CN105924432B - Pyridazinone derivative and its preparation method and application - Google Patents

Pyridazinone derivative and its preparation method and application Download PDF

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CN105924432B
CN105924432B CN201610548582.6A CN201610548582A CN105924432B CN 105924432 B CN105924432 B CN 105924432B CN 201610548582 A CN201610548582 A CN 201610548582A CN 105924432 B CN105924432 B CN 105924432B
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halogen
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孙家隆
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Qingdao Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines

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Abstract

The present invention relates to one kind to haveThe pyridazinone derivative of structure, wherein R1、R2Group is selected from specification specific meanings.The invention discloses the structure of these compounds and to agricultural insect management effect, application of these compounds as insecticide is also disclosed.

Description

Pyridazinone derivative and its preparation method and application
Technical field
The invention belongs to pesticide field, technical solution is related to one group of pyridazinone derivative, and in particular to pyridazinone derivative And preparation method thereof and its agricultural insecticide application.
Background technology
Pyridazinone compound often has a high bioactivity, but the ripe pesticide species of exploitation are only rattled away mite at present Ketone is widely used in the prevention of all kinds of mites.Due to the excessive use of pyridaben in recent years, most evil mites have produced it Serious drug resistance causes the plant protection sexual valence of pyridaben pesticide species more serious than declining, agriculture mite evil large area generation, agriculture The phenomenon that industry good harvest significantly declines 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 pyridazinone derivative, and determines its mite killing, desinsection work Property.
Invention content
The object of the present invention is to provide one group of pyridazinone derivatives；
The present invention provides one group of pyridazinone derivative, and structural formula is as shown in formula I：
Formulas I,
R in formula I1Group can be selected from：、；Wherein X is halogen, m is 1 or 2 or 3, and Y isOrOrOrOr；R2Group can be selected from：Or；Wherein R3ForOrOrOrOr, A is halogen or H, and B is O or S；The halogen be F or Cl or Br or I.
It is further preferred that the one kind of the derivative in following：
Number Chemical structural formula Number Chemical structural formula
LK20150205 LK20150301
LK20150305 LK20150313
LK20150314 LK20150316
LK20150319 LK20150322
LK20150327 LK20150401
LK20150407 LK20150409
LK20150411 LK20150413
LK20150416 LK20150418
LK20150424 LK20150429
LK20150502 LK20150504
LK20150505 LK20150508
LK20150513 LK20150514
LK20150515 LK20150516
LK20150517 LK20150520
LK20150523 LK20150524
ZJ201505221 ZJ201505291
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）Using ethylene glycol as solvent, to dissolving, 20 ± 5 DEG C are added calculation amounts for stirring after calculation amount KOH is added, 130 ± 10 DEG C are gradually heating to, TLC monitors reaction process, whenIt, will be anti-after reaction thoroughly It answers liquid to pour into distilled water, with hydrochloric acid solution tune pH=1 of 6 mol/L, white solid is precipitated, decompression filters, with distilled water water It washes, solid is dryCrude product recrystallizesSterling；
WithN,NDimethylformamide is solvent, and calculation amount is added, calculation amount is slowly added dropwise at -5 ± 2 DEG C Then 30% sodium hydrosulfide aqueous solution controls 0 ~ 5 DEG C of temperature, TLC monitors reaction process, whenAfter reaction thoroughly, Reaction solution is poured into distilled water, with hydrochloric acid solution tune pH=1 of 6 mol/L, white solid is precipitated, decompression filters, and uses distilled water Washing, solid are dryCrude product recrystallizesSterling；
（2）Using acetonitrile as solvent, calculation amount is sequentially added under the conditions of 20 ± 5 DEG C, potassium carbonate powder, Calculation amount is slowly added dropwise at 0 ± 5 DEG CAcetonitrile solution, then control 20 ± 5 DEG C of temperature, TLC monitoring react into Journey removes solvent after the completion of reaction, uses saturated sodium bicarbonate aqueous solution, distillation water washing precipitation obtained solid, solid successively DryCrude product recrystallizesSterling；
（3）Using acetonitrile as solvent, calculation amount is sequentially added under the conditions of 20 ± 5 DEG C, potassium carbonate powder, 0 ± 5 DEG C is slowly added dropwise calculation amountAcetonitrile solution, then control 20 ± 5 DEG C of temperature, TLC monitoring react into Journey removes solvent after the completion of reaction, uses saturated sodium bicarbonate aqueous solution, distillation water washing precipitation obtained solid, solid successively DryCrude product recrystallizesSterling.
Third object of the present invention is to provide the preparation containing pyridazinone derivative, by the auxiliary material of derivative and pesticide, Weight percent content is 0.1%-99.9% to middle pyridazinone derivative in the formulation.
It is a further object of the present invention to provide the pyridazinone derivatives as agricultural insecticide application.
Pyridazinone derivative provided by the invention is used to prevent one of the important feature that agricultural pests are the present invention.
Derivative provided by the invention has the following advantages：
1, pyridazinone derivative of the invention can be used for preventing agricultural pests, and can obtain good effect.
2, " three wastes " generated in noval chemical compound preparation process of the present invention are less, are 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 agricultural evil as new insecticide Worm can be applied to the pest to develop immunity to drugs, and effect is good, and has the advantages that at low cost.
