CN103833744B - 1 ethyl pyrazolyl acrylonitrile compound and application thereof - Google Patents

1 ethyl pyrazolyl acrylonitrile compound and application thereof Download PDF

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CN103833744B
CN103833744B CN201210484570.3A CN201210484570A CN103833744B CN 103833744 B CN103833744 B CN 103833744B CN 201210484570 A CN201210484570 A CN 201210484570A CN 103833744 B CN103833744 B CN 103833744B
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CN103833744A (en
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李斌
于海波
王斌
李琴
宋玉泉
王洋
冯聪
褚岩凤
英君伍
陈霖
杨辉斌
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Abstract

The invention discloses 1 ethyl pyrazolyl acrylonitrile compound or its stereoisomer of a kind of novel structure, compound structure is as shown in formula I:In formula: R is selected from C1‑C6Alkyl, halo C1‑C6Alkyl, C3‑C8Cycloalkyl or C1‑C6Alkoxyl；X is selected from hydrogen, halogen, cyano group or methyl；Q is selected from following group:R1Selected from H, halogen, methyl or trifluoromethyl；R2Selected from H or halogen；Compound of Formula I has the insecticidal activity of excellence, can be used for pest control.

Description

1-ethyl pyrazolyl acrylonitrile compound and application thereof
Technical field
The invention belongs to field of pesticides.It is specifically related to a kind of 1-ethyl pyrazolyl acrylonitrile compound and application thereof.
Background technology
Due to insecticide in use for some time, insect can produce resistance to it, accordingly, it would be desirable to constantly invention is novel Compound and compositions with the tool insecticidal activity improved.Meanwhile, along with people to growing needs such as agricultural and animal products and Pay attention to day by day to environmental conservation, also has always a demand for use cost new insecticide lower, environment amenable.
Nissan Chemical Ind Ltd, in WO9740009 applies for, discloses and has parasite killing, mite killing or bactericidal activity Ethene derivatives.In JP2005008628 applies for, it was recently reported that compound K C1The preparation of (numbering 1 in patent) and insecticidal activity, Compound K C1Under the concentration of 500ppm to the preventive effect of black peach aphid more than 80%.In WO2007100160 and WO2007100161 Shen In please, further disclose compound K C2Preparation, insecticidal activity and the Study on Preparation of (numbering 1 in patent), compound K C2 Under the concentration of 25ppm, black peach aphid is had high prevention effect.CN101875633 discloses killing of 1-ethylpyrazol compounds Demodicid mite activity, compound K C3(numbering 5 in patent) under 2.5ppm concentration to Tetranychus cinnabarinus preventive effect more than 90%.
In prior art, 1-ethyl pyrazolyl acrylonitrile compound and insecticidal activity thereof as representative of the present invention have no public Open.
Summary of the invention
It is an object of the invention to provide the 1-ethyl pyrazolyl acrylonitrile compound of a kind of novel structure, it can be applied The preventing and treating of insect in the health of agricultural, forestry or non-treatment purpose.
Technical scheme is as follows:
The invention provides a kind of 1-ethyl pyrazolyl acrylonitrile compound, as shown in formula I:
In formula:
R is selected from C1-C6Alkyl, halo C1-C6Alkyl, C3-C8Cycloalkyl or C1-C6Alkoxyl；
X is selected from hydrogen, halogen, cyano group or methyl；
Q is selected from following group:
R1Selected from H, halogen, methyl or trifluoromethyl；
R2Selected from H or halogen；
Or its stereoisomer.
The further preferred compound of the present invention is, in formula I:
R is selected from C1-C6Alkyl, halo C1-C6Alkyl, C3-C8Cycloalkyl or C1-C6Alkoxyl；
X is selected from hydrogen, halogen or methyl；
Q is selected from following group:
R1Selected from H or halogen；
R2Selected from H or halogen；
Or its stereoisomer.
The present invention further preferably compound is, in formula I:
R is selected from C3-C6Alkyl, halo C3-C6Alkyl or C1-C4Alkoxyl；
X is selected from hydrogen；
Q is selected from following group:
R1Selected from H, fluorine or chlorine；
R2Selected from H, fluorine or chlorine；
Or its stereoisomer.
In the definition of compound of Formula I given above, collect term used and be typically defined as follows:
Alkyl refers to straight or branched form, such as methyl, ethyl, n-pro-pyl, isopropyl etc..Cycloalkyl includes ring third Base, cyclobutyl, Cvclopropvlmethvl, methylcyclopropyl groups etc..Haloalkyl refers to the base that alkyl is optionally substituted with one or more halogen atoms Group, such as chloroethyl, trifluoromethyl etc..Alkoxyl refers to that alkyl end is connected with the group of oxygen atom, such as methoxyl group, ethyoxyl, Positive propoxy, isopropoxy etc..Halogen refers to fluorine, chlorine, bromine, iodine.Stereoisomer refers in Formulas I, taking on carbon-carbon double bond B For base CN and OCOR in the same side (Z configuration) of B key or both sides (E).
The compound of Formula I of the present invention can be prepared by the following method, and in reaction equation, each group definition is the same.
In formula: L represents suitable leaving group, such as chlorine, bromine or tolysulfonyl epoxide etc..
Compounds of formula II and compound of formula III in suitable solvent, temperature be-10 DEG C to reaction under reflux temperature 0.5-48 hour prepared target compound I.
Suitable solvent is selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrochysene Furan, dioxane, N,N-dimethylformamide or dimethyl sulfoxide etc..
