CN105924432A - Pyridazinone derivative, and preparation method and application thereof - Google Patents

Pyridazinone derivative, and preparation method and application thereof Download PDF

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CN105924432A
CN105924432A CN201610548582.6A CN201610548582A CN105924432A CN 105924432 A CN105924432 A CN 105924432A CN 201610548582 A CN201610548582 A CN 201610548582A CN 105924432 A CN105924432 A CN 105924432A
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CN105924432B (en
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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 invention relates to a pyridazinone derivative with the structure shown in the description. R1 and R2 groups in the structure are selected from specific groups in the description. The invention discloses the structure of the compound, and an agriculture pest prevention and control effect of the compound, and also discloses an application of the compound as a pesticide.

Description

Pyridazinone derivative and its preparation method and application
Technical field
The invention belongs to pesticide field, technical scheme relates to one group of pyridazinone derivative, is specifically related to pyridazinone derivative And preparation method thereof and its agricultural insecticide apply.
Background technology
Pyridazinone compound often has high biologically active, the mite but the pesticide species that exploitation is ripe at present is only rattled away Ketone, is widely used in the preventing and treating of all kinds of mite.Owing to the excessive of pyridaben uses in recent years, it has been created by most evil mites The serious resistance to the action of a drug, the plant protection sexual valence causing pyridaben pesticide species is more serious than declining, and agricultural mite evil large area occurs, agriculture The phenomenon that industry good harvest significantly declines happens occasionally.
Accordingly, it would be desirable to continually develop research and provide new environmental friendliness, high selective pesticide kind pesticide.Root According to pharmaceutical molecule biologically active principle, we design and have synthesized serial pyridazinone derivative, and determine its mite killing, desinsection work Property.
Summary of the invention
It is an object of the invention to provide one group of pyridazinone derivative；
The present invention provides one group of pyridazinone derivative, and structural formula is as shown in formula I:
Formulas I,
R in formula I1Group is selected from:、；Wherein X be halogen, m be 1 or 2 or 3, Y isOrOrOrOr；R2Group is selected from:Or；Wherein R3ForOrOrOrOr, A is halogen or H, and B is O or S；Described halogen be F or Cl or Br or I.
It is further preferred that the one that described derivative is in following:
Numbering Chemical structural formula Numbering 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 described compound, its preparation process is as follows:
。
Concrete, said method comprising the steps of:
(1) with ethylene glycol as solvent, after adding amount of calculation KOH, stirring is to dissolving, and 20 ± 5 DEG C add amount of calculation, Being gradually heating to 130 ± 10 DEG C, TLC monitors reaction process, whenAfter reaction thoroughly, pour reactant liquor into distillation In water, adjusting pH=1 with the hydrochloric acid solution of 6 mol/L, separate out white solid, reduce pressure suction filtration, washes with distilled water, and solid is driedCrude product, recrystallizesSterling；
WithN,N-dimethylformamide is solvent, adds amount of calculation, it is slowly added dropwise amount of calculation 30% at-5 ± 2 DEG C The NaHS aqueous solution, then controls temperature 0 ~ 5 DEG C, and TLC monitors reaction process, whenAfter reaction thoroughly, will be anti- Answering liquid to pour in distilled water, adjust pH=1 with the hydrochloric acid solution of 6 mol/L, separate out white solid, reduce pressure suction filtration, uses distilled water water Washing, solid is driedCrude product, recrystallizesSterling；
(2) with acetonitrile as solvent, under the conditions of 20 ± 5 DEG C, it is sequentially added into amount of calculation, potassium carbonate powder, 0 ± 5 DEG C are slowly added dropwise amount of calculationAcetonitrile solution, then controls temperature 20 ± 5 DEG C, and TLC monitors reaction process, when instead After should completing, desolvation, successively with saturated sodium bicarbonate aqueous solution, distilled water washing precipitation gained solid, solid is driedCrude product, recrystallizesSterling；
(3) with acetonitrile as solvent, under the conditions of 20 ± 5 DEG C, it is sequentially added into amount of calculation, potassium carbonate powder, 0 ± 5 DEG C are slowly added dropwise amount of calculationAcetonitrile solution, then controls temperature 20 ± 5 DEG C, and TLC monitors reaction process, when After having reacted, desolvation, successively with saturated sodium bicarbonate aqueous solution, distilled water washing precipitation gained solid, solid is dried ?Crude product, recrystallizesSterling.
