AMIDE COMPOUND AND USE THEREOF

Abstract

The present invention discloses an amide compound and a use thereof, and the structure of the compound is shown in General Formula I:

##STR00001##

The definitions of each substituent in the formula can be found in the description; and the uses as an insecticide and an animal parasite control agent are also disclosed in the description.

Claims

1. An amide compound shown in General Formula I: ##STR00108## in General Formula I: R.sub.1 is selected from hydrogen, fluorine, cyano, trifluoromethyl or difluoromethyl; R.sub.2 is selected from allyl or propargyl; R.sub.3 selected from halogen; R.sub.4 is selected from halogen, C.sub.1-C.sub.3 haloalkyl, or C.sub.1-C.sub.3 haloalkoxy; and X is selected from CH or N.

2. The amide compound according to claim 1, wherein in General Formula I, R.sub.1 is selected from hydrogen, fluorine, cyano, trifluoromethyl or difluoromethyl; R.sub.2 is selected from allyl or propargyl; R.sub.3 is selected from bromine or iodine; R.sub.4 is selected from bromine, iodine, trifluoromethyl or difluoromethoxy; and X is selected from CH or N.

3. The amide compound according to claim 2, wherein the amide compound is selected from: compounds in Table 1; the compounds in Table 1 have the structure shown in General Formula I, and R.sub.1, X, R.sub.2, R.sub.3, and R.sub.4 are shown in Table 1: TABLE-US-00015 TABLE 1 Compound Number R.sub.1 X R.sub.2 R.sub.3 R.sub.4 1 H CH Allyl Br Br 2 H CH Ally1 Br I 3 H CH Allyl Br CF.sub.3 4 H CH Allyl I CF.sub.3 5 F CH Allyl Br Br 6 F CH Allyl Br I 7 F CH Allyl Br CF.sub.3 8 F CH Allyl I CF.sub.3 9 CN CH Allyl Br Br 10 CN CH Allyl Br I 11 CN CH Ally1 Br CF.sub.3 12 CN CH Allyl I CF.sub.3 13 CF.sub.3 CH Allyl Br Br 14 CF.sub.3 CH Allyl Br I 15 CF.sub.3 CH Allyl Br CF.sub.3 16 CF.sub.3 CH Allyl I CF.sub.3 17 F N Allyl Br Br 18 F N Allyl Br I 19 F N Allyl Br CF.sub.3 20 F N Allyl I CF.sub.3 21 CN N Ally1 Br Br 22 CN N Allyl Br I 23 CN N Allyl Br CF.sub.3 24 CN N Allyl I CF.sub.3 25 CF.sub.3 N Allyl Br Br 26 CF.sub.3 N Allyl Br I 27 CF.sub.3 N Allyl Br CF.sub.3 28 CF.sub.3 N Allyl I CF.sub.3 29 H CH Propargyl Br Br 30 H CH Propargyl Br I 31 H CH Propargyl Br CF.sub.3 32 H CH Propargyl I CF.sub.3 33 F CH Propargyl Br Br 34 F CH Propargyl Br I 35 F CH Propargyl Br CF.sub.3 36 F CH Propargyl I CF.sub.3 37 CN CH Propargyl Br Br 38 CN CH Propargyl Br I 39 CN CH Propargyl Br CF.sub.3 40 CN CH Propargyl I CF.sub.3 41 CF.sub.3 CH Propargyl Br Br 42 CF.sub.3 CH Propargyl Br I 43 CF.sub.3 CH Propargyl Br CF.sub.3 44 CF.sub.3 CH Propargyl I CF.sub.3 45 F N Propargyl Br Br 46 F N Propargyl Br I 47 F N Propargyl Br CF.sub.3 48 F N Propargyl I CF.sub.3 49 CN N Propargyl Br Br 50 CN N Propargyl Br I 51 CN N Propargyl Br CF.sub.3 52 CN N Propargyl I CF.sub.3 53 CF.sub.3 N Propargyl Br Br 54 CF.sub.3 N Propargyl Br I 55 CF.sub.3 N Propargyl Br CF.sub.3 56 CF.sub.3 N Propargyl I CF.sub.3 57 H CH Ally1 Br OCHF.sub.2 58 H CH Allyl I OCHF.sub.2 59 F CH Allyl Br OCHF.sub.2 60 F CH Allyl I OCHF.sub.2 61 CN CH Allyl Br OCHF.sub.2 62 CN CH Allyl I OCHF.sub.2 63 CF.sub.3 CH Allyl Br OCHF.sub.2 64 CF.sub.3 CH Allyl I OCHF.sub.2 65 F N Allyl Br OCHF.sub.2 66 F N Ally1 I OCHF.sub.2 67 CN N Allyl Br OCHF.sub.2 68 CN N Allyl I OCHF.sub.2 69 CF.sub.3 N Ally1 Br OCHF.sub.2 70 CF.sub.3 N Allyl I OCHF.sub.2 71 H CH Propargyl Br OCHF.sub.2 72 H CH Propargyl I OCHF.sub.2 73 F CH Propargyl Br OCHF.sub.2 74 F CH Propargyl I OCHF.sub.2 75 CN CH Propargyl Br OCHF.sub.2 76 CN CH Propargyl I OCHF.sub.2 77 CF.sub.3 CH Propargyl Br OCHF.sub.2 78 CF.sub.3 CH Propargyl I OCHF.sub.2 79 F N Propargyl Br OCHF.sub.2 80 F N Propargyl I OCHF.sub.2 81 CN N Propargyl Br OCHF.sub.2 82 CN N Propargyl I OCHF.sub.2 83 CF.sub.3 N Propargyl Br OCHF.sub.2 84 CF.sub.3 N Propargyl I OCHF.sub.2

4. The amide compound according to claim 3, wherein the amide compound is selected from: compounds in Table 2; the compounds in Table 2 have the structure shown in General Formula I, and R.sub.1, X, R.sub.2, R.sub.3, and R.sub.4 are shown in Table 2: TABLE-US-00016 TABLE 2 Compound Number R.sub.1 X R.sub.2 R.sub.3 R.sub.4 1 H CH Allyl Br Br 2 H CH Allyl Br I 3 H CH Allyl Br CF.sub.3 4 H CH Allyl I CF.sub.3 5 F CH Allyl Br Br 6 F CH Allyl Br I 7 F CH Allyl Br CF.sub.3 8 F CH Allyl I CF.sub.3 9 CN CH Allyl Br Br 10 CN CH Allyl Br I 11 CN CH Allyl Br CF.sub.3 12 CN CH Allyl I CF.sub.3 13 CF.sub.3 CH Allyl Br Br 14 CF.sub.3 CH Allyl Br I 15 CF.sub.3 CH Allyl Br CF.sub.3 16 CF.sub.3 CH Allyl I CF.sub.3 17 F N Allyl Br Br 18 F N Allyl Br I 19 F N Allyl Br CF.sub.3 20 F N Allyl I CF.sub.3 21 CN N Allyl Br Br 22 CN N Allyl Br I 23 CN N Allyl Br CF.sub.3 24 CN N Allyl I CF.sub.3 25 CF.sub.3 N Allyl Br Br 26 CF.sub.3 N Allyl Br I 27 CF.sub.3 N Allyl Br CF.sub.3 28 CF.sub.3 N Allyl I CF.sub.3 29 H CH Propargyl Br Br 30 H CH Propargyl Br I 31 H CH Propargyl Br CF.sub.3 32 H CH Propargyl I CF.sub.3 33 F CH Propargyl Br Br 34 F CH Propargyl Br I 35 F CH Propargyl Br CF.sub.3 36 F CH Propargyl I CF.sub.3 37 CN CH Propargyl Br Br 38 CN CH Propargyl Br I 39 CN CH Propargyl Br CF.sub.3 40 CN CH Propargyl I CF.sub.3 41 CF.sub.3 CH Propargyl Br Br 42 CF.sub.3 CH Propargyl Br I 43 CF.sub.3 CH Propargyl Br CF.sub.3 44 CF.sub.3 CH Propargyl I CF.sub.3 45 F N Propargyl Br Br 46 F N Propargyl Br I 47 F N Propargyl Br CF.sub.3 48 F N Propargyl I CF.sub.3 49 CN N Propargyl Br Br 50 CN N Propargyl Br I 51 CN N Propargyl Br CF.sub.3 52 CN N Propargyl I CF.sub.3 53 CF.sub.3 N Propargyl Br Br 54 CF.sub.3 N Propargyl Br I 55 CF.sub.3 N Propargyl Br CF.sub.3 56 CF.sub.3 N Propargyl I CF.sub.3

