2-SUBSTITUTED IMIDAZOLIDINE DERIVATIVE CONTAINING ARYL BIPYRIDYLOXY STRUCTURE AND PREPARATION METHOD AND USE THEREOF

Abstract

The present disclosure relates to a 2-substituted imidazolidine derivative containing an aryl bipyridyloxy structure, and a preparation method and use thereof, which is obtained by the reaction of 2-substituted imidazolidine and aryl bipyridyloxy compound. The 2-substituted imidazolidine derivative containing an aryl bipyridyloxy structure has a good insecticidal effect on harmful insects, and the compound can be used to prepare insecticides in the fields of agriculture, horticulture, etc.

Claims

1. A 2-substituted imidazolidine derivative containing an aryl bipyridyloxy structure, wherein having a structure represented by general formula I, ##STR00010## in the general formula I, Y includes 4-F, 4-Cl, 4-Br, H, 2, 4-Cl.sub.2, 2, 3-F.sub.2.

2. The 2-substituted imidazolidine derivative containing an aryl bipyridyloxy structure according to claim 1, wherein the structure is as follows: ##STR00011##

3. A method for preparing the 2-substituted imidazolidine derivative containing an aryl bipyridyloxy structure according to claim 1, wherein the method is as follows: ##STR00012##

4. The preparation method according to claim 3, wherein the Method 1 is as follows: adding 7 mmol of intermediate II, 8 mmol of intermediate IIIa, and 30 mL of acetone, and then adding 50 mmol of triethylamine; then heating the reaction solution to reflux for 12 h; and purifying the crude product obtained after desolventization by column chromatography to obtain the target Ia.

5. The preparation method according to claim 3, wherein the Method 2 is as follows: adding 6 mmol of intermediate II, 5 mmol of intermediate IIIb, and 30 mL of acetonitrile, and then adding 20 mmol of potassium carbonate; heating the reaction solution to reflux for 10 h; and purifying the crude product obtained after desolventization by column chromatography to obtain the target compound Ib.

6. The preparation method according to claim 3, wherein the Method 3 is as follows: adding 8 mmol of intermediate II, 8 mmol of intermediate IIIc, and 35 mL of DMF, and then adding 20 mmol of cesium carbonate; heating the reaction solution to 80° C. and reacting for 15 h; and purifying the crude product obtained after desolventization by column chromatography to obtain the target compound Ic.

7. The preparation method according to claim 3, wherein the Method 4 is as follows: adding 8 mmol of intermediate II, 9 mmol of intermediate IIId and 30 mL of DMF, and then adding 30 mmol of sodium bicarbonate; heating the reaction solution to 80° C. and reacting for 18 h; and purifying the crude product obtained after desolventization by column chromatography to obtain the target compound Id.

8. The preparation method according to claim 3, wherein the Method 5 is as follows: adding 4 mmol of intermediate II, 5 mmol of intermediate IIIe, and 35 mL of DMSO, and then adding 10 mmol of potassium carbonate; heating the reaction solution to 85° C. and reacting for 22 h; and purifying the crude product obtained after desolventization by column chromatography to obtain the target compound Ie.

9. The preparation method according to claim 3, wherein the Method 6 is as follows: adding 10 mmol of intermediate II, 11 mmol of intermediate IIIf and 30 mL of acetonitrile, and then adding 30 mmol of cesium carbonate; heating the reaction solution to reflux for 8 h; and purifying the crude product obtained after desolventization by column chromatography to obtain the target compound If.

10-16. (canceled)

17. An insecticidal composition, wherein the insecticidal composition is processed into an emulsion in water, a suspension, a water dispersible granule, and an emulsifiable concentrate by using the compound represented by ##STR00013## as the active ingredient, with insecticide adjuvants commonly used in the art.

18. The insecticidal composition according to claim 17, wherein the commonly used insecticide adjuvants include liquid carriers, organic solvents, commonly used surfactants, and other adjuvants.

19. The insecticidal composition according to claim 17, wherein the liquid carrier is water; the organic solvents are toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and vegetable oils and fatty acids; the commonly used surfactants are emulsifiers and dispersants; and the other adjuvants are humectants and thickeners.