Third object of the present invention is to provide the preparation containing pyridazinone derivative, by derivative and the auxiliary material of agricultural chemicals, its Middle pyridazinone derivative weight percent content in the formulation is 0.1%-99.9%.
It is a further object of the present invention to provide described pyridazinone derivative to apply as agricultural insecticide.
The pyridazinone derivative that the present invention provides is for preventing and treating one of the key character that agricultural pests are the present invention.
The derivative that the present invention provides has the advantage that
1, the pyridazinone derivative of the present invention can be used for preventing and treating agricultural pests, and can obtain good effect.
2, " three wastes " that produce in noval chemical compound preparation process of the present invention are less, it is easy to process, as insecticide agriculture Medicine compares environmental protection when producing.
3, the invention provides one group of new compound, this compound is applied to prevent and treat agricultural evil as new insecticide Worm, can apply to the insect developed immunity to drugs, effective, and the advantage with low cost.
Detailed description of the invention
The present invention by the preparation of specific preparation and biological activity determination embodiment specific description pyridazinone derivative and Biologically active, described embodiment is only used for the specific description present invention and the unrestricted present invention.
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
The preparation of embodiment 1 compound L K20150205
(1)
Concrete operations: in 250 mL there-necked flasks, add 100 mmol KOH, 70 mL ethylene glycol, stir under the conditions of 20 ± 5 DEG C Mixing after dissolving to KOH, add 20 mmol C, be gradually heating to 130 DEG C, TLC monitors reaction process, when after reaction thoroughly, by anti- Answering liquid to pour in 500 mL distilled water, adjust pH=1 with the hydrochloric acid solution of 6 mol/L, separate out a large amount of white solid, reduce pressure suction filtration, uses Distilled water washs, and filter cake is placed under infrared lamp and is dried, and obtains object D crude product, ethyl alcohol recrystallization, obtains target compound D sterling.
(2)
Concrete operations: equipped with magnetic stirring apparatus, calcium chloride tube, constant pressure funnel 100 mL single port flasks in, 20 Add the D of 10 mmol, 15 mmol potassium carbonate powder, the acetonitrile of 30 mL under the conditions of ± 5 DEG C, under the conditions of 0 ± 5 DEG C, be slowly added dropwise With 11 mmol E of 30 mL solvent dilutions, being to slowly warm up to 20 ± 5 DEG C and continue insulation reaction after being added dropwise to complete, TLC monitoring is anti- Answer process, when, after D reaction thoroughly, rotary evaporation removes solvent, adds 50 mL saturated sodium bicarbonate aqueous solutions, room temperature with constant Stirring 1 h, reduce pressure suction filtration, washs with distilled water, and filter cake is placed under infrared lamp and is dried, and obtains object F crude product, and recrystallization obtains mesh Mark compound F sterling.Proterties: white solid, fusing point: 92.8 ~ 93.1 DEG C, yield: 77%.
Embodiment 2 compound、Preparation
、
Concrete operations: with the preparation of compound LK20150205, difference: the C in the preparation (1) of LK20150205 is replaced For required specific pyridazinone derivative, the pyrazole acyl chloride of the preparation (2) of LK20150205 is replaced with required specific Pyrazole acyl chloride.With the physicochemical data such as table 1 of the preferred pyridazinone derivative of part prepared by the method.