5. The amide compound according to claim 4, wherein the amide compound is selected from: compounds in Table 3; the compounds in Table 3 have the structure shown in General Formula I, and R.sub.1, X, R.sub.2, R.sub.3, and R.sub.4 are shown in Table 3: TABLE-US-00017 TABLE 3 Compound Number R.sub.1 X R.sub.2 R.sub.3 R.sub.4 3 H CH Allyl Br CF.sub.3 4 H CH Allyl I CF.sub.3 7 F CH Allyl Br CF.sub.3 8 F CH Allyl I CF.sub.3 11 CN CH Allyl Br CF.sub.3 12 CN CH Allyl I CF.sub.3 19 F N Allyl Br CF.sub.3 20 F N Ally1 I CF.sub.3 23 CN N Allyl Br CF.sub.3 24 CN N Allyl I CF.sub.3 27 CF.sub.3 N Allyl Br CF.sub.3 28 CF.sub.3 N Allyl I CF.sub.3 31 H CH Propargyl Br CF.sub.3 32 H CH Propargyl I CF.sub.3 35 F CH Propargyl Br CF.sub.3 36 F CH Propargyl I CF.sub.3 39 CN CH Propargyl Br CF.sub.3 40 CN CH Propargyl I CF.sub.3 47 F N Propargyl Br CF.sub.3 48 F N Propargyl I CF.sub.3 51 CN N Propargyl Br CF.sub.3 52 CN N Propargyl I CF.sub.3 55 CF.sub.3 N Propargyl Br CF.sub.3 56 CF.sub.3 N Propargyl I CF.sub.3

6. A compound being an intermediate for preparing the amide compound according to claim 1, wherein the compound has a structure shown in General Formula II below: ##STR00109## in General Formula II: R.sub.1 is selected from hydrogen, fluorine, cyano, trifluoromethyl or difluoromethyl; R.sub.2 is selected from allyl or propargyl; and X is selected from CH or N.

7. The compound according to claim 6, wherein the compound is selected from: compounds in Table 4; the compounds in Table 4 have the structure shown in General Formula II, and R.sub.1, X, and R.sub.2 are shown in Table 4: TABLE-US-00018 TABLE 4 Compound Number R.sub.1 X R.sub.2 II.1 H CH Allyl II.2 F CH Allyl II.3 CN CH Allyl II.4 F N Allyl II.5 CN N Allyl II.6 CF.sub.3 N Allyl II.7 H CH Propargyl II.8 F CH Propargyl II.9 CN CH Propargyl II.10 F N Propargyl II.11 CN N Propargyl II.12 CF.sub.3 N Propargyl

8. A compound being an intermediate for preparing the compound according to claim 6, wherein the compound has a structure shown in General formula III below: ##STR00110## in General Formula III: R.sub.1 is selected from hydrogen, fluorine, cyano, trifluoromethyl or difluoromethyl; X is selected from CH or N; R.sub.2 is selected from allyl or propargyl; and R.sub.5 is selected from C.sub.1-C.sub.6 alkyl.

9. The compound according to claim 8, wherein the compound is selected from: compounds in Table 5; the compounds in Table 5 have the structure shown in General Formula III, and R.sub.1, X, R.sub.2, and R.sub.5 are shown in Table 5: TABLE-US-00019 TABLE 5 Compound Number R.sub.1 X R.sub.2 R.sub.5 III.1 H CH Allyl CH.sub.3 III.2 F CH Allyl CH.sub.3 III.3 CN CH Allyl CH.sub.3 III.4 F N Allyl CH.sub.3 III.5 CN N Allyl CH.sub.3 III.6 CF.sub.3 N Allyl CH.sub.3 III.7 H CH Propargyl CH.sub.3 III.8 F CH Propargyl CH.sub.3 III.9 CN CH Propargyl CH.sub.3 III.10 F N Propargyl CH.sub.3 III.11 CN N Propargyl CH.sub.3 III.12 CF.sub.3 N Propargyl CH.sub.3 III.13 H CH Allyl CH.sub.2CH.sub.3 III.14 F CH Allyl CH.sub.2CH.sub.3 III.15 CN CH Allyl CH.sub.2CH.sub.3 III.16 F N Allyl CH.sub.2CH.sub.3 III.17 CN N Allyl CH.sub.2CH.sub.3 III.18 CF.sub.3 N Allyl CH.sub.2CH.sub.3 III.19 H CH Propargyl CH.sub.2CH.sub.3 III.20 F CH Propargyl CH.sub.2CH.sub.3 III.21 CN CH Propargyl CH.sub.2CH.sub.3 III.22 F N Propargyl CH.sub.2CH.sub.3 III.23 CN N Propargyl CH.sub.2CH.sub.3 III.24 CF.sub.3 N Propargyl CH.sub.2CH.sub.3

10. A compound being an intermediate for preparing the compound according to claim 8, wherein the compound has a structure shown in General Formula IV below: ##STR00111## in General Formula IV: R.sub.2 is selected from allyl or propargyl; and R.sub.5 is selected from C.sub.1-C.sub.6 alkyl.

11. The compound according to claim 10, wherein the compound is selected from: compounds in Table 6; the compounds in Table 6 have the structure shown in General formula IV, and R.sub.1 and R.sub.5 are shown in Table 6: TABLE-US-00020 TABLE 6 Compound Number R.sub.2 R.sub.5 IV.1 Allyl CH.sub.3 IV.2 Allyl CH.sub.2CH.sub.3 IV.3 Allyl CH.sub.2CH.sub.2CH.sub.3 IV.4 Ally1 CH.sub.2CH.sub.2CH.sub.2CH.sub.3 IV.5 Allyl CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.3 IV.6 Allyl CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.3 IV.7 Propargyl CH.sub.3 IV.8 Propargyl CH.sub.2CH.sub.3 IV.9 Propargyl CH.sub.2CH.sub.2CH.sub.3 IV.10 Propargyl CH.sub.2CH.sub.2CH.sub.2CH.sub.3 IV.11 Propargyl CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.3 IV.12 Propargyl CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.3

12. A compound being an intermediate for preparing the amide compound according to claim 1, wherein the compound has a structure shown in General Formula V below: ##STR00112## in General Formula V: R.sub.2 is selected from allyl or propargyl; R.sub.3 selected from halogen; and R.sub.4 is selected from halogen, C.sub.1-C.sub.3 haloalkyl, or C.sub.1-C.sub.3 haloalkoxy.

13. The compound according to claim 12, wherein in General Formula V, R.sub.2 is selected from allyl or propargyl; R.sub.3 is selected from bromine or iodine; and R.sub.4 is selected from bromine, iodine, trifluoromethyl or difluoromethoxy.

14. The compound according to claim 13, wherein the compound is selected from: compounds in Table 7; the compounds in Table 7 have the structure shown in General Formula V, and R.sub.2, R.sub.3 and R.sub.4 are shown in Table 7: TABLE-US-00021 TABLE 7 Compound Number R.sub.2 R.sub.3 R.sub.4 V.1 Allyl Br Br V.2 Allyl Br I V.3 Allyl Br CF.sub.3 V.4 Allyl I CF.sub.3 V.5 Ally1 Br OCHF.sub.2 V.6 Allyl I OCHF.sub.2 V.7 Propargyl Br Br V.8 Propargyl Br I V.9 Propargyl Br CF.sub.3 V.10 Propargyl I CF.sub.3 V.11 Propargyl Br OCHF.sub.2 V.12 Propargyl I OCHF.sub.2

15. The compound according to claim 14, wherein the compound is selected from: compounds in Table 8; the compounds in Table 8 have the structure shown in General Formula V, and R.sub.2, R.sub.3 and R.sub.4 are shown in Table 8: TABLE-US-00022 TABLE 8 Compound Number R.sub.2 R.sub.3 R V.3 Allyl Br CF.sub.3 V.4 Allyl I CF.sub.3 V.9 Propargyl Br CF.sub.3 V.10 Propargyl I CF.sub.3

16. A compound being an intermediate for preparing the amide compound according to claim 1, wherein the compound has a structure shown in General Formula VI below: ##STR00113## in General Formula VI: R.sub.1 is selected from hydrogen, fluorine, cyano, trifluoromethyl or difluoromethyl; R.sub.2 is selected from allyl or propargyl; R.sub.4 is selected from halogen, C.sub.1-C.sub.3 haloalkyl, or C.sub.1-C.sub.3 haloalkoxy; and X is selected from CH or N.

