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

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-Ethylpyrazolylacrylonitrile compound and its application

technical field

The invention belongs to the field of pesticides. Specifically relates to a 1-ethylpyrazolyl acrylonitrile compound and application thereof.

Background technique

Since pests develop resistance to insecticides over a period of time, there is a continuing need to invent new and improved compounds and compositions having insecticidal activity. Simultaneously, along with people's increasing demand for agricultural and livestock products and the increasing emphasis on environmental protection, new insecticides with lower cost and environmental friendliness have always been required.

In WO9740009, Nissan Chemical Industry Co., Ltd. disclosed ethylene derivatives having insecticidal, acaricidal or fungicidal activities. In the JP2005008628 application, the preparation and insecticidal activity of compound KC ₁ (No. 1 in the patent) was reported. The control effect of compound KC ₁ on peach aphid was over 80% at a concentration of 500 ppm. In WO2007100160 and WO2007100161 applications, the preparation, insecticidal activity and preparation process of compound KC ₂ (No. 1 in the patent) are further disclosed. Compound KC ₂ has a high control effect on green peach aphid at a concentration of 25ppm. CN101875633 discloses the acaricidal activity of 1-ethylpyrazole compounds, and the compound KC ₃ (No. 5 in the patent) has a control effect of more than 90% on Tetranychus cinnabarinus at a concentration of 2.5ppm.

In the prior art, there is no disclosure of the 1-ethylpyrazolylacrylonitrile compound and its insecticidal activity as shown in the present invention.

Contents of the invention

The object of the present invention is to provide a 1-ethylpyrazolylacrylonitrile compound with a novel structure, which can be used in the prevention and control of agricultural, forestry or non-therapeutic sanitary pests.

Technical scheme of the present invention is as follows:

The present invention provides a kind of 1-ethylpyrazolyl acrylonitrile compound, as shown in general formula I:

In the formula:

R is selected from C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₃ -C ₈ cycloalkyl or C ₁ -C ₆ alkoxy;

X is selected from hydrogen, halogen, cyano or methyl;

Q is selected from the following groups:

R _{is selected from H, halogen, methyl or trifluoromethyl;}

R _{is selected from H or halogen;}

or its stereoisomers.

Further preferred compounds of the present invention are, in general formula I:

R is selected from C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₃ -C ₈ cycloalkyl or C ₁ -C ₆ alkoxy;

X is selected from hydrogen, halogen or methyl;

Q is selected from the following groups:

R _{is selected from H or halogen;}

R _{is selected from H or halogen;}

or its stereoisomers.

The further preferred compound of the present invention is, in general formula I:

R is selected from C ₃ -C ₆ alkyl, halogenated C ₃ -C ₆ alkyl or C ₁ -C ₄ alkoxy;

X is selected from hydrogen;

Q is selected from the following groups:

R is selected from H, fluorine or chlorine _;

R is selected from H, fluorine or chlorine _;

or its stereoisomers.

In the definitions of the compounds of general formula I given above, the collectively used terms are generally defined as follows:

Alkyl refers to straight chain or branched chain forms, such as methyl, ethyl, n-propyl, isopropyl and the like. Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopropylmethyl, methylcyclopropyl and the like. Haloalkyl refers to a group in which the alkyl group is substituted by one or more halogen atoms, such as chloroethyl, trifluoromethyl and the like. Alkoxy refers to a group with an oxygen atom attached to the end of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy and the like. Halogen means fluorine, chlorine, bromine, iodine. Stereoisomer means that in formula I, the substituents CN and OCOR on the carbon-carbon double bond B are on the same side of the B bond (Z configuration) or both sides (E configuration).

The compound of general formula I of the present invention can be prepared by the following method, and the definitions of each group in the reaction formula are the same as above.

In the formula: L represents a suitable leaving group, such as chlorine, bromine or p-toluenesulfonyloxy and the like.

The target compound I is prepared by reacting the compound of general formula II with the compound of general formula III in a suitable solvent at a temperature ranging from -10°C to reflux temperature for 0.5-48 hours.

Suitable solvents are selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N,N-dimethylformamide or dimethylmethylene Sulfone etc.

