CN102952080B - Benzoheterocycle contained ether compound and its use - Google Patents
Benzoheterocycle contained ether compound and its use Download PDFInfo
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- CN102952080B CN102952080B CN201110240155.9A CN201110240155A CN102952080B CN 102952080 B CN102952080 B CN 102952080B CN 201110240155 A CN201110240155 A CN 201110240155A CN 102952080 B CN102952080 B CN 102952080B
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- BSNPZUACSISQOW-MRXNPFEDSA-N C[C@H](COc(cc1)ccc1-c(cc1)ccc1OC(F)(F)F)COc(c(Cl)cc(OCC=C(Cl)Cl)c1)c1Cl Chemical compound C[C@H](COc(cc1)ccc1-c(cc1)ccc1OC(F)(F)F)COc(c(Cl)cc(OCC=C(Cl)Cl)c1)c1Cl BSNPZUACSISQOW-MRXNPFEDSA-N 0.000 description 1
- HNWIIRSSSGIUTJ-UHFFFAOYSA-N FC(c(cc1)ccc1-c(cc1)nnc1OCCCOc(c(Cl)cc(OCC=C(Cl)Cl)c1)c1Cl)(F)F Chemical compound FC(c(cc1)ccc1-c(cc1)nnc1OCCCOc(c(Cl)cc(OCC=C(Cl)Cl)c1)c1Cl)(F)F HNWIIRSSSGIUTJ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a benzoheterocycle contained ether compound. The structure of the ether compound is represented by general formula I shown in the specification; R1, R2, R3, R4 and R5 in the general formula I can be same or different and are respectively selected from hydrogen, halogens, a cyan group, a nitro group, C1-C3 alkyl groups, C1-C3 halogenated alkyl groups, C1-C3 alkyloxy groups or C1-C3 halogenated alkyloxy groups; Q in the general formula I is anyone selected from six-membered heterocycles shown in the specification; and n in the general formula I is 2, 3, 4, 5 or 6. The compound of the general formula I has an excellent insecticidal activity and can be used for controlling agricultural or forestal insect attack.
Description
Technical field
The invention belongs to field of pesticides, relate to a kind of ether compound containing benzene connection heterocycle and uses thereof.
Background technology
Due to sterilant in use for some time, insect can produce resistance to it, therefore, need constantly invention novel or the compound of tool insecticidal activity that improves and composition.
Ether compound and the insecticidal activity of some benzene cyclohexyl biphenyls is disclosed in patent WO9604228A, wherein compound 115 (specification sheets the 169th page of compound 115 in patent, structure is as follows) under the concentration of 100ppm, more than 80% is reached to twill diamond-back moth lethality rate, under the concentration of 50ppm, more than 80% is reached to Heliothis virescens lethality rate.
In prior art, the ether compound containing benzene connection heterocycle that the present invention relates to and insecticidal activity have no open.
Summary of the invention
The object of the present invention is to provide a kind of ether compound containing benzene connection heterocycle of novel structure, it can be applicable to the control of agricultural or forestry insect pest.
Technical scheme of the present invention is as follows:
An ether compound containing benzene connection heterocycle, as shown in general formula I:
In formula:
R
1, R
2, R
3, R
4, R
5may be the same or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
3alkyl, C
1-C
3haloalkyl, C
1-C
3alkoxyl group or C
1-C
3halogenated alkoxy;
Q is selected from any one hexa-member heterocycle following:
N=2,3,4,5 or 6.
In the present invention, more preferably compound is, in general formula I:
R
1, R
2, R
3, R
4, R
5be selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, methyl or trifluoromethyl respectively, but wherein have one at least for H;
Q is selected from any one hexa-member heterocycle following:
N=2,3 or 4.
In the present invention, preferred compound is, in general formula I further:
R
1, R
2, R
3, R
4, R
5be selected from hydrogen, chlorine or trifluoromethyl respectively, but wherein have one at least for H;
Q is selected from any one hexa-member heterocycle following:
N=2,3 or 4.