Specific implementation mode
The present invention by it is specific preparation and biological activity determination embodiment specific description pyridazinone derivative preparation and Bioactivity, 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 L K20150205 of embodiment
（1）
Concrete operations：In 250 mL three-necked flasks, 100 mmol KOH, 70 mL second two are added under the conditions of 20 ± 5 DEG C After stirring to KOH is dissolved, 20 mmol C are added in alcohol, are gradually heating to 130 DEG C, and TLC monitors reaction process, when reaction is thorough Afterwards, reaction solution is poured into 500 mL distilled water, with hydrochloric acid solution tune pH=1 of 6 mol/L, a large amount of white solids is precipitated, depressurized It filters, is washed with distilled water, filter cake is placed in drying under infrared lamp, obtains object D crude products, ethyl alcohol recrystallization obtains target compound D Sterling.
（2）
Concrete operations：In the 100 mL single-necked flasks equipped with magnetic stirring apparatus, calcium chloride tube, constant pressure funnel In, it is added the D of 10 mmol, the acetonitrile of 15 mmol potassium carbonate powders, 30 mL under the conditions of 20 ± 5 DEG C, under the conditions of 0 ± 5 DEG C, delays The slow dropwise addition diluted 11 mmol E of 30 mL solvents are to slowly warm up to 20 ± 5 DEG C of continuation insulation reactions, TLC after being added dropwise to complete Reaction process is monitored, after D reactions are thorough, rotary evaporation removes solvent, and 50 mL saturated sodium bicarbonate aqueous solutions, room temperature is added 1 h is persistently stirred down, and decompression is filtered, is washed with distilled water, and filter cake is placed in drying under infrared lamp, obtains object F crude products, ties again Crystalline substance obtains target compound F sterlings.Character：White solid, fusing point：92.8 ~ 93.1 DEG C, yield：77%.
2 compound of embodiment、Preparation
、
Concrete operations：With the preparation of compound LK20150205, difference：By the preparation of LK20150205（1）In C Required specific pyridazinone derivative is replaced with, by the preparation of LK20150205（2）Pyrazole acyl chloride replace with it is required Specific pyrazole acyl chloride.With the physicochemical data such as table 1 of the preferred pyridazinone derivative in part prepared by this method.
The physicochemical data of the preferred pyridazinone derivative in 1 part of table
The preparation of 3 compound L K20150313 of embodiment
（1）
Concrete operations：In 100 mL three-necked flasks, 40 mmol C, 40 mL are sequentially added under the conditions of 20 ± 5 DEG CN,N- Dimethylformamide, is slowly added dropwise the sodium hydrosulfide aqueous solution of 80 mmol 30% when being cooled to -5 DEG C, control temperature at 0-5 DEG C, TLC monitors reaction process, when C reactions thoroughly after, reaction solution is poured into 800 mL water, with the hydrochloric acid solution tune pH of 6 mol/L= 1, white solid is precipitated, decompression is filtered, is washed with distilled water, and filter cake is placed in drying under infrared lamp, obtains object G crude products, ties again Crystalline substance obtains target compound G sterlings.
（2）
Concrete operations：With the preparation of 1 compound L K20150205 of embodiment（2）, difference：D is changed to G.Obtain target Object LK20150313 crude products, recrystallization, obtain target compound LK20150313 sterlings.Character：White solid, fusing point：128.9~ 129.2 DEG C, yield：77%.
4 compound of embodiment、Preparation
、
Concrete operations：With the preparation of compound LK20150313, difference：By the preparation of LK20150313（1）In C Required specific pyridazinone derivative is replaced with, by the preparation of LK20150313（2）Pyrazole acyl chloride replace with it is required Specific pyrazole acyl chloride.With the physicochemical data such as table 2 of the preferred pyridazinone derivative in part prepared by this method.
The physicochemical data of the preferred pyridazinone derivative in 2 part of table
5 part preferred compound of embodiment1H-NMR and IR parametric measurements and Identification of chemical structure
The preferred pyridazinone compound in 3 part of table1H-NMR data
Number Hydrogen nuclear magnetic resonance modal data1H NMR/ppm
LK20150205 1H NMR (500 MHz, CDCl3) δ 7.82 (s, 1H,N=CH), 4.16 (s, 3H,N-CH3), 2.70 (q, J = 7.6 Hz, 2H,-CH2), 1.68 (s, 9H,t-C4H9), 1.28 (t, J = 7.6 Hz, 3H,-CH3).
LK20150301 1H NMR (500 MHz, CDCl3) δ 8.01 (s, 1H,C=CH), 7.84 (s, 1H,N=CH), 3.92 (s, 3H,N-CH3), 2.51 (s, 3H,-CH3), 1.67 (s, 9H,t-C4H9).
LK20150305 1H NMR (500 MHz, CDCl3) δ 8.19 (s, 1H,C=CH), 7.83 (s, 1H,N=CH), 4.06 (s, 3H,N-CH3), 1.67 (s, 9H,t-C4H9).
LK20150313 1H NMR (500 MHz, CDCl3) δ 7.76 (s, 1H,N=CH), 4.04 (d, J = 6.2 Hz, 3H, =N-CH3), 2.69 (q, J = 7.6 Hz, 2H,-CH2), 1.69 (s, 9H,t-C4H9), 1.27 (t, J = 7.6 Hz, 3H,-CH3).
