CN106432210B - One group of pyrazoles acid oxo spiroheterocyclic ester derivant and its preparation method and application - Google Patents
One group of pyrazoles acid oxo spiroheterocyclic ester derivant and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The present invention relates to one group to have
Description
Technical field
The invention belongs to pesticide field, technical solution is related to one group of pyrazoles acid oxo spiroheterocyclic ester derivant, and in particular to
Pyrazoles acid oxo spiroheterocyclic ester derivant and preparation method thereof and its agricultural insecticide application.
Background technique
Pyrazoles acid oxo spiroheterocyclic ester type compound often has high bioactivity, at present the mature pesticide species of exploitation
Only Envidor, spiral shell worm ethyl ester etc. are widely used in the prevention and treatment of all kinds of mites.Due to spiral shells such as Envidor, spiral shell worm ethyl ester in recent years
The acaricidal excessive use of ring, most harmful mites have produced serious drug resistance to it, have led to the spiral shells such as Envidor, spiral shell worm ethyl ester
The plant protection sexual valence of ring acaricide pesticide species is more serious than declining, under agriculture mite does harm to large area generation, agricultural foison significantly
The phenomenon that drop, happens occasionally.
Therefore, it is necessary to continually develop research and provide new environmental-friendly, highly selective pesticide species pesticide.Root
According to pharmaceutical molecule bioactivity principle, we, which design, has synthesized serial pyrazoles acid oxo spiroheterocyclic ester derivant, and determines it
Mite killing, insecticidal activity.
Summary of the invention
The object of the present invention is to provide one group of pyrazoles acid oxo spiroheterocyclic ester derivants；
The present invention provides one group of pyrazoles acid oxo spiroheterocyclic ester derivant, and structural formula is as shown in formula I:
Formulas I,
Y group can be selected from O, NH in formula I；X is halogen, and m is 1 or 2 or 3 or 4；R group can be selected fromOr, wherein R1ForOrOrOrOr, A is halogen or H；Wherein halogen
Refer to F or Cl or Br or I.
It is further preferred that the derivative is selected from one of following:
| Number | Chemical structural formula | Number | Chemical structural formula |
| W201502031 | W201502041 | ||
| W201502051 | W201503121 | ||
| W201503032 | W20150309 | ||
| W20150409 | W201504073 | ||
| W201503251 | W201504151 | ||
| W201504141 | W201504161 | ||
| W201504211 | W20150423 | ||
| W20150426 |
It is also another object of the present invention to provide the preparation method of the compound, preparation process is as follows:
。
Specifically, the described method comprises the following steps:
(1) h dissolved with acetonitrile is added drop-wise to B or C under the conditions of 0 ± 5 DEG C using potassium carbonate as acid binding agent for solvent by acetonitrile
Acetonitrile solution in, and maintain 0 ± 5 DEG C the reaction was continued, TLC monitoring removes solvent when after the reaction was completed, being filtered to remove solid,
It is washed with distilled water precipitation obtained solid, corresponding obtained object D or E；
(2) ethyl alcohol is solvent, the ethanol solution of potassium tert-butoxide is added drop-wise in the ethanol solution of D under the conditions of 25 ± 5 DEG C, so
Heating reflux reaction afterwards, TLC monitoring remove solvent when after the reaction was completed, reducing temperature to 25 ± 5 DEG C, add distilled water stirring molten
Solution, with 10% salt acid for adjusting pH=1, filters to obtain F crude product, obtains sterling F with ethyl alcohol recrystallization；
Ethyl alcohol is solvent, and the ethanol solution of sodium ethoxide is added drop-wise in the ethanol solution of E under the conditions of 25 ± 5 DEG C, then plus
Hot back flow reaction, TLC monitoring remove solvent, add distilled water stirring and dissolving when after the reaction was completed, reducing temperature to 25 ± 5 DEG C,
With 10% salt acid for adjusting pH=1, F crude product is filtered to obtain, obtains sterling G with ethyl alcohol recrystallization；
(3) acetonitrile is solvent, using potassium carbonate as acid binding agent, will be dissolved with acetonitrile under the conditions of 0 ± 5 DEG CIt is added drop-wise to
In the acetonitrile solution of F or G, 25 ± 5 DEG C are then heated to, and the reaction was continued for 25 ± 5 DEG C of maintenance, TLC monitoring, when reaction is completed
Afterwards, it is filtered to remove solid, removes solvent, is washed with distilled water precipitation obtained solid, corresponding object is made in drying, use second
Alcohol recrystallization is madeSterling.