20. The insecticidal composition according to claim 17, wherein the commonly used surfactants include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.

21. The insecticidal composition according to claim 17, wherein the weight content of the compound represented by the general formula I as an active ingredient in the insecticidal composition is 0.1%-99.5%.

22. The insecticide composition according to claim 17, wherein the emulsion in water contains 5%-50% of the active ingredient by weight.

23. The insecticide composition according to claim 17, wherein the suspension contains 5%-50% of the active ingredient by weight.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0020] The above technical scheme will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are used to illustrate the present disclosure and not to limit the scope of the present disclosure. The implementation conditions used in the examples can be further adjusted according to the conditions of specific manufacturers, and implementation conditions not specified are usually conditions in routine experiments.

EXAMPLE 1

[0021] ##STR00004##

[0022] In a reaction flask, 7 mmol of intermediate II, 8 mmol of intermediate IIIa, and 30 mL of acetone were added, and then 50 mmol of trimethylamine was added thereto. Then, it was heated and refluxed for 12 h. The crude product obtained after desolventization was purified by column chromatography to obtain the target Ia; .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.17 (s, 1H, NH), 8.06 (s, 1H, Py-H), 7.72-7.75 (m, 1H, Py-H), 7.09 (d, J=6.4 Hz, 4H, Ar-H), 6.93 (d, J=8.4 Hz, 1H, Py-H), 4.50 (s, 2H, CH.sub.2), 3.77 (t, J=9.2 Hz, 2H, CH.sub.2), 3.50 (t, J=9.2 Hz, 2H, CH.sub.2).

EXAMPLE 2

[0023] ##STR00005##

[0024] In a reaction flask, 6 mmol of intermediate II, 5 mmol of intermediate IIIb, and 30 mL of acetonitrile were added, and then 20 mmol of potassium carbonate was added thereto. Then, the reaction solution was heated and refluxed for 10 h. The crude product obtained after desolventization was purified by column chromatography to obtain the target Ib; .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.17 (s, 1H, NH), 8.07 (d, J=2.0 Hz, 1H, Py-H), 7.73-7.76 (m, 1H, Py-H), 7.36 (d, J=8.8 Hz, 2H, Ar-H), 7.08 (d, J=8.8 Hz, 2H, Ar-H), 6.95 (d, J=8.4 Hz, 1H, Py-H), 4.50 (s, 2H, CH.sub.2), 3.77 (t, J=9.2 Hz, 2H, CH.sub.2), 3.50 (t, J=9.2 Hz, 2H, CH.sub.2).

EXAMPLE 3

[0025] ##STR00006##

[0026] In a reaction flask, 8 mmol of intermediate II, 8 mmol of intermediate IIIc, and 35 mL of DMF were added, and then 20 mmol of cesium carbonate was added thereto. Then, the reaction solution was heated to 80° C. and reacted for 15 h. The crude product obtained after desolventization was purified by column chromatography to obtain the target Ic; .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.17 (s, 1H, NH), 8.07 (s, 1H, Py-H), 7.75 (d, J=8.0 Hz, 1H, Py-H), 7.51 (d, J=8.4 Hz, 2H, Ar-H), 7.03 (d, J=8.8 Hz, 2H, Ar-H), 6.95 (d, J=8.4 Hz, 1H, Py-H), 4.50 (s, 2H, CH.sub.2), 3.78 (t, J=8.4 Hz, 2H, CH.sub.2), 3.51 (t, J=8.4 Hz, 2H, CH.sub.2).

EXAMPLE 4

[0027] ##STR00007##

[0028] In a reaction flask, 8 mmol of intermediate II, 9 mmol of intermediate IIId, and 30 mL of DMF were added, and then 30 mmol of sodium bicarbonate was added thereto. Then, the reaction solution was heated to 80° C. and reacted for 18 h. The crude product obtained after desolventization was purified by column chromatography to obtain the target Id; .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.17 (s, 1H, NH), 8.08 (d, J=2.4 Hz, 1H, Py-H), 7.71-7.73 (m, 1H, Py-H), 7.39-7.43 (m, 2H, Ar-H), 7.20-7.24 (m, 1H, Ar-H), 7.13 (d, J=7.6 Hz, 2H, Ar-H), 6.92 (d, J=8.8 Hz, 1H, Py-H), 4.50 (s, 2H, CH.sub.2), 3.76 (t, J=9.2 Hz, 2H, CH.sub.2), 3.50 (t, J=9.2 Hz, 2H, CH.sub.2).