Add suitable alkaloids favourable to reaction.Suitable alkali can be selected from organic base, such as triethylamine, N, N-bis- Monomethylaniline., pyridine, Feldalat NM, sodium tert-butoxide or potassium tert-butoxide etc.；Or inorganic base such as sodium hydroxide, potassium hydroxide, bicarbonate Sodium, sodium carbonate or sodium hydride etc..
Difference according to reaction condition or the difference of initiation material, there is stereo-isomerism in compound of Formula I.Such as carbon Substituent group CN in carbon double bond B and OCOR are in the same side (Z configuration) of B key or both sides (E).By selecting suitable initiateing Raw material or control reaction condition, can obtain product or the individual isomer of a kind of isomer excess.Can also be by producing thick Thing carries out the separation of conventional means, such as, by the method such as column chromatography, recrystallization, obtain individual isomer.These isomers The conventionals method of analysis such as structure can pass through X-ray single crystal diffraction, nuclear magnetic resonance, NMR determine.
Compound of formula III is commercially available.
The preparation method of Compounds of formula II is as follows:
In formula: L1Represent suitable leaving group, such as chlorine, bromine, pyrazolyl, imidazole radicals, methoxyl group, ethyoxyl or to toluene Sulfonyloxy etc..
Compound of Formula IV and compounds of formula V in suitable solvent, in the presence of base, temperature be-10 DEG C to boiling The lower 0.5-48 hour prepared general formula compound II of reaction of point.
Suitable solvent is mainly selected from: dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, methanol, ethanol, ethyl acetate, Acetonitrile, oxolane, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, 2-methylpentane, methyl cyclopentane, oneself Alkane, hexamethylene, hexahydrotoluene, heptane, octane, nonane, butyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol Dibutyl ethers, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether etc., or as above two or three not Mixture with solvent.
Add suitable alkaloids favourable to reaction.Suitable alkali is selected from organic base such as triethylamine, N, N-dimethyl benzene Amine, pyridine, 2-picoline, 3-picoline, 4-picoline, aldehydecollidine, 2,3 dimethyl pyridine, 2, 4-lutidines, 3,5-lutidines, 2,6-lutidines, 2,4,6-trimethylpyridine, quinoline, Feldalat NM, ethanol Sodium, sodium tert-butoxide or potassium tert-butoxide etc., or inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate etc..
The preparation of compound of Formula IV sees the operational approach described in WO9740009, DE2633992.
The preparation of compounds of formula V sees the operational approach described in CN101875633.
Table 1 lists structure and the physical property of partial Formula I.
Table 1
Part of compounds1H NMR(300MHz,CDCl3) data are as follows:
Compound 1:7.91 (m, 2H), 7.72 (s, 1H), 7.49 (m, 3H), 6.57 (s, 1H), 4.24 (q, 2H), 2.32 (s,3H),1.49(t,3H)。
Compound 5:7.90 (m, 2H), 7.70 (s, 1H), 7.48 (m, 3H), 6.54 (s, 1H), 4.24 (q, 2H), 2.59 (t,2H),2.32(s,3H),1.66(sext.,2H),1.49(t,3H),0.91(t,3H)。
Compound 7:7.91 (m, 2H), 7.68 (s, 1H), 7.48 (m, 3H), 6.48 (s, 1H), 4.26 (q, 2H), 2.60 (hept,1H),2.32(s,3H),1.51(t,3H),1.21(d,6H)。
Compound 15:7.94 (m, 2H), 7.65 (s, 1H), 7.46 (m, 3H), 6.37 (s, 1H), 4.28 (q, 2H), 2.31 (s,3H),1.55(t,3H),1.25(s,9H)。
Compound 17:7.95 (m, 2H), 7.65 (s, 1H), 7.46 (m, 3H), 6.35 (s, 1H), 4.28 (q, 2H), 2.32 (s,3H),1.59(q,2H),1.55(t,3H),1.22(s,6H),0.73(t,3H)。
Compound 19:7.93 (m, 2H), 7.71 (s, 1H), 7.47 (m, 3H), 6.30 (s, 1H), 4.28 (q, 2H), 3.62 (s,2H),2.32(s,3H),1.55(t,3H),1.32(s,6H)。
Compound 21:8.01 (m, 2H), 7.71 (s, 1H), 7.47 (m, 3H), 6.57 (s, 1H), 4.26 (q, 2H), 2.32 (s,3H),1.92(m,1H),1.48(t,3H),1.13-1.03(m,4H)。
Compound 29:7.97 (m, 2H), 7.75 (s, 1H), 7.47 (m, 3H), 6.64 (s, 1H), 4.26 (q, 2H), 3.87 (s,3H),2.32(s,3H),1.49(t,3H)。
Compound 31:7.98 (m, 2H), 7.74 (s, 1H), 7.46 (m, 3H), 6.63 (s, 1H), 4.28 (q, 2H), 4.26 (q,2H),2.32(s,3H),1.49(t,3H),1.32(t,3H)。
