CN102731363B - Pyrrole pesticide compounds - Google Patents
Pyrrole pesticide compounds Download PDFInfo
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- CN102731363B CN102731363B CN 201110419276 CN201110419276A CN102731363B CN 102731363 B CN102731363 B CN 102731363B CN 201110419276 CN201110419276 CN 201110419276 CN 201110419276 A CN201110419276 A CN 201110419276A CN 102731363 B CN102731363 B CN 102731363B
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- compound
- bromo
- nitrile
- trifluoromethyl
- rubigan
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- 0 CCCNC(C)=C(*)C(*)=C(C)c(cc1)ccc1N Chemical compound CCCNC(C)=C(*)C(*)=C(C)c(cc1)ccc1N 0.000 description 2
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- Plural Heterocyclic Compounds (AREA)
- Pyrrole Compounds (AREA)
Abstract
The invention provides a set of pyrrole pesticide compounds which have a general formula as described in the specification, wherein R in the general formula is selected from isopropyl groups, methyl groups and ethyl groups. The invention discloses structures of the compounds and effects of the compounds on controlling agricultural insects and discloses application of the compounds as pesticides at the same time.
Description
(1) technical field
The invention belongs to pesticide field, technical scheme relates to one group of azole compounds, is specifically related to the preparation method of aryl-pyrrolidine carbonitrile derivatives and this compounds and is the sterilant of activeconstituents with it.
(2) background technology
The aryl-pyrrolidine carbonitrile derivatives is effective insecticidal agent, miticide and invertebrate poison, 4-bromo-2-(rubigan)-1-(ethoxymethyl)-5-(trifluoromethyl) pyrroles-3-nitrile by American Cyanamid Company's exploitation, it is bromothalonil, come into the market for many years, but agricultural application proves in recent years, and the bromothalonil insecticidal effect can not be satisfactory.We have carried out deep researching and analysing to the bromothalonil structure, think that this compound has lipotropy preferably, and wetting ability a little less than.For this reason, we have carried out optimization design to this aryl-pyrrolidine carbonitrile derivatives structure, the hydrophilic radical ethanoyl is introduced, synthesized one group of 4-bromo-2-(rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound, improved the profit partition ratio of target compound preferably, its lipotropy and hydrophilic balance are more reasonable, more are conducive to penetrate the defensive barrier of insect and arrive target position smoothly; On the other hand, the polarization of the ethanoyl of introducing has the dipole effect, can form dipolar interaction with target; Thereby greatly improved the insecticidal activity (related data is seen embodiment 4 and embodiment 5) of the new compound of inventing.The waste water that produces in the new compound building-up process is less, and is easy to handle.Therefore, relatively environmental protection when new compound is produced as sterilant is beneficial to industrialization and serves agriculture, rural areas and farmers.
(3) summary of the invention
The purpose of this invention is to provide one group of 4-bromo-2-(rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound and synthetic method thereof.
It is agricultural insecticide that another object of the present invention provides 4-bromo-2-(rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound.
4-bromo-2-provided by the invention (rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound chemical structural formula general formula is as follows, and its particular chemical formula expression sees Table 1,
4-bromo-2-(rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound that table 1 the present invention synthesizes
The synthetic method of 4-bromo-2-of the present invention (rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound is as follows:
Be specially following steps:
In the 70ml tetrahydrofuran (THF), add 0.016molNaH under the ice-water bath, add 0.0062mol4-bromo-2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile afterwards in batches, stir behind the mixture backflow 20min and be cooled to 30 ± 5 ℃, drip 0.019mol alkoxyl group Acetyl Chloride 98Min., and then the 10 ± 2h that refluxes; Stopped reaction filters to such an extent that clarify yellow transparent liquid, and the decompression precipitation gets light yellow solid, column chromatography, and sherwood oil: ethyl acetate=5: 1 obtains corresponding solid target product; The consumption of above-claimed cpd enlarges by corresponding proportion or dwindles.
