the compsn.
5. the method for a non-therapeutic purpose control insect pest is characterized in that: the effective dose that the described compsn of claim 4 is restrained 1000 grams with per hectare 10 imposes on the medium of insect that needs control or its growth.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100818584A CN101863828B (en) | 2009-04-14 | 2009-04-14 | 3, 5, 6-three-halogenated pyridyl ethers compound and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100818584A CN101863828B (en) | 2009-04-14 | 2009-04-14 | 3, 5, 6-three-halogenated pyridyl ethers compound and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101863828A CN101863828A (en) | 2010-10-20 |
| CN101863828B true CN101863828B (en) | 2012-01-11 |
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|---|---|---|---|
| CN2009100818584A Expired - Fee Related CN101863828B (en) | 2009-04-14 | 2009-04-14 | 3, 5, 6-three-halogenated pyridyl ethers compound and application thereof |
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| CN102391177A (en) * | 2011-10-18 | 2012-03-28 | 沈阳农业大学 | Novel tri-ether compound, as well as synthetic method, process and usages thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137265A (en) * | 1994-08-04 | 1996-12-04 | 住友化学工业株式会社 | Dihalopropene compounds, insecticides/acaricides containing them and intermediates for their production |
| US5922880A (en) * | 1994-10-14 | 1999-07-13 | Sumitomo Chemical Company, Limited | Dihalopropene compounds, insecticidal/acaricidal agents containing same, and intermediates for their production |
| US6590104B1 (en) * | 2002-01-25 | 2003-07-08 | Sumitomo Chemical Company, Limited | Production method of an ether compound |
| CN1860874A (en) * | 2006-05-16 | 2006-11-15 | 王正权 | Dichloropropylene type pesticide |
| CN101337940A (en) * | 2008-08-12 | 2009-01-07 | 国家农药创制工程技术研究中心 | Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity |
-
2009
- 2009-04-14 CN CN2009100818584A patent/CN101863828B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137265A (en) * | 1994-08-04 | 1996-12-04 | 住友化学工业株式会社 | Dihalopropene compounds, insecticides/acaricides containing them and intermediates for their production |
| US5922880A (en) * | 1994-10-14 | 1999-07-13 | Sumitomo Chemical Company, Limited | Dihalopropene compounds, insecticidal/acaricidal agents containing same, and intermediates for their production |
| US6590104B1 (en) * | 2002-01-25 | 2003-07-08 | Sumitomo Chemical Company, Limited | Production method of an ether compound |
| CN1860874A (en) * | 2006-05-16 | 2006-11-15 | 王正权 | Dichloropropylene type pesticide |
| CN101337940A (en) * | 2008-08-12 | 2009-01-07 | 国家农药创制工程技术研究中心 | Nitrogen heterocyclic ring dichlorin allyl ether compounds with insecticidal activity |
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| Publication number | Publication date |
|---|---|
| CN101863828A (en) | 2010-10-20 |
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