Compound 295:8.04 (m, 2H), 8.02 (s, 1H), 7.49 (m, 3H), 6.37 (s, 1H), 4.25 (q, 2H), 2.31 (s,3H),1.53(t,3H),1.35(s,9H)。
Compound 296:7.92 (m, 2H), 7.45 (m, 3H), 7.39 (s, 1H), 6.18 (s, 1H), 3.93 (q, 2H), 2.33 (s,3H),1.36(t,3H),1.34(s,9H)。
Compound 311:8.07 (m, 2H), 8.06 (s, 1H), 7.49 (m, 3H), 6.61 (s, 1H), 4.32 (q, 2H), 4.24 (q,2H),2.32(s,3H),1.48(t,3H),1.37(t,3H)。
Compound 312:7.91 (m, 2H), 7.45 (m, 3H), 7.45 (s, 1H), 6.27 (s, 1H), 4.30 (q, 2H), 3.95 (q,2H),2.34(s,3H),1.37(t,3H),1.36(t,3H)。
Compound 447:8.13 (s, 1H), 7.46 (m, 1H), 7.07 (m, 2H), 6.49 (s, 1H), 4.24 (q, 2H), 2.90 (hept.,1H),2.31(s,3H),1.49(t,3H),1.25(d,6H)。
Compound 455:8.13 (s, 1H), 7.48 (m, 1H), 7.07 (m, 2H), 6.39 (s, 1H), 4.25 (q, 2H), 2.31 (s,3H),1.52(t,3H),1.29(s,9H)。
Compound 459:8.19 (s, 1H), 7.51 (m, 1H), 7.08 (m, 2H), 6.40 (s, 1H), 4.25 (q, 2H), 3.69 (s,2H),2.31(s,3H),1.52(t,3H),1.37(s,6H)。
Compound 461:8.15 (s, 1H), 7.44 (m, 1H), 7.07 (m, 2H), 6.56 (s, 1H), 4.24 (q, 2H), 2.31 (s,3H),1.94(m,1H),1.49(t,3H),1.14(m,2H),1.06(m,2H)。
Compound 463:8.11 (s, 1H), 7.46 (m, 1H), 7.07 (m, 2H), 6.53 (s, 1H), 4.23 (q, 2H), 3.33 (m,1H),2.33(m,2H),2.31(s,3H),1.96(m,2H),1.47(t,3H)。
Compound 465:8.13 (s, 1H), 7.46 (m, 1H), 7.07 (m, 2H), 6.49 (s, 1H), 4.24 (q, 2H), 2.92 (m,1H),2.31(s,3H),1.94-1.59(m,8H),1.48(t,3H)。
Compound 469:8.18 (s, 1H), 7.47 (m, 1H), 7.07 (m, 2H), 6.63 (s, 1H), 4.24 (q, 2H), 3.92 (s,2H),2.31(s,3H),1.46(t,3H)。
Compound 471:8.18 (s, 1H), 7.45 (m, 1H), 7.06 (m, 2H), 6.62 (s, 1H), 4.32 (q, 2H), 4.25 (q,2H),2.31(s,3H),1.47(t,3H),1.34(t,3H)。
Compound 575:7.95 (d, 1H), 7.71 (m, 2H), 7.48 (m, 2H), 7.35 (m, 1H), 6.76 (d, 1H), 6.35 (s,1H),4.26(q,2H),2.31(s,3H),1.54(t,3H),1.28(s,9H)。
Compound 577:7.95 (d, 1H), 7.71 (m, 2H), 7.47 (m, 2H), 7.36 (m, 1H), 6.76 (d, 1H), 6.33 (s,1H),4.26(q,2H),2.30(s,3H),1.63(q,2H),1.54(t,3H),1.19(s,6H),0.76(t,3H)。
Compound 579:7.95 (d, 1H), 7.69 (m, 2H), 7.48 (m, 2H), 7.34 (m, 1H), 6.81 (d, 1H), 6.35 (s,1H),4.27(q,2H),3.65(s,2H),2.31(s,3H),1.54(t,3H),1.35(s,6H)。
Compound 581:7.96 (d, 1H), 7.71 (m, 2H), 7.46 (m, 2H), 7.34 (m, 1H), 6.77 (d, 1H), 6.33 (s,1H),4.26(q,2H),2.32(s,3H),1.92(m,1H),1.48(t,3H),1.13-1.03(m,4H)。
Compound 583:7.94 (d, 1H), 7.68 (m, 2H), 7.47 (m, 2H), 7.35 (m, 1H), 6.74 (d, 1H), 6.50 (s,1H),4.23(q,2H),3.40(pent.,1H),2.31(s,3H),2.45-2.25(m,2H),2.10-1.92(m,2H), 1.49(t,3H)。
Compound 585:7.95 (d, 1H), 7.70 (m, 2H), 7.47 (m, 2H), 7.35 (m, 1H), 6.76 (d, 1H), 6.46 (s,1H),4.25(q,2H),3.01(pent.,1H),2.33(s,3H),1.96-1.85(m,4H),1.69-1.58(m,4H), 1.50(t,3H)。
Compound 587:7.95 (d, 1H), 7.68 (m, 2H), 7.46 (m, 2H), 7.35 (m, 1H), 6.76 (d, 1H), 6.45 (s,1H),4.25(q,2H),2.58(m,1H),2.31(s,3H),2.08-1.95(m,2H),1.77-1.70(m,4H),1.50 (t,3H),1.52-1.48(m,2H),1.33-1.28(m,2H)。
Compound 595:7.98 (d, 1H), 7.74 (m, 2H), 7.47 (m, 2H), 7.38 (m, 1H), 6.82 (d, 1H), 6.61 (s,1H),4.91(pent.,1H),4.24(q,2H),2.32(s,3H),1.48(t,3H),1.29(d,6H)。
Compound 596:7.81 (d, 1H), 7.63 (m, 2H), 7.44 (m, 2H), 7.33 (m, 1H), 6.29 (s, 1H), 5.81 (d,1H),4.92(hept.,1H),3.90(q,2H),2.33(s,3H),1.48(t,3H),1.33(d,6H)。
Compound 597:7.99 (d, 1H), 7.72 (m, 2H), 7.47 (m, 2H), 7.38 (m, 1H), 6.83 (d, 1H), 6.61 (s,1H),4.26(q,2H),3.99(d,2H),2.32(s,3H),2.01(hept.,1H),1.48(t,3H),0.92(d,6H)。
Compound 598:7.81 (d, 1H), 7.64 (m, 2H), 7.45 (m, 2H), 7.35 (m, 1H), 6.29 (s, 1H), 5.81 (d,1H),4.02(d,2H),3.90(q,2H),2.33(s,3H),2.08(hept.,1H),1.32(t,3H),0.97(d,6H)。
Compound 1295:8.19 (s, 1H), 7.48 (m, 1H), 7.07 (m, 2H), 4.23 (q, 2H), 2.28 (s, 3H), 1.53(t,3H),1.31(s,9H)。
Compound 1297:8.19 (s, 1H), 7.46 (m, 1H), 7.06 (m, 2H), 4.22 (q, 2H), 2.27 (s, 3H), 1.65(q,2H),1.53(t,3H),1.27(s,6H),0.77(t,3H)。
Compound 1299:8.25 (s, 1H), 7.51 (m, 1H), 7.08 (m, 2H), 4.22 (q, 2H), 3.70 (s, 2H), 2.28(s,3H),1.52(t,3H),1.39(s,6H)。
Compound 1311:8.24 (s, 1H), 7.48 (m, 1H), 7.07 (m, 2H), 4.31 (q, 2H), 4.20 (q, 2H), 2.29(s,3H),1.47(t,3H),1.35(t,3H)。
Compound 1317:8.24 (s, 1H), 7.46 (m, 1H), 7.06 (m, 2H), 4.20 (q, 2H), 4.03 (d, 2H), 2.29(s,3H),2.03(m,1H),1.47(t,3H),0.93(d,6H)。
