Pyrazole derivative

Abstract

A pyrazole derivative having the following formula stru-1: ##STR00001##
The pyrazole derivative is used for prevention and control of pests.

Claims

1. A pyrazole derivative having the following formula stru-1: ##STR00285## wherein: R1, R2, R4, R5 are hydrogen; R3 is t-butyl; R6 is methyl; R7 is selected from hydrogen, chlorine, and methyl; R8 is ethyl; R9 is selected from hydrogen, and methyl; L is oxygen; Q is oxygen; R10 is selected from C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6 cycloalkyl, and C.sub.2-C.sub.6 alkenyl.

2. The pyrazole derivative according to claim 1, wherein the pyrazole derivative is selected from at least one of the compounds represented by the following structural formula: ##STR00286## ##STR00287## ##STR00288## ##STR00289## ##STR00290##

3. The pyrazole derivative according to claim 1, wherein the pyrazole derivative represented by the formula stru-1 comprises at least one selected from the group consisting of an E-type pyrazole derivative and a Z-type pyrazole derivative.

4. A preparation method of a pyrazole derivative represented by the formula stru-1 of claim 1, comprising: ##STR00291## wherein the X is selected from halogen, R11 is ethyl, M is the metal ion from a base, the base is at least one selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium oxide, potassium hydroxide, sodium hydride, sodium alkoxide and potassium alkoxide.

5. The preparation method according to claim 4, wherein: an acid is at least one selected from an organic acid and an inorganic acid, a solvent is at least one independently selected from a protic solvent and an aprotic solvent, and the catalyst is at least one selected from potassium iodide, sodium iodide, and a phase transfer catalyst.

6. The preparation method according to claim 5, wherein: the X is selected from chlorine, bromine or iodine, the acid is at least one selected from hydrochloric acid, sulfuric acid and acetic acid, and the solvent is at least one independently selected from acetone, methyl ethyl ketone, tetrahydrofuran, acetonitrile, N, N-dimethylformamide, toluene and chlorobenzene.

7. An agricultural insecticide and acaricide, wherein the insecticide and acaricide contain a compound represented by the formula stru-1 of claim 1 with a mass percentage of 0.1˜99%.

8. The pyrazole derivative according to claim 2, comprising at least one selected from the group consisting of an E-type pyrazole derivative and a Z-type pyrazole derivative.

9. An agricultural insecticide and acaricide, wherein the insecticide and acaricide contain a compound represented by the formula stru-1 of claim 2 with a mass percentage of 0.1˜99%.

10. A pyrazole derivative, wherein the pyrazole derivative is selected from the compounds represented by the following structural formula: ##STR00292## ##STR00293## ##STR00294## ##STR00295## ##STR00296## ##STR00297## ##STR00298## ##STR00299## ##STR00300##

11. An agricultural insecticide and acaricide, wherein the insecticide and acaricide contain a pyrazole derivative of claim 10 with a mass percentage of 0.1˜99%.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The sole FIGURE is a single crystal diffraction pattern of Compound 251.

DETAILED DESCRIPTION OF THE EMBODIMENT

(2) The present invention is further described in combination with particular embodiments, but the present invention is not limited to these particular embodiments. Those skilled in the art should be aware that the present invention encompasses all alternatives, modifications, and equivalents that may be included within the scope of the appended claims.

I. Preparation of Compounds

Example 1 Preparation of Intermediates

(1) Synthesis of intermediate 1-ethyl-3-methyl-5-pyrazolecarboxylic acid ethyl ester

(3) ##STR00259##

(4) 154.1 g (1 mol) of intermediate A was added to a 1000 ml flask, then 500 ml of acetonitrile and 138 g of potassium carbonate were added, and then 1 mol of diethyl sulfate was added, and the system was stirred and heated to reflux until the reaction was finished in about 3 hr by thin-layer chromatography method. The system was filtered and the mother liquor was evaporated to dryness by a rotary evaporator, and the residue was distilled under a reduced pressure to give 140 g of intermediate B, with a yield of 77.0%.