In the present invention, preferred compound is, in general formula I further again:
R
1, R
2, R
3, R
4, R
5be selected from hydrogen or trifluoromethyl respectively, but wherein have one at least for H;
Q is selected from any one hexa-member heterocycle following:
N=3 or 4.
In the present invention, further preferred compound is, in general formula I:
R
3select trifluoromethyl, R
1, R
2, R
4, R
5be H;
Q is selected from any one hexa-member heterocycle following:
N=3 or 4.
In the definition of the compound of Formula I provided above, collect term used and be generally defined as follows:
Alkyl refers to the group of straight or branched form, such as methyl, ethyl, n-propyl, sec.-propyl etc.Haloalkyl refers to the group that alkyl is optionally substituted with one or more halogen atoms, such as trifluoromethyl.Alkoxyl group refers to that alkyl end is connected with the group of Sauerstoffatom, such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy etc.Halogenated alkoxy refers to that alkyl is optionally substituted with one or more halogen atoms, and end is connected with the group of Sauerstoffatom, such as trifluoromethoxy.Halogen refers to fluorine, chlorine, bromine, iodine.
Compound of Formula I of the present invention can be prepared by the following method:
In formula:
R
1, R
2, R
3, R
4may be the same or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively
1-C
3alkyl, C
1-C
3haloalkyl, C
1-C
3alkoxyl group or C
1-C
3halogenated alkoxy;
Q is selected from any one hexa-member heterocycle following:
N=2,3,4,5 or 6.
Compounds of formula II and compound of formula III are in suitable solvent, under suitable alkali exists, and temperature reacts 0.5-48 hour obtained target compound I under being-10 DEG C to boiling point.
Suitable solvent is selected from methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, DMF or dimethyl sulfoxide (DMSO) etc.
Suitable alkali comprises the hydrogen compound of basic metal as lithium, sodium or potassium as sodium hydride, basic metal if the oxyhydroxide of lithium, sodium or potassium is as sodium hydroxide, can also be alkali-metal carbonate as sodium carbonate, also can be that organic bases is as triethylamine, sodium tert-butoxide etc.
The preparation of Compounds of formula II is carried out with reference to the operation of following documents: Bioorganic & Medicinal ChemistryLetters, 2008,18 (11): 3376-3381; Bioorganic & Medicinal Chemistry Letters, 2008,18 (7): 2404-2408.
The preparation of compound of formula III is carried out with reference to the operation of following documents: CN1860874A (embodiment 1,2,3).
Table 1 lists the structure of partial Formula I and physical properties so that the present invention to be described, but does not limit the present invention.
Part of compounds
1h NMR (300MHz, CDCl
3), δ (ppm) data are as follows:
Compound 1:2.38-2.42 (m, 2H), 4.17 (t, 2H), 4.58 (d, 2H), 4.88 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.10 (d, 1H), 7.76 (d, 2H), 7.83 (d, 2H), 8.14 (d, 1H).
Compound 8:2.35-2.39 (m, 2H), 4.18 (t, 2H), 4.58 (d, 2H), 4.76 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.74 (d, 2H), 8.16 (d, 2H), 8.23 (s, 1H), 8.64 (s, 1H).
Compound 10:2.33-2.37 (m, 2H), 4.13 (t, 2H), 4.57 (d, 2H), 4.73 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.69 (d, 2H), 8.12 (d, 1H), 8.21 (d, 2H), 8.28 (d, 1H).
Ether compound containing benzene connection heterocycle of the present invention has high insecticidal activity.Therefore, the present invention also comprises compound of Formula I for controlling the purposes of insect pest.Specifically, technical scheme of the present invention also comprises the purposes of compound of Formula I for the preparation of insecticidal materials.
The present invention also comprises the insect-killing composition using compound of Formula I as active ingredient.In this insect-killing composition, the weight percentage of active ingredient is between 1-99%.Acceptable carrier in agricultural or forestry is also comprised in this insect-killing composition.