Adding suitable base substances is beneficial to the reaction. Suitable bases can be selected from organic bases, such as triethylamine, N,N-dimethylaniline, pyridine, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.; or inorganic bases such as sodium hydroxide, potassium hydroxide , sodium bicarbonate, sodium carbonate or sodium hydride, etc.

Depending on the difference in reaction conditions or the difference in starting materials, the compound of general formula I has stereoisomerism. For example, the substituents CN and OCOR on the carbon-carbon double bond B are on the same side of the B bond (Z configuration) or both sides (E configuration). By selecting appropriate starting materials or controlling the reaction conditions, one isomer excess product or a single isomer can be obtained. The crude product can also be separated by conventional means, such as column chromatography, recrystallization, etc., to obtain single isomers. The structures of these isomers can be determined by conventional analytical methods such as X-ray single crystal diffraction and nuclear magnetic resonance.

Compounds of general formula III are commercially available.

The preparation method of general formula II compound is as follows:

In the formula: L ₁ represents a suitable leaving group, such as chlorine, bromine, pyrazolyl, imidazolyl, methoxy, ethoxy or p-toluenesulfonyloxy and the like.

The compound of the general formula IV is reacted with the compound of the general formula V in a suitable solvent in the presence of a base at a temperature ranging from -10°C to boiling point for 0.5-48 hours to prepare the compound of the general formula II.

Suitable solvents are mainly selected from: dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N,N-dimethylformamide, di Methyl sulfoxide, 2-methylpentane, methylcyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, nonane, butyl ether, ethylene glycol dimethyl ether , ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc., or two or three different mixture of solvents.

Adding suitable base substances is beneficial to the reaction. Suitable bases are selected from organic bases such as triethylamine, N,N-dimethylaniline, pyridine, 2-picoline, 3-picoline, 4-picoline, 5-ethyl-2-methyl Pyridine, 2,3-lutidine, 2,4-lutidine, 3,5-lutidine, 2,6-lutidine, 2,4,6-collidine, quinol morphine, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, etc.

For the preparation of the compound of general formula IV, refer to the operating methods described in WO9740009 and DE2633992.

For the preparation of the compound of general formula V, refer to the operating method described in CN101875633.

Table 1 lists the structures and physical properties of some compounds of general formula I.

Table 1

The ¹ H NMR (300MHz, CDCl ₃ ) data of some compounds 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-ethylpyrazolyl acrylonitrile compound of the present invention has high insecticidal activity, and can control diamondback moth, beet armyworm, litura, cotton bollworm, lawn armyworm, Trichoplusia, pea aphid, soybean Aphids, beet aphids, cotton aphids, apple aphids, peach aphids, corn aphids, whiteflies, leafhoppers, planthoppers, rice planthoppers, mealybugs, cotton net bugs, tomato mirid bugs, rice green bugs, rice stinkbugs, cotton Thrips, alfalfa thrips, soybean thrips, potato beetle, beetle, flies, mosquitoes and other pests. Compared with known acrylonitriles, the 1-ethylpyrazolylacrylonitriles of the present invention have unexpectedly high insecticidal activity. Therefore, the present invention also includes the use of compounds of general formula I for controlling pests.

The present invention also includes the pesticidal composition with the compound of general formula I as an active ingredient. The weight percentage of active components in the insecticidal composition is between 1-99%. The pesticidal composition also includes an agriculturally, forestry or hygienically acceptable carrier.

The compositions of the invention may be administered in the form of formulations. The compound of general formula I is dissolved or dispersed in the carrier as an active ingredient or formulated into a preparation so that it is easier to disperse when used as an insecticide. For example: These chemicals can be formulated as wettable powders or emulsifiable concentrates. In these compositions, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant may be added.

The technical solution of the present invention also includes a method for controlling pests: applying the pesticidal composition of the present invention to the pests to be controlled or their growth medium. Usually, the more suitable effective dose is 10 grams to 1000 grams per hectare, and the preferred effective dose is 50 grams to 500 grams per hectare.

For some applications, for example, in agriculture, one or more other bactericides, insecticides, herbicides, plant growth regulators or fertilizers, etc. can be added to the pesticidal composition of the present invention, thereby producing additional advantages and effects.