LK20150314 1H NMR (500 MHz, CDCl3) δ 8.17 (s, 1H,C=CH), 7.84 (s, 1H,N=CH), 4.05 (s, 3H,N-CH3), 1.67 (s, 9H,t-C4H9).
LK20150316 1H NMR (500 MHz, CDCl3) δ 7.81 (s, 1H,N=CH), 4.11 (s, 3H,N-CH3), 1.95 (ddd, J = 16.8, 8.3, 5.2 Hz, 1H,-CH), 1.68 (s, 9H,t-C4H9), 1.00 – 0.91 (m, 4H,-CH2CH2-).
LK20150319 1H NMR (500 MHz, CDCl3) δ 7.80 (s, 1H,C=CH), 6.93 (s, 1H,N=CH), 4.17 (s, 3H,N-CH3), 1.68 (s, 9H,N-t-C4H9), 1.34 (s, 9H,C-t-C4H9).
LK20150322 1H NMR (500 MHz, CDCl3) δ 8.06 (s, 1H,C=CH), 8.04 (s, 1H,N=CH), 7.69 (d,, J = 9.0 Hz, 2H,-PhH), 7.34 (d, J = 8.7 Hz, 2H,-PhH), 3.94 (s, 3H,N-CH3), 2.53 (s, 3H,-CH3).
LK20150327 1H NMR (500 MHz, CDCl3) δ 8.23 (s, 1H,C=CH), 8.04 (s, 1H,N=CH), 7.70 – 7.67 (m, 2H,-PhH), 7.34 (d, J = 8.5 Hz, 2H,-PhH), 4.08 (s, 3H,-CH3).
LK20150401 1H NMR (500 MHz, CDCl3) δ 7.81 (s, 1H,N=CH), 4.13 (s, 3H,N-CH3), 1.68 (s, 9H,N-t-C4H9), 1.54 (s, 3H,-CH3), 1.42 (s, 9H,C-t-C4H9).
LK20150407 1H NMR (500 MHz, CDCl3) δ 7.76 (s, 1H,N=CH), 4.02 (s, 3H,N-CH3), 1.69 (s, 9H,N-t-C4H9), 1.42 (s, 9H,C-t-C4H9).
LK20150409 1H NMR (500 MHz, CDCl3) δ 7.73 (s, 1H,C=CH), 6.83 (s, 1H,N=CH), 4.01 (s, 3H,N-CH3), 1.61 (s, 9H,N-t-C4H9), 1.27 (s, 9H,C-t-C4H9).
LK20150411 1H NMR (500 MHz, CDCl3) δ 7.76 (s, 1H,N=CH), 4.00 (s, 3H,N-CH3), 1.92 (ddd, J = 13.4, 6.6, 4.2 Hz, 1H,-CH), 1.69 (s, 9H,N-t- C4H9), 1.00 – 0.95 (m, 4H,-CH2CH2-)
LK20150413 1H NMR (500 MHz, CDCl3) δ 7.94 (s, 1H,N=CH), 7.87 (d, J = 2.4 Hz, 1H,-PhH), 7.61 (d, J = 2.4 Hz, 1H,-PhH), 7.58 (s, 1H,-PhH), 4.04 (s, 3H,N-CH3), 1.43 (s, 9H,t-C4H9).
LK20150416 1H NMR (500 MHz, CDCl3) δ 7.95 (s, 1H,N=CH), 7.62 (d, J = 8.8 Hz, 2H,-PhH), 7.28 (d, J = 8.7 Hz, 2H,-PhH), 4.09 (s, 3H,N-CH3), 1.37 (s, 9H,t-C4H9).
LK20150418 1H NMR (500 MHz, CDCl3) δ 8.03 (s, 1H,N=CH), 7.69 (d, J = 8.9 Hz, 2H,-PhH), 7.35 (d, J = 8.7 Hz, 2H,-PhH), 4.13 (s, 3H,N-CH3), 1.96 (ddd, J = 13.4, 8.3, 5.1 Hz, 1H,-CH), 1.00 – 0.92 (m, 4H,-CH2CH2-).
LK20150424 1H NMR (500 MHz, CDCl3) δ 7.95 (s, 1H,N=CH), 7.87 (d, J = 2.4 Hz, 1H,-PhH), 7.62 (dd, J = 8.7, 2.4 Hz, 1H,-PhH), 7.57 (d, J = 8.7 Hz, 1H,-PhH), 4.02 (s, 3H,N-CH3), 1.94 (ddd, J = 13.4, 8.4, 5.1 Hz, 1H,-CH), 1.02 – 0.91 (m, 4H,-CH2CH2-).
LK20150429 1H NMR (500 MHz, CDCl3) δ 8.02 (s, 1H,N=CH), 7.82 (d, J = 1.3 Hz, 1H,-PhH), 7.57 (d, J = 2.1 Hz, 2H,-PhH), 4.16 (s, 3H,N-CH3), 1.43 (s, 9H,t-C4H9).