The 1-ethyl pyrazolyl acrylonitrile compound of the present invention has high insecticidal activity, can prevent and treat diamondback moth, Radix Betae Noctuid, Prodenia litura, bollworm, meadow mythimna separata, cabbage looper, pea aphid, bean aphid, aphis fabae, cotten aphid, apple aphid, black peach aphid, Semen Maydis Aphid, aleyrodid, leafhopper, plant hopper, planthopper, mealybug, web stinkbug, tomato bug, Nezara viridula smaragdula Fabricius., the smelly stinkbug of rice, cotton thrips, alfalfa thrips, The various pests such as soybean thrip, colorado potato bug, click beetle, fly, mosquito.Compared with known acrylonitrile compound, the present invention's 1-ethyl pyrazolyl acrylonitrile compound has beyond thought high insecticidal activity.Therefore, present invention additionally comprises formula I chemical combination Thing is for controlling the purposes of insect.
Present invention additionally comprises the Pesticidal combination using compound of Formula I as active component.Activity in this Pesticidal combination The weight percentage of component is between 1-99%.This Pesticidal combination also includes acceptable load in agricultural, forestry or health Body.
The compositions of the present invention can be used with the form of preparation.Compound of Formula I is dissolved or dispersed in as active component In carrier or be configured to preparation so that more readily dispersible when using as insecticide.Such as: these chemicals can be made into can WP or cream.In these compositionss, at least add a kind of liquid or solid carrier, and can add when needed Suitable surfactant.
Technical scheme also includes the method for pest control: is imposed on by the Pesticidal combination of the present invention and needs to control Insect or its somatomedin on.The more suitable effective amount being generally selected is per hectare 10 grams to 1000 grams, preferably effective dose For per hectare 50 grams to 500 grams.
Some is applied, such as, agriculturally can add one or more other in the Pesticidal combination of the present invention Antibacterial, Insecticides (tech) & Herbicides (tech), plant growth regulator or fertilizer etc., thus can produce additional advantage and effect.
It should be appreciated that, in scope defined by the claims of the present invention, various conversion and change can be carried out.
Detailed description of the invention
Following synthetic example and raw result of the test of surveying can be used to further illustrate the present invention, but are not intended to limit this Bright.
Synthetic example
Embodiment 1, the preparation of compound 15
(1) synthesis of 4-chloromethyl-2-phenyl thiazole
Aminothiocarbonylbenzene (20.00 grams, 0.146 mole), methanol 200 milliliters, 1,3-dichloro third is added in there-necked flask Ketone (22.21 grams, 0.157 mole), is warming up to backflow, back flow reaction 3 hours.Reaction is cooled to less than 30 DEG C after terminating, reaction Liquid is poured in 50 milliliters of water, with 3 × 50 milliliters of ethyl acetate extractions, gained organic facies saturated sodium bicarbonate aqueous solution (50 millis Rise), saturated sodium-chloride water solution (50 milliliters) washing after, be dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue pass through post color Spectrum separates (leacheate: ethyl acetate: petroleum ether=1:10) and obtains 21.00 grams of 4-chloromethyl-2-phenyl thiazoles, yellow oil, yield 69%。
(2) synthesis of 4-cyanogen methyl-2-phenyl thiazole
In reaction bulb, add Cyanogran. (4.91 grams, 0.100 mole), 100 milliliters of water, drip 4-chloromethyl-2-phenyl Ethanol (100 milliliters) solution of thiazole (21.00 grams, 0.100 mole), drips complete, is warming up to backflow, refluxes 16 hours.Instead After should terminating, reactant liquor is poured in 200 milliliters of water, with 3 × 200 milliliters of ethyl acetate extractions, the saturated chlorination of gained organic facies After sodium water solution (200 milliliters) washing, being dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue passes through pillar layer separation (drip washing Liquid: ethyl acetate: petroleum ether=1:10) obtain 13.22 grams of 4-cyanogen methyl-2-phenyl thiazoles, yellow oil, yield 66%.