17. The compound according to claim 16, wherein in General Formula VI, R.sub.1 is selected from hydrogen, fluorine, cyano, trifluoromethyl or difluoromethyl; R.sub.2 is selected from allyl or propargyl; R.sub.4 is selected from bromine, iodine, trifluoromethyl or difluoromethoxy; and X is selected from CH or N.

18. The compound according to claim 17, wherein the compound is selected from: compounds in Table 9; the compounds in Table 9 have the structure shown in General Formula VI, and R.sub.1, X, R.sub.2 and R.sub.4 are shown in Table 9: TABLE-US-00023 TABLE 9 Compound Number R.sub.1 X R.sub.2 R4 VI.1 H CH Allyl CF.sub.3 VI.2 F CH Allyl CF.sub.3 VI.3 CN CH Allyl CF.sub.3 VI.4 F N Allyl CF.sub.3 VI.5 CN N Allyl CF.sub.3 VI.6 CF.sub.3 N Allyl CF.sub.3 VI.7 H CH Propargyl CF.sub.3 VI.8 F CH Propargyl CF.sub.3 VI.9 CN CH Propargyl CF.sub.3 VI.10 F N Propargyl CF.sub.3 VI.11 CN N Propargyl CF.sub.3 VI.12 CF.sub.3 N Propargyl CF.sub.3 VI.13 H CH Allyl OCHF.sub.2 VI.14 F CH Allyl OCHF.sub.2 VI.15 CN CH Allyl OCHF.sub.2 VI.16 F N Allyl OCHF.sub.2 VI.17 CN N Allyl OCHF.sub.2 VI.18 CF.sub.3 N Allyl OCHF.sub.2 VI.19 H CH Propargyl OCHF.sub.2 VI.20 F CH Propargyl OCHF.sub.2 VI.21 CN CH Propargyl OCHF.sub.2 VI.22 F N Propargyl OCHF.sub.2 VI.23 CN N Propargyl OCHF.sub.2 VI.24 CF.sub.3 N Propargyl OCHF.sub.2

19. The compound according to claim 18, wherein the compound is selected from: compounds in Table 10; the compounds in Table 10 have the structure shown in General Formula VI, and R.sub.1, X, R.sub.2 and R.sub.4 are shown in Table 10: TABLE-US-00024 TABLE 10 Compound Number R.sub.1 X R.sub.2 R.sub.4 VI.1 H CH Allyl CF.sub.3 VI.2 F CH Allyl CF.sub.3 VI.3 CN CH Allyl CF.sub.3 VI.4 F N Allyl CF.sub.3 VI.5 CN N Allyl CF.sub.3 VI.6 CF.sub.3 N Allyl CF.sub.3 VI.7 H CH Propargyl CF.sub.3 VI.8 F CH Propargyl CF.sub.3 VI.9 CN CH Propargyl CF.sub.3 VI.10 F N Propargyl CF.sub.3 VI.11 CN N Propargyl CF.sub.3 VI.12 CF.sub.3 N Propargyl CF.sub.3

20. A compound being an intermediate for preparing the compound according to claim 16, wherein the compound has a structure shown in General Formula VII below: ##STR00114## in General Formula VII: R.sub.2 is selected from allyl or propargyl; and R.sub.4 is selected from halogen, C.sub.1-C.sub.3 haloalkyl, or C.sub.1-C.sub.3 haloalkoxy.

21. The compound according to claim 20, wherein in General Formula VII, R.sub.2 is selected from allyl or propargyl; and R.sub.4 is selected from bromine, iodine, trifluoromethyl or difluoromethoxy.

22. The compound according to claim 21, wherein the compound is selected from: compounds in Table 11; the compounds in Table 11 have the structure shown in General Formula VII, and R.sub.2 and R.sub.4 are shown in Table 11: TABLE-US-00025 TABLE 11 Compound Number R.sub.2 R.sub.4 VII.1 Allyl CF.sub.3 VII.2 Allyl OCHF.sub.2 VII.3 Propargyl CF.sub.3 VII.4 Propargyl OCHF.sub.2

23. A preparation method for the amide compound according to claim 1, wherein the preparation method comprises: reacting the intermediate compound shown in General Formula VI with a suitable halogenated reagent in a suitable solvent to prepare the compound of General Formula I, and a compound reaction formula is as follows: ##STR00115##

24. The preparation method for the amide compound according to claim 23, wherein the compound of General Formula VI reacts with a suitable alkali or halogenated reagent in a suitable solvent at a temperature from ?10? C. to the boiling point of the solvent for 0.5-48 h to prepare the compound of General Formula I.

25. The preparation method for the amide compound according to claim 23, wherein the suitable halogenated reagent is selected from the group consisting of chlorine gas, liquid bromine, iodine, NBS, NCS, NIS, a mixture of hydrogen peroxide and hydrobromic acid, a mixture of hydrogen peroxide and hydroiodic acid, a mixture of sodium hypochlorite and hydrobromic acid, and a mixture of sodium hypochlorite and hydroiodic acid; the suitable solvent is selected from the group consisting of benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, chloroform, dichloromethane, methyl acetate, ethyl acetate, tetrahydrofuran, dioxane, diethyl ether, 1,2-dimethoxyethane, water, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and mixed solvents of the above solvents; and the reaction temperature is preferably 0? C.-100? C.; and more preferably 25? C.-80? C.

26. The preparation method for the amide compound according to claim 24, wherein the suitable alkali is selected from the group consisting of trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine, N,N-diisopropylmethylamine, N,N-diisopropylethylamine, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium methanol, sodium ethanol, potassium ethanol, potassium tert-butanol and sodium tert-butanol; and preferably, the suitable alkali is selected from the group consisting of sodium hydride, potassium hydride, sodium hydroxide, and potassium hydroxide.

27. An insecticide prepared from the amide compound according to claim 1.

28. The insecticideaccording to claim 27, wherein the insecticide is used to prevent and control one or more of Diamondback moth, Mythimna separata, Spodoptera exigua, Spodoptera litura, Chilo suppressalis, Myzus persicae, thripid, and flea beetle.

29. An insecticide formulation, wherein the insecticide formulation comprises the amide compound according to claim 1 as an active component, and also comprises one or more auxiliary materials; optionally, the amount of the amide compound according to claim 1 in the insecticide formulation is 0.1 to 99% by weight, and further optionally 0.5 to 90% by weight.

30. An insecticide composition, comprising a mixture of the amide compound according to claim 1 and other active compounds, wherein the other active compounds are selected from one or more of an insecticide, a poison bait agent, a disinfectant, an acaricide, a nematicide, a fungicide, a growth regulator, and a herbicide.

31. A method for controlling an agricultural or forestal pest, comprising: applying an effective amount of a material to the pest that needs to be controlled or its growth medium, wherein the material is one or more selected from the group consisting of: the amide compound according to claim 1; the insecticide formulation comprising the amide compound according to claim 1; and the insecticide composition comprising a mixture of the amide compound according to claim 1 and other active compounds.

32. An animal parasite control agent prepared from the amide compound according to claim 1.

33. The control agent according to claim 32, wherein the animal parasite control agent is used to prevent and control one or more of cat flea and American dog tick.

34. An animal parasite control agent, wherein the animal parasite control agent comprises the amide compound according to claim 1 as an active component, and further comprises one or more auxiliary materials; and optionally, the amount of the amide compound according to claim 1 in the animal parasite control agent is 1 to 80% by weight.

35. An animal parasite control agent, comprising a mixture of the amide compound according to claim 1 and other animal parasite control active compounds, wherein the other animal parasite control active compounds are one or more selected from the group consisting of an acaricide, an insecticide, a parasiticide, and an antiplasmodial agent.

36. A method for controlling an animal parasite comprising the following steps: applying an effective amount of a material to the animal parasite that needs to be controlled or its growth medium, wherein the material is one or more selected from the group consisting of the following groups: the amide compound according to claim 1; the animal parasite control agent comprising the amide compound according to claim 1; and the animal parasite control composition comprising the amide compound according to claim 1 and other animal parasite control active compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0168] In order to make the purposes, technical solutions, and advantages of the examples of the present invention clearer, the technical solutions in the examples of the present invention are clearly and completely described below. Apparently, the examples described are a part of the examples of the present invention, not all of the examples. Based on the examples in the present invention, all other examples obtained by those of ordinary skill in the art without creative labor shall fall within the scope of protection of the present invention.