The physicochemical data of the preferred pyridazinone derivative of table 1 part
The preparation of embodiment 3 compound L K20150313
(1)
Concrete operations: in 100 mL there-necked flasks, are sequentially added into 40 mmol C, 40 mL under the conditions of 20 ± 5 DEG CN,N-diformazan Base formamide, is cooled to when-5 DEG C be slowly added dropwise the NaHS aqueous solution of 80 mmol 30%, controls temperature at 0-5 DEG C, TLC Monitoring reaction process, when after C reaction thoroughly, pours into reactant liquor in 800 mL water, adjusts pH=1 with the hydrochloric acid solution of 6 mol/L, Separating out white solid, reduce pressure suction filtration, washs with distilled water, and filter cake is placed under infrared lamp and is dried, and obtains object G crude product, recrystallization, Obtain target compound G sterling.
(2)
Concrete operations: with the preparation (2) of embodiment 1 compound L K20150205, difference: D is changed to G.Obtain object LK20150313 crude product, recrystallization, obtain target compound LK20150313 sterling.Proterties: white solid, fusing point: 128.9 ~ 129.2 DEG C, yield: 77%.
Embodiment 4 compound、Preparation
、
Concrete operations: with the preparation of compound LK20150313, difference: the C in the preparation (1) of LK20150313 is replaced For required specific pyridazinone derivative, the pyrazole acyl chloride of the preparation (2) of LK20150313 is replaced with required specific Pyrazole acyl chloride.With the physicochemical data such as table 2 of the preferred pyridazinone derivative of part prepared by the method.
The physicochemical data of the preferred pyridazinone derivative of table 2 part
Embodiment 5 part preferred compound1H-NMR and IR parametric measurement and Identification of chemical structure
The preferred pyridazinone compound of table 3 part1H-NMR data
Numbering 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 of table 4 part
Numbering 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
From table 3 and table 4, part preferably pyridazinone derivative1H-NMR shows chemical shift corresponding with its structure, H Number coincide with its structure, and corresponding skeleton absworption peak occurs in IR.
Beet exigua larvae insecticidal bioactivity is tested by the preferred pyridazinone compound of embodiment 6 part
(1) laboratory apparatus: assay balance, supports worm plate, incubator, culture dish；
(2) for examination worm source: beet armyworm 3 instar larvae；
(3) test method: stomach poison toxicity test, endless takes food method；
(4) reagent agent standard preparation is become 1000ppm solution (solvent, acetone), stand-by after diluting 100 times.Beet by 3 ages Exigua larvae does 4h Nature enemy, and often group chooses 24 health beet exigua larvae tests in 3 ages, each medicament parallel determination two Group；Taking appropriate feed mean allocation in the interval of each foster worm plate, each interval micropipettor injects 5.00uL equivalent The reagent agent solution of 10ppm, that chooses 24 is evenly distributed in the interval of each foster worm plate for examination polypide, each interval One, cover with the toilet paper after sterilization and support worm plate, spray appropriate distilled water moisturizing.Do blank test simultaneously, rest worm Plate is placed in moisturizing in the illumination box of (25 ± 1) DEG C, respectively at 24h, the dead feelings of 48h, 72h statistics beet exigua larvae Condition, touches polypide with writing brush, motionless with polypide or can not just produce and creep as death standard.The dead polypide quantity of record, and calculate Its death rate.
(5) comparison medicament: pyridaben (), rattle away children ketone (), change Compound N ()；
(6) experimental result is shown in Table 5.
Table 5 insecticidal activity (concentration: 10mg/L, fatal rate/%)
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
Rattle away children ketone 4.2 33.3 62.5
Compound N 8.3 29.2 58.5
Blank 0 0 0
From table 5, data are found out, beet armyworm, under 10mg/L concentration, is had necessarily by part preferably pyridazinone derivative 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 at 72 hours to 3 beet nights in age Moth larvae fatal rate is near or above comparison medicament pyridaben (58.5%), rattle away children's ketone (62.5%), compound N (58.5%).
Result shows, the compound that the present invention provides becomes positive correlation to beet armyworm 3 instar larvae fatal rate with administration time Relation.
