Urea hydrazones derivatives, process for their preparation and use

Abstract

The application discloses a urea hydrazine derivative as shown in the following general formula (I): each substituent is shown in the specification. The application further discloses a preparation method and application of the urea hydrazine derivative, and the urea hydrazine derivative is especially suitable for preventing and treating crop pests.

Description

Technical Field

[0001] This invention belongs to the field of agricultural insecticides, and specifically relates to a class of ureahydrazone derivatives, their preparation methods and applications. Technical Background

[0002] Due to the long-term use of existing pesticides, diseases have developed resistance to them, thus requiring the continuous discovery of new pesticides with different mechanisms of action. At the same time, the excessive use of existing insecticides has put more pressure on the environment, thus requiring the discovery of new pesticides that are more efficient, less toxic, and environmentally compatible.

[0003] The existing WO2011017504A1, WO2013116053A1, WO2015007682A1, WO2016196280A1, WO2016116445A1, and WO2016113272 are listed below. Patents A1, WO2018108671A1, WO2018177781A1, WO2019121159A1, WO2020083733A1, WO2020109039A1, WO2020229398A1, WO2021013561A1, WO2021013721A1, WO2022053453A1, and WO2023156402A1 disclose ureahydrazone compounds used for controlling crop pests in the field of plant protection. The following compound structure is disclosed in WO2016116445A1:

[0004]

[0005] Although the aforementioned patents disclose urea hydrazone derivatives, they do not disclose the substituted aryl thiazole, substituted aryl oxazole, and substituted aryl imidazole urea hydrazone derivatives of this invention. In addition, under the same conditions, the compounds of this invention exhibit significantly better activity against pests such as diamondback moth at low doses than P31-P34. By comparing different linkage structures, the compounds exhibit different action spectra and biological activities. Summary of the Invention

[0006] To address the above problems, this invention proposes ureahydrazone derivatives, as shown in formula (Ⅰ):

[0007]

[0008] In the formula:

[0009] X, Y, Q, and M are independently selected from nitrogen, C-R5, where R5 can be selected from hydrogen, halogen, cyano, C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C3-C 10 cycloalkyl, C1-C 10 Alkoxyalkyl, C1-C 10 Halogenated alkoxyalkyl, C1-C 10 Alkyl thioalkyl, C1-C 10 Haloalkanes and thioalkyl groups;

[0010] Z is independently selected from oxygen, sulfur, and NR4, where R4 can be selected from hydrogen, C1-C 10 Alkyl, C1-C 10 Halogenated alkyl groups;

[0011] R3 is independently selected from hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C5 cycloalkyl, and C3-C5 substituted cycloalkyl;

[0012] L and J are independently selected from nitrogen and CR6, where R6 can be selected from hydrogen, halogens, and C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C3-C 10 cycloalkyl;

[0013] G is selected from oxygen and sulfur;

[0014] G1 and G2 are independently selected from hydrogen, halogen, cyano, and C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, C3-C 10 Substituted cycloalkyl groups.

[0015] Preferably, X, Y, Q, and M are independently selected from nitrogen and C-R5, wherein R5 can be selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, C3-C5 cycloalkyl, C1-C5 alkoxyalkyl, C1-C5 haloalkoxyalkyl, C1-C5 alkylthioalkyl, and C1-C5 haloalkylthioalkyl.

[0016] Z is independently selected from oxygen, sulfur, and N-R4, where R4 can be selected from hydrogen, C1-C5 alkyl, and C1-C5 haloalkyl;

[0017] R3 is independently selected from hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C5 cycloalkyl, and C3-C5 substituted cycloalkyl;

[0018] L and J are independently selected from nitrogen and C-R6, where R6 can be selected from hydrogen, halogen, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, and C3-C5 cycloalkyl.

[0019] G is selected from oxygen and sulfur;

[0020] G1 and G2 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 alkylthio, and C3-C5 substituted cycloalkyl.

[0021] More preferably, X, Y, Q, and M are independently selected from nitrogen and C-R5, wherein R5 can be selected from hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, C3-C5 cycloalkyl, C1-C3 alkoxyalkyl, C1-C3 haloalkoxyalkyl, C1-C3 alkylthioalkyl, and C1-C3 haloalkylthioalkyl.

[0022] Z is independently selected from oxygen, sulfur, and N-R4, where R4 can be selected from hydrogen, C1-C3 alkyl, and C1-C3 haloalkyl;

[0023] R3 is independently selected from hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, and C3-C5 substituted cycloalkyl;

[0024] L and J are independently selected from nitrogen and C-R6, where R6 can be selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, and C3-C5 cycloalkyl.

[0025] G is selected from oxygen and sulfur;

[0026] G1 and G2 are independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 alkylthio, and C3-C5 substituted cycloalkyl.

[0027] More preferably, X, Y, Q, and M are independently selected from nitrogen, C-R5, wherein R5 can be selected from hydrogen, fluorine, chlorine, cyano, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, methylthio, ethylthio, trifluoromethylthio, cyclopropane, and C1-C3 alkoxyalkyl.