(3) intermediate 3-hydroxyl-3-(1-ethyl-3-methylpyrazole-5-base)-2-(2-phenyl thiazole-4-base) acrylonitrile Synthesis
Under ice-water bath, (3.00 grams, 0.015 rubs to add 2-phenyl-4-cyanogen methylthiazol in 100 milliliters of reaction bulbs You), anhydrous tetrahydro furan 25 milliliters, (1-ethyl-3-methyl isophthalic acid H-pyrazoles-5-base) (1H-pyrazol-1-yl) ketone (1.02 grams, 0.005 mole), then potassium tert-butoxide (3.37 grams, 0.030 mole) is joined in reaction bulb on a small quantity in multiple times, it is warming up to room temperature Stirring reaction 4 hours, is poured into reactant liquor in 50 milliliters of water, with ethyl acetate 2 × 20 milliliters washing, discards organic facies.By water Mutually by hydrochloric acid regulation system pH=2～3, then with 3 × 25 milliliters of abundant extractions of ethyl acetate, it is dried with anhydrous magnesium sulfate, reduces pressure dense Contracting obtains 2.86 grams of intermediate 3-hydroxyl-3-(1-ethyl-3-methylpyrazole-5-base)-2-(2-phenyl thiazole-4-base) propylene Nitrile, brown oil, yield 57%.
(4) synthesis of compound 15
Under ice-water bath, be sequentially added in 50 milliliters of reaction bulbs 3-hydroxyl-3-(1-ethyl-3-methylpyrazole-5-base)- 2-(2-phenyl thiazole-4-base) acrylonitrile (0.30 gram, 0.001 mole), (0.47 gram, 0.005 rubs acetonitrile 15 milliliters with triethylamine You), then pivaloyl chloride (0.47 gram, 0.004 mole) is added drop-wise in reaction bulb, it is warming up to be stirred at room temperature reaction 4 hours, reaction Liquid is poured in 50 milliliters of water, is extracted with ethyl acetate (2 × 50 milliliters), and gained organic facies is molten with 15 milliliters of saturated sodium bicarbonate waters After liquid, 25 milliliters of saturated sodium-chloride water solution washings, being dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue passes through column chromatography Separate (leacheate: ethyl acetate: petroleum ether=1:8) and obtain 0.15 g of compound 15, yellow oil, yield 39%.
Embodiment 2, the preparation of compound 37
Under ice-water bath, in reaction bulb, add 3-hydroxyl-3-(1-ethyl-3-methylpyrazole-5-base)-2-(2-phenyl Thiazole-4-yl) acrylonitrile (0.30 gram, 0.001 mole), acetonitrile 15 milliliters, triethylamine (0.47 gram, 0.005 mole), then by chlorine Tetryl formate. (0.53 gram, 0.004 mole) is added drop-wise in reaction bulb, completion of dropwise addition, is warming up to reaction 4 hour is stirred at room temperature, Reactant liquor is poured in 50 milliliters of water, is extracted with ethyl acetate (2 × 50 milliliters), and gained organic facies is with 15 milliliters of saturated sodium bicarbonates After aqueous solution, 25 milliliters of saturated sodium-chloride water solution washings, being dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue passes through post Chromatographic isolation (leacheate: ethyl acetate: petroleum ether=1:8) obtains 0.21 g of compound 37, is one group of stereoisomer mixing Thing (Z:E=1:3), yellow oil, yield 54%.
Embodiment 3, the preparation of compound 455
(1) synthesis of 4-chloromethyl-2-(2,6-difluorophenyl) azoles
Addition 2,6-difluorobenzamide (10.00 grams, 0.064 mole) and 1,3-dichloro in 100 milliliters of round-bottomed flasks Acetone (16.20 grams, 0.128 mole), is warming up to reflux and keep reacting under reflux conditions carry out 4 hours.After stopped reaction, Naturally cooling to room temperature, be poured in 500 milliliters of water, with 3 × 100 milliliters of ethyl acetate extractions, organic facies is satisfied through 3 × 100 milliliters After washing with sodium-chloride water solution, it is dried with anhydrous magnesium sulfate, pillar layer separation (leacheate: ethyl acetate: petroleum ether after concentration =1:3) obtain 11.50 grams of 4-chloromethyl-2-(2,6-difluorophenyl) azoles, yellow solid, yield 76%.