LK20150502 1H NMR (500 MHz, CDCl3) δ 7.95 (s, 1H,N=CH), 7.74 (d, J = 8.9 Hz, 2H,-PhH), 7.35 (d, J = 8.7 Hz, 2H,-PhH), 4.08 (s, 3H,N-CH3), 2.70 (q, J = 7.6 Hz, 2H,-CH2), 1.28 (t, J = 7.6 Hz, 3H,-CH3).
LK20150504 1H NMR (500 MHz, CDCl3) δ 7.95 (s, 1H,N=CH), 7.87 (d, J = 2.4 Hz, 1H,-PhH), 7.62 (dd, J = 8.7, 2.4 Hz, 1H,-PhH), 7.57 (d, J = 8.7 Hz, 1H,-PhH), 4.07 (s, 3H,N-CH3), 2.70 (q, J = 7.6 Hz, 2H,-CH2), 1.28 (t, J = 7.6 Hz, 3H,-CH3).
LK20150505 1H NMR (500 MHz, CDCl3) δ 8.02 (s, 1H,N=CH), 7.63 (d, J = 1.8 Hz,2H, -PhH), 7.43 (t, J = 1.8 Hz, 1H,-PhH), 4.16 (s, 3H,N-CH3), 1.43 (s, 9H,t-C4H9).
LK20150508 1H NMR (500 MHz, CDCl3) δ 8.03 (s, 1H,N=CH), 7.63 (d, J = 1.8 Hz, 2H,-PhH), 7.43 (t, J = 1.8 Hz, 1H,-PhH), 4.18 (s, 3H,N-CH3), 2.71 (q, J = 7.6 Hz, 2H,-CH2), 1.29 (t, J = 7.6 Hz, 3H,-CH3).
LK20150513 1H NMR (500 MHz, CDCl3) δ 8.03 (s, 1H,N=CH), 7.63 (d, J = 1.8 Hz, 2H,-PhH), 7.43 (t, J = 1.8 Hz, 1H,-PhH), 4.13 (s, 3H,N-CH3), 1.97 (ddd, J = 16.8, 8.3, 5.1 Hz, 1H,-CH), 1.01-0.97 (m, 2H,-CH2), 0.96 -0.93 (m, 2H,-CH2).
LK20150514 1H NMR (500 MHz, CDCl3) δ 8.00 (s, 1H,N=CH), 7.59 (d, J = 2.1 Hz, 1H,-PhH), 7.42 (dd, J = 8.5, 2.2 Hz, 1H,-PhH), 7.38 (d, J = 8.5 Hz, 1H,-PhH), 4.16 (s, 3H,N-CH3), 1.44 (s, 9H,t-C4H9).
LK20150515 1H NMR (500 MHz, CDCl3) δ 8.01 (s, 1H,N=CH), 7.59 (d, J = 2.2 Hz, 1H,-PhH), 7.43 (dd, J = 8.5, 2.2 Hz, 1H,-PhH), 7.38 (d, J = 8.5 Hz, 1H,-PhH), 4.19 (s, 3H,N-CH3), 2.72 (q, J = 7.6 Hz, 2H,-CH2), 1.29 (t, J = 7.6 Hz, 3H-CH3).
LK20150516 1H NMR (500 MHz, CDCl3) δ 8.01 (s, 1H,N=CH), 7.59 (d, J = 2.2 Hz, 1H,-PhH), 7.42 (dd, J = 8.5, 2.2 Hz, 1H,-PhH), 7.38 (d, J = 8.5 Hz, 1H,-PhH), 4.13 (s, 3H,N-CH3), 1.97 (ddd, J = 16.8, 8.3, 5.1 Hz, 1H,-CH), 1.01 – 0.98 (m, 2H,-CH2), 0.97 – 0.93 (m, 2H,- CH2).
LK20150517 1H NMR (500 MHz, CDCl3) δ 7.96 (s, 1H,N=CH), 7.63 (d, J = 9.0 Hz, 2H,-PhH), 7.28 (d, J = 8.4 Hz, 2H,-PhH), 4.11 (s, 3H,N-CH3), 2.65 (q, J = 7.6 Hz, 2H,-CH2), 1.22 (t, J = 7.6 Hz, 3H,-CH3).
LK20150520 1H NMR (500 MHz, CDCl3) δ 7.96 (s, 1H,N=CH), 7.75 (d, J = 1.4 Hz, 1H,-PhH), 7.50 (d, J = 2.0 Hz, 2H,-PhH), 4.11 (s, 3H,N-CH3), 2.64 (q, J = 7.6 Hz, 2H,-CH2), 1.22 (t, J = 7.6 Hz, 3H,-CH3).
LK20150523 1H NMR (500 MHz, CDCl3) δ 7.88 (s, 1H,N=CH), 7.67 (dd, J = 9.5, 2.5 Hz, 2H,-PhH), 7.28 (d, J = 8.6 Hz, 2H,-PhH), 3.98 (s, 3H,N- CH3), 1.36 (s, 9H,t-C4H9).
LK20150524 1H NMR (500 MHz, CDCl3) δ 7.93 (s, 1H,N=CH), 7.60 (d, J = 1.8 Hz, 2H,-PhH), 7.35 (t, J = 1.8 Hz, 1H,-PhH), 3.99 (s, 3H,N-CH3), 1.88 (ddd, J = 13.4, 8.4, 5.0 Hz, 1H,-CH), 0.94 – 0.90 (m, 2H,-CH2), 0.72 (dt, J = 6.7, 4.6 Hz, 2H,-CH2).