Third object of the present invention is to provide the preparations of the oxo spiroheterocyclic ester derivant of acid containing pyrazoles, by derivative and agriculture
The auxiliary material of medicine, wherein weight percent content is 0.1%-99.9% to pyrazoles acid oxo spiroheterocyclic ester derivant in the formulation.
It is a further object of the present invention to provide the pyrazoles acid oxo spiroheterocyclic ester derivants as agricultural insecticide application.
Pyrazoles acid oxo spiroheterocyclic ester derivant provided by the invention is important spy of the invention for preventing and treating agricultural pests
One of sign.
Derivative provided by the invention has the advantage that
1, pyrazoles acid oxo spiroheterocyclic ester derivant of the invention can be used for preventing and treating agricultural pests, and can obtain good effect
Fruit.
2, noval chemical compound of the present invention " three wastes " produced during the preparation process is less, is easily handled, as insecticide agriculture
Medicine is more environmentally friendly when producing.
3, the present invention provides one group of new compound, which is applied to prevention and treatment agricultural evil as new insecticide
Worm can be applied to the pest to develop drug resistance, and effect is good, and has the advantages that at low cost.
Specific embodiment
The present invention is spread out by specific preparation and biological activity determination embodiment specific description pyrazoles acid oxo spiroheterocyclic ester
The preparation and bioactivity of biology, the embodiment are only used for the specific description present invention and are not intended to limit the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
The preparation of 1 compound W201502031 of embodiment
(1)
Concrete operations: the B of 10 mmol, the potassium carbonate of 15 mmol, 15 mL acetonitriles are added in single port bottle, in ice water
Under bath, constant pressure forces down the J that 10 mL dilution in acetonitrile are added dropwise in liquid funnel, maintains temperature at 0 ± 5 DEG C, 20 ± 5 DEG C after being added dropwise
Reaction, TLC detect reaction process, remove solvent acetonitrile after the reaction was completed, add 15 mL water washings, filtering, dry product K, should
Product can be directly used for reacting in next step.
(2)
Concrete operations: the ethyl alcohol of the K of 10 mmol, 15 mmol potassium tert-butoxides, 20 mL are added to the single port bottle of 100 mL
In, it is warming up to back flow reaction 10 hours or so, TLC monitoring removes etoh solvent after the reaction was completed, adds the stirring of 10 mL water molten
Solution, with 10% salt acid for adjusting pH=1, filters to obtain L crude product, obtains object L sterling with ethyl alcohol recrystallization.
(3)
Concrete operations: the acetonitrile of the L of 10 mmol, 15 mmol potassium carbonate powders, 20 mL are added to equipped with magnetic agitation
Device, condenser pipe, calcium chloride tube, constant pressure funnel and thermometer 100 mL three neck round bottom flask in, ice-water bath condition
Under, the 11 mmol pyrazole acyl chlorides with about 10 mL dilution in acetonitrile are slowly added dropwise, are to slowly warm up to environment temperature after being added dropwise to complete
(20 ± 5 DEG C) continuation insulation reactions, TLC monitoring are filtered to remove solid insoluble, filtrate concentration, cooling knot after the reaction was completed
It is brilliant.It is dried under infrared lamp, object W201502031 is made.Character: white crystal, fusing point: 181.5 ~ 182.2 DEG C, yield:
81%。
2 compound of embodimentPreparation
Concrete operations: with the preparation of compound W201502031；Difference: the J of the preparation (1) of W201502031 is replaced
Specific phenyllacetyl chloride derivative required for being changed to, required for the pyrazole acyl chloride of the preparation (3) of W201502031 is replaced with
Specific pyrazole acyl chloride.The physicochemical data of the preferred pyrazoles acid oxo spiroheterocyclic ester derivant in part prepared with this method is shown in Table 1.
The physicochemical data of the preferred pyrazoles acid oxo spiroheterocyclic ester derivant in 1 part of table
The preparation of 3 compound W201504151 of embodiment
(1)
Concrete operations: with the preparation (1) of compound W201502031；Difference: will be in the preparation (1) of W201502031
B replace with C, J and be changed to M.
