A pyridine oxime ether amide compound and its use

Abstract

The invention provides a pyridine oxime ether amide compound, the structure of which is shown in Formula III: the compound has a high inhibitory effect on adult mites of Tetranychus cinnabarinus, and can be used for the prevention and treatment of agricultural harmful mites.

Description

Technical Field The invention belongs to the field of acaricides in pesticides and relates to a pyridine oxime ether amide compound and a use thereof. Background Art Mites are a common pest in agriculture and forestry, which harm crops such as vegetables, cotton, and fruit trees, causing a reduction in grain production and causing great damage to crop growth. Therefore, it is of great significance to invent green, low-toxic, highly effective, low-residue, and long-lasting pesticide acaricides. Mites are small in size, fast in reproduction, highly adaptable, and easy to develop drug resistance. They are recognized as a harmful biological community that is difficult to control. Since agricultural mites are prone to drug resistance, some commercial acaricides lose their original high efficiency due to drug resistance, and gradually cannot meet the requirements of modern agriculture for ultra-high efficiency, long-lasting effect, and low pollution of acaricides. It is necessary to continuously develop new varieties of high-efficiency acaricides. In the prior art, a pyridine oxime ether amide compound and its use as acaricide as described in the present invention have not been disclosed. Summary of the invention The purpose of the present invention is to provide a novel structure, safe use, high efficiency and low toxicity pyridine oxime ether amide compound, which is used as a crop acaricide and can be used for the prevention and treatment of agricultural or forestry pest mites.

[0001] The technical solution of the present invention is as follows:

[0002] A pyridine oxime ether amide compound, the structure of which is shown in Formula III:

[0003]

[0004] The compound of formula III of the present invention can be prepared by the following reaction method.

[0005] (1) 3-cyanopyridine and hydroxylamine hydrochloride react to produce a compound of formula I:

[0006]

[0007] (2) The compound of formula I reacts with 4-tert-butylbenzyl chloride to generate a compound of formula II:

[0008]

[0009] (3) The compound of formula II reacts with propionic anhydride to generate the compound of formula III:

[0010]

[0011] The specific preparation method is shown in the examples of the present invention.

[0012] Advantages and positive effects of the present invention:

[0013] The pyridine ring is an important group of neonicotinoid insecticides. The pyridine oxime ether amide compound of the present invention contains a pyridine ring and a benzyl oxime ether and an amide structure. It is not only novel in structure, but also has excellent acaricidal activity (see Table 1). The efficacy is significantly higher than that of the commercialized special acaricide cypermethrin, which is a control. It is particularly suitable for the treatment of currently common resistant agricultural pests and mites, and can better deal with the problem of acaricide resistance. The compound of the present invention also has the advantages of good biodegradability, low residue, and good environmental compatibility. The compound of the present invention has a simple synthesis process, easy-to-obtain raw materials, no need to purify the intermediates, low control cost, high efficiency and low toxicity, and has the prospect of industrialization and commercialization potential as a new variety of creative acaricides.

[0014] When the compound of the present invention is used for preventing crop mites, it can be used alone or in combination with other insecticides and miticides to improve the comprehensive function of the product.

[0015] The present invention also includes an insecticide and acaricide composition containing the compound of formula III as an active ingredient, and the composition also includes an agriculturally or forestry-acceptable carrier.

[0016] The composition of the present invention can be applied in the form of a preparation, wherein the compound of formula III is dissolved or dispersed in a carrier or solvent as an active ingredient, and a suitable surfactant is added to prepare an emulsifiable concentrate, a suspension, a microemulsion, etc.

[0017] It should be clear that various changes and modifications can be made within the scope of the present invention as defined by the claims. DETAILED DESCRIPTION

[0018] The following synthesis examples and biological test results can be used to further illustrate the present invention, but are not intended to limit the present invention.