[0028] Z is independently selected from oxygen, sulfur, and N-R4, where R4 can be selected from hydrogen, methyl, ethyl, and 2,2,2-trifluoroethyl.

[0029] R3 is independently selected from hydrogen, trifluoromethyl, methyl, and ethyl.

[0030] L and J are independently selected from nitrogen and C-R6, where R6 can be selected from hydrogen, fluorine, chlorine, methyl, trifluoromethyl, methoxy, and trifluoromethoxy.

[0031] G is selected from oxygen and sulfur;

[0032] G1 and G2 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, heptafluoroisopropyl, methoxy, ethoxy, trifluoromethoxy, methylthio, and trifluoromethylthio.

[0033] Most preferably, the ureahydrazone derivative is selected from at least one of the following structures:

[0034]

[0035] The following table illustrates some of the compounds in general formula (I) of this invention, but these specific compounds do not limit the scope of this invention.

[0036]

[0037] Where: X is N, M and Y are CH, Q is C-R5, Z is N-R4, G is S, L and J are CH, and R3 is H.

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] serial number R5 R4 G1 G2 144. H H H H 145. <![CDATA[CF3]]> <![CDATA[CH3]]> <![CDATA[CH(CH3)2]]> H 146. <![CDATA[CF3]]> <![CDATA[CH3]]> <![CDATA[CH(CH3)2]]> F 147. <![CDATA[CF3]]> <![CDATA[CH3]]> <![CDATA[CH(CH3)2]]> Cl 148. <![CDATA[CF3]]> <![CDATA[CH3]]> <![CDATA[CH(CH3)2]]> <![CDATA[CH3]]> 149. <![CDATA[CF3]]> <![CDATA[CH3]]> <![CDATA[CH(CH3)2]]> <![CDATA[CH3O]]> 150. <![CDATA[CF3]]> <![CDATA[CH3]]> <![CDATA[CH(CH3)2]]> <![CDATA[CF3O]]> 151. <![CDATA[CF3]]> <![CDATA[CH3]]> <![CDATA[CH(CH3)2]]> <![CDATA[CHF2O]]> 152. <![CDATA[CF3]]> <![CDATA[CH3CH2]]> <![CDATA[CH(CH3)2]]> H 153. <![CDATA[CF3]]> <![CDATA[CH 3 CH 2 ]]> <![CDATA[CH(CH3)2]]> F 154. <![CDATA[CF3]]> <![CDATA[CH 3 CH 2 ]]> <![CDATA[CH(CH3)2]]> Cl 155. <![CDATA[CF3]]> <![CDATA[CH 3 CH 2 ]]> <![CDATA[CH(CH3)2]]> <![CDATA[CH3]]> 156. <![CDATA[CF3]]> <![CDATA[CH 3 CH 2 ]]> <![CDATA[CH(CH3)2]]> <![CDATA[CH3O]]> 157. <![CDATA[CF3]]> <![CDATA[CH 3 CH 2 ]]> <![CDATA[CH(CH3)2]]> <![CDATA[CF3O]]> 158. <![CDATA[CF3]]> <![CDATA[CH 3 CH 2 ]]> <![CDATA[CH(CH3)2]]> <![CDATA[CHF2O]]>

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058] The NMR data for some compounds are as follows:

[0059] 2: 1 H NMR (CDCl3, 400MHz) δ: 10.61 (s, 1H, -NH), 9.05 (s, 1H, -CH), 8.09 (d, J = 13.6Hz, 2H, Ph-H), 7.85- 7.30(m,10H,Ph-H,-NH),3.95(s,1H,-CH3),3.23-3.16(m,1H,-CH),1.32(d,J=6.8Hz,6H,-CH3). 19 F NMR (CDCl3, 376MHz) δ: -60.68. 13 C NMR(CDCl3,100MHz)δ:177.31,154.65,144.62,142.28,141.92,138.51,135.04,13 4.92,131.16,129.88,128.32,127.63,126.25,126.16,125.35,125.03,124.37(q,J C-F =270.0 Hz,-CF3),123.41,121.67,120.01,119.99,117.65,117.59,117.55,117.52,110.17,32.10,28.50,23.29.HRMS(DART)for C 26 H 24 F3N5S m / z:Calculated,496.1777,Found,496.1782[M+H] +.

[0060] 9: 1 H NMR(CDCl3,400 MHz)δ:10.62(s,1H,-NH),9.04(s,1H,-CH),8.09(d,J=12.4Hz,2H,Ph-H),7.80-7.86(m,4H,Ph-H),7.58-7.61(m,2H,Ph-H),7.52-7.54(m,1H,Ph-H),7.28-7.42(m,3H,Ph-H),4.36(q,J=7.2 Hz,2H,-CH2),3.17-3.23(m,1H,-CH),1.52(t,J=8.8 Hz,3H,-CH3),1.31(d,J=6.8 Hz,6H,-CH3). 19 F NMR(CDCl3,376 MHz)δ:-60.72. 13 CNMR(CDCl3,100 MHz)δ:177.43,154.27,144.51,142.59,141.48,137.38,134.87,131.67,129.73,128.21,127.68,126.28,126.14,124.99,124.04(q,J C-F =272.6 Hz,-CF3),119.95,117.76,110.38,40.03,28.49,23.29,15.33.HRMS(DART)for C 27 H 26 F3N5S m / z:Calculated,510.1934,Found,510.1939[M+H] + .