The screening method of 4-bromo-2-of the present invention (rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound is as follows:
Toxicity Determination to beet armyworm
Toxicity Determination adopts leaf dipping method to carry out.According to the pilot study scheme, by geometric ratio or etc. difference method reagent agent is diluted to 5 concentration.The back is cleaned, dried to the blade of removing the surface wax layer with the bore punch tool identical with 12 orifice plate internal diameters it is broken into disk, dipping is 10 seconds in soup, dries again after the taking-up, puts into 12 orifice plates, 2 in every hole, 3 instar larvaes of access neat and consistent.Compare with the space management that does not contain medicament (containing solvent and emulsifying agent).Every processing repeats 4 times, and totally 48 examination worms place in the incubator of temperature (27 ± 0.5) ℃, humidity (70 ± 10) %, illumination 16L:8D.48h checks the dead quantity of larva, and touching the motionless person of polypide larva with tweezers is death.Calculate medicament toxicity regression rate of curve, standard error, LC with dosage logarithm-mortality ratio probit value method
50Value, LC
90Value, 95% fiducial limit etc.
48h blank group mortality ratio meets to give birth to and surveys requirement less than 10% behind the medicine of this test, is efficiency test.
Toxicity Determination to small cabbage moth
Adopt dip method to handle with reference to NY/T1154.6-2006, to try worm inserts and soaks in the worm cage, in different liquid medicines, flooded for 8 seconds, inhale unnecessary soup on the debug body with filter paper then, to try worm again is transferred in the plastics insect box that is placed with fresh cabbage leaves, be 28.0 ± 1.0 ℃ in temperature, relative humidity remains on 80 ± 5%, and the photoperiod (L/D) raises in the illumination box of 16h/8h.24h checks the dead quantity of larva, and touching the motionless person of polypide larva with tweezers is death.Calculate medicament toxicity regression rate of curve, standard error, LC with dosage logarithm-mortality ratio probit value method
50Value, LC
90Value, 95% fiducial limit etc.
48h blank group mortality ratio meets to give birth to and surveys requirement less than 10% behind the medicine of this test, is efficiency test.
Toxicity Determination to apple yellow aphid
The mother liquor that will prepare in advance with deionized water dilutes by setting concentration, with little watering can spraying, establishes solvent control, parent solution solvents+emulsifier tween 80, solvent (2%)+tween 80 (0.1%).Use before the spraying and remove young aphid, parasitic aphid and alatae.Want during spraying evenly, prevent that aphid from being swept away by soup or drowned.After having sprayed a kind of compound, carefully scrub little watering can with liquid detergent, and with flushing with clean water twice, prevent the cross interference influence.
Toxicity Determination to Bemisia tabaci
Test period is selected in before 8 of mornings or after at 5 in afternoon, the Bemisia tabaci torpescence was beneficial to and checked the aleyrodid number this moment.At first check adult whitefly number on the wild cabbage, check that the back covers with gauze, fixes with clip all around.Open gauze one osculum during spraying,, in time seal after having sprayed at the gauze internal spraying with little watering can, prevent that Bemisia tabaci from flying out.The mother liquor that will prepare in advance with deionized water dilutes by setting concentration, places little watering can to spray respectively, establishes solvent control, parent solution solvents+emulsifier tween 80, solvent (2%)+tween 80 (0.1%).After having sprayed a kind of compound, carefully scrub little watering can with liquid detergent, and with flushing with clean water twice, prevent the cross interference influence.
The invention has the beneficial effects as follows: 4-bromo-2-of the present invention (rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound is used for the control Agricultural pests can obtain good effect.
It is one of key characters of the present invention that 4-bromo-2-of the present invention (rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound is used for the control Agricultural pests.
The present invention is by the more specifically synthetic and biological activity of bright 4-bromo-2-(rubigan)-1-(alcoxyl ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound of specific preparation and biological activity determination embodiment; described embodiment only is used for specific description the present invention and unrestricted the present invention, and embodiment is as follows:
Embodiment 1
Synthetic and the structure evaluation of the preparation of 4-bromo-2-(rubigan)-1-(isopropyl oxygen ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile
In the 100ml there-necked flask, add the 70ml tetrahydrofuran (THF), add 0.016molNaH under the ice-water bath, in mixed solution, add 0.0062mol4-bromo-2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile in batches; With mixed solution reflux 20min, stirring at room is cooled to 35 ℃, drips 0.019mol isopropoxy Acetyl Chloride 98Min., and 1min finishes, heating reflux reaction, backflow 11h.Stopped reaction filters, and gets the clarification yellow transparent liquid, and concentrating under reduced pressure is removed acyl chlorides, gets light yellow solid, column chromatography (300～400 order), and sherwood oil: ethyl acetate=5: 1 obtains white solid target product R100721.126.4～128.3 ℃ of fusing points, yield 85.3%.