[0169] In addition, in order to describe the present invention better, numerous specific details are provided in the following specific implementation modes. It should be understood by those skilled in the art that, without certain specific details, the present invention may also be implemented. In some examples, raw materials, elements, methods, means and the like familiar to those skilled in the art are not described in detail, as to highlight the main idea of the present invention.

[0170] Unless otherwise explicitly stated, throughout the entire description and claims, the term include(s)/including or its variations such as contain(s)/containing or comprise(s)/comprising may be understood to include the stated elements or constituent parts, without excluding other elements or constituent parts.

[0171] Unless otherwise specified, all raw materials used are commercially available.

[0172] In the present invention, the terms used have the following meanings: [0173] Halogen: referring to fluorine, chlorine, bromine, or iodine. [0174] Haloalkyl: straight or branched alkyls on which hydrogen atoms may be partially or completely replaced by halogen(s), such as difluoromethyl (CHF.sub.2), and trifluoromethyl (CF.sub.3). [0175] Haloalkoxy: hydrogen atoms on alkoxy may be partially or completely replaced by halogen(s), such as difluoromethoxy (OCHF.sub.2), and trifluoromethoxy (OCF.sub.3). [0176] Allyl: CH.sub.2CH?CH.sub.2. [0177] Propargyl: CH.sub.2C?CH. [0178] Insecticide: a substance that has insecticidal effects on pests. [0179] Animal parasite control agent: referring to an active compound that may effectively reduce the incidence rate of various parasites in animals infected by the parasites. Prevention and control means that the active compound may effectively kill the parasites, and inhibit their growth or reproduction.

SYNTHESIS EXAMPLE

[0180] According to the synthesis routes described above, different raw material compounds may be used to prepare and obtain the compounds shown in General Formulas I-VII of the present invention, and they are further described specifically as follows:

Example 1: Preparation of IntermediateCcompound II.7

[0181] ##STR00017##

(1) Preparation of methyl 2-fluoro-3-(N-(prop-2-yn-1-yl) benzoylamino)benzoate (III.7)

[0182] 0.50 g (2.96 mmol) of methyl 2-fluoro-3-aminobenzoate, 0.70 g (5.94 mmol) of propargyl bromide, and 1.15 g (8.90 mmol) of N,N-diisopropylethylamine were added to 10 mL of toluene, and the temperature was raised for a reflux reaction. The reaction process was monitored by TLC, and after raw materials were reacted completely, 0.58 g (4.14 mmol) of benzoyl chloride was added. After TLC monitored the completion of the reaction, water and ethyl acetate were added for extraction. The organic phase was depressurized and desolventized, and the residue was purified by column chromatography to obtain 0.72 g of a white solid, namely methyl 2-fluoro-3-(N-(prop-2-yn-1-yl) benzoylamino)benzoate (III.7). Nuclear magnetism and mass spectrometry data of the intermediate III.7 are as follows:

[0183] .sup.1H NMR (600 MHZ, Chloroform-d) ? 7.82 (t, 1H), 7.42-7.13 (m, 6H), 7.07 (t, 1H), 5.05 (s, 1H), 4.28 (s, 1H), 3.91 (s, 3H), 2.23 (t, 1H). LC-MS (m/z, ESI): 312.10 (M+H).sup.+.

(2) Preparation of 2-fluoro-3-(N-(prop-2-yn-1-yl) benzoylamino) benzoic acid (II.7)

[0184] 0.58 g (1.86 mmol) of methyl 2-fluoro-3-(N-(prop-2-yn-1-yl) benzoylamino)benzoate, 1.62 g (18.65 mmol) of lithium bromide, 0.94 g (9.29 mmol) of triethylamine, and 0.17 g (9.44 mmol) of water were added to 10 mL of acetonitrile, and the temperature was raised to 50? C. for a reaction. After TLC monitored the completion of the reaction, the pH value was adjusted to about 2-3 with a dilute hydrochloric acid, and water and ethyl acetate were added for extraction. The organic phase was depressurized and desolventized to obtain 0.52 g of a white solid, namely the intermediate II.7. Nuclear magnetism and mass spectrometry data of the intermediate II.7 are as follows:

[0185] .sup.1H NMR (600 MHZ, DMSO-d.sub.6) ? 7.79-7.64 (m, 2H), 7.42-7.17 (m, 6H), 4.61 (s, 2H), 3.22 (s, 1H). LC-MS (m/z, ESI): 296.11 (M?H).sup.?.

Example 2: Preparation of Intermediate Compound V.3

[0186] ##STR00018##

[0187] 1.00 g (1.84 mmol) of 3-amino-N-(2-bromo-4-(perfluoroprop-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (prepared by referring to a method reported in WO2011093415 or WO2010018714) and 0.30 g (2.00 mmol) of sodium iodide were added to 10 mL of dimethylformamide (DMF), 0.22 g (1.83 mmol) of allyl bromide was dropwise added under stirring, and a reaction was performed at room temperature. After TLC monitored the completion of the reaction, water and ethyl acetate were added for extraction. The organic phase was depressurized and desolventized, and the residue was purified by column chromatography to obtain 0.34 g of a white solid, namely the intermediate compound V.3. Nuclear magnetism and mass spectrometry data of the intermediate compound V.3 are as follows:

[0188] .sup.1H NMR (600 MHz, Chloroform-d) ? 8.26 (d, 1H), 8.14 (d, 1H), 7.91 (d, 1H), 7.42-7.36 (m, 1H), 7.14 (t, 1H), 6.95-6.87 (m, 1H), 6.03-5.91 (m, 1H), 5.34 (dd, 1H), 5.24 (dd, 1H), 4.26 (s, 1H), 3.87 (d, 2H). LC-MS (m/z, ESI): 585.08 (M+H).sup.+.

Example 3: Preparation of Intermediate Compound V.4

[0189] ##STR00019##

[0190] 2.00 g (3.38 mmol) of 3-amino-2-fluoro-N-(2-iodo-4-(perfluoroprop-2-yl)-6-(trifluoromethyl)phenyl)benzamide (prepared by referring to a method reported in WO2011093415 or WO2010018714) and 0.30 g (3.81 mmol) of sodium iodide were added to 20 mL of DMF, 0.41 g (3.42 mmol) of allyl bromide was dropwise added under stirring, and a reaction was performed at a room temperature. After TLC monitored the completion of the reaction, water and ethyl acetate were added for extraction. The organic phase was depressurized and desolventized, and the residue was purified by column chromatography to obtain 0.60 g of a white solid, namely the intermediate compound V.4. Nuclear magnetism and mass spectrometry data of the intermediate compound V.4 are as follows:

[0191] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.35 (d, 1H), 8.30 (d, 1H), 7.93 (d, 1H), 7.40 (td, 1H), 7.15 (t, 1H), 6.92 (td, 1H), 6.02-5.92 (m, 1H), 5.34 (dd, 1H), 5.24 (dd, 1H), 4.26 (s, 1H), 3.88 (d, 2H). LC-MS (m/z, ESI): 633.07 (M+H).sup.+.

Example 4: Preparation of Intermediate Compound V.9

[0192] ##STR00020##

[0193] 1.00 (1.84 mmol) of 3-amino-N-(2-bromo-4-(perfluoroprop-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide and 0.31 g (2.07 mmol) of sodium iodide were added to 10 mL of DMF, 0.22 g (1.87 mmol) of propargyl bromide was dropwise added under stirring, and the temperature was raised to 40? C. for a reaction. After TLC monitored the completion of the reaction, water and ethyl acetate were added for extraction. The organic phase was depressurized and desolventized, and the residue was purified by column chromatography to obtain 0.26 g of a white solid, namely the intermediate compound V.9. Nuclear magnetism and mass spectrometry data of the intermediate compound V.9 are as follows:

[0194] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.24 (d, 1H), 8.14 (d, 1H), 7.91 (d, 1H), 7.51-7.45 (m, 1H), 7.21 (t, 1H), 7.05 (td, 1H), 4.41-4.34 (m, 1H), 4.05 (dd, 2H), 2.28 (t, 1H). LC-MS (m/z, ESI): 583.06 (M+H).sup.+.