ZJ201505221 1H NMR (500 MHz, CDCl3) δ 7.95 (s, 1H,N=CH), 7.75 (d, J = 1.3 Hz, 1H,-PhH), 7.50 (d, J = 2.0 Hz, 2H,-PhH), 4.06 (s, 3H,N-CH3), 1.91 – 1.87 (m, 1H,-CH), 0.94 – 0.90 (m, 2H,-CH2), 0.90 – 0.86 (m, 2H,-CH2).
Xh201505291 1H NMR (500 MHz, CDCl3) δ 8.04 (s, 1H,N=CH), 7.60 (d, J = 8.5 Hz, 2H,-PhH), 7.45 (d, J = 8.1 Hz, 1H,-PhH), 4.19 (s, 3H,N-CH3), 2.72 (q, J = 7.6 Hz, 2H,-CH2), 2.28 (s, 3H,-CH3), 1.29 (t, J = 7.6 Hz, 3H,-CH3).
Xh201505292 1H NMR (500 MHz, CDCl3) δ 7.96 (s, 1H,N=CH), 7.53 (d, J = 8.6 Hz, 2H,-PhH), 7.38 (d, J = 8.1 Hz, 1H,-PhH), 4.10 (s, 3H,N-CH3), 2.22 (s, 3H,-CH3), 1.37 (s, 9H,t-C4H9).
ZJ201505291 1H NMR (500 MHz, CDCl3) δ 7.97 (s, 1H,N=CH), 7.53 (d, J = 8.7 Hz, 2H,-PhH), 7.38 (d, J = 8.1 Hz, 1H,-PhH), 4.07 (s, 3H,N-CH3), 2.21 (s, 3H,-CH3), 1.92 – 1.88 (m, 1H,-CH), 0.94 – 0.91 (m, 2H,-CH2), 0.90 – 0.87 (m, 2H,-CH2).
The ir data of the preferred pyridazinone compound in 4 part of table
Number Infrared spectrum data1H NMR/ppm
LK20150205 2990 2934 2881 2857 1756 1668 1615 1518 1450 1365 1256 1227
LK20150301 3128 3078 2993 2946 1756 1653 1615 1542 1500 1459 1394 1300 1277
LK20150305 3055 2934 1751 1651 1621 1545 1489 1456 1386 1294 1224
LK20150313 2981 2963 1674 1659 1577 1509 1462 1439 1297 1259
LK20150314 3122 2990 2937 1718 1689 1651 1577 1530 1497 1456 1388 1280 1206
LK20150316 3001 2982 2923 1751 1650 1605 1487 1445 1386 1366 1307 1263 1236
LK20150319 3076 2966 2932 2901 2868 1762 1664 1614 1530 1482 1398 1364 1269 1223
LK20150322 3134 3084 3031 1765 1651 1624 1553 1503 1485 1459 1386 1306 1277 1224
LK20150327 3083 1784 1665 1609 1543 1508 1447 1422 1374 1297 1260 1222
LK20150401 2981,2960,2940,2869,1759,1662,1648,1609,1509,1480,1450,1309,1250
LK20150407 2984,2963,2925,1659,1580,1480,1456,1400,1368,1312,1238
LK20150411 3011 2985 2926 2872 2854 1665 1650 1575 1458 1436 1397 1366 1298 1201
LK20150413 3083 2968 2928 2873 2854 1669 1639 1576 1476 1440 1394 1337
LK20150416 2977 2937 2878 1748 1682 1616 1515 1487 1453 1413 1376 1342
LK20150418 3012 2952 1752 1678 1615 1511 1458 1413 1377 1321
LK20150424 3096 2919 2855 1669 1574 1474 1442 1400 1309
LK20150429 3077 2999 2972 2934 2913 1759 1680 1624 1465 1394 1321
LK20150502 3090,2993,2919,2854,1680,1662,1574,1506,1436,1403,1300,1268
LK20150504 3099 2975 2937 1674 1580 1471 1433 1403 1297 1235 1206
LK20150505 3090 2981 2963 2916 2863 1748 1685 1618 1574 1489 1433 1347 1271 1250
LK20150508 3086 2975 2878 1736 1683 1580 1524 1433 1415 1377 1300 1247
LK20150509 3084 2925 2849 1653 1583 1566 1459 1427 1377 1297 1244
LK20150513 3090 3010 2955 2925 2849 1742 1683 1612 1586 1497 1439 1371 1271 1233
LK20150514 3093 2966 2928 2907 2875 1759 1656 1612 1586 1477 1456 1374 1336 1244
LK20150515 3037 2978 2931 2872 2857 1751 1668 1586 1486 1453 1377 1297 1230
LK20150516 3102 3037 2957 2925 2852 1757 1676 1606 1586 1481 1451 1413 1383 1303
LK20150517 3119 3090 2984 2925 1745 1680 1618 1512 1456 1380 1306 1271 1238
LK20150520 3096 2985 2928 1741 1675 1620 1467 1411 1373 1298 1236
LK20150523 2969,2931,2913,2872,1668,1648,1580,1509,1444,1403,1274
LK20150527 3090,3043,2960,2919,1668,1639,1583,1568,1433,1374,1259
ZJ201505221 3078,2963,2916,1756,1668,1659,1459,1303,1283
ZJ201505291 3099,2955,2925,2854,1745,1677,1474,1374,1241
By table 3 and table 4 as it can be seen that part preferably pyridazinone derivative1H-NMR shows chemical potential corresponding with its structure It moves, the number of H and its structure are coincide, the corresponding skeleton absorption peak of IR appearance.