(2)
Concrete operations: with the preparation (2) of compound W201502031；Difference: will be in the preparation (2) of W201502031
K replace with N, potassium tert-butoxide replaces with sodium ethoxide.
(3)
Concrete operations: with the preparation (3) of compound W201502031；Difference: will be in the preparation (2) of W201502031
L replace with O,It is changed to.Character: white powder, fusing point: 232.4 ~ 233.0 DEG C, yield:
71%。
4 compound of embodimentPreparation
Concrete operations: with the preparation of compound W201504151.Difference: the M of the preparation (1) of W201504151 is replaced
Specific phenyllacetyl chloride derivative required for being changed to, required for the pyrazole acyl chloride of the preparation (3) of W201504151 is replaced with
Specific pyrazole acyl chloride.The physicochemical data of the preferred pyrazoles acid oxo spiroheterocyclic ester derivant in part prepared with this method is shown in Table 2.
The physicochemical data of the preferred pyrazoles acid oxo spiroheterocyclic ester derivant in 2 part of table
5 part preferred compound of embodiment1H-NMR and IR parametric measurement and Identification of chemical structure
The 1H-NMR data of the preferred pyrazoles acid oxo spiroheterocyclic ester compounds in 3 part of table
| Number NO. | Hydrogen nuclear magnetic resonance modal data1H NMR/ppm |
| W201502031 | 1H NMR (500 MHz, CDCl3) δ 7.47 (d, J=8.3 Hz, 1H, PhCH6), 7.37 (d, J=2.0 Hz, 1H, PhCH3), 7.34 (dd, J=8.3, 2.1 Hz, 1H, PhCH5), 3.83 (s, 3H, N- CH3), 2.36 (s, 3H, -CH3), 1.93–1.77 (m, 10H, Cyclohexyl). |
| W201502041 | 1H NMR (500 MHz, CDCl3) δ 7.47 (d, J=8.3 Hz, 1H, PhCH6), 7.37 (d, J=2.0 Hz, 1H, PhCH3), 7.34 (dd, J=8.3, 2.1 Hz, 1H, PhCH5), 3.96 (s, 3H, N- CH3), 1.93–1.78 (m, 10H, Cyclohexyl). |
| W201502051 | 1H NMR (500 MHz, CDCl3) δ 7.47 (d, J=8.3 Hz, 1H, PhCH6), 7.37 (d, J=2.0 Hz, 1H, PhCH5), 7.34 (dd, J=8.3, 2.1 Hz, 1H, PhCH3), 3.93 (s, 3H, N- CH3), 2.70–2.65 (m, 2H, -CH2-), 2.01–1.78 (m, 10H, Cyclohexyl), 1.27 (t,J=6.7 Hz, 3H, -CH3). |
| W201503121 | 1H NMR (500 MHz, CDCl3) δ 7.86 (s, 1H, Pyrazole-H), 7.47 (d, J=8.3 Hz, 1H, PhCH6), 7.34 (d, J=2.0 Hz, 1H, PhCH5), 7.31 (dd, J=8.3, 2.0 Hz, 1H, PhCH3), 3.88 (s, 3H, N-CH3), 2.38 (s, 3H, -CH3), 1.82 (dd, J=13.3, 5.6 Hz, 10H, Cyclohexyl). |
| W201503032 | 1H NMR (500 MHz, CDCl3) δ 8.03 (s, 1H, Pyrazole-H), 7.47 (d, J=8.3 Hz, 1H, PhCH6), 7.35 (d, J=2.0 Hz, 1H, PhCH3), 7.31 (dd, J=8.4, 2.1 Hz, 1H, PhCH5), 4.00 (s, 3H, N-CH3), 1.91–1.77 (m, 10H, Cyclohexyl). |
| W20150309 | 1H NMR (500 MHz, CDCl3) δ 7.42 (d, J=8.4 Hz, 1H, PhCH6), 7.36 (d, J=2.0 Hz, 1H, PhCH3), 7.32 (dd, J=8.4, 2.0 Hz, 1H, PhCH5), 6.63 (s, 1H, Pyrazole-H), 3.93 (s, 3H, N-CH3), 1.93 (td, J=8.5, 4.2 Hz, 1H, cyclopropyl-CH-), 1.83 (d, J=12.4 Hz, 10H, Cyclohexyl), 0.99–0.94 (m, 2H, cyclopropyl-CH2-), 0.77 (dt, J=6.5, 4.4 Hz, 2H, cyclopropyl-CH2-). |