EXAMPLE 5

[0029] ##STR00008##

[0030] In a reaction flask, 4 mmol of intermediate II, 5 mmol of intermediate IIIe, and 35 mL of DMSO were added, and then 10 mmol of potassium carbonate was added thereto. Then, the reaction solution was heated to 85° C. and reacted for 22 h. The crude product obtained after desolventization was purified by column chromatography to obtain the target Ie; .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.17 (s, 1H, NH), 8.02 (d, J=2.0 Hz, 1H, Py-H), 7.75-7.78 (m, 1H, Py-H), 7.48 (d, J=2.4 Hz, 1H, Ar-H), 7.28-7.31 (m, 1H, Ar-H), 7.15 (d, J=8.8 Hz, 1H, Ar-H), 7.02 (d, J=8.8 Hz, 1H, Py-H), 4.50 (s, 2H, CH.sub.2), 3.78 (t, J=9.2 Hz, 2H, CH.sub.2), 3.51 (t, J=9.2 Hz, 2H, CH.sub.2).

EXAMPLE 6

[0031] ##STR00009##

[0032] In a reaction flask, 10 mmol of intermediate II, 11 mmol of intermediate IIIf, and 30 mL of acetonitrile were added, and then 30 mmol of cesium carbonate was added thereto. Then, the reaction solution was heated and reacted for 8 h. The crude product obtained after desolventization was purified by column chromatography to obtain the target If; .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.16 (s, 1H, NH), 8.04 (d, J=2.0 Hz, 1H, Py-H), 7.76-7.79 (m, 1H, Py-H), 7.03-7.13 (m, 4H, Ar-H and Py-H), 4.51 (s, 2H, CH.sub.2), 3.77 (t, J=9.2 Hz, 2H, CH.sub.2), 3.50 (t, J=9.2 Hz, 2H, CH.sub.2).

EXAMPLE 7

[0033] Screening of insecticidal activity of compounds against Mythimna separate

[0034] Adopting the leaf soaking method proposed by the International Resistance Action Committee (IRAC): the test target is Mythimna separata, e.g. the appropriate amount of corn leaves was fully infiltrated in the prepared liquid and then dried naturally in the shade, and placed in a petri dish with a filter paper. The 3rd instar larvas of Mythimna separata were added 10 heads per dish, cultured in the observation room at 24-27° C., and the results were investigated after 48 h. Using a brush to touch the body of the Mythimna separata, if there is no response, it is regarded as a dead insect. The test concentration is 500 μg/mL (the other concentrations of the drug solution can be obtained by diluting the drug solution with the concentration of 500 μg/mL).

[0035] The insecticidal activity of compounds Ia-If are shown in Table 1. When the tested concentration is 500 μg/mL, the compounds Ia-If have good insecticidal effects on Mythimna separata, and the insecticidal activities are 100%, 100%, 80%, 100%, 100% and 100%, respectively.

TABLE-US-00001 TABLE 1 Insecticidal activity of compound Ia-If concentration death rate % compound (μg/mL) Mythimna separata I a 500 100 I b 500 100 I c 500  80 I d 500 100 I e 500 100 I f 500 100

[0036] The above experimental results show that the aryl bipyridyloxy group and the 2-substituted imidazolidine unit are organically combined, and the new compound obtained has good insecticidal activity.

[0037] The basic principles, main features and advantages of the present disclosure have been shown and described above. Those skilled in the industry should understand that the present disclosure is not limited by the above examples. The above examples and descriptions only illustrate the principles of the present disclosure. The present disclosure will have various changes without departing from the spirit and scope of the present disclosure. These changes and improvements fall within the scope of the claimed disclosure. The scope of protection claimed by the present disclosure is defined by the appended claims and their equivalents.