The preferred pyridazinone compound in 6 part of embodiment tests beet exigua larvae insecticidal bioactivity
（1）Laboratory apparatus：Assay balance supports worm plate, incubator, culture dish；
（2）Selected insect source：3 instar larvae of beet armyworm；
（3）Test method：Stomach poison toxicity test, endless feeding method；
（4）By reagent agent standard preparation at 1000ppm solution（Solvent, acetone）, for use after 100 times of dilution.By 3 ages Beet exigua larvae does 4h Nature enemies, 24 3 age health beet exigua larvaes experiments of every group of selection, each medicament parallel determination Two groups；Take appropriate feed mean allocation in the interval of each foster worm plate, 5.00uL etc. is injected in each interval with micropipettor The reagent agent solution for measuring 10ppm, by 24 choose be evenly distributed in the interval of each foster worm plate for test worm body, between each Every one, worm plate is supported with the toilet paper covering after disinfection, sprays 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 or cannot just produce and creep as death standard with polypide.The dead polypide quantity of record, and calculate Its death rate.
（5）Comparison medicament：Pyridaben (), young ketone of rattling away (), change Conjunction object N ()；
（6）Experimental result is shown in Table 5.
5 insecticidal activity of table（Concentration:10mg/L, lethality/%）
Compound number 24h 48h 72h
LK20150205 4.2 25.0 50.0
LK20150301 0 8.3 29.2
LK20150305 4.2 12.5 20.8
LK20150313 8.3 29.2 62.5
LK20150314 4.2 25.0 50.0
LK20150316 4.2 12.5 54.3
LK20150319 0 8.3 16.7
LK20150322 0 12.5 20.8
LK20150327 0 12.5 33.3
LK20150401 0 16.7 37.5
LK20150407 8.3 33.3 62.5
LK20150409 0 20.8 41.7
LK20150411 8.3 37.5 70.9
LK20150413 4.2 33.3 66.7
LK20150416 8.3 20.8 25.0
LK20150418 4.2 25.0 62.5
LK20150424 8.3 37.5 70.9
LK20150429 4.2 25.0 62.5
LK20150502 4.2 29.2 62.5
LK20150504 8.3 33.3 66.7
LK20150505 0 29.2 58.5
LK20150508 4.2 20.8 58.5
LK20150513 4.2 20.8 58.5
LK20150514 8.3 25.0 62.5
LK20150515 4.2 37.5 62.5
LK20150516 4.2 37.5 66.7
LK20150517 8.3 25.0 62.5
LK20150520 8.3 29.2 58.5
LK20150523 0 25.0 58.5
LK20150524 4.2 25.0 62.5
ZJ201505221 8.3 37.5 70.9
Xh201505291 8.3 29.2 62.5
Xh201505292 4.2 33.3 66.7
ZJ201505291 8.3 25.0 62.5
Pyridaben 0 29.2 58.5
It rattles away young ketone 4.2 33.3 62.5
Compound N 8.3 29.2 58.5
Blank 0 0 0
Data are found out from table 5, and part preferably pyridazinone derivative has beet armyworm certain under 10mg/L concentration Insecticidal activity.Wherein LK20150313, LK20150407, LK20150411, LK20150413, LK20150416, LK20150418、LK20150424、LK20150429、LK20150502、LK20150504、LK20150505、LK20150508、 LK20150513、LK20150514、LK20150515、LK20150516、LK20150517、LK20150520、LK20150523、 LK20150524, ZJ201505221, Xh201505291, Xh201505292, ZJ201505291 are at 72 hours to 3 beet nights in age Moth larvae lethality is near or above comparison medicament pyridaben（58.5%）, young ketone of rattling away（62.5%）, compound N（58.5%）.
The result shows that compound provided by the invention is positively correlated 3 instar larvae lethality of beet armyworm with administration time Relationship.
The preferred pyridazinone compound in 7 part of embodiment tests Tetranychus urticae larva insecticidal bioactivity
1 experiment condition
(1) laboratory apparatus：Artificial intelligence climate box (Ningbo Jiangnan instrument plant produces, model RXZ types), stereomicroscope (Motic SMZ168), tweezers, filter paper, culture dish, sprayer, sponge, marking pen, small size writing brush；
(2) test method：Infusion process；
(3) biology examination material：It is collected in the Tetranychus urticae of academy of agricultural sciences of Shandong Province Institute of Plant Protection greenhouse kidney bean leaf；
(4) compound is tested：98% active compound of created compound；
(5) comparison medicament：The active compound of pyridaben 98%, the active compound for young ketone 98% of rattling away, the active compound of compound N 98%；
(6) blank control：The organic solvent of 0.1% Tween-80.