| W20150409 | 1H NMR (500 MHz, CDCl3) δ 7.40 (d, J=8.3 Hz, 1H, PhCH6), 7.29 (d, J=2.0 Hz, 1H,PhCH3 ), 7.26 (dd, J=8.3, 2.0 Hz, 1H, PhCH5), 3.81 (s, 3H, N- CH3), 1.94–1.74 (m, 10H, Cyclohexyl), 0.92–0.83 (m, 5H, Cyclopropyl). |
| W201504073 | 1H NMR (500 MHz, CDCl3) δ 7.42 (d, J=8.4 Hz, 1H, PhCH6), 7.37 (d, J=2.0 Hz, 1H, PhCH3), 7.32 (dd, J=8.4, 2.1 Hz, 1H, PhCH5), 6.76 (s, 1H, Pyrazole-H), 3.97 (s, 3H, N-CH3), 1.90–1.79 (m, 10H, Cyclohexyl), 1.33 (d, J=1.8 Hz, 9H, Tert butyl). |
| W201503251 | 1H NMR (500 MHz, DMSO) δ 7.34 (d, J=2.2 Hz, 1H, PhCH6), 7.29 (d, J=8.4 Hz, 1H, PhCH3), 7.18 (dd, J=8.4, 2.3 Hz, 1H, PhCH5), 3.82 (s, 3H, N- CH3), 1.66 – 1.45 (m, 10H, Cyclohexyl), 1.29 (s, 9H, Tert butyl). |
| W201504151 | 1H NMR (500 MHz, CDCl3) δ 7.66–7.62 (m, 2H, PhCH3, PhCH5), 7.04 (t, J=8.8 Hz, 2H, PhCH2, PhCH6), 6.87 (s, 1H -NH,), 3.93 (s, 3H, N-CH3), 1.92 – 1.66 (m, 10H, Cyclohexyl), 1.43 (s, 9H, Tert butyl). |
| W201504141 | 1H NMR (500 MHz, CDCl3) δ 7.62–7.59 (m, 2H, PhCH3, PhCH5), 7.34–7.31 (m, 2H, PhCH2, PhCH6) , 6.57 (s,1H, -NH), 3.94 (s, 3H, N-CH3), 1.92 – 1.63 (m, 10H, Cyclohexyl), 1.43 (s, 9H, Ter butyl). |
| W201504161 | 1H NMR (500 MHz, CDCl3) δ 7.43 (d, J=8.4 Hz, 1H, PhCH6 ), 7.37 (d, J= 2.0Hz, 1H, PhCH3), 7.31 (dd, J=8.4, 2.0 Hz, 1H, PhCH5), 6.91 (s, 1H, - NH), 3.90 (s,3H, N-CH3), 1.72 (s, 10H, Cyclohexyl), 1.40 (d, J=5.3 Hz, 9H, Ter butyl). |
| W201504211 | 1H NMR (500 MHz, CDCl3) δ 7.70 (dd, J=17.1, 9.1 Hz, 1H, PhCH3), 6.85 (dd, J=16.2, 9.7 Hz, 1H, PhCH6), 6.56 (s, 1H, -NH), 3.93 (s, 3H, N-CH3), 2.02 – 1.37 (m, 10H, Cyclohexyl), 1.29-0.95 (m, 5H, Cyclopropyl). |
| W20150423 | 1H NMR (500 MHz, CDCl3) δ 7.62 – 7.59 (m, 2H, PhCH3, PhCH5), 7.34 – 7.31 (m, 2H, PhCH2, PhCH6), 6.45 (s, 1H, -NH), 3.92 (s, 3H, N-CH3), 2.01 – 1.69 (m, 10H, Cyclohexyl), 1.01 – 0.92 (m, 5H, Cyclopropyl). |
| W20150426 | 1H NMR (500 MHz, CDCl3) δ 7.64 (dd, J=8.7, 5.5 Hz, 2H, PhCH3, PhCH5), 7.04 (t, J=8.7 Hz, 2H, PhCH2, PhCH6), 6.51 (s, 1H, -NH), 3.92 (s, 3H, N- CH3), 1.99 – 1.66 (m, 10H, Cyclohexyl), 1.01 – 0.91 (m, 5H, Cyclopropyl). |
The ir data of the preferred pyrazoles acid oxo spiroheterocyclic ester compounds in 4 part of table
| Number NO. | Infrared spectrum data IR/ppm (KBr) |
| W201502031 | 2939.45, 2849.06, 1754.97, 1663.69, 1527.14, 1229.75, 1105.80, 996.61, 870.70, 825.09, 777.07 |
| W201502041 | 3028.62, 2944.01, 2857.89, 1762.45, 1518.49, 1339.01, 1285.00, 1172.44, 999.69, 766.07, 745.83 |
| W201502051 | 2984.46, 2943.19, 2852.00, 1757.11, 1479.82, 1339.25, 1232.94, 1196.57, 1134.70, 1100.88,1011.54 |
| W201503121 | 3143.42, 3096.32, 2955.03, 2837.29, 1749.05, 1544.93, 1478.24, 1336.91, 1293.09, 1223.61,1190.20, 1095.97, 1012.76, 863.23 |
| W201503032 | 3149.30, 3096.32, 3072.77, 2956.76, 2846.12,1751.44, 1544.69, 1477.21, 1279.99, 1186.91, 997.71 |
| W20150309 | 3087.49, 3010.96, 1710.23, 1539.17, 1468.03, 1318.40, 1244.40, 1164.38, 1045.45, 769.07 |