(2) synthesis of intermediate 2-(2,6-difluorophenyl)-4-cyanogen methyl azoles
In the lower 50 milliliters of round-bottomed flasks of room temperature add 4-chloromethyl-2-(2,6-difluorophenyl) azoles (20.00 grams, 0.087 Mole), add 50 milliliters of abundant dissolvings of ethanol, add Cyanogran. (5.10 grams, 0.105 mole), be warming up to backflow and keep anti- Should under reflux conditions carry out 4 hours.After stopped reaction, naturally cool to room temperature, be poured in 100 milliliters of water, with 3 × 30 milliliters Ethyl acetate extracts, and organic facies, after 3 × 50 milliliters of saturated sodium-chloride water solution washings, is dried with anhydrous magnesium sulfate, after concentration Pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:1) obtains 14.60 grams of 2-(2,6-difluorophenyl)-4-cyanogen methyl Azoles, white solid, yield 76%.
(3) intermediate 3-hydroxyl-3-(1-ethyl-3-methyl isophthalic acid H-pyrazoles-5-base)-2-(2-(2,6-difluorophenyl) Azoles-4-base) synthesis of acrylonitrile
Under ice-water bath, in 100 milliliters of reaction bulbs add 2-(2,6-difluorophenyl)-4-cyanogen methyl azoles (4.00 grams, 0.018 mole), anhydrous tetrahydro furan 50 milliliters, (1-ethyl-3-methyl isophthalic acid H-pyrazoles-5-base) (1H-pyrazol-1-yl) ketone (4.08 grams, 0.020 mole), then potassium tert-butoxide (4.07 grams, 0.036 mole) is joined in reaction bulb on a small quantity in multiple times, rise Warm to room temperature stirring reaction 4 hours, reactant liquor is poured in 50 milliliters of water, with ethyl acetate 2 × 20 milliliters washing, discards organic Phase.By aqueous phase hydrochloric acid regulation system pH=2～3, separating out solid, filtration is dried and is obtained 5.20 grams of intermediate 3-hydroxyl-3-(1- Ethyl-3-methyl isophthalic acid H-pyrazoles-5-base)-2-(2-(2,6-difluorophenyl) azoles-4-base) acrylonitrile, yellow solid, yield 80%。
(5) synthesis of compound 455
Under ice-water bath, in 50 milliliters of reaction bulbs, it is sequentially added into 3-hydroxyl-3-(1-ethyl-3-methyl isophthalic acid H-pyrazoles-5- Base)-2-(2-(2,6-difluorophenyl) azoles-4-base) acrylonitrile (0.30 gram, 0.001 mole), acetonitrile 15 milliliters and triethylamine (0.12 gram, 0.001 mole), then methylchloroformate (0.10 gram, 0.001 mole) is added drop-wise in reaction bulb, it is warming up to room temperature Stirring reaction 4 hours, reactant liquor is poured in 50 milliliters of water, is extracted with ethyl acetate (2 × 50 milliliters), and gained organic facies is with 15 in the least After rising saturated sodium bicarbonate aqueous solution, 25 milliliters of saturated sodium-chloride water solution washings, it is dried with anhydrous magnesium sulfate, concentrating under reduced pressure After, residue obtains 0.25 g of compound 455, yellow by pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:5) Oil, yield 67%.
Embodiment 4, the preparation of compound 469
Under ice-water bath, in 50 milliliters of reaction bulbs, it is sequentially added into 3-hydroxyl-3-(1-ethyl-3-methyl isophthalic acid H-pyrazoles-5- Base)-2-(2-(2,6-difluorophenyl) azoles-4-base) acrylonitrile (0.30 gram, 0.001 mole), acetonitrile 15 milliliters and triethylamine (0.10 gram, 0.001 mole), then methylchloroformate (0.10 gram, 0.001 mole) is added drop-wise in reaction bulb, it is warming up to room temperature Stirring reaction 4 hours, reactant liquor is poured in 50 milliliters of water, is extracted with ethyl acetate (2 × 50 milliliters), and gained organic facies is with 15 in the least After rising saturated sodium bicarbonate aqueous solution, 25 milliliters of saturated sodium-chloride water solution washings, it is dried with anhydrous magnesium sulfate, concentrating under reduced pressure After, residue obtains 0.23 g of compound 469, yellow by pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:5) Oil, yield 66%.
Embodiment 5, the preparation of compound 589
(1) synthesis of 3-methyl isophthalic acid-phenyl-1H-pyrazoles
Addition phenylhydrazine (5.00 grams, 0.046 mole) in reaction bulb, and 4,4-dimethoxy-2-butanones (7.30 grams, 0.055 Mole), ethanol 40 milliliters, it is warming up to backflow, refluxes 2 hours.In reactant liquor, drip concentrated hydrochloric acid (0.5 milliliter), continue backflow 2 Hour.Reaction is cooled to less than 30 DEG C after terminating, and reactant liquor is poured in 200 milliliters of water, extracts by 3 × 150 milliliters of ethyl acetate, After gained organic facies is washed with saturated sodium-chloride water solution (150 milliliters), it is dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, remaining Thing obtains 5.00 grams of 3-methyl isophthalic acid-phenyl-1H-pyrazoles by pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:10), Yellow oil, yield 68%.
(2) synthesis of 3-bromomethyl-1-phenyl-1H-pyrazoles
In reaction bulb, add 3-methyl isophthalic acid-phenyl-1H-pyrazoles (0.50 gram, 0.003 mole), toluene 5 milliliters, heat up To 70 DEG C, add N-bromo-succinimide (0.40 gram, 0.003 mole), azodiisobutyronitrile (catalytic amount) to reactant liquor, add Finishing, reactant liquor is warming up to backflow, back flow reaction 1 hour.Reaction is cooled to less than 30 DEG C after terminating, and reactant liquor is poured into 50 milliliters of water In, with 3 × 50 milliliters of ethyl acetate extractions, gained organic facies saturated sodium bicarbonate aqueous solution (50 milliliters), saturated sodium-chloride Aqueous solution (50 milliliters) washing after, be dried with anhydrous magnesium sulfate, after concentrating under reduced pressure, residue by pillar layer separation (leacheate: Ethyl acetate: petroleum ether=1:100) obtain 0.40 gram of 3-bromomethyl-1-phenyl-1H-pyrazoles, yellow oil, yield 56%.