Composition of the present invention can the form of preparation be used.Compound of Formula I is dissolved or dispersed in carrier as active ingredient or is mixed with preparation to be easier to dispersion when using as desinsection.Such as: these chemicals can be made into wettable powder or missible oil.In these compositions, at least add a kind of liquid or solid carrier, and suitable tensio-active agent can be added when needed.
The technical scheme of invention also comprises the method for pest control: imposed on by insect-killing composition of the present invention on described insect or its growth medium.The comparatively suitable significant quantity of usual selection is per hectare 10 grams to 1000 grams, and preferably having effective amount is per hectare 20 grams to 500 grams.
For some application, such as, one or more other sterilant, Insecticides (tech) & Herbicides (tech), plant-growth regulator or fertilizer etc. agriculturally can be added in insect-killing composition of the present invention, additional advantage and effect can be produced thus.
Should it is clear that, in claim limited range of the present invention, can various conversion and change be carried out.
Embodiment
Following synthesis example, raw test-results of surveying can be used to further illustrate the present invention, but do not mean that restriction the present invention.
Synthesis example
The preparation of example 1 compound 1:
3-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group) the third-1-alcohol (0.50 gram, 1.44 mmole, embodiment 1,2,3 in synthetic method referenced patent CN1860874A), tetrahydrofuran (THF) (10 milliliters), stirred at ambient temperature, to dissolving, adds sodium hydride (0.70 gram, 2.88 mmoles).Stir after 2 hours, add the chloro-6-of 3-(4-(trifluoromethyl) phenyl) pyridazine (0.37 gram, 1.44 mmole, synthetic method is with reference to Bioorganic & Medicinal Chemistry Letters, 2008,18 (11): 3376-3381), reaction 6 hours is continued under room temperature.By in reaction solution impouring water (50 milliliters), with ethyl acetate (3 × 150 milliliters) extraction, organic layer uses saturated sodium bicarbonate aqueous solution, saturated common salt water washing respectively, anhydrous magnesium sulfate drying, and solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 100) obtain 0.07 g of compound 1, yellow solid, yield 9%, fusing point: 64-66 DEG C.
The preparation of example 2 compound 8:
3-(2 is added in reaction flask, the chloro-4-(3 of 6-bis-, the chloro-allyloxy of 3-bis-) phenoxy group) the third-1-alcohol (0.50 gram, 1.44 mmoles, tetrahydrofuran (THF) (10 milliliters), stirred at ambient temperature is to dissolving, add sodium hydride (0.70 gram, 2.88 mmoles).Stir after 2 hours, add the chloro-6-of 2-(4-(trifluoromethyl) phenyl) pyrazine (0.37 gram, 1.44 mmole, synthetic method is with reference to Bioorganic & Medicinal Chemistry Letters, 2008,18 (11): 3376-3381), reaction 6 hours is continued under room temperature.Afterwards, by in reaction solution impouring water (50 milliliters), extract by ethyl acetate (3 × 150 milliliters), organic layer uses saturated sodium bicarbonate aqueous solution (3 × 50 milliliters), saturated aqueous common salt (3 × 50 milliliters) to wash respectively, anhydrous magnesium sulfate drying, solvent is to the greatest extent steamed in decompression.Resistates is by chromatography over CC (leacheate: ethyl acetate: sherwood oil=1: 120) obtain 0.28 gram of yellow solid, yield 34%, fusing point: 82-84 DEG C.
Other compound of Formula I of the present invention can refer to aforesaid method synthesis.
Biological activity determination example
The mensuration of example 3 insecticidal activity
According to the solvability of testing compound, dissolve former medicine with acetone or methyl-sulphoxide, then become the liquid to be measured 50 milliliters of desired concn with the tween 80 solution preparation of 1 ‰, acetone or the content of methyl-sulphoxide in total solution are no more than 10%.