Example 5: Preparation of Intermediate Compound V.10

[0195] ##STR00021##

[0196] 1.00 g (1.69 mmol) of 3-amino-2-fluoro-N-(2-iodo-4-(perfluoroprop-2-yl)-6-(trifluoromethyl)phenyl)benzamide and 0.30 g (2.00 mmol) of sodium iodide were added to 10 mL of DMF, 0.20 g (1.70 mmol) of propargyl bromide was dropwise added under stirring, and the temperature was raised to 40? C. for a reaction. After TLC monitored the completion of the reaction, water and ethyl acetate were added for extraction. The organic phase was depressurized and desolventized, and the residue was purified by column chromatography to obtain 0.31 g of a white solid, namely the intermediate compound V.10. Nuclear magnetism and mass spectrometry data of the intermediate compound V.10 are as follows:

[0197] .sup.1H NMR (600 MHz, Chloroform-d) ? 8.35 (d, 1H), 8.28 (d, 1H), 7.96-7.92 (m, 1H), 7.49 (td, 1H), 7.22 (t, 1H), 7.05 (td, 1H), 4.38 (s, 1H), 4.08-4.03 (m, 2H), 2.28 (t, 1H). LC-MS (m/z, ESI): 631.05 (M+H).sup.+.

Example 6: Preparation of Compound 7

[0198] ##STR00022##

[0199] 0.15 g (0.26 mmol) of an intermediate V.3, 0.04 g (0.27 mmol) of sodium iodide and 0.04 g (0.25 mmol) of para-fluorobenzoyl chloride were added to 10 mL of toluene, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, the reaction product was depressurized and desolventized, and the obtained residue was purified by column chromatography to obtain 0.13 g of a white solid, namely the compound 7. Nuclear magnetism and mass spectrometry data of the compound 7 are as follows:

[0200] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.12 (d, 1H), 8.07-7.95 (m, 2H), 7.89 (d, 1H), 7.51-7.44 (m, 1H), 7.36 (s, 2H), 7.32-7.25 (m, 1H), 6.90 (s, 2H), 6.06-5.92 (m, 1H), 5.26-5.15 (m, 2H), 4.50 (d, 2H). LC-MS (m/z, ESI): 707.04 (M+H).sup.+.

Example 7: Preparation of Compound 8

[0201] 0.15 g (0.24 mmol) of an intermediate V.4, 0.04 g (0.27 mmol) of sodium iodide, 0.04 g (0.25 mmol) of para-fluorobenzoyl chloride were added to 10 mL of toluene, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, the reaction product was depressurized and desolventized, and the obtained residue was purified by column chromatography to obtain 0.11 g of a white solid, namely the compound 8. Nuclear magnetism and mass spectrometry data of the compound 8 are as follows:

[0202] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.33 (d, 1H), 8.11-7.98 (m, 2H), 7.94-7.89 (m, 1H), 7.48 (dt, 1H), 7.36 (s, 2H), 7.29 (t, 1H), 6.90 (s, 2H), 6.07-5.90 (m, 1H), 5.26-5.15 (m, 2H), 4.52 (d, 2H). LC-MS (m/z, ESI): 755.07 (M+H).sup.+.

Example 8: Preparation of Compound 19

[0203] ##STR00023##

[0204] 0.15 g (0.26 mmol) of an intermediate V.3, 0.06 g (0.40 mmol) of sodium iodide, and 0.06 g (0.38 mmol) of 6-fluoronicotinoyl chloride were added to 10 mL of toluene, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, the reaction product was depressurized and desolventized, and the obtained residue was purified by column chromatography to obtain 0.14 g of a yellow oily substance, namely the compound 19. Nuclear magnetism and mass spectrometry data of the compound 19 are as follows:

[0205] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.18 (s, 1H), 8.13 (d, 1H), 8.08-8.02 (m, 1H), 8.017.79 (m, 3H), 7.54-7.48 (m, 1H), 7.34 (t, 1H), 6.83 (s, 1H), 6.05-5.91 (m, 1H), 5.27-5.18 (m, 2H), 4.53 (d, 2H). LC-MS (m/z, ESI): 708.05 (M+H).sup.+.

Example 9: Preparation of Compound 20

[0206] ##STR00024##

[0207] 0.15 g (0.24 mmol) of an intermediate V.4, 0.05 g (0.33 mmol) of sodium iodide, and 0.05 g (0.31 mmol) of 6-fluoronicotinoyl chloride were added to 10 mL of toluene, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, the reaction product was depressurized and desolventized, and the obtained residue was purified by column chromatography to obtain 0.09 g of a white solid, namely the compound 20. Nuclear magnetism and mass spectrometry data of the compound 20 are as follows:

[0208] .sup.1H NMR (600 MHz, Chloroform-d) ? 8.35-8.31 (m, 1H), 8.19 (s, 1H), 8.09-8.03 (m, 1H), 8.02-7.79 (m, 3H), 7.52 (dt, 1H), 7.35 (t, 1H), 6.83 (s, 1H), 6.05-5.93 (m, 1H), 5.28-5.19 (m, 2H), 4.53 (d, 2H). LC-MS (m/z, ESI): 756.05 (M+H).sup.+.

Example 10: Preparation of Compound 31

Method I:

[0209] ##STR00025##

[0210] 0.15 g (0.26 mmol) of an intermediate V.9, 0.04 g (0.27 mmol) of sodium iodide, and 0.04 g (0.29 mmol) of benzoyl chloride were added to 10 mL of toluene, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, the reaction product was depressurized and desolventized, and the obtained residue was purified by column chromatography to obtain 0.09 g of a yellow oily substance, namely the compound 31. Nuclear magnetism and mass spectrometry data of the compound 31 are as follows:

[0211] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.13 (d, 1H), 8.09-7.95 (m, 2H), 7.92-7.88 (m, 1H), 7.63-7.53 (br, 1H), 7.43-7.14 (m, 6H), 4.93 (s, 1H), 4.51 (s, 1H), 2.30 (t, 1H). LC-MS (m/z, ESI): 687.07 (M+H).sup.+.

Method II:

[0212] ##STR00026##

[0213] 0.22 g (0.68 mmol) of an intermediate II.7 and 0.44 g (3.70 mmol) of sulfoxide chloride were added to 10 mL of toluene, and the mixture was heated for reflux for 4 h; and the reaction product was depressurized and desolventized to obtain an intermediate 2-fluoro-3-(N-(prop-2-yn-1-yl)benzoylamino)benzoyl chloride, which was sealed for standby. The intermediate 2-fluoro-3-(N-(prop-2-yn-1-yl)benzoylamino)benzoyl chloride prepared above, 0.08 g (0.78 mmol) of sodium bromide, and 0.30 g (0.74 mmol) of 2-bromo-4-(perfluoroprop-2-yl)-6-(trifluoromethyl)aniline (prepared by referring to a method reported in WO2011093415 or WO2010018714) were added to 10 mL of acetonitrile, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, the reaction product was depressurized and desolventized, and the obtained residue was purified by column chromatography to obtain 0.23 g of a white solid, namely the compound 31. Nuclear magnetism and mass spectrometry data of the compound 31 are as follows:

[0214] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.13 (d, 1H), 8.09-7.95 (m, 2H), 7.92-7.88 (m, 1H), 7.63-7.53 (br, 1H), 7.43-7.14 (m, 6H), 4.93 (s, 1H), 4.51 (s, 1H), 2.30 (t, 1H). LC-MS (m/z, ESI): 687.07 (M+H).sup.+.

Method III:

[0215] ##STR00027##

(1) Preparation of Intermediate Compound VI.7

[0216] 0.29 g (0.68 mmol) of an intermediate 2-fluoro-3-(N-(prop-2-yn-1-yl) benzoylamino)benzoyl chloride, 0.09 g (0.87 mmol) of sodium bromide, and 0.30 g (0.91 mmol) of 4-(perfluoroprop-2-yl)-2-(trifluoromethyl)aniline (prepared by referring to a method reported in WO2011093415 or WO2010018714) were added to 10 mL of acetonitrile, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, water and ethyl acetate were added for extraction. The organic phase was depressurized and desolventized, and the residue was purified by column chromatography to obtain 0.39 g of a white solid, namely the intermediate compound VI.7.

(2) Preparation of Compound 31

[0217] 0.30 g (0.49 mmol) of an intermediate VI.7, 0.02 g (0.50 mmol) of sodium hydride (60% mass fraction), and 0.10 g (0.56 mmol) of N-bromosuccinimide were added to 10 mL of N,N-dimethylformamide, and the temperature was raised to 40? C. for a reaction. After TLC monitored the completion of the reaction, water and ethyl acetate were added for extraction. The organic phase was depressurized and desolventized, and the residue was purified by column chromatography to obtain 0.06 g of a white solid, namely the compound 31. Nuclear magnetism and mass spectrometry data of the compound 31 are as follows:

[0218] .sup.1H NMR (600 MHz, Chloroform-d) ? 8.13 (d, 1H), 8.09-7.95 (m, 2H), 7.92-7.88 (m, 1H), 7.63-7.53 (br, 1H), 7.43-7.14 (m, 6H), 4.93 (s, 1H), 4.51 (s, 1H), 2.30 (t, 1H). LC-MS (m/z, ESI): 687.07 (M+H).sup.+.