(2) Synthesis of intermediate 1-ethyl-3-methyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester

(5) ##STR00260##

(6) 18.2 g (0.1 mol) of intermediate B was added to a 100 ml flask, and 50 ml of dichloroethane and 138 g of potassium carbonate were added, and then 0.11 mol of sulfonyl chloride was added. The system was stirred and heated to reflux until the reaction was finished in about 2.5 hr by thin-layer chromatography method. The mother liquor was evaporated to dryness and the residue was used in the next reaction without treatment.

(3) Synthesis of intermediate 1-ethyl-3-methyl-4-methyl-5-pyrazolecarboxylic acid ethyl ester

(7) ##STR00261##

(8) The intermediate D was prepared with reference to the method provided in JP2001342178A.

(4) Synthesis of intermediate 1-methyl-3-methyl-4-methyl-5-pyrazolecarboxylic acid ethyl ester

(9) ##STR00262##

(10) The intermediate D-1 was prepared with reference to the method provided in JP2001342178A.

(5) Synthesis of intermediate 1-methyl-3-methyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester

(11) ##STR00263##

(12) The intermediate C-1 is prepared according to the same method as preparation of interemdicate C.

(6) Preparation of Intermediate F

(13) ##STR00264##
Conventional procedure; The substituted aldehyde and zinc chloride at the catalytic amount were uniformly stirred in a reactor, and the substituted acyl chloride was slowly added dropwise under a cooling state. After dropwise addition, the mixture was stirred continuously for 1-2 hr at a low temperature, and warmed up to continue reaction for 5 hr, and purified by distillation under a reduced pressure.

(14) Preparation of Intermediate Chloromethyl Acetate:

(15) ##STR00265##

(16) 50 g (0.6 mol) of acetyl chloride was added dropwise to a mixture of 85 g paraformaldehyde and 1.75 g zinc chloride after cooled to 0° C. The dropwise addition was finished in about 2 hr, and then the reaction system was allowed to warm to room temperature for reaction for 1 hr, and then heated to 90° C. to continue reaction for 10 hr, cooled, filtered to remove solid, and then 45 g of intermediate F-1 was obtained by reduced pressure distillation.

(7) Preparation of Intermediate H

(17) ##STR00266##

(18) Conventional procedure: The chloro chloroformate was slowly added dropwise to the substituted alcohol and triethylamine solution under cooling state, after dropwise addition, the mixture was stirred continuously for 1-2 hr at a low temperature, and warmed up to continue reaction for 1 hr, filtered and the solvent was distilled off, and then purified by reduced pressure distillation to obtain the intermediate H.

(19) Preparation of Intermediate H-1:

(20) ##STR00267##

(21) When cooled to 0° C., 71.5 g (0.5 mol) of 1-chloroethyl chloroformate was added dropwise to 40 g and 52.0 g of triethylamine in 250 ml of toluene solution. The dropwise addition was finished in about 2 hr, and then the reaction system was allowed to warm to room temperature for reaction for 1 hr, and then filtered to remove solid, to obtain 78.5 g of intermediate H-1 by reduced pressure distillation.

(8) Preparation of Intermediate TA-1

(22) ##STR00268##

(23) 17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of anhydrous THF when the system was cooled to −5° C., equimolar amount of solid sodium methoxide was added, and then equimolar amount of intermediate B was added dropwise while stirring. When the dropwise addition was finished in 2 hr, the mixture was stirred continuously for 1.5 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the THF was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-1, which was used in the next reaction without purification.

(9) Preparation of Intermediate TA-2

(24) ##STR00269##

(25) 17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of anhydrous THF, when the system was cooled to −5° C., equimolar amount of solid potassium tert-butoxide was added, and then equimolar amount of intermediate C was added dropwise while stirring. When the dropwise addition was finished in 2.5 hr, the mixture was stirred continuously for 2.0 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the THF was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-2, which was used in the next reaction without purification.

(10) Preparation of Intermediate TA-3

(26) ##STR00270##

(27) 17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of methyl tert-butyl ether, when the system was cooled to −5° C., equimolar amount of solid potassium tert-butoxide was added, and then equimolar amount of intermediate D was added dropwise while stirring. When the dropwise addition was finished in 3.0 hr, the mixture was stirred continuously for 2.0 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the methyl tert-butyl ether was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-3, which was used in the next reaction without purification.