It should be understood that various changes and modifications can be made within the scope of the present invention defined by the claims.

detailed description

The following synthesis examples and bioassay results can be used to further illustrate the present invention, but are not meant to limit the present invention.

Synthetic example

Embodiment 1, the preparation of compound 15

(1) Synthesis of 4-chloromethyl-2-phenylthiazole

Add thiobenzamide (20.00 g, 0.146 mol), 200 ml of methanol, and 1,3-dichloroacetone (22.21 g, 0.157 mol) into the three-necked flask, raise the temperature to reflux, and react under reflux for 3 hours. After the reaction, the temperature was lowered to below 30°C, the reaction solution was poured into 50 ml of water, extracted with 3×50 ml of ethyl acetate, and the organic phase was washed with saturated aqueous sodium bicarbonate (50 ml), saturated aqueous sodium chloride (50 ml) After washing, drying with anhydrous magnesium sulfate, and concentration under reduced pressure, the residue was separated by column chromatography (eluent: ethyl acetate: petroleum ether = 1:10) to obtain 21.00 g of 4-chloromethyl-2-phenyl Thiazole, yellow oil, yield 69%.

(2) Synthesis of 4-cyanomethyl-2-phenylthiazole

Add sodium cyanide (4.91 g, 0.100 mol) and 100 ml of water to the reaction flask, add dropwise a solution of 4-chloromethyl-2-phenylthiazole (21.00 g, 0.100 mol) in ethanol (100 ml), dropwise Complete, be warming up to reflux, reflux 16 hours. After the reaction was completed, the reaction solution was poured into 200 ml of water, extracted with 3×200 ml of ethyl acetate, and the obtained organic phase was washed with saturated aqueous sodium chloride solution (200 ml), dried with anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was separated by column chromatography (eluent: ethyl acetate:petroleum ether=1:10) to obtain 13.22 g of 4-cyanomethyl-2-phenylthiazole as a yellow oil with a yield of 66%.

(3) Synthesis of intermediate 3-hydroxy-3-(1-ethyl-3-methylpyrazol-5-yl)-2-(2-phenylthiazol-4-yl)acrylonitrile

In an ice-water bath, 2-phenyl-4-cyanomethylthiazole (3.00 g, 0.015 moles), 25 ml of anhydrous tetrahydrofuran, (1-ethyl-3-methyl-1H- Pyrazol-5-yl) (1H-pyrazol-1-yl) ketone (1.02 grams, 0.005 moles), then potassium tert-butoxide (3.37 grams, 0.030 moles) was added to the reaction flask several times in small amounts, The temperature was raised to room temperature and the reaction was stirred for 4 hours. The reaction solution was poured into 50 ml of water, washed with 2×20 ml of ethyl acetate, and the organic phase was discarded. The aqueous phase was adjusted to pH=2~3 with hydrochloric acid, then fully extracted with ethyl acetate 3×25 ml, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 2.86 g of intermediate 3-hydroxy-3-(1-ethyl Base-3-methylpyrazol-5-yl)-2-(2-phenylthiazol-4-yl)acrylonitrile, brown oil, yield 57%.

(4) Synthesis of compound 15

Under ice-water bath, add 3-hydroxy-3-(1-ethyl-3-methylpyrazol-5-yl)-2-(2-phenylthiazol-4-yl) successively into the 50ml reaction flask Acrylonitrile (0.30 g, 0.001 mole), 15 ml of acetonitrile and triethylamine (0.47 g, 0.005 mole), and then pivaloyl chloride (0.47 g, 0.004 mole) were added dropwise to the reaction flask, and the temperature was raised to room temperature and stirred for reaction 4 hours, the reaction solution was poured into 50 ml of water, extracted with ethyl acetate (2 × 50 ml), the resulting organic phase was washed with 15 ml of saturated aqueous sodium bicarbonate solution, 25 ml of saturated aqueous sodium chloride solution, and dried with anhydrous magnesium sulfate , and concentrated under reduced pressure, the residue was separated by column chromatography (eluent: ethyl acetate: petroleum ether = 1:8) to obtain 0.15 g of compound 15, a yellow oil, with a yield of 39%.