1H-NMR(500MHz，CDCl
3)δ7.41～7.53(4H，dd，J＝8.5Hz，Ph-H)，3.99(2H，s，O＝C-CH
2-O)，3.29～3.33(1H，m，CH(CH
3)
2)，0.98～0.99(6H，d，CH(CH
3)
2)；IR(KBr)v：3444，1628，1561，1134cm
-1。
Embodiment 2
Synthetic and the structure evaluation of the preparation of 4-bromo-2-(rubigan)-1-(methoxy ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile
In the 100ml there-necked flask, add the 70ml tetrahydrofuran (THF), add 0.016molNaH under the ice-water bath, in mixed solution, add 0.0062mol4-bromo-2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile in batches; With mixed solution reflux 25min, stirring at room is cooled to 25 ℃, drips the 0.019mol methoxyacetyl chloride, and 2min finishes, heating reflux reaction, backflow 10h.Stopped reaction filters, and gets the clarification yellow transparent liquid, and concentrating under reduced pressure is removed acyl chlorides, gets light yellow solid, column chromatography (300～400 order), and sherwood oil: ethyl acetate=5: 1 obtains white solid target product R100729.Fusing point 145.4-146.7 ℃, yield 77.8%.
1H-NMR(500MHz，CDCl
3)δ7.50～7.50(4H，dd，J＝8.5Hz，Ph-H)，4.01(2H，s，O＝C-CH
2-O)，1.07～1.16(3H，s，CH
3)；IR(KBr)v：3448，2970，2880，1600，1501，1900，1010，820，543cm
-1。
Embodiment 3
Synthetic and the structure evaluation of the preparation of 4-bromo-2-(rubigan)-1-(ethoxy ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile
In the 100ml there-necked flask, add the 70ml tetrahydrofuran (THF), add 0.016molNaH under the ice-water bath, in mixed solution, add 0.0062mol4-bromo-2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile in batches; With mixed solution reflux 20min, stirring at room is cooled to 30 ℃, drips 0.019mol oxyethyl group Acetyl Chloride 98Min., and 1min finishes, heating reflux reaction, backflow 11h.Stopped reaction filters, and gets the clarification yellow transparent liquid, and concentrating under reduced pressure is removed acyl chlorides, gets light yellow solid, column chromatography (300～400 order), and sherwood oil: ethyl acetate=5: 1 obtains white solid target product R100717.Fusing point 141.3-143.5 ℃, yield 86.4%.
1H-NMR(500MHz，CDCl
3)δ7.51～7.49(4H，dd，J＝8.5Hz，Ph-H)，3.98(2H，s，O＝C-CH
2-O)，3.29～3.33(2H，q，CH
2CH
3)，1.07～1.10(3H，t，CH
2CH
3)；IR(KBr)v：3444，2971，2876，1598，1494，1088，1017，818，532cm
-1。
Embodiment 4
4-bromo-2-(rubigan)-1-(ethoxy ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100717), 4-bromo-2-(rubigan)-1-(isopropyl oxygen ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100721) and bromothalonil are to the virulence effect of beet armyworm
Test compound R100717, R100721 and bromothalonil the results are shown in Table 3, LC to the toxicity test of beet armyworm 3 instar larvae 48h
50Value, LC
90Value, 95% fiducial limit and corresponding b value, standard error (SD) see Table 2.
Table 2R100717, R100721 and bromothalonil are to the virulence of beet armyworm 3 instar larvaes
As shown in Table 2, compound R 100717, R100721 and bromothalonil are to Tengzhou population beet population at night 3 instar larvae virulence LC
50Be respectively 8.99mg/L, 5.12mg/L and 9.98mg/L.