(11) Preparation of Intermediate TA-4

(28) ##STR00271##

(29) 17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of anhydrous THF, when the system was cooled to −5° C., equimolar amount of solid sodium methoxide was added, and then equimolar amount of intermediate M was added dropwise while stirring. When the dropwise addition was finished in 2 hr, the mixture was stirred continuously for 1.5 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the THF was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-1, which was used in the next reaction without purification.

Preparation of Intermediate TA-5

(30) ##STR00272##

(31) 17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of anhydrous THF when the system was cooled to −5° C., equimolar amount of solid potassium tert-butoxide was added, and then equimolar amount of intermediate C was added dropwise while stirring. When the dropwise addition was finished in 2.5 hr, the mixture was stirred continuously for 2.0 hr, and then warmed up to room temperature to continue stirring for 2 hr, after reaction, the THF was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-5, which was used in the next reaction without purification.

Preparation of Intermediate TA-6

(32) ##STR00273##

(33) 17.3 g of p-tert-butyl phenylacetonitrile was dissolved in 70 ml of THF, when the system was cooled to −5° C., equimolar amount of solid potassium tert-butoxide was added, and then equimolar amount of intermediate D-1 was added dropwise while stirring. When the dropwise addition was finished in 3.0 hr, the mixture was stirred continuously for 2.0 hr. and then warmed up to room temperature to continue stirring for 2 hr, after reaction, MTBE was evaporated. The residue was dissolved in water and then neutralized with hydrochloric acid to about pH 4, extracted with ethyl acetate, dried over anhydrous sodium sulfate to evaporate ethyl acetate and obtain the intermediate TA-3, which was used in the next reaction without purification.

Example 2 Preparation of Target Compounds

(34) (1) Preparation of Target Compound 226

(35) ##STR00274##

(36) 0.31 g (0.001 mol) of intermediate TA-1 and 0.12 g (0.0011 mol) of intermediate F-1, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 7 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.32 g of product, with a yield of 84%.

(37) (2) Preparation of Target Compound 251

(38) ##STR00275##

(39) 31 g (0.1 mol) of intermediate TA-1 and 13 g (0.11 mol) of intermediate F-2, 15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 10 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 35.1 g of product, with a yield of 89%.

(40) (3) Preparation of Target Compound 259

(41) ##STR00276##

(42) 0.31 g (0.001 mol) of intermediate TA-1 and 0.13 g (0.0011 mol) of intermediate F-3, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 12 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.28 g of product, with a yield of 66%.

(43) (4) Preparation of Target Compound 326

(44) ##STR00277##

(45) 0.34 g (0.001 mol) of intermediate TA-2 and 0.13 g (0.0011 mol) of intermediate F-2, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 N, N-Dimethylformamide, heated to 70° C. to react for 4 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate the solvent under a reduced pressure. The residue was purified by column chromatography to obtain 0.24 g of product, with a yield of 56%.

(46) (5) Preparation of Target Compound 401

(47) ##STR00278##

(48) 0.32 g (0.001 mol) of intermediate TA-2 and 0.13 g (0.0011 mol) of intermediate F-2, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 11 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate the solvent under a reduced pressure. The residue was purified by column chromatography to obtain 0.29 g of product, with a yield of 71%.

(49) (6) Preparation of Target Compound 105

(50) ##STR00279##

(51) 0.33 g (0.001 mol) of intermediate TA-5 and 0.18 g (0.0011 mol) of intermediate F-4, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 11 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.25 g of product, with a yield of 55%.

(52) (7) Preparation of Target Compound 4

(53) ##STR00280##

(54) 0.295 g (0.1 mol) of intermediate TA-4 and 0.15 g (0.11 mol) of intermediate F-6, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 5 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.31 g of product, with a yield of 78%.

(55) (8) Preparation of Target Compound 91

(56) ##STR00281##

(57) 0.33 g (0.1 mol) of intermediate TA-5 and 0.18 g (0.11 mol) of intermediate F-4, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 11 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.25 g of product, with a yield of 55%.

(58) (9) Preparation of Target Compound 548

(59) ##STR00282##

(60) 0.31 g (0.001 mol) of intermediate TA-1 and 0.16 g (0.0011 mol) of intermediate H-1, 0.15 sodium carbonate and a catalytic amount of sodium iodide were added to 25 ml of acetonitrile, heated to reflux for 6 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.33 g of product, with a yield of 78%.