Dosage is arranged
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：One piece of diameter 8cm, thickness 1cm and the sponge through water saturates are placed on a diameter of 12 cm's In culture dish, sponge upper surface covers the filter paper of a diameter of 6 cm, and water is added in culture dish, keeps its liquid level high less than sponge Degree.By clean fresh kidney bean blade, it is about the blade face (2cm, width 1.5cm) and is put on filter paper downward.
(2) the sheet glass infusion process that the medicament test of pesticide effectiveness is recommended with reference to FAO, 2cm × 2cm sizes are cut by double faced adhesive tape, It is attached to one end of microscopic slide, select active female of in the same size, action with No. 0 writing brush makes its back downwards gently at mite It is sticked on adhesive tape, every piece of glass slide is 30 viscous, and each chemicals treatment is repeated 3 times.The female sheet glass at mite will be stained with to be placed on totally 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 female immerses respectively by what is be stained at sheet glass one end of mite Wait 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 foster 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:20mg/L, corrected mortality/%）
Compound number 24h 48h 72h
LK20150205 5.6 15.3 32.1
LK20150301 4.5 15.3 20.8
LK20150305 3.2 8.9 22.3
LK20150313 15.3 40.1 58.6
LK20150314 15.3 38.6 50.3
LK20150316 15.3 40.2 60.0
LK20150319 4.5 32.1 55.3
LK20150322 3.2 8.5 26.5
LK20150327 3.2 8.5 25.1
LK20150401 3.2 8.9 33.3
LK20150407 20.5 48.6 71.2
LK20150409 4.5 38.6 50.5
LK20150411 22.3 48.6 69.8
LK20150413 20.5 48.6 70.1
LK20150416 4.5 35.5 50.8
LK20150418 4.5 20.3 47.9
LK20150424 20.5 48.6 70.8
LK20150429 3.2 18.5 33.5
LK20150502 4.5 20.3 53.8
LK20150504 4.5 20.3 54.6
LK20150505 3.2 18.5 48.3
LK20150508 4.5 18.5 46.8
LK20150513 4.5 20.3 50.3
LK20150514 18.5 38.6 67.5
LK20150515 3.2 20.3 50.3
LK20150516 20.3 48.6 66.9
LK20150517 4.5 20.3 49.8
LK20150520 4.5 20.3 50.3
LK20150523 3.2 18.5 52.1
LK20150524 4.5 20.3 50.6
ZJ201505221 18.5 38.6 69.8
Xh201505291 18.5 38.6 59.8
Xh201505292 20.3 48.6 72.2
ZJ201505291 18.5 33.3 58.8
Pyridaben 20.3 48.6 70.6
It rattles away young ketone 18.5 38.6 62.2
Compound N 20.3 38.6 58.8
Data are found out from table 6, and part preferably pyridazinone derivative has Tetranychus urticae certain under 20mg/L concentration Insecticidal activity.Wherein LK20150316, LK20150411, LK20150413, LK20150424, LK20150514, LK20150516, ZJ201505221, Xh201505291, Xh201505292, ZJ201505291 are at 72 hours to Tetranychus urticae Lethality is near or above comparison medicament pyridaben（70.6%）, young ketone of rattling away（62.2%）, compound N（58.8%）.
The result shows that compound provided by the invention is positively correlated relationship to Tetranychus urticae lethality and administration time.
The preferred pyridazinone compound in 8 part of embodiment gives birth to cotton bollworm larvae, diamondback moth larvae and cabbage caterpillar larva desinsection Object active testing
For test process with embodiment 6, difference is as follows：
（1）Change 3 age beet exigua larvaes into 3 instar bollworm grubs, diamondback moth larvae and cabbage caterpillar larva；
（2）In 72h statistics for trying the death condition of larva, and calculate its death rate；
（3）Test result：It is shown in Table 7
7 insecticidal activity of table（Concentration:10 mg/L, 72h lethality/%）
Compound number Bollworm Diamondback moth Cabbage caterpillar
LK20150205 50.0 45.8 50.0
LK20150301 16.7 29.2 20.8
LK20150305 16.7 20.8 20.8
LK20150313 58.5 62.5 66.7
LK20150314 50.0 45.8 54.3
LK20150316 33.3 54.3 45.8
LK20150319 16.7 12.5 12.5
LK20150322 20.8 20.8 20.8
LK20150327 16.7 20.8 33.3
LK20150401 37.5 37.7 37.5
LK20150407 62.5 58.5 66.7
LK20150409 37.5 41.7 33.3
LK20150411 58.5 62.5 70.9
LK20150413 66.7 66.7 70.9
LK20150416 20.8 25.0 25.0
LK20150418 62.5 66.7 66.7
LK20150424 70.9 70.9 75.0
LK20150429 58.5 62.5 66.7
LK20150502 62.5 58.5 66.7
LK20150504 58.5 66.7 70.9
LK20150505 58.5 58.5 58.5
LK20150508 58.5 58.5 66.7
LK20150513 62.5 58.5 58.5
LK20150514 62.5 58.5 62.5
LK20150515 62.5 62.6 62.5
LK20150516 58.5 66.7 70.9
LK20150517 58.5 58.5 62.5
LK20150520 58.5 58.5 62.5
LK20150523 58.5 62.5 58.5
LK20150524 62.5 62.5 66.7
ZJ201505221 58.5 62.5 70.9
Xh201505291 58.5 62.5 66.7
Xh201505292 66.7 58.5 70.9
ZJ201505291 58.5 62.5 62.5
Pyridaben 58.5 58.5 62.5
It rattles away young ketone 58.5 62.5 62.5
Compound N 58.5 62.5 58.5
Blank 0 0 0
Data are found out from table 7, and part preferably pyridazinone derivative is under 10mg/L concentration, to bollworm, diamondback moth, dish Green worm has certain insecticidal activity.Wherein LK20150313, LK20150407, LK20150411, LK20150413, LK20150416、LK20150418、LK20150424、LK20150429、LK20150502、LK20150504、LK20150505、 LK20150508、LK20150513、LK20150514、LK20150515、LK20150516、LK20150517、LK20150520、 LK20150523, LK20150524, ZJ201505221, Xh201505291, Xh201505292, ZJ201505291 were at 72 hours To bollworm, diamondback moth, cabbage caterpillar lethality near or above comparison medicament pyridaben, rattle away young ketone, compound N.