| W20150409 | 3078.66, 2931.48, 2860.83, 1756.11, 1662.80, 1481.16, 1331.95, 1230.62, 1100.93, 1008.94,961.68 |
| W201504073 | 3155.19, 2952.08, 2863.78, 1751.30, 1677.51, 1586.26, 1480.75, 1333.95, 1220.09, 1138.84,1103.09, 1002.27, 962.22 |
| W201503251 | 3178.74, 2937.42, 2863.78, 1698.12, 1576.32, 1486.18, 1371.19, 1233.03, 953.39, 815.04 |
| W201504151 | 3190.52, 3066.88, 2934.44, 1762.36, 1701.57, 1603.92, 1512.25, 1365.49, 1212.37, 1094.69, |
| W201504141 | 3178.74, 3072.77, 2943.25, 1764.17, 1700.35, 1493.85, 1212.13, 1093.87, 1016.59, 994.89, 826.82 |
| W201504161 | 3172.85, 3072.77, 2950.65, 1759.06, 1695.15, 1583.32, 1474.41, 1339.65, 1246.67, 1213.20, 1099.42, 817.99 |
| W201504211 | 3166.97, 3066.88, 2943.25, 2854.95, 1762.88, 1692.23, 1521.50, 1233.03, 1100.57, 1015.21 |
| W20150423 | 3181.68, 3072.77, 2928.54, 2863.78, 1748.16, 1692.23, 1233.03, 1094.69, 1015.21 |
| W20150426 | 3190.52, 3075.72, 2946.20, 2863.78, 1756.99, 1689.29, 1512.67, 1227.15, 1094.69 |
By table 3 and table 4 as it can be seen that part preferably pyrazoles acid oxo spiroheterocyclic ester compounds1H-NMR is shown and its structure phase
The number and its structure of the chemical shift, H answered are coincide, and corresponding skeleton absorption peak occurs in IR.
The preferred pyrazoles acid oxo spiroheterocyclic ester derivant in 6 part of embodiment surveys beet exigua larvae insecticidal bioactivity
Examination
(1) laboratory apparatus: assay balance supports worm plate, incubator, culture dish；
(2) selected insect source: 3 instar larvae of beet armyworm；
(3) control drug: Envidor (), compound N (), change
Close object M(), compound O()；
(4) test method: stomach poison toxicity test, endless feeding method；
(5) stand-by after 100 times of dilution by reagent agent standard preparation at 1000ppm solution (solvent, acetone).By 3 ages
Beet exigua larvae does 4h Nature enemy, 24 3 age health beet exigua larvaes tests of every group of selection, and each medicament is measured in parallel
Two groups；Take appropriate feed mean allocation in the interval of each feeding worm plate, 5.00uL etc. is injected with micropipettor in each interval
The reagent agent solution for measuring 10ppm, by 24 choose be evenly distributed in the interval of each feeding worm plate for test worm body, between each
Every one, is covered with the toilet paper after disinfection and support worm plate, spray appropriate distilled water moisturizing.Blank control test is done simultaneously, is rested
Worm plate is placed in moisturizing in the illumination box of (25 ± 1) DEG C, and respectively at for 24 hours, 48h, 72h count the dead feelings of beet exigua larvae
Condition touches polypide with writing brush, motionless with polypide or cannot just produce and creep as death standard.Dead polypide quantity is recorded, and is calculated
Its death rate.