(61) (10) Preparation of Target Compound 739

(62) ##STR00283##

(63) 0.34 g (0.001 mol) of intermediate TA-2 and 0.13 g (0.0011 mol) of intermediate H-2, 0.15 potassium carbonate and a catalytic amount of sodium iodide were added to 25 N, N-Dimethylformamide, heated to 70° C. to react for 5 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate the solvent under a reduced pressure. The residue was purified by column chromatography to obtain 0.28 g of product, with a yield of 65%.

(64) (11) Preparation of Target Compound 835

(65) ##STR00284##

(66) 0.31 g (0.001 mol) of intermediate TA-6 and 0.13 g of intermediate H-3, 0.15 potassium carbonate and a catalytic amount of sodium iodide were added to 25 ml of THF, heated to reflux for 10 hr, when the reaction was finished by thin-layer chromatography method, the system was cooled to room temperature to filter solid and evaporate acetonitrile. The residue was purified by column chromatography to obtain 0.25 g of product, with a yield of 61%.

II. Preparation of Reagents

(67) Reagents were prepared according to a mass ratio in the following embodiments.

Example 3. 30% Suspension

(68) TABLE-US-00004 Compound 251 30% Ethylene glycol 10% Nonylphenol polyglycol ether  6% Sodium lignosulfonate 10% Carboxymethyl cellulose  1% 37% formaldehyde solution   0.7% 75% silicone oil emulsion   0.8% Water added to 100%

(69) The compound 251 was fully mixed with other components, to obtain 30% suspension. The 30% suspension could be diluted with water to obtain diluent at any concentration.

Example 4. 30% Emulsion

(70) TABLE-US-00005 Compound 548 30% Phosphorous acid 10% Ethoxylated triglyceride 15% Toluene added to 100%

(71) Phosphorous acid was dissolved in toluene, then the compound 548 and ethoxylated triglyceride were added to obtain a transparent solution, i.e. 30% emulsion.

Example 5. 60% Wettable Powder

(72) TABLE-US-00006 Compound 91 60% Sodium dodecylnaphthalene sulfonate  2% Sodium lignosulfonate  9% Diatomite added to 100%

(73) The compound 91, sodium dodecylnaphthalene sulfonate, sodium lignosulfonate and diatomite were mixed together, and pulverized in a pulverizer until particles reached the standard, to obtain 60% wettable powder.

III. Biological Activity Assay

Example 6. Activity Assay of Eggs of Tetranychus Cinnabarinus

(74) According to the solubility of the test compound, the crude drug was dissolved in N N-dimethylformamide, and then prepared into a test solution of the desired concentration with 1‰ Tween 80 aqueous solution. The content of N. N-dimethylformamide in the solution should not exceed 10%.

(75) Spray method. The broad bean leaves with petioles were cut and inserted into a bottle with water. A certain number of female mites were placed, 24h later, adult mites were removed, and spray treatment was performed in 24 h. The experiment was repeated three times, and a blank control was set, and placed to an observation room (26±2° C., humidity 70%˜80%, 16h light per day) for culture. When the blank control group was incubated, the results were investigated. The non-incubated ones were used as death for investigation.

(76) According to the above method, the activity assay found that the ovicidal activity was equal to or higher than 90% at the concentration of 5 mg/L for the compounds 1-17, 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494, 499, 500, 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835-838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468; while the ovicidal activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO 01/68589 was less than 30% at a concentration of 5 mg/L.

(77) According to the above method, the activity assay found that the ovicidal activity was equal to or higher than 90% at the concentration of 2 mg/L for the compounds 230, 234, 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969; while the ovicidal activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 was 0% at a concentration of 2 mg/L.

(78) According to the above method, parallel determination of ovicidal activity was performed for the compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 of the present invention and the compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589. The results were shown in Table 4.