Method IV:

[0219] ##STR00028##

[0220] 0.50 g (0.82 mmol) of an intermediate VI.7, 0.12 g (1.17 mmol) of sodium bromide, 0.02 g (0.50 mmol) of sodium hydroxide, and 0.21 g of water were added to 10 mL of dichloromethane, and the temperature was raised to 40? C. for a reaction; and 0.64 g (1.21 mmol) of an aqueous solution of sodium hypochlorite (14% mass fraction) was dropwise added to the reaction solution, and a reaction was continuously performed at 40? C. After TLC monitored the completion of the reaction, water and ethyl acetate were added for extraction. The organic phase was depressurized and desolventized, and the residue was purified by column chromatography to obtain 0.23 g of a white solid, namely the compound 31. Nuclear magnetism and mass spectrometry data of the compound 31 are as follows:

[0221] .sup.1H NMR (600 MHz, Chloroform-d) ? 8.13 (d, 1H), 8.09-7.95 (m, 2H), 7.92-7.88 (m, 1H), 7.63-7.53 (br, 1H), 7.43-7.14 (m, 6H), 4.93 (s, 1H), 4.51 (s, 1H), 2.30 (t, 1H). LC-MS (m/z, ESI): 687.07 (M+H).sup.+.

Example 11: Preparation of Compound 36

[0222] ##STR00029##

[0223] 0.15 g (0.24 mmol) of an intermediate V.10, 0.04 g (0.27 mmol) of sodium iodide, and 0.04 g (0.25 mmol) of para-fluorobenzoyl chloride were added to 10 mL of toluene, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, the reaction product was depressurized and desolventized, and the obtained residue was purified by column chromatography to obtain 0.13 g of a yellow oily substance, namely the compound 36. Nuclear magnetism and mass spectrometry data of the compound 36 are as follows:

[0224] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.34 (d, 1H), 8.19-8.01 (m, 2H), 7.98-7.89 (m, 1H), 7.60 (t, 1H), 7.47-7.36 (br s, 2H), 7.33 (t, 1H), 7.03-6.83 (br s, 2H), 4.90 (s, 1H), 4.53 (s, 1H), 2.31 (t, 1H). LC-MS (m/z, ESI): 753.04 (M+H).sup.+.

Example 12: Preparation of Compound 47

[0225] ##STR00030##

[0226] 0.15 g (0.26 mmol) of an intermediate V.9, 0.06 g (0.40 mmol) of sodium iodide, and 0.06 g (0.38 mmol) of 6-fluoronicotinoyl chloride were added to 10 mL of toluene, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, the reaction product was depressurized and desolventized, and the obtained residue was purified by column chromatography to obtain 0.09 g of a white solid, namely the compound 47. Nuclear magnetism and mass spectrometry data of the compound 47 are as follows:

[0227] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.22 (s, 1H), 8.13 (d, 1H), 8.12-8.08 (m, 1H), 8.03 (d, 1H), 7.94-7.81 (m, 2H), 7.62 (t, 1H), 7.37 (t, 1H), 6.85 (d, 1H), 4.90 (s, 1H), 4.54 (s, 1H), 2.39-2.26 (m, 1H). LC-MS (m/z, ESI): 706.03 (M+H).sup.+.

Example 13: Preparation of Compound 48

[0228] ##STR00031##

[0229] 0.15 g (0.24 mmol) of an intermediate V.10, 0.05 g (0.33 mmol) of sodium iodide, and 0.06 g (0.38 mmol) of 6-fluoronicotinoyl chloride were added to 10 mL of toluene, and the mixture was heated for reflux. After TLC monitored the completion of the reaction, the reaction product was depressurized and desolventized, and the obtained residue was purified by column chromatography to obtain 0.09 g of a yellow oily substance, namely the compound 48. Nuclear magnetism and mass spectrometry data of the compound 48 are as follows:

[0230] .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.34 (d, 1H), 8.22 (s, 1H), 8.14-7.99 (m, 2H), 7.96-7.90 (m, 1H), 7.86 (s, 1H), 7.69-7.59 (m, 1H), 7.38 (t, 1H), 6.84 (d, 1H), 4.90 (s, 1H), 4.55 (s, 1H), 2.33 (t, 1H). LC-MS (m/z, ESI): 754.05 (M+H).sup.+.

[0231] Other compounds in General Formulas I-VII of the present invention can be prepared by referring to the above examples.

[0232] The physicochemical properties, nuclear magnetism and mass spectrometry data of some compounds of the present invention are as follows:

##STR00032##

[0233] White solid. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.12 (d, 1H), 7.98 (t, 1H), 7.89 (d, 1H), 7.46 (t, 1H), 7.42-7.11 (m, 7H), 6.07-5.93 (br s, 1H), 5.27-5.15 (m, 2H), 4.53 (d, 3H). LC-MS (m/z, ESI): 689.10 (M+H).sup.+.

##STR00033##

[0234] Yellow solid. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.32 (d, 1H), 7.98 (t, 1H), 7.92 (d, 1H), 7.51-7.44 (m, 1H), 7.43-7.10 (m, 7H), 6.10-5.90 (br s, 1H), 5.28-5.14 (m, 2H), 4.54 (d, 2H). LC-MS (m/z, ESI): 737.07 (M+H).sup.+.

##STR00034##

[0235] White solid. .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.13 (d, 1H), 8.03 (t, 1H), 7.99-7.86 (m, 2H), 7.67-7.37 (m, 5H), 7.30 (t, 1H), 6.07-5.89 (br, 1H), 5.29-5.16 (m, 2H), 4.54 (d, 2H). LC-MS (m/z, ESI): 714.11 (M+H).sup.+.

##STR00035##

[0236] White solid. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.34 (d, 1H), 8.10-7.90 (m, 3H), 7.61-7.37 (m, 5H), 7.31 (t, 1H), 6.06-5.91 (br, 1H), 5.29-5.17 (m, 2H), 4.54 (d, 2H). LC-MS (m/z, ESI): 762.05 (M+H).sup.+.

##STR00036##

[0237] Oily substance. .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.62 (s, 1H), 8.13 (d, 1H), 8.06 (t, 1H), 7.97-7.89 (m, 2H), 7.82 (d, 1H), 7.58 (d, 1H), 7.51 (t, 1H), 7.35 (t, 1H), 6.07-5.89 (m, 1H), 5.28-5.21 (m, 2H), 4.55 (d, 2H). LC-MS (m/z, ESI): 715.11 (M+H).sup.+.

##STR00037##

[0238] Yellow solid. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.62 (s, 1H), 8.36-8.31 (m, 1H), 8.07 (t, 1H), 8.01-7.89 (m, 2H), 7.82 (d, 1H), 7.58 (d, 1H), 7.52 (d, 1H), 7.36 (t, 1H), 6.06-5.90 (m, 1H), 5.30-5.19 (m, 2H), 4.56 (d, 2H). LC-MS (m/z, ESI): 763.04 (M+H).sup.+.

##STR00038##

[0239] White solid. .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.64 (s, 1H), 8.15-8.10 (m, 1H), 8.07 (t, 1H), 7.97-7.84 (m, 3H), 7.64-7.50 (m, 2H), 7.36 (t, 1H), 6.07-5.92 (br, 1H), 5.29-5.20 (m, 2H), 4.57 (s, 2H). LC-MS (m/z, ESI): 758.09 (M+H).sup.+.

##STR00039##

[0240] White solid. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.65 (s, 1H), 8.32 (s, 1H), 8.07 (t, 1H), 8.02-7.80 (m, 3H), 7.64-7.50 (m, 2H), 7.37 (t, 1H), 6.07-5.92 (br, 1H), 5.29-5.21 (m, 2H), 4.57 (s, 2H). LC-MS (m/z, ESI): 806.08 (M+H).sup.+.

##STR00040##

[0241] Oily substance. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.35-8.31 (m, 1H), 8.17-7.96 (m, 2H), 7.95-7.90 (m, 1H), 7.63-7.55 (br, 1H), 7.51-7.04 (m, 6H), 4.93 (s, 1H), 4.52 (s, 1H), 2.30 (t, 1H). LC-MS (m/z, ESI): 735.06 (M+H).sup.+.