Although above having used general explanation, specific implementation mode and experiment, 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 (6)

1. one group of pyridazinone derivative, structural formula is as shown in formula I：
Formula I,
R in formula I1Group can be selected from：、；Wherein X is halogen, m is 1 or 2 or 3, and Y isOrOrOrOr；R2Group can be selected from：Or；Wherein R3ForOrOrOrOr, A is halogen or H, and B is O or S；The halogen be F or Cl or Br or I.
2. pyridazinone derivative according to claim 1, it is characterised in that：Any of the derivative in following Kind：
Number Chemical structural formula Number Chemical structural formula LK20150205 LK20150301 LK20150305 LK20150313 LK20150314 LK20150316 LK20150319 LK20150322 LK20150327 LK20150401 LK20150407 LK20150409 LK20150411 LK20150413 LK20150416 LK20150418 LK20150424 LK20150429 LK20150502 LK20150504 LK20150505 LK20150508 LK20150513 LK20150514 LK20150515 LK20150516 LK20150517 LK20150520 LK20150523 LK20150524 ZJ201505221 ZJ201505291 XH201505291 XH201505292
。
3. a kind of method preparing any one of claim 1-2 derivatives, it is characterised in that：Its preparation process is as follows：
,
Wherein R1Group can be selected from：、, wherein X is halogen, m is 1 or 2 or 3, and Y isOrOrOrOr；R3It can be selected fromOrOrOrOr, A is halogen or H, and B is O or S；The halogen is F or Cl or Br or I.
4. the preparation process of any one of claim 1-2 derivatives according to claim 3, it is characterised in that：It has Gymnastics is made as follows：
（1）Using ethylene glycol as solvent, to dissolving, 20 ± 5 DEG C are added calculation amounts for stirring after calculation amount KOH is added, 130 ± 10 DEG C are gradually heating to, TLC monitors reaction process, whenAfter reaction thoroughly, reaction solution is poured into distillation In water, with hydrochloric acid solution tune pH=1 of 6 mol/L, white solid is precipitated, decompression is filtered, washed with distilled water, and solid is dryCrude product recrystallizesSterling；
WithN,NDimethylformamide is solvent, and calculation amount is added, calculation amount 30% is slowly added dropwise at -5 ± 2 DEG C Then sodium hydrosulfide aqueous solution controls 0 ~ 5 DEG C of temperature, TLC monitors reaction process, whenIt, will be anti-after reaction thoroughly It answers liquid to pour into distilled water, with hydrochloric acid solution tune pH=1 of 6 mol/L, white solid is precipitated, decompression filters, with distilled water water It washes, solid is dryCrude product recrystallizesSterling；
（2）Using acetonitrile as solvent, calculation amount is sequentially added under the conditions of 20 ± 5 DEG C, potassium carbonate powder, 0 ± 5 DEG C calculation amount is slowly added dropwiseThen acetonitrile solution controls 20 ± 5 DEG C of temperature, TLC monitors reaction process, when anti- After the completion of answering, solvent is removed, uses saturated sodium bicarbonate aqueous solution, distillation water washing precipitation obtained solid, solid dry successivelyCrude product recrystallizesSterling；
（3）Using acetonitrile as solvent, calculation amount is sequentially added under the conditions of 20 ± 5 DEG C, potassium carbonate powder, 0 ± 5 DEG C calculation amount is slowly added dropwiseThen acetonitrile solution controls 20 ± 5 DEG C of temperature, TLC monitors reaction process, when After the completion of reaction, solvent is removed, uses saturated sodium bicarbonate aqueous solution, distillation water washing precipitation obtained solid, solid drying successively Crude product recrystallizesSterling；
Wherein R1Group can be selected from：、, wherein X is halogen, m is 1 or 2 or 3, and Y isOrOrOrOr；R3It can be selected fromOrOrOrOr, A is halogen or H, and B is O or S；The halogen is F or Cl or Br or I.
5. the preparation of any one of 1-2 containing the claim derivatives, is made of derivative and pesticide auxiliary material, wherein derivative Weight content is 0.1% ~ 99.9%.
6. preparation described in any one of the claim 1-2 derivatives or claim 5 is in the pesticide for preparing prevention agricultural pests In application.
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