(79) TABLE-US-00007 TABLE 4 Compound Concentration (mg/L) Death rate (%) 226 2 100 227 2 97 230 2 100 234 2 100 241 2 100 251 2 100 252 2 100 254 2 99 255 2 96 301 2 95 302 2 97 547 2 100 585 2 100 675 2 100 771 2 100 772 2 100 931 2 98 932 2 97 937 2 100 8-1 2 0 8-2 2 0 8-3 2 0 8-4 2 0

Example 7 Activity Assay of Adult Tetranychus cinnabarnnus

(80) According to the solubility of the test compound, the crude drug was dissolved in N, N-dimethlfornamide, and then prepared into a test solution of the desired concentration with 1‰ Tween 80 aqueous solution. The content of N,N-dimethylformamide in the solution should not exceed 10%.

(81) Two euphylla bean seedlings were taken, after inoculated with adult Tetranychus cinnabarinus and the base number was investigated, whole plants were sprayed with a hand-held sprayer. The experiment was repeated three times for each treatment, after treatment, placed in a standard observation room after treatment, to investigate the survival number of mites in 48 hand calculate the death rate.

(82) According to the above method, the activity assay found that the adult mite-killing activity was equal to or higher than 90% at the concentration of 2.5 mg/L for the compounds 1-17, 26-72, 76-92 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494, 499, 500, 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835-838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468; while the adult mite-killing activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO 01/68589 was less than 80% at a concentration of 2.5 mg/L.

(83) According to the above method, the activity assay found that the adult mite-killing activity was equal to or higher than 90% at the concentration of 1.25 mg/L for the compounds 230, 234, 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969; while the adult mite-killing activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO 01/68589 was less than 50% at a concentration of 1.25 mg/L.

(84) According to the above method, parallel determination of adult mite-killing activity was performed for the compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 of the present invention and the compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589. The results were shown in Table 5.

(85) TABLE-US-00008 TABLE 5 Compound Concentration (mg/L) Death rate (%) 226 1.25 96 227 1.25 98 230 1.25 100 234 1.25 100 241 1.25 100 251 1.25 100 252 1.25 100 254 1.25 97 255 1.25 95 301 1.25 90 302 1.25 96 547 1.25 100 585 1.25 100 771 1.25 100 772 1.25 100 931 1.25 95 932 1.25 90 937 1.25 100 8-1 1.25 45 8-2 1.25 30 8-3 1.25 45 8-4 1.25 50

Example 8 Activity Assay of Tetranychus cinnabarinus Nymphs

(86) According to the solubility of the test compound, the crude drug was dissolved in N, N-dimethylformamide, and then prepared into a test solution of the desired concentration with 1‰ Tween 80 aqueous solution. The content of N,N-dimethylformamide in the solution should not exceed 10%.

(87) The broad bean leaves with petioles were cut and inserted into a small bottle with water. A certain number of brightly colored, active female adult mites were placed, 24h later, adult mites were removed, and leaves with insufficient eggs were removed. When eggs were hatched and grew into nymphs, spray treatment was performed. The experiment was repeated three times, and a blank control was set, and placed to an observation room (26±2° C., humidity 70%˜80%, 16h light per day) for culture. 48 h later, the results were investigated. The nymphs were gently touched during investigation, and if no response, they were regarded as deaths.

(88) According to the above method, the activity assay found that the nymph-killing activity was equal to or higher than 95% at the concentration of 2.5 mg/L for the compounds 1-17 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483, 486, 488, 489, 490, 492, 494, 499 500 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835-838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468, while the nymph-killing activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 was less than 80% at a concentration of 2.5 mg/L.

(89) According to the above method, the activity assay found that the nymph-killing activity was equal to or higher than 90% at the concentration of 2 mg/L for the compounds 230, 234. 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969 while the nymph-killing activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 was less than 30% at a concentration of 0.5 mg/L.

(90) According to the above method, parallel determination of nymph-killing activity was performed for the compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 of the present invention and the compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589. The results were shown in Table 6.

(91) TABLE-US-00009 TABLE 6 Compound Concentration (mg/L) Death rate (%) 226 0.5 90 227 0.5 94 230 0.5 98 234 0.5 96 241 0.5 100 251 0.5 100 252 0.5 100 254 0.5 96 255 0.5 95 301 0.5 90 302 0.5 96 547 0.5 93 585 0.5 96 675 0.5 675 771 0.5 95 772 0.5 90 931 0.5 95 937 0.5 90 937 0.5 93 8-1 0.5 25 8-2 0.5 0 8-3 0.5 30 8-4 0.5 15