##STR00041##

[0242] White solid. .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.13 (d, 1H), 8.11-7.99 (m, 2H), 7.93-7.88 (m, 1H), 7.63-7.54 (m, 1H), 7.47-7.35 (m, 2H), 7.32 (t, 1H), 7.02-6.82 (br, 2H), 4.89 (s, 1H), 4.51 (s, 1H), 2.30 (t, 1H). LC-MS (m/z, ESI): 705.04 (M+H).sup.+.

##STR00042##

[0243] Oily substance. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.14 (d, 1H), 8.09 (t, 1H), 8.05-7.95 (br s, 1H), 7.91 (d, 1H), 7.72-7.38 (m, 5H), 7.34 (t, 1H), 4.93 (s, 1H), 4.52 (s, 1H), 2.33 (s, 1H). LC-MS (m/z, ESI): 712.07 (M+H).sup.+.

##STR00043##

[0244] White solid. .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.34 (d, 1H), 8.19-7.97 (m, 2H), 7.93 (d, 1H), 7.72-7.39 (m, 5H), 7.34 (t, 1H), 4.94 (s, 1H), 4.53 (s, 1H), 2.33 (s, 1H). LC-MS (m/z, ESI): 760.04 (M+H).sup.+.

##STR00044##

[0245] White solid. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.64 (s, 1H), 8.16-8.08 (m, 2H), 7.97 (d, 1H), 7.91 (d, 1H), 7.85 (s, 1H), 7.68-7.56 (m, 2H), 7.38 (t, 1H), 4.93 (d, 1H), 4.55 (d, 1H), 2.35 (s, 1H). LC-MS (m/z, ESI): 735.05 (M+Na).sup.+.

##STR00045##

[0246] White solid. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.64 (s, 1H), 8.34 (d, 1H), 8.12 (t, 1H), 8.07-7.96 (m, 1H), 7.93 (d, 1H), 7.84 (s, 1H), 7.70-7.54 (m, 2H), 7.39 (t, 1H), 4.93 (d, 1H), 4.56 (d, 1H), 2.35 (s, 1H). LC-MS (m/z, ESI): 761.00 (M+H).sup.+.

##STR00046##

[0247] White solid. .sup.1H NMR (600 MHz, Chloroform-d) ? 8.67 (s, 1H), 8.17-8.07 (m, 2H), 8.03-7.85 (m, 3H), 7.70-7.55 (m, 2H), 7.43-7.34 (m, 1H), 4.93 (d, 1H), 4.58 (d, 1H), 2.35 (s, 1H). LC-MS (m/z, ESI): 756.09 (M+H).sup.+.

##STR00047##

[0248] White solid. .sup.1H NMR (600 MHZ, Chloroform-d) ? 8.67 (s, 1H), 8.36-8.31 (m, 1H), 8.12 (t, 1H), 8.00 (d, 1H), 7.95-7.85 (m, 2H), 7.68 (t, 1H), 7.63-7.55 (m, 1H), 7.40 (t, 1H), 4.93 (d, 1H), 4.59 (d, 1H), 2.35 (s, 1H). LC-MS (m/z, ESI): 804.07 (M+H).sup.+.

Bioactivity Determination

Example 14: Determination of Insecticidal Bioactivity

[0249] The insecticidal activity of the compound of the present invention was determined on several insects. A determination method was as follows:

[0250] After the compound to be determined was dissolved in a mixed solvent of acetone/methanol (1:1), it was diluted with water containing 0.1% (wt) Tween-80 to a desired concentration.

[0251] Mythimna separata, Diamondback moth, Chilo suppressalis, Spodoptera exigua, Myzus persicae, and Franklinella occidentalis were used as targets, and the activity was tested by an Airbrush spray method.

(1) Determination of Activity Against Mythimna separata

[0252] Determination method: maize leaves were cut into 2 cm leaf pieces, and the front and back of each leaf piece were sprayed under an Airbrush spray treatment pressure of 10 psi (approximate to 0.7 kg/cm.sup.2) and with a spray volume of 0.5 mL. After drying in the shade, 10 3rd-instar larvae were inoculated for each treatment, and each treatment was repeated for 3 times. After the treatment, the leaf pieces were put into an observation chamber at 25? C. and with a relative humidity of 60% to 70%, and the number of living larvae was investigated 3 days after the administration of the compounds, and the mortality rates were calculated.

[0253] Partial test results for Mythimna separata were as follows:

[0254] At a dosage of 0.05 mg/L, 3 days after the administration, compounds 3, 4, 7, 8, 11, 12, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 47, 48, 51, 52, 55, and 56 had a mortality rate of more than 90% against Mythimna separata.

(2) Determination of Activity Against Diamondback Moth

[0255] Determination method: cabbage leaves were formed into leaf discs having a diameter of 2 cm using a puncher, and the front and back of each leaf disc were sprayed under an Airbrush spray treatment pressure of 10 psi (approximate to 0.7 kg/cm.sup.2) and with a spray volume of 0.5 mL. After drying in the shade, 10 3rd-instar larvae were inoculated for each treatment, and each treatment was repeated for 3 times. After the treatment, the leaf discs were placed into an observation chamber at 25? C. and with a relative humidity of 60% to 70%, and the number of living larvae was investigated 3 days after the administration of the compounds, and the mortality rates were calculated.

[0256] Partial test results for Diamondback moth were as follows:

[0257] At a dosage of 1.25 mg/L, compounds 3, 4, 7, 8, 11, 12, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 47, 48, 51, 52, 55, and 56 had a mortality rate of more than 90% against Diamondback moth.

[0258] According to the above experimental methods, some compounds of the present invention were further selected for parallel determinations of the activity against Diamondback moth with control compounds KC1, KC2, KC9, and KC10, and experimental results are shown in Table 12.

TABLE-US-00012 TABLE 12 Parallel comparative experiments of insecticidal activity of some compounds of the present invention against Diamondback moth with control compounds KCI, KC2, KC9, and KC10 Mortality rate (%, 3 days Compound after the administration) Number Structural formula 10 mg/L 3 [00048] 100 4 [00049] 100 7 [00050] 100 8 [00051] 100 11 [00052] 100 12 [00053] 100 19 [00054] 100 20 [00055] 100 23 [00056] 100 24 [00057] 100 27 [00058] 100 28 [00059] 100 31 [00060] 100 32 [00061] 100 35 [00062] 100 36 [00063] 100 39 [00064] 100 40 [00065] 100 47 [00066] 100 48 [00067] 100 51 [00068] 100 52 [00069] 100 55 [00070] 100 56 [00071] 100 KC1 [00072] 0 KC2 [00073] 0 KC9 [00074] 100 KC10 [00075] 100

[0259] Note: KC9 and KC10 in the table are control compounds additionally provided in the present application, which can be obtained by referring to the method in Example 10 of the present invention. The raw materials are all those that may be prepared or purchased according to the methods in the examples of the present invention, or may be prepared according to conventional methods.

[0260] By comparing the compounds of the present invention with the control compounds KC1, KC2, KC9, and KC10, comparing KC9 with KC1, and comparing KC10 with KC2, it may be concluded that: compared to existing technologies, the compound of the present invention has unexpectedly high insecticidal activity and substantial progress.

[0261] According to the above experimental methods, the compounds 3, 7, 8, 19, 20, 31, 35, 36, 47, and 48 of the present invention were further selected for parallel determinations of the activity against Diamondback moth with control compounds KC3, KC4, KC5, KC6, KC7, and KC8, and experimental results are shown in Table 13.

TABLE-US-00013 TABLE 13 Parallel comparative experiments of insecticidal activity of some compounds of the present invention against Diamondback moth with control compounds Mortality rate (%, 3 days after the administration) Compound 0.313 0.156 Number Structural formula mg/L mg/L 3 [00076] 100 100 31 [00077] 100 100 KC3 [00078] 93.33 50 7 [00079] 100 100 35 [00080] 100 100 KC4 [00081] 100 60 8 [00082] 100 100 36 [00083] 100 100 KC5 [00084] 100 73.33 19 [00085] 100 100 47 [00086] 100 100 KC7 [00087] 100 56.67 20 [00088] 100 100 48 [00089] 100 100 KC6 [00090] 90 46.67 KC8 [00091] 86.67 53.33

[0262] As shown in Table 13, by comparing the compounds 3 and 31 with the control compound KC3. comparing the compounds 7 and 35 with the control compound KC4, comparing the compounds 8 and 36 with the control compound KC5, comparing the compounds 19 and 47 with the control compound KC7, and comparing the compounds 20 and 48 with the control compounds KC6 and KC8, it may be seen that: in the examples of the present invention, allyl and propargyl are introduced into Re in the compound in General Formula I, so the compound with better insecticidal effect is obtained compared to existing technologies.