(1) mensuration of small cabbage moth activity, is killed
Cabbage leaves punch tool is broken into the leaf dish of diameter 3 centimetres, with Airbrush spraying process, sprayed at every leaf dish pros and cons by certain density test compound liquid, spouting liquid is 0.5 milliliter, separately establishes clear water to be treated to blank, often processes 3 times and repeats.Access 8 examination worm (3 age) is often processed after drying in the shade.Put into after process 24 DEG C, relative humidity 60% ~ 70%, unglazed photograph indoor cultivation, 72 hours " Invest, Then Investigate "s survival borer population, calculates mortality ratio.
In the compound of part for examination, following compounds is better to the prevention effect of small cabbage moth when concentration is 600ppm, and mortality ratio is 100%: 1,8.
In the compound of part for examination, following compounds is better to the prevention effect of small cabbage moth when concentration is 100ppm, and mortality ratio is 100%: 1.
According to above method, choose the mensuration that compound 1 and compound K C (be compound in patent WO9604228A, its structure and the compounds of this invention are the most close) have carried out killing small cabbage moth activity.Its test-results is in table 2.
Table 2: the compounds of this invention 1 kills comparing of small cabbage moth activity with patents KC
(mortality ratio, %)
(2), the mensuration of mythimna separate
Maize leaf is cut into 4-5 cm long segment, with Airbrush spraying process, sprayed in every leave dual sides by certain density test compound liquid, spouting liquid is 0.5 milliliter, separately establishes clear water to be treated to blank, often processes 3 times and repeats.Access 8 examination worm (3 age) is often processed after drying in the shade.Put into after process 24 DEG C, relative humidity 60% ~ 70%, unglazed photograph indoor cultivation, 72 hours " Invest, Then Investigate "s survival borer population, calculates mortality ratio.
In the compound of part for examination, following compounds is better to the prevention effect of mythimna separata when concentration is 600ppm, and mortality ratio is 100%: 1,8,10.
In the compound of part for examination, following compounds is better to the prevention effect of mythimna separata when concentration is 100ppm, and mortality ratio is 100%: 1.
According to above method, choose compound 1 and carried out the mensuration of mythimna separate with compound K C, test-results is in table 3.
Table 3: the compounds of this invention 1 compares with patents KC mythimna separate
(mortality ratio, %)
Claims (4)
1. the ether compound containing benzene connection heterocycle, its structure is as follows:
2. control a purposes for agricultural or forestry insect pest according to compound according to claim 1, wherein said insect pest is small cabbage moth or mythimna separata.
3. an insect-killing composition, containing, for example compound according to claim 1 as active ingredient and agricultural, forestry or health acceptable carrier, is 1-99% as the weight percentage of the compound of active ingredient in composition.
4. control a method for insect pest, it is characterized in that: imposed on the insect of needs control or the medium of its growth with the effective dose of per hectare 10 grams to 1000 grams by composition according to claim 3, described insect is small cabbage moth or mythimna separata.
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|---|---|---|---|
| CN201110240155.9A CN102952080B (en) | 2011-08-19 | 2011-08-19 | Benzoheterocycle contained ether compound and its use |
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|---|---|---|---|
| CN201110240155.9A CN102952080B (en) | 2011-08-19 | 2011-08-19 | Benzoheterocycle contained ether compound and its use |
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|---|---|
| CN102952080A CN102952080A (en) | 2013-03-06 |
| CN102952080B true CN102952080B (en) | 2015-04-08 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208088A (en) * | 2005-06-02 | 2008-06-25 | 拜尔农作物科学股份公司 | Phenylalkyl substituted heteroaryl devivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208088A (en) * | 2005-06-02 | 2008-06-25 | 拜尔农作物科学股份公司 | Phenylalkyl substituted heteroaryl devivatives |
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Effective date of registration: 20160128 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Patentee before: Sinochem Corporation Patentee before: Shenyang Research Institute of Chemical Industry |