(5) experimental result is shown in Table 5
5 insecticidal activity of table (concentration: 10mg/L, lethality/%)
| Compound number | 24h | 48h | 72h |
| W201502031 | 8.3 | 20.8 | 37.5 |
| W201502041 | 12.5 | 20.8 | 41.7 |
| W201502051 | 0 | 16.7 | 33.3 |
| W201503121 | 8.3 | 25.0 | 37.5 |
| W201503032 | 16.7 | 39.2 | 41.7 |
| W20150309 | 12.5 | 29.2 | 45.8 |
| W20150409 | 29.2 | 41.7 | 58.3 |
| W201504073 | 8.3 | 16.7 | 33.3 |
| W201503251 | 8.3 | 12.5 | 37.5 |
| W201504151 | 12.5 | 29.2 | 45.8 |
| W201504141 | 20.8 | 37.5 | 58.3 |
| W201504161 | 16.7 | 33.3 | 41.7 |
| W201504211 | 20.8 | 41.7 | 62.5 |
| W20150423 | 12.5 | 20.8 | 33.3 |
| W20150426 | 0 | 16.7 | 29.2 |
| Envidor | 8.3 | 12.5 | 29.2 |
| Compound N | 12.5 | 29.2 | 41.7 |
| Compound M | 0 | 8.3 | 29.2 |
| Compound O | 0 | 8.3 | 12.5 |
| Blank | 0 | 0 | 0 |
Data are found out from table 5, and part preferably pyrazoles acid oxo spiroheterocyclic ester derivant is to beet exigua larvae desinsection table
Reveal certain kill activity, comparison medicament Envidor is higher than to beet exigua larvae bioactivity, W20150309,
W20150409, W201504151, W201504141, W201504211 are higher than control chemical combination to beet exigua larvae bioactivity
Object N, M, O.
The result shows that the preferred pyrazoles acid oxo spiroheterocyclic ester derivant in part provided by the invention is to 3 age of beet armyworm children
Worm lethality and administration time positive correlation.
The preferred pyrazoles acid oxo spiroheterocyclic ester derivant in 7 part of embodiment surveys Tetranychus urticae larva insecticidal bioactivity
Examination
1 experiment condition
(1) laboratory apparatus: artificial intelligence climate box (production of Ningbo Jiangnan instrument plant, model RXZ type), stereomicroscope
(Motic SMZ168), tweezers, filter paper, culture dish, sprayer, sponge, marking pen, small size writing brush.
(2) test method: infusion process；
(3) biological test material: it is collected in the Tetranychus urticae of academy of agricultural sciences, Shandong Province Institute of Plant Protection greenhouse kidney bean leaf；
(4) compound: 98% raw medicine of created compound is tested；
(5) comparison medicament: Envidor () 98% raw medicine, compound N () 98% raw medicine, compound M() 98% raw medicine, compound O() 98% raw medicine；
(6) blank control: the organic solvent of 0.1% Tween-80.
Dosage setting
The compound of initiative is made into mother liquor with chloroform, then corresponding concentration is diluted to 0.1% Tween 80 aqueous solution.
Mother liquor is with indoor biometrics experiment standard preparation.
Created compound is dissolved with suitable solvent, is configured to mother liquor, then be diluted to 0.1% Tween 80 aqueous solution
20 ppm。
Experimental procedure
(1) reaction utensil is arranged: by one piece of 8 cm of diameter, 1 cm of thickness and the sponge through water saturates is placed on diameter as 12 cm
Culture dish in, sponge upper surface covers the filter paper that diameter is 6 cm, and water is added in culture dish, makes its liquid level lower than sponge
Highly.By clean fresh kidney bean blade, it is about the blade face (2 cm, wide 1.5 cm) and is put on filter paper downward.