(3) Determination of Activity Against Chilo suppressalis

[0263] Determination method: 1) Preparation of rice seedlings: rice was cultured in a plastic small cup with a diameter of 4.5 cm and a height of 4 cm in a constant temperature room (the temperature was 26-28? C., the relative humidity was about 60-80%, and the illumination was 16hL:8hD), when the rice grown to a 4-5 leaf stage, robust and uniformly grown rice seedlings were selected for pharmaceutical treatment, and 3 replicates were set for each treatment. 2) Preparation of test insects: 3rd-instar larvae of Chilo suppressalis were continuously reared indoors. 3) Rice stems were sprayed and insects were introduced. A spray method was used to treat whole rice seedlings with uniform spray, and each treatment was 15 mL. Blank controls were treated firstly, and then the above operation was repeated in an order of experimental concentrations from low to high. After the spray treatment of the rice seedlings, they were placed in the shade to air-dry drug liquid, about 5 cm of the stem from a basal part of the stem was cut and fed to the test insects. A glass culture dish with a diameter of 90 mm was prepared, filter paper was placed on the bottom of the dish, then water was added to moisturize. About 5 rice stems were placed in each dish, 10 larvae were introduced, and the culture dish was closed with non-woven fabric and placed in the constant-temperature room for culture. 3 days after the administration, the number of residual live insects was investigated.

[0264] Partial test results of Chilo suppressalis were as follows:

[0265] At a dosage of 0.625 mg/L, the compounds 3, 4, 7, 8, 11, 12, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 47, 48, 51, 52, 55, and 56 had a mortality rate of more than 90% against Chilo suppressalis.

(4) Determination of Activity Against Spodoptera exigua

[0266] Determination method: the activity was tested by using a leaf disc dipping feeding method. Leaf discs were dipped in a drug solution for 10 s, and placed in a culture dish after being air-dried, there were 4 discs in each dish, and a filter paper was placed in the culture dish for moisture retention. 10 test insects of Spodoptera exigua were introduced to each dish, with 3 replicates.

[0267] They were placed in a light incubator for culture at a temperature of 25? C. and an illumination of 14hL:10hD. On the 1st, 2nd, and 3rd day after the administration, the number of dead Spodoptera exigua was investigated and the mortality rate was calculated.

[0268] Test results of Spodoptera exigua were as follows:

[0269] At a dosage of 0.625 mg/L, 3 days after the administration, the compounds 3, 4, 7, 8, 11, 12, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 47, 48, 51, 52, 55, and 56 had a mortality rate of more than 90% against Spodoptera exigua.

(5) Determination of Activity Against Myzus persicae

[0270] Determination method: a culture dish with a diameter of 6 cm was taken, the bottom of the dish was covered by a layer of filter paper, and an appropriate amount of tap water was added to moisturize the paper. Cabbage leaves with an appropriate size (the diameter was about 3 cm) and 15-30 aphids grown were cut from cabbage plants used to culture Myzus persicae, winged aphids and aphids on the front of the leave were removed, and it was placed in the culture dish while the back of the leave was upward. The pressure of airbrush spray treatment was 10 psi (about 0.7 kg/cm.sup.2), the liquid spray volume was 0.5 mL, and there were 3 replicates for each treatment. After the treatment, the leave was put into an observation room for culture at 25? C. and a relative humidity of 60-70%. After 48 h, the number of live insects was investigated and the mortality rate was calculated.

[0271] Test results for Myzus persicae were as follows:

[0272] At a dosage of 50 mg/L, the compounds 3, 4, 7, 8, 11, 12, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 47, 48, 51, 52, 55, and 56 had a mortality rate of more than 90% against Myzus persicae.

(6) Determination of Activity Against Franklinella occidentalis

[0273] Determination method: fresh bean leaves cultivated in a greenhouse were selected, a hand-held Airbrush sprayer was used to spray uniformly, each treatment was 1 mL, and after being air-dried naturally, the leaves were placed in a finger-shaped tube. Neat and healthy Franklinella occidentalis nymphs were introduced, there were 15 nymphs for each treatment, 3 replicates were set for the experiment, and water treatment was set as a blank control. After the treatment, the leaves were put into an indoor culture room for culture at 24? C., a relative humidity of 60-70%, and natural light. After 72 h, the number of live insects was investigated and the mortality rate was calculated.

[0274] Test results for Franklinella occidentalis were as follows:

[0275] At a dosage of 100 mg/L, the compounds 3, 4, 7, 8, 11, 12, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 47, 48, 51, 52, 55, and 56 had a mortality rate of more than 90% against Franklinella occidentalis.

[0276] According to the above experimental methods, the compounds 3, 7, 8, 19, 20, 31, 35, 36, 47, and 48 of the present invention were further selected for parallel determinations of the activity against Franklinella occidentalis nymphs with control compounds KC3, KC4, KC5, KC6, KC7, and KC8, and experimental results are shown in Table 14.

TABLE-US-00014 TABLE 14 Parallel comparative experiments of insecticidal activity of some compounds of the present invention against Franklinella occidentalis nymphs with control compounds Mortality rate (%, 3 days after the Compound administration) Number Structural formula 100 mg/L 10 mg/L 3 [00092] 100 93.33 31 [00093] 100 97.78 KC3 [00094] 57.78 31.11 7 [00095] 100 91.11 35 [00096] 100 100 KC4 [00097] 62.22 40.00 8 [00098] 100 88.89 36 [00099] 100 95.56 KC5 [00100] 51.11 28.89 19 [00101] 100 100 47 [00102] 100 100 KC7 [00103] 80.00 53.33 20 [00104] 100 100 48 [00105] 100 100 KC6 [00106] 77.78 57.78 KC8 [00107] 82.22 53.33

[0277] As shown in Table 14. by comparing the compounds 3 and 31 with the control compound KC3. comparing the compounds 7 and 35 with the control compound KC4, comparing the compounds 8 and 36 with the control compound KC5, comparing the compounds 19 and 47 with the control compound KC7, and comparing the compounds 20 and 48 with the control compounds KC6 and KC8, it may be seen that: in the examples of the present invention, allyl and propargyl are introduced into Re in the compound in General Formula I, so the compound with better insecticidal effect is obtained compared to existing technologies.

Example 15: Insecticidal Experiment on Cat Flea

[0278] 4 mg of the compound to be determined was dissolved in 40 mL of acetone to obtain an acetone solution with a concentration of 100 mg/L. 400 ?L of the drug solution was applied on the bottom and sides of a culture dish with an inner diameter of 5.3 cm, then after acetone was evaporated, a thin film of the compound of the present invention was made on the inner wall of the culture dish. The inner wall of the culture dish used was 40 cm.sup.2, and the treatment dosage was 1 ?g/cm.sup.2. 10 adult cat fleas (mixed male and female) were put into the dish, and it was stored in a constant-temperature room at 25? C. after being covered. The number of dead insects after 72 h was checked and the mortality rate was calculated. The experiment was repeated for 3 times. Test result: the compounds 3, 4, 7, 8, 11, 12, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 47, 48, 51, 52, 55, and 56 showed a mortality rate of more than 90%.

Example 16: Insecticidal Experiment on American Dog Tick

[0279] 4 mg of the compound to be determined was dissolved in 40 mL of acetone to obtain an acetone solution with a concentration of 100 mg/L. 400 ?L of the drug solution was applied on the bottom and sides of a culture dish with an inner diameter of 5.3 cm, then after acetone was evaporated, a thin film of the compound of the present invention was made on the inner wall of the culture dish. The inner wall of the culture dish used is 40 cm.sup.2, and the treatment dosage was 1 ?g/cm.sup.2. 10 1st-nymphs (mixed male and female) of the American dog tick were put into the dish, 2 culture dishes were merged, a junction portion were sealed with an adhesive tape to prevent escape, and the dishes were stored in a constant-temperature room at 25? C. The number of dead insects after 24 h was checked and the mortality rate was calculated. The experiment was repeated for 3 times. Test result: the compounds 3, 4, 7, 8, 11, 12, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 47, 48, 51, 52, 55, and 56 showed a mortality rate of more than 90%.