Embodiment 2, the preparation of compound 37

Under ice-water bath, add 3-hydroxyl-3-(1-ethyl-3-methylpyrazol-5-yl)-2-(2-phenylthiazol-4-yl)acrylonitrile ( 0.30 g, 0.001 mole), 15 milliliters of acetonitrile, triethylamine (0.47 g, 0.005 mole), and isobutyl chloroformate (0.53 g, 0.004 mole) were added dropwise to the reaction flask, after the addition was completed, the temperature was raised to room temperature The reaction was stirred for 4 hours, the reaction solution was poured into 50 ml of water, extracted with ethyl acetate (2 × 50 ml), the obtained organic phase was washed with 15 ml of saturated aqueous sodium bicarbonate solution, 25 ml of saturated aqueous sodium chloride solution, and washed with anhydrous After drying over magnesium sulfate and concentrating under reduced pressure, the residue was separated by column chromatography (eluent: ethyl acetate:petroleum ether=1:8) to obtain 0.21 g of compound 37, which was a mixture of stereoisomers (Z:E= 1:3), yellow oil, yield 54%.

Embodiment 3, the preparation of compound 455

(1) Synthesis of 4-chloromethyl-2-(2,6-difluorophenyl)oxazole

Add 2,6-difluorobenzamide (10.00 g, 0.064 mol) and 1,3-dichloroacetone (16.20 g, 0.128 mol) to a 100 mL round bottom flask, raise the temperature to reflux and keep the reaction under reflux conditions for 4 hours. After stopping the reaction, cool to room temperature naturally, pour into 500 ml of water, extract with 3 × 100 ml of ethyl acetate, wash the organic phase with 3 × 100 ml of saturated aqueous sodium chloride solution, dry with anhydrous magnesium sulfate, and concentrate the column Chromatographic separation (eluent: ethyl acetate:petroleum ether=1:3) gave 11.50 g of 4-chloromethyl-2-(2,6-difluorophenyl)oxazole as a yellow solid with a yield of 76%.

(2) Synthesis of intermediate 2-(2,6-difluorophenyl)-4-cyanomethyloxazole

Add 4-chloromethyl-2-(2,6-difluorophenyl) oxazole (20.00 g, 0.087 mol) into a 50 ml round bottom flask at room temperature, add 50 ml of ethanol to fully dissolve, add sodium cyanide (5.10 g, 0.105 moles), warming to reflux and maintaining the reaction at reflux for 4 hours. After stopping the reaction, cool to room temperature naturally, pour into 100 ml of water, extract with 3 × 30 ml of ethyl acetate, wash the organic phase with 3 × 50 ml of saturated aqueous sodium chloride solution, dry with anhydrous magnesium sulfate, and concentrate the column Chromatographic separation (eluent: ethyl acetate: petroleum ether = 1:1) gave 14.60 g of 2-(2,6-difluorophenyl)-4-cyanomethyloxazole as a white solid, yield 76%.

(3) Intermediate 3-hydroxy-3-(1-ethyl-3-methyl-1H-pyrazol-5-yl)-2-(2-(2,6-difluorophenyl)oxazole- Synthesis of 4-yl)acrylonitrile

In an ice-water bath, add 2-(2,6-difluorophenyl)-4-cyanomethyloxazole (4.00 g, 0.018 mol), 50 ml of anhydrous tetrahydrofuran, (1-ethane Base-3-methyl-1H-pyrazol-5-yl)(1H-pyrazol-1-yl)methanone (4.08 grams, 0.020 moles), and a small amount of potassium tert-butoxide (4.07 grams, 0.036 moles) Added to the reaction bottle several times, warmed up to room temperature and stirred for 4 hours, poured the reaction liquid into 50 ml of water, washed with 2×20 ml of ethyl acetate, and discarded the organic phase. Use hydrochloric acid to adjust the pH of the system to 2 to 3 in the aqueous phase, precipitate a solid, filter and dry to obtain 5.20 g of intermediate 3-hydroxy-3-(1-ethyl-3-methyl-1H-pyrazol-5-yl) -2-(2-(2,6-difluorophenyl)oxazol-4-yl)acrylonitrile, yellow solid, yield 80%.