(2) the sheet glass infusion process that medicament pharmacodynamic test is recommended referring to FAO, is cut into 2cm × 2cm size for double faced adhesive tape,
It is attached to one end of microscopic slide, selecting female adult mite in the same size, that action is active with No. 0 writing brush makes its back downwards gently
It is sticked on adhesive tape, every piece of glass slide is 30 viscous, and each chemicals treatment is repeated 3 times.The sheet glass for being stained with female adult mite is placed on completely
It is big support in worm ware, and put a wet cotton balls, cover glass plate is placed in 25 DEG C, in the artificial intelligence climate box of relative humidity 85%.
Microscopy after 2h rejects dead or torpescence individual.When measurement, test group immerses the sheet glass one end for the female adult mite being stained with respectively
To in reagent liquid, taken out after 5 s in control group leaching clear water, blotted with fritter filter paper rapidly be attached to it is more around mite body and on adhesive tape
Extraction raffinate body.Treated, and sheet glass is put back to again in original big feeding worm ware, is placed in above-mentioned growth cabinet.Using stereoscopic micro-
Mirror respectively at for 24 hours, microscopy when 48h, 72h.When microscopy, mite body is gently touched with writing brush point, limbs are motionless, nonresponder is denoted as extremely
Die individual.
Data statistics and analysis
The death rate and corrected mortality are counted and calculated as the following formula, and make to carry out the significance of difference point to each processing data
Analysis.
The calculating of the death rate and corrected mortality.
Experimental result is shown in Table 6
6 acaricidal activity of table (concentration: 50mg/L, corrected mortality/%)
| Compound number | 24h | 48h | 72h |
| W201502031 | 23.6 | 50.2 | 77.9 |
| W201502041 | 25.4 | 59.8 | 86.7 |
| W201502051 | 24.6 | 60.0 | 87.2 |
| W201503121 | 20.8 | 58.4 | 69.8 |
| W201503032 | 18.9 | 46.3 | 71.6 |
| W20150309 | 19.8 | 50.3 | 81.2 |
| W20150409 | 38.5 | 69.3 | 90.6 |
| W201504073 | 16.9 | 40.6 | 68.3 |
| W201503251 | 40.6 | 70.8 | 93.1 |
| W201504151 | 17.5 | 46.7 | 70.5 |
| W201504141 | 16.9 | 50.1 | 70.8 |
| W201504161 | 37.5 | 66.5 | 90.8 |
| W201504211 | 40.1 | 69.5 | 91.7 |
| W20150423 | 20.0 | 42.6 | 78.2 |
| W20150426 | 18.6 | 45.7 | 77.1 |
| Envidor | 41.6 | 69.3 | 92.4 |
| Compound N | 25.3 | 58.1 | 85.3 |
| Compound M | 18.6 | 40.6 | 68.3 |
| Compound O | 17.5 | 42.6 | 68.3 |
Data are found out from table 6, and part preferably pyrazoles acid oxo spiroheterocyclic ester derivant is under 10mg/L concentration, to two spots
Tetranychid has the kill activity of higher degree.Wherein tetra- kinds of W20150409, W201503251, W201504161, W201504211
Compound 72 hours are more than 90% to Tetranychus urticae lethality, a little higher than comparison medicine suitable with comparison medicament Envidor acaricidal activity
Immunomodulator compounds N, M, O, W201502041, W201502051 activity and N are suitable.
The result shows that the preferred pyrazoles acid oxo spiroheterocyclic ester derivant in part provided by the invention is to Tetranychus urticae lethality
With administration time positive correlation.
The preferred pyrazoles acid oxo spiroheterocyclic ester derivant in 8 part of embodiment is to cotton bollworm larvae, diamondback moth larvae and dark greyish green
The test of worm larva insecticidal bioactivity
For test process with embodiment 6, difference is as follows:
(1) 3 age beet exigua larvaes are changed into 3 instar bollworm grubs, diamondback moth larvae and cabbage caterpillar larva；
(2) death condition for trying larva is counted in 72h, and calculates its death rate；
(3) 7 test result: are shown in Table.