[0019] Synthesis Example

[0020] Example 1, preparation of compound of formula III:

[0021] (1) Preparation of Compound I:

[0022]

[0023] In a 250mL three-necked flask, add 20.8g (0.3mol) of hydroxylamine hydrochloride, 30.3g (0.3mol) of triethylamine and 50g of ethanol. Stir at room temperature for 30min to liberate the hydroxylamine. Add 10.4g (0.1mol) of 3-cyanopyridine dropwise, raise the temperature to reflux, react for 3h, monitor the reaction by TLC until it is complete, cool to room temperature, filter with suction, and remove the solvent by rotary evaporation to obtain a white solid, which is compound I.

[0024] (2) Preparation of Compound II:

[0025]

[0026] In a 250mL three-necked flask, add 13.7g (0.10mol) of intermediate Ⅰ into 50mL DMF, and slowly add 4.2g (0.105mol) of NaOH powder and 18.2g (0.1mol) of 4-tert-butylbenzyl chloride dissolved in 10mL DMF at 0℃. After the addition is complete, transfer to room temperature and react for 3h. Monitor the reaction by TLC until the reaction is complete. Pour the reaction solution into 150mL of water and extract three times with 60mL of ethyl acetate. Dry the organic phase and remove the solvent by rotary evaporation to obtain a brown oil, which is the crude product of compound Ⅱ.

[0027] (3) Preparation of Compound III:

[0028]

[0029] In a 100mL single-mouth bottle, add 2.83g (10.0mmol) of intermediate II and 2.60g (20.0mmol) of propionic anhydride to 30mL of toluene, heat to reflux and react for 5h, detect by TLC until the reaction is complete, cool to room temperature, add the reaction solution to 40mL of saturated sodium chloride aqueous solution, extract with ethyl acetate (3×30mL), dry the organic phase with anhydrous sodium sulfate, remove the solvent, and separate the crude product by column chromatography (V (ethyl acetate): V (petroleum ether) = 1:15) to obtain compound III with a yield of 90%. The melting point of compound III is 135-136°C; 1 H NMR (500MHz, DMSO-d6) δ8.89(d,J=2.4Hz,1H),8.66(dd,J=4.7,1.7Hz,1H),8.07(dt,J=8.1,2.0Hz,1H),7.48(dd,J=8.1,4.8 Hz,1H),7.40(d,J=8.2Hz,2H),7.31(d,J=8.2Hz,2H),5.24(s,2H),2.53(q,J=7.0Hz,4H),1.26(s,9H),0.92(t,J=7.2Hz,6H); 13 C NMR(126MHz,DMSO-d6)δ174.06,151.11,150.81,146.68,144.65,133.48,1 33.16,128.33,127.28,125.16,123.93,76.82,34.25,31.00,29.52,8.31.

[0030] Biological activity test

[0031] The cinnabar spider mite was used as the test object and the spray method was adopted. The test compound was dissolved in N, N-dimethylformamide (DMF) to prepare a solution with a concentration of 200 mg / L, and then diluted to the required concentration (100, 50, 20 mg / L) with water containing 10% Tween-20. Take 2 true leaf bean seedlings, inoculate 30 adult cinnabar spider mites, spray the whole plant with a handheld sprayer, and then put it in a standard observation room, and observe and record the death of mites for 48 hours. With clean water as the blank control, each group of test solutions was set up with 3 repeated tests and 1 blank test, and the lethality of cinnabar spider mites was calculated.

[0032] Mortality rate (%) = (mortality rate of drug treatment - mortality rate of blank control) / (1 - mortality rate of blank control) × 100%

[0033] Table 1. Test results of the activity of the compounds of the present invention (Formula III) against adult Tetranychus cinnabarinus

[0034]

[0035] The results in Table 1 show that the acaricidal activity of the compound of formula III of the present invention against adult Tetranychus cinnabarinus mites is significantly better than that of the commonly used specific acaricide fenamipropargyl.

Claims

1. A pyridine oxime ether amide compound, the structure of which is shown in Formula III:

2. The use of a pyridine oxime ether amide compound according to claim 1, characterized in that The compound of formula III is used as an agricultural and forestry acaricide to control agricultural and forestry pest mites.

3. An acaricide composition comprising the compound of formula III as claimed in claim 1 as an active ingredient and an agriculturally acceptable carrier.

Images