Table 3R100717, R100721 and bromothalonil are to the toxicity test result of beet armyworm 3 instar larvaes
Embodiment 5
4-bromo-2-(rubigan)-1-(ethoxy ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100721) and bromothalonil are to the virulence effect of small cabbage moth
Test compound R100721 and bromothalonil the results are shown in Table 5 to the toxicity test of small cabbage moth 3 instar larvae 24h, virulence regression equation, LC
50Value, LC
90Value, 95% fiducial limit and corresponding P value see Table 4.
Table 4R100721 and bromothalonil are to the virulence of small cabbage moth 3 instar larvaes
As shown in Table 4, compound R 100721 and bromothalonil are to small cabbage moth population 3 instar larvae 24h virulence LC
50Be respectively 0.315mg/L and 5.661mg/L.
Table 5R100721 and bromothalonil are to the toxicity test result of small cabbage moth 3 instar larvaes
Embodiment 6
4-bromo-2-(rubigan)-1-(isopropyl oxygen ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100717), 4-bromo-2-(rubigan)-1-(methoxy ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100721) and 4-bromo-2-(rubigan)-1-(ethoxy ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100729) are to the virulence effect of apple yellow aphid
The toxicity test of test compound R100717, R100721 and the apple yellow aphid of R100729 the results are shown in Table 6.
The toxicity test result of table 6 compound R 100717, R100721 and the apple yellow aphid of R100729
Embodiment 7
4-bromo-2-(rubigan)-1-(isopropyl oxygen ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100717), 4-bromo-2-(rubigan)-1-(methoxy ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100721) and 4-bromo-2-(rubigan)-1-(ethoxy ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100729) are to the virulence effect of Bemisia tabaci
The toxicity test of test compound R100717, R100721 and the Bemisia tabaci of R100729 the results are shown in Table 6.
The toxicity test result of table 7 compound R 100717, R100721 and the Bemisia tabaci of R100729
Embodiment 8
4-bromo-2-(rubigan)-1-(ethoxy ethanoyl)-5-(trifluoromethyl) pyrroles-3-nitrile (R100729) is to the virulence effect of beet armyworm
The toxicity test of the beet armyworm 3 instar larvae 48h of test compound R100729 the results are shown in Table 8.
The toxicity test result of beet armyworm 3 instar larvaes of table 8R100729
Claims (4)
1. one group of azole pesticides compound is characterized in that having following chemical structural formula
R is sec.-propyl, methyl, ethyl in the formula.
2. according to the described pesticide compound of claim 1, it is characterized in that the concrete synthetic method of this compound is as follows:
In the 70ml tetrahydrofuran (THF), add 0.016molNaH under the ice-water bath, add 0.0062mol4-bromo-2-(4-chloro-phenyl-)-5-trifluoromethyl pyrpole-3-nitrile afterwards in batches, stir behind the mixture backflow 20min and be cooled to 30 ± 5 ℃, drip 0.019mol alkoxyl group Acetyl Chloride 98Min., and then the 10 ± 2h that refluxes; Stopped reaction filters to such an extent that clarify yellow transparent liquid, and the decompression precipitation gets light yellow solid, column chromatography, and sherwood oil: ethyl acetate=5: 1 obtains corresponding solid target product.
3. according to the described pesticide compound of claim 1, it is characterized in that the application of this compound in sterilant.
4. according to the described pesticide compound of claim 1, it is characterized in that the purposes of this compound in sterilant.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110419276 CN102731363B (en) | 2011-12-15 | 2011-12-15 | Pyrrole pesticide compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110419276 CN102731363B (en) | 2011-12-15 | 2011-12-15 | Pyrrole pesticide compounds |
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| CN102731363B true CN102731363B (en) | 2013-09-25 |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE195116T1 (en) * | 1990-12-26 | 2000-08-15 | American Cyanamid Co | 4-CHLORINE-1-(ETHOXYMETHYL)-2-(P-CHLOROPHENYL)-5-(TRIFLUOROMETHYL)PYRROLE-3-CARBONITRILE AND THE USE THEREOF AS INSECTICIDE, NEMATOCIDE AND ACARICIDE |
| AU722204B2 (en) * | 1995-10-31 | 2000-07-27 | Sumitomo Chemical Company, Limited | Pesticidal composition |
| CN101591284B (en) * | 2009-06-29 | 2011-10-12 | 湖南化工研究院 | Method for preparing chlorfenapyr and analog thereof |
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