(3) synthesis of 3-cyanogen methyl isophthalic acid-phenyl-1H-pyrazoles
3-bromomethyl-1-phenyl-1H-pyrazoles (0.55 gram, 0.003 mole), ethanol 15 milliliters, cyanogen is added in reaction bulb Change sodium (0.15 gram, 0.003 mole), room temperature reaction 6 hours.Reactant liquor is poured in 100 milliliters of water after terminating by reaction, with 3 × 100 milliliters of ethyl acetate extractions, after gained organic facies is washed with saturated sodium-chloride water solution (100 milliliters), use anhydrous magnesium sulfate Being dried, after concentrating under reduced pressure, residue obtains 0.20 gram of 3-by pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:20) Cyanogen methyl isophthalic acid-phenyl-1H-pyrazoles, yellow oil, yield 36%.
(4) intermediate 3-hydroxyl-3-(1-ethyl-3-methylpyrazole-5-base)-2-(1-Phenylpyrazole-3-base) acrylonitrile Synthesis
Under ice-water bath, (0.92 gram, 0.005 rubs to add 1-phenyl-3-cyanogen methyl isophthalic acid H-pyrazoles in 50 milliliters of reaction bulbs You), anhydrous tetrahydro furan 25 milliliters, (1-ethyl-3-methyl isophthalic acid H-pyrazoles-5-base) (1H-pyrazol-1-yl) ketone (1.02 grams, 0.005 mole), then potassium tert-butoxide (1.12 grams, 0.010 mole) is joined in reaction bulb on a small quantity in multiple times, it is warming up to room temperature Stirring reaction 4 hours, is poured into reactant liquor in 50 milliliters of water, with ethyl acetate 2 × 20 milliliters washing, discards organic facies.By water Mutually by hydrochloric acid regulation system pH=2～3, then with 3 × 25 milliliters of abundant extractions of ethyl acetate, it is dried with anhydrous magnesium sulfate, reduces pressure dense Contracting obtains 0.96 gram of intermediate 3-(1-ethyl-3-methyl isophthalic acid H-pyrazoles-5-base)-3-hydroxyl-2-(2-methyl isophthalic acid-phenyl-1H- Pyrazole-3-yl) acrylonitrile, yellow oil, yield 60%.
(5) synthesis of compound 589
Under ice-water bath, in reaction bulb, add 3-(1-ethyl-3-methyl isophthalic acid H-pyrazoles-5-base)-3-hydroxyl-2-(2- Methyl isophthalic acid-phenyl-1H-pyrazole-3-yl) acrylonitrile (0.30 gram, 0.001 mole), acetonitrile 20 milliliters, triethylamine (0.11 gram, 0.001 mole), then methylchloroformate (0.09 gram, 0.001 mole) is added drop-wise in reaction bulb, completion of dropwise addition, it is warming up to room temperature Stirring reaction 4 hours, reactant liquor is poured in 50 milliliters of water, is extracted with ethyl acetate (2 × 50 milliliters), and gained organic facies is with 15 in the least After rising saturated sodium bicarbonate aqueous solution, 25 milliliters of saturated sodium-chloride water solution washings, it is dried with anhydrous magnesium sulfate, concentrating under reduced pressure After, it is one group that residue obtains 0.15 g of compound 589 by pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:5) Stereoisomer mixture (Z:E=1:6), yellow oil, yield 45%.
Embodiment 6, the preparation of compound 1299
(1) intermediate 3-hydroxyl-3-(4-chloro-1-ethyl-3-methylpyrazole-5-base)-2-(2-(2,6-difluorophenyl) Azoles-4-base) synthesis of acrylonitrile
Under ice-water bath, in 100 milliliters of reaction bulbs add 2-(2,6-difluorophenyl)-4-cyanogen methyl azoles (4.00 grams, 0.018 mole), anhydrous tetrahydro furan 50 milliliters, (4-chloro-1-ethyl-3-methyl isophthalic acid H-pyrazoles-5-base) (1H-pyrazol-1-yl) Ketone (4.77 grams, 0.020 mole), then potassium tert-butoxide (4.07 grams, 0.036 mole) is joined reaction bulb on a small quantity in multiple times In, it is warming up to reaction 4 hour is stirred at room temperature, reactant liquor is poured in 50 milliliters of water, with ethyl acetate 2 × 20 milliliters washing, abandons Go organic facies.By aqueous phase hydrochloric acid regulation system pH=2～3, separate out solid, filter dry obtain 5.77 grams of intermediate 3-hydroxyls- 3-(4-chloro-1-ethyl-3-methyl isophthalic acid H-pyrazoles-5-base)-2-(2-(2,6-difluorophenyl) azoles-4-base) acrylonitrile, yellow Solid, yield 82%.