Tetranychus urticae larva insecticidal bioactivity is tested by the preferred pyridazinone compound of embodiment 7 part
1 experiment condition
(1) laboratory apparatus: artificial intelligence climate box (south of the River, Ningbo instrument plant produces, 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 examination material: be collected in the Tetranychus urticae of greenhouse, Institute of Plant Protection, academy of agricultural sciences of Shandong Province kidney bean leaf；
(4) test compound: the former medicine of created compound 98%；
(5) comparison medicament: the former medicine of pyridaben 98%, rattle away the children former medicine of ketone 98%, the former medicine of compound N 98%；
(6) blank: the organic solvent of 0.1% Tween-80.
Dosage is arranged
The compound chloroform of initiative is made into mother liquor, then is diluted to corresponding concentration with the 0.1% Tween 80 aqueous solution.
Mother liquor is prepared with indoor biometrics testing standard.
Created compound is dissolved with appropriate solvent, is configured to mother liquor, then is diluted to the 0.1% Tween 80 aqueous solution 20 ppm。
Experimental procedure
(1) reaction utensil is arranged: one piece of diameter 8cm, thick 1cm the sponge through water saturates are placed on the cultivation of a diameter of 12 cm In ware, sponge upper surface adds water in covering the filter paper of a diameter of 6 cm, culture dish so that it is liquid level is less than sponge height. By the freshest kidney bean blade, it is about (2cm, wide 1.5cm) blade face and is put in down on filter paper.
(2) the sheet glass infusion process that the medicament test of pesticide effectiveness is recommended with reference to FAO, is cut into 2cm × 2cm size by two-sided tape, It is attached to one end of microslide, selects in the same size, the active female one-tenth mite that takes action with No. 0 writing brush and make its back the most gently Being bonded on adhesive tape, every piece of slide glues 30, and each chemicals treatment is repeated 3 times.The sheet glass being stained with female one-tenth mite is placed on totally Big support in worm ware, and put a wet cotton balls, cover glass plate, be placed in 25 DEG C, in the artificial intelligence climate box of relative humidity 85%. Microscopy after 2h, rejects dead or torpescence is individual.During mensuration, the sheet glass one end of the female one-tenth mite being stained with is immersed by test group respectively Treat in reagent liquid, control group leaching clear water takes out after 5 s, blots with fritter filter paper rapidly and be attached to around mite body and many on adhesive tape Remaining liquid.Sheet glass after process is put back in original big foster worm ware again, is placed in above-mentioned growth cabinet.Utilize stereoscopic micro- Mirror is microscopy when 24h, 48h, 72h.During microscopy, touching mite body gently with writing brush point, limbs are motionless, nonresponder is designated as extremely Die individuality.
Data statistics and analysis
Add up and calculate the death rate and corrected mortality as the following formula, and make each process data are carried out significance of difference analysis.
The death rate and the calculating of corrected mortality.
Experimental result is shown in Table 6
Table 6 acaricidal activity (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
Rattle away children ketone 18.5 38.6 62.2
Compound N 20.3 38.6 58.8
From table 6, data are found out, Tetranychus urticae, under 20mg/L concentration, is had necessarily by part preferably pyridazinone derivative Insecticidal activity.Wherein LK20150316, LK20150411, LK20150413, LK20150424, LK20150514, LK20150516, ZJ201505221, Xh201505291, Xh201505292, ZJ201505291 at 72 hours to Tetranychus urticae Fatal rate is near or above comparison medicament pyridaben (70.6%), rattle away children's ketone (62.2%), compound N (58.8%).
Result shows, the compound that the present invention provides becomes positive correlation to Tetranychus urticae fatal rate with administration time.