(5) Synthesis of Compound 455

In an ice-water bath, add 3-hydroxy-3-(1-ethyl-3-methyl-1H-pyrazol-5-yl)-2-(2-(2,6- Difluorophenyl)oxazol-4-yl)acrylonitrile (0.30g, 0.001mol), acetonitrile 15ml and triethylamine (0.12g, 0.001mol), then methyl chloroformate (0.10g, 0.001mol) Add it dropwise into the reaction bottle, raise the temperature to room temperature and stir for 4 hours. The reaction solution is poured into 50 ml of water and extracted with ethyl acetate (2×50 ml). After washing with aqueous sodium chloride solution, drying with anhydrous magnesium sulfate, and concentrating under reduced pressure, the residue was separated by column chromatography (eluent: ethyl acetate: petroleum ether = 1:5) to obtain 0.25 g of compound 455, a yellow oil, Yield 67%.

Embodiment 4, the preparation of compound 469

In an ice-water bath, add 3-hydroxy-3-(1-ethyl-3-methyl-1H-pyrazol-5-yl)-2-(2-(2,6- Difluorophenyl)oxazol-4-yl)acrylonitrile (0.30g, 0.001mol), acetonitrile 15ml and triethylamine (0.10g, 0.001mol), then methyl chloroformate (0.10g, 0.001mol) Add it dropwise into the reaction bottle, raise the temperature to room temperature and stir for 4 hours. The reaction solution is poured into 50 ml of water and extracted with ethyl acetate (2×50 ml). After washing with aqueous sodium chloride solution, drying with anhydrous magnesium sulfate, and concentrating under reduced pressure, the residue was separated by column chromatography (eluent: ethyl acetate:petroleum ether=1:5) to obtain 0.23 g of compound 469, a yellow oil, The yield is 66%.

Embodiment 5, the preparation of compound 589

(1) Synthesis of 3-methyl-1-phenyl-1H-pyrazole

Add phenylhydrazine (5.00 g, 0.046 mol), 4,4-dimethoxy-2-butanone (7.30 g, 0.055 mol), and 40 ml of ethanol into the reaction flask, heat up to reflux, and reflux for 2 hours. Concentrated hydrochloric acid (0.5 ml) was added dropwise to the reaction solution, and reflux was continued for 2 hours. After the reaction was completed, the temperature was lowered to below 30°C, the reaction solution was poured into 200 ml of water, extracted with 3×150 ml of ethyl acetate, the organic phase was washed with saturated aqueous sodium chloride solution (150 ml), and dried with anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was separated by column chromatography (eluent: ethyl acetate: petroleum ether = 1:10) to obtain 5.00 g of 3-methyl-1-phenyl-1H-pyrazole, yellow oil, yield 68%.

(2) Synthesis of 3-bromomethyl-1-phenyl-1H-pyrazole

Add 3-methyl-1-phenyl-1H-pyrazole (0.50 g, 0.003 mol) and 5 ml of toluene into the reaction flask, heat up to 70 °C, add N-bromosuccinimide ( 0.40 g, 0.003 moles), azobisisobutyronitrile (catalytic amount), after the addition is complete, the reaction solution is heated to reflux, and the reflux reaction is carried out for 1 hour. After the reaction, the temperature was lowered to below 30°C, the reaction solution was poured into 50 ml of water, extracted with 3×50 ml of ethyl acetate, and the organic phase was washed with saturated aqueous sodium bicarbonate (50 ml), saturated aqueous sodium chloride (50 ml) After washing, dry with anhydrous magnesium sulfate, concentrate under reduced pressure, the residue is separated by column chromatography (eluent: ethyl acetate: petroleum ether = 1:100) to obtain 0.40 g of 3-bromomethyl-1-phenyl -1H-pyrazole, yellow oil, yield 56%.

(3) Synthesis of 3-cyanomethyl-1-phenyl-1H-pyrazole

Add 3-bromomethyl-1-phenyl-1H-pyrazole (0.55 g, 0.003 mol), 15 ml of ethanol, and sodium cyanide (0.15 g, 0.003 mol) into the reaction flask, and react at room temperature for 6 hours. After the reaction, the reaction solution was poured into 100 ml of water, extracted with 3×100 ml of ethyl acetate, and the obtained organic phase was washed with saturated aqueous sodium chloride solution (100 ml), dried with anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was separated by column chromatography (eluent: ethyl acetate:petroleum ether=1:20) to obtain 0.20 g of 3-cyanomethyl-1-phenyl-1H-pyrazole as a yellow oil with a yield of 36%.