7 insecticidal activity of table (concentration: 10 mg/L, 72h lethality/%)
| Compound number | Bollworm | Diamondback moth | Cabbage caterpillar |
| W201502031 | 12.5 | 16.7 | 29.2 |
| W201502041 | 16.7 | 20.8 | 20.8 |
| W201502051 | 29.2 | 20.8 | 33.3 |
| W201503121 | 20.8 | 25.0 | 29.2 |
| W201503032 | 33.3 | 33.3 | 37.5 |
| W20150309 | 20.8 | 25.0 | 33.3 |
| W20150409 | 37.5 | 33.3 | 45.8 |
| W201504073 | 25.0 | 20.8 | 29.2 |
| W201503251 | 39.2 | 37.5 | 41.7 |
| W201504151 | 20.8 | 29.2 | 29.2 |
| W201504141 | 12.5 | 29.2 | 33.3 |
| W201504161 | 33.3 | 37.5 | 39.2 |
| W201504211 | 37.5 | 39.2 | 45.8 |
| W20150423 | 16.7 | 8.3 | 20.8 |
| W20150426 | 12.5 | 20.8 | 25.0 |
| Envidor | 16.7 | 29.2 | 33.3 |
| Compound N | 25.0 | 33.3 | 33.3 |
| Compound M | 16.7 | 33.3 | 39.2 |
| Compound O | 12.5 | 20.8 | 33.3 |
Data are found out from table 7, and the preferred pyrazoles acid oxo spiroheterocyclic ester compounds in part provided by the invention are in 10mg/L
Under concentration, after medication 72h, there is certain insecticidal activity to cabbage caterpillar, bollworm and diamondback moth, there are multiple compound activities good
In or be equivalent to comparison medicament Envidor and compound N, M, O.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (5)
1. one group of pyrazoles acid oxo spiroheterocyclic ester derivant, it is characterised in that: the derivative is selected from one of following:
。
2. a kind of method for preparing any one of claim 1 derivative, it is characterised in that: its preparation process is as follows:
,
Y group can be selected from O, NH in formula I；X is halogen, and m is 1 or 2 or 3 or 4；R group can be selected fromOr
, wherein R1ForOrOrOr, A is halogen or H；The halogen Cl.
3. according to the method described in claim 2, it is characterized by: the described method comprises the following steps: acetonitrile is solvent, with carbon
Sour potassium is acid binding agent, will be dissolved with acetonitrile under the conditions of 0 ± 5 DEG CIt is added drop-wise toAcetonitrile solution
In, then heat to 20 ± 5 DEG C, and maintain 20 ± 5 DEG C the reaction was continued, TLC monitoring, when after the reaction was completed, being filtered to remove solid,
Solvent is removed, precipitation obtained solid is washed with distilled water, corresponding object is made in drying, use ethyl alcohol
Recrystallization is madeSterling;
Y group can be selected from O, NH in formula I；X is halogen, and m is 1 or 2 or 3 or 4；R group can be selected fromOr
, wherein R1ForOrOrOr, A is halogen or H；The halogen is Cl.
4. the preparation of the derivative containing any one of claim 1, is made of, wherein the weight of derivative derivative and pesticide auxiliary material
Measuring content is 0.1% ~ 99.9%.
5. preparation described in any one of claim 1 derivative or claim 4 is in the pesticide of preparation prevention and treatment agricultural pests
Application.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193960A (en) * | 1995-06-30 | 1998-09-23 | 拜尔公司 | Dialkyl phenyl halide-substituted keto-enols for use as herbicides and pesticides |
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2016
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193960A (en) * | 1995-06-30 | 1998-09-23 | 拜尔公司 | Dialkyl phenyl halide-substituted keto-enols for use as herbicides and pesticides |
Non-Patent Citations (4)
| Title |
|---|
| "Spirodiclofen Derivatives as Highly Potential Acaricides: Synthesis, Structure and Bioactivity";FENG Xian-guo，et al.;《CHEM. RES. CHINESE UNIVERSITIES》;20111130;第27卷(第6期);968—972 |
| "螺环季酮酸的羧酸酯衍生物的合成及其杀螨活性";高树坤，等;《应用化学》;20120831;第29卷(第8期);885-891 |
| "螺环季酮酸衍生物的合成及生物活性研究";赵金浩等;《有机化学》;20111031;第31卷(第10期);1631-1638 |
| "螺环季酮酸衍生物的合成及生物活性研究";高聪杰;《现代农药》;20120229;第11卷(第1期);15-21 |
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