The preferred pyridazinone compound of embodiment 8 part is raw to cotton bollworm larvae, diamondback moth larvae and cabbage caterpillar larva desinsection Thing active testing
Test process is with embodiment 6, and difference is as follows:
(1) by 3 age beet exigua larvae change 3 instar bollworm grubs, diamondback moth larvae and cabbage caterpillar larva into；
(2) in 72h statistics for trying the death condition of larva, and its death rate is calculated；
(3) result of the test: be shown in Table 7
Table 7 insecticidal activity (concentration: 10 mg/L, 72h fatal rate/%)
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
Rattle away children ketone 58.5 62.5 62.5
Compound N 58.5 62.5 58.5
Blank 0 0 0
From table 7, data are found out, part preferably pyridazinone derivative is under 10mg/L concentration, to bollworm, diamondback moth, dish Blue or 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 fatal rate near or above comparison medicament pyridaben, rattle away children ketone, compound N.
Although, use general explanation, detailed description of the invention and test, the present invention is described in detail, But on the basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Cause This, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.

Claims (6)

1. one group of pyridazinone derivative, structural formula is as shown in formula I:
Formula I,
R in formula I1Group is selected from:、；Wherein X be halogen, m be 1 or 2 or 3, Y isOrOrOrOr；R2Group is selected from:Or；Wherein R3 ForOrOrOrOr, A is halogen or H, and B is O or S；Described halogen is F or Cl Or Br or I.
Pyridazinone derivative the most according to claim 1, it is characterised in that: arbitrary in following of described derivative Kind:
3. prepare the method for derivative described in any one of claim 1-2 for one kind, it is characterised in that: its preparation process is as follows:
。
Method the most according to claim 3, it is characterised in that: said method comprising the steps of:
(1) with ethylene glycol as solvent, after adding amount of calculation KOH, stirring is to dissolving, and 20 ± 5 DEG C add amount of calculation, Being gradually heating to 130 ± 10 DEG C, TLC monitors reaction process, whenAfter reaction thoroughly, pour reactant liquor into distillation In water, adjusting pH=1 with the hydrochloric acid solution of 6 mol/L, separate out white solid, reduce pressure suction filtration, washes with distilled water, and solid is driedCrude product, recrystallizesSterling；
WithN,N-dimethylformamide is solvent, adds amount of calculation, it is slowly added dropwise amount of calculation 30% at-5 ± 2 DEG C The NaHS aqueous solution, then controls temperature 0 ~ 5 DEG C, and TLC monitors reaction process, whenAfter reaction thoroughly, will be anti- Answering liquid to pour in distilled water, adjust pH=1 with the hydrochloric acid solution of 6 mol/L, separate out white solid, reduce pressure suction filtration, uses distilled water water Washing, solid is driedCrude product, recrystallizesSterling；
(2) with acetonitrile as solvent, under the conditions of 20 ± 5 DEG C, it is sequentially added into amount of calculation, potassium carbonate powder, 0 ± 5 DEG C it is slowly added dropwise amount of calculationAcetonitrile solution, then controls temperature 20 ± 5 DEG C, and TLC monitors reaction process, when instead After should completing, desolvation, successively with saturated sodium bicarbonate aqueous solution, distilled water washing precipitation gained solid, solid is driedCrude product, recrystallizesSterling；
(3) with acetonitrile as solvent, under the conditions of 20 ± 5 DEG C, it is sequentially added into amount of calculation, potassium carbonate powder, 0 ± 5 DEG C it is slowly added dropwise amount of calculationAcetonitrile solution, then controls temperature 20 ± 5 DEG C, and TLC monitors reaction process, when After having reacted, desolvation, successively with saturated sodium bicarbonate aqueous solution, distilled water washing precipitation gained solid, solid is dried ?Crude product, recrystallizesSterling.
5. containing the preparation of derivative described in any one of claim 1-2, it is made up of derivative and agricultural chemicals auxiliary material, wherein derivative Weight content is 0.1% ~ 99.9%.
6. preparation described in derivative described in any one of claim 1-2 or claim 5 is at the agricultural chemicals of preparation preventing and treating agricultural pests In application.
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