(4) Synthesis of intermediate 3-hydroxyl-3-(1-ethyl-3-methylpyrazol-5-yl)-2-(1-phenylpyrazol-3-yl)acrylonitrile

In an ice-water bath, add 1-phenyl-3-cyanomethyl-1H-pyrazole (0.92 g, 0.005 mol), 25 ml of anhydrous tetrahydrofuran, (1-ethyl-3-methyl Base-1H-pyrazol-5-yl)(1H-pyrazol-1-yl)methanone (1.02 g, 0.005 mol), then potassium tert-butoxide (1.12 g, 0.010 mol) was added to In the reaction flask, the temperature was raised to room temperature and the reaction was stirred for 4 hours. The reaction solution was poured into 50 ml of water, washed with 2×20 ml of ethyl acetate, and the organic phase was discarded. The aqueous phase was adjusted to pH=2~3 with hydrochloric acid, then fully extracted with ethyl acetate 3×25 ml, dried with anhydrous magnesium sulfate, concentrated under reduced pressure to obtain 0.96 g of intermediate 3-(1-ethyl-3- Methyl-1H-pyrazol-5-yl)-3-hydroxy-2-(2-methyl-1-phenyl-1H-pyrazol-3-yl)acrylonitrile, yellow oil, yield 60%.

(5) Synthesis of Compound 589

In an ice-water bath, add 3-(1-ethyl-3-methyl-1H-pyrazol-5-yl)-3-hydroxy-2-(2-methyl-1-phenyl- 1H-pyrazol-3-yl) acrylonitrile (0.30 g, 0.001 mole), 20 milliliters of acetonitrile, triethylamine (0.11 g, 0.001 mole), and then methyl chloroformate (0.09 g, 0.001 mole) was added dropwise to In the reaction flask, after the dropwise addition was completed, the temperature was raised to room temperature and stirred for 4 hours. The reaction solution was poured into 50 ml of water and extracted with ethyl acetate (2×50 ml). After washing with saturated aqueous sodium chloride solution, drying with anhydrous magnesium sulfate, and concentrating under reduced pressure, the residue was separated by column chromatography (eluent: ethyl acetate:petroleum ether=1:5) to obtain 0.15 g of compound 589 as a group Stereoisomer mixture (Z:E=1:6), yellow oil, yield 45%.

Embodiment 6, the preparation of compound 1299

(1) Intermediate 3-hydroxy-3-(4-chloro-1-ethyl-3-methylpyrazol-5-yl)-2-(2-(2,6-difluorophenyl)oxazole Synthesis of -4-yl)acrylonitrile

In an ice-water bath, add 2-(2,6-difluorophenyl)-4-cyanomethyloxazole (4.00 g, 0.018 mol), 50 ml of anhydrous tetrahydrofuran, (4-chloro -1-Ethyl-3-methyl-1H-pyrazol-5-yl)(1H-pyrazol-1-yl)methanone (4.77 g, 0.020 mole), and potassium tert-butoxide (4.07 g, 0.036 mol) was added to the reaction flask several times in small amounts, heated to room temperature and stirred for 4 hours, the reaction solution was poured into 50 ml of water, washed with 2×20 ml of ethyl acetate, and the organic phase was discarded. Use hydrochloric acid to adjust the pH of the system to 2~3 in the aqueous phase, and precipitate a solid, filter and dry to obtain 5.77 g of intermediate 3-hydroxy-3-(4-chloro-1-ethyl-3-methyl-1H-pyrazole- 5-yl)-2-(2-(2,6-difluorophenyl)oxazol-4-yl)acrylonitrile, yellow solid, yield 82%.