(2) synthesis of compound 1299
Under ice-water bath, in 50 milliliters of reaction bulbs, it is sequentially added into 3-hydroxyl-3-(4-chloro-1-ethyl-3-methyl isophthalic acid H-pyrrole Azoles-5-base)-2-(2-(2,6-difluorophenyl) azoles-4-base) acrylonitrile (0.30 gram, 0.001 mole), acetonitrile 15 milliliters and three Ethamine (0.12 gram, 0.001 mole), then by chloro-for 3-2,2-dimethylpropionic acid chloride (0.15 gram, 0.001 mole) is added drop-wise to reaction In bottle, being warming up to reaction 4 hour is stirred at room temperature, reactant liquor is poured in 50 milliliters of water, is extracted with ethyl acetate (2 × 50 milliliters), Gained organic facies, with after 15 milliliters of saturated sodium bicarbonate aqueous solutions, 25 milliliters of saturated sodium-chloride water solution washings, uses anhydrous slufuric acid Magnesium is dried, and after concentrating under reduced pressure, residue obtains 0.33 gram by pillar layer separation (leacheate: ethyl acetate: petroleum ether=1:5) Compound 1299, yellow oil, yield 85%.
Biological activity determination
According to the dissolubility of testing compound, former medicinal acetone or dimethyl sulfoxide dissolve, then with 1 ‰ Tween 80 solution Being configured to the liquid to be measured 50 milliliters of desired concn, acetone or dimethyl sulfoxide content in the solution is less than 10%.Parasite killing is dead Rate activity classification is as follows: A:100%；B:99%-80%；C:79%-60%；D:59%-0.
Embodiment 7, the mensuration of insecticidal activity
7.1 kill the mensuration of black peach aphid activity
Cut-off footpath 6 cm dishes, covers a metafiltration paper, and drips appropriate tap water moisturizing at the bottom of ware.From cultivating the sweet of black peach aphid On blue plant, clip suitable size (diameter about 3 centimetres) and the long cabbage leaves having 15～30 aphids, remove alatae and leaf The aphid in sheet front, after investigation radix, blade back is upwards placed in culture dish, carries out at spraying with hand-held Airbrush aerosol apparatus Reason, pressure is that 10psi (is roughly equal to 0.7kg/cm2), spouting liquid is 0.5mL, often processes 3 times and repeats, processes and be placed on standard sight Indoor, 48 hours " Invest, Then Investigate " survival borer populations, calculate mortality rate classification.
According to above method, partial test compound and known compound KC1(No. 1 chemical combination in JP2005008628 Thing), KC2(No. 1 compound in WO2007100160) and KC3(No. 5 compounds in CN101875633) have carried out killing black peach aphid The parallel assay of activity.Result of the test is shown in Table 2.
Table 2:1-ethyl pyrazolyl acrylonitrile compound and known compound KC1、KC2、KC3Kill the parallel ratio of black peach aphid activity Relatively
7.2 kill the mensuration of diamondback moth activity
Cabbage leaves card punch breaking into the leaf dish of diameter 2 centimetres, uses Airbrush spraying treatment, pressure is 10psi (it is roughly equal to 0.7kg/cm2), every leaf dish positive and negative is sprayed, and spouting liquid is 0.5mL.Often process to access after drying in the shade and try worm, often 10 2 ages Process 3 repetitions.Put into 25 DEG C, relative humidity 60～70% after process and observe indoor cultivation, 72 hours " Invest, Then Investigate " survival borer populations, Calculate mortality rate classification.
In the part compound for examination, following compounds is preferable to the prevention effect of diamondback moth when concentration is 600ppm, Mortality rate is more than B level: 1,5,7,15,19,21,29,31,35,37,456,469,471,1297,1311.
In the part compound for examination, following compounds is preferable to the prevention effect of diamondback moth when concentration is 100ppm, Mortality rate is more than B level: 5,31,1297.
The mensuration of 7.3 mythimna separates
Maize leaf being cut into the leaf section of long 2 centimetres, uses Airbrush spraying treatment, pressure is that 10psi (is roughly equal to 0.7kg/ cm2), every leaf section positive and negative is sprayed, and spouting liquid is 0.5mL.Often process to access after drying in the shade and try worm 10 2 ages, often process 3 weights Multiple.Put into 25 DEG C, relative humidity 60～70% observation indoor cultivation, 72 hours " Invest, Then Investigate " survival borer populations after process, calculate mortality rate And classification.
In the part compound for examination, following compounds is preferable, extremely to the prevention effect of mythimna separata when concentration is 600ppm Rate of dying is more than B level: 1,5,7,15,19,21,29,31,35,447,456,459,577,581,583,589,591,598, 1295、1297、1311。

Claims (5)

1. a 1-ethyl pyrazolyl acrylonitrile compound, as shown in formula I:
In formula:
R is selected from the tert-butyl group, 2-methyl-2-butyl, isopropoxy or isobutoxy；
X is selected from hydrogen；
Q is selected from following group:
2. according to the compound described in claim 1, it is characterised in that in formula I:
R is selected from the tert-butyl group or 2-methyl-2-butyl；
X is selected from hydrogen；
Q is selected from following group:
3. the purposes controlling black peach aphid according to the compound of Formula I described in claim 1.
4. kill a black peach aphid compositions, containing compound shown in formula I as claimed in claim 1 be active component and agricultural, Acceptable carrier in forestry or health, in compositions, the weight percentage of active component is 1-99%.
5. the method controlling black peach aphid, it is characterised in that: by the compositions described in claim 4 with per hectare 10 grams to 1000 Gram effective dose impose on need control black peach aphid or its growth medium on.
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