(2) Synthesis of compound 1299

Under an ice-water bath, 3-hydroxyl-3-(4-chloro-1-ethyl-3-methyl-1H-pyrazol-5-yl)-2-(2-( 2,6-difluorophenyl) oxazol-4-yl) acrylonitrile (0.30 g, 0.001 mol), 15 ml of acetonitrile and triethylamine (0.12 g, 0.001 mol), then 3-chloro-2,2 -Dimethylpropionyl chloride (0.15 g, 0.001 mol) was added dropwise into the reaction flask, heated to room temperature and stirred for 4 hours, the reaction liquid was poured into 50 ml of water, extracted with ethyl acetate (2×50 ml), the obtained organic The phase was washed with 15 ml of saturated aqueous sodium bicarbonate solution and 25 ml of saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was separated by column chromatography (eluent: ethyl acetate: petroleum ether = 1:5) to obtain 0.33 g of compound 1299, a yellow oil, with a yield of 85%.

Bioactivity assay

According to the solubility of the compound to be tested, the original drug is dissolved with acetone or dimethyl sulfoxide, and then 50 milliliters of the test solution of the required concentration is prepared with 1‰ Tween 80 solution, and the amount of acetone or dimethyl sulfoxide in the solution is The content does not exceed 10%. The insecticidal mortality activity is graded as follows: A: 100%; B: 99%-80%; C: 79%-60%; D: 59%-0.

Embodiment 7, the mensuration of insecticidal activity

7.1 Determination of activity against green peach aphid

Take a petri dish with a diameter of 6 cm, cover the bottom of the dish with a layer of filter paper, and add an appropriate amount of tap water to moisturize it. Cut the cabbage leaves with a suitable size (about 3 cm in diameter) and 15 to 30 aphids from the cabbage plants for cultivating peach aphids, remove the winged aphids and the aphids on the front of the leaves, check the base, and place the leaves back up for cultivation In the dish, use a hand-held Airbrush sprayer for spray treatment, the pressure is 10psi (about 0.7kg/cm ² ), the spray volume is 0.5mL, and each treatment is repeated 3 times. After treatment, it is placed in a standard observation room and investigated after 48 hours The number of surviving insects was calculated and graded.

According to the above method, part of the test compounds were compared with the known compounds KC ₁ (Compound No. 1 in JP2005008628), KC ₂ (Compound No. 1 in WO2007100160) and KC ₃ (Compound No. 5 in CN101875633) for the activity of killing peach aphids. Parallel determination. The test results are shown in Table 2.

Table 2: Parallel comparison of the activity of 1-ethylpyrazolylacrylonitrile compound and known compounds KC ₁ , KC ₂ , KC ₃ against peach aphids

7.2 Determination of Plutella xylostella activity

The cabbage leaves were punched into discs with a diameter of 2 cm, sprayed with an Airbrush at a pressure of 10 psi (about 0.7 kg/cm ² ), and the front and back sides of each disc were sprayed with a spray volume of 0.5 mL. After drying in the shade, 10 second-instar test insects were inserted into each treatment, and each treatment was repeated 3 times. After treatment, put them in an observation room at 25°C and a relative humidity of 60-70% for cultivation. After 72 hours, investigate the number of surviving insects, calculate the mortality rate and grade them.

Among some of the tested compounds, the following compounds have a better control effect on diamondback moth when the concentration is 600ppm, and the mortality rate is above grade B: 1, 5, 7, 15, 19, 21, 29, 31, 35, 37, 456, 469, 471, 1297, 1311.

Among some tested compounds, the following compounds have better control effects on diamondback moth at a concentration of 100ppm, and the mortality rate is above grade B: 5, 31, 1297.

7.3 Determination of armyworm activity

The corn leaves were cut into 2 cm long leaf segments, sprayed with Airbrush at a pressure of 10 psi (about 0.7 kg/cm ² ), sprayed on the front and back of each leaf segment, and the spray volume was 0.5 mL. After drying in the shade, 10 second-instar test insects were inserted into each treatment, and each treatment was repeated 3 times. After treatment, put them in an observation room at 25°C and a relative humidity of 60-70% for cultivation. After 72 hours, investigate the number of surviving insects, calculate the mortality rate and grade them.

Among some tested compounds, the following compounds have better control effect on armyworm when the concentration is 600ppm, and the mortality rate is above grade B: 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.