[0061] 16: 1 H NMR(CDCl3,400 MHz)δ:10.76(s,1H,-NH),9.04(s,1H,-CH),8.10(s,2H,Ph-H),7.84(d,J=8.4 Hz,2H,Ph-H),7.70-7.78(m,3H,Ph-H),7.60(d,J=7.6Hz,1H,Ph-H),7.54(d,J=8.4 Hz,1H,Ph-H),7.28-7.42(m,3H,Ph-H),4.82-4.89(m,1H,-CH),3.17-3.23(m,1H,-CH),1.69(d,J=6.8 Hz,6H,-CH3)1.32(d,J=6.8 Hz,6H,-CH3). 19F NMR(CDCl3,376MHz)δ:-60.88. 13 C NMR(CDCl3,100 MHz)δ:177.31,154.52,144.68,143.18,141.98,135.55,135.01,134.91,131.97,129.92,128.36,128.13,127.61,126.23,126.14,124.88,124.56,124.23(q,J C-F =271.5 Hz,-CF3),123.37,119.35,119.31,117.95,117.91,112.66,49.28,28.48,23.28,21.47.HRMS(DART)for C 28 H 28 F3N5S m / z:Calculated,524.2090,Found,524.2095[M+H] + .

[0062] 17: 1 H NMR(CDCl3,400 MHz)δ:10.81(s,1H,-NH),9.07(s,1H,-CH),8.10-8.12(m,4H,Ph-H,-NH),7.82(d,J=8.4 Hz,2H,Ph-H),7.28-7.70(m,6H,Ph-H),3.58-3.64(m,1H,-CH),3.17-3.24(m,1H,cyclopropyl-H),1.32(d,J=7.2 Hz,6H,-CH3),1.19(d,J=6.4 Hz,2H,-CH2),0.77-0.81(m,2H,cyclopropyl-H). 19 F NMR(CDCl3,376 MHz)δ:-60.73. 13 C NMR(CDCl3,100 MHz)δ:177.31,154.94,144.63,142.09,141.88,139.06,134.95,134.81,131.70,129.73,128.31,127.32,126.24,126.14,126.10,125.40,125.08,124.12(q,J C-F =272.6 Hz,-CF3),123.39,121.39,119.92,117.59,111.43,28.49,26.58,23.30,9.10.HRMS(DART)for C28 H 26 F3N5S m / z:Calculated,522.1934,Found,522.1939[M+H] + .

[0063] 18: 1 H NMR(CDCl3,400 MHz)δ:10.59(s,1H,-NH),9.03(s,1H,-CH),7.66-8.13(m,7H,Ph-H),7.60(d,J=8.0 Hz,1H,Ph-H),7.53(d,J=8.4Hz,1H,Ph-H),7.38-7.30(m,3H,Ph-H),3.16-3.25(m,1H,-CH),3.15-3.23(m,1H,-CH),1.73(d,J=7.2 Hz,6H,-CH3),1.32(d,J=7.2 Hz,6H,-CH3),0.65(t,J=6.8 Hz,3H,sec-butyl-CH3). 19 F NMR(CDCl3,376 MHz)δ:-60.88. 13 C NMR(CDCl3,100 MHz)δ:177.4,155.4,144.7,142.9,141.9,135.4,134.9,132.0,130.4,128.3,127.6,126.8,126.3,126.1,126.1,125.1,124.1(q,J C-F =271.5 Hz,-CF3),123.3,119.5,117.9,117.9,112.6,55.4,28.5,28.1,23.3,19.9,11.0.HRMS(DART)for C 29 H 30 F3N5S m / z:Calculated,538.2247,Found,538.2252[M+H] + .

[0064] 19: 1H NMR(CDCl3,400 MHz)δ::11.28(s,1H,-NH),9.07(s,1H,-CH),8.15(d,J=13.2 Hz,2H,Ph-H),7.84(d,J=8.4 Hz,2H,Ph-H),7.73(d,J=8.0 Hz,2H,Ph-H),7.29-7.65(m,6H,Ph-H,-NH),4.90-4.99(m,1H,cyclopentane-H),3.17-3.24(m,1H,-CH),1.76-2.27(m,8H,cyclopentane-H),1.31(d,J=6.8 Hz,6H,-CH3). 19 F NMR(CDCl3,376 MHz)δ:-60.82. 13 C NMR(CDCl3,100 MHz)δ:177.39,155.17,144.66,142.82,142.01,135.14,131.67,130.43,130.01,128.34,127.65,126.23,126.14,126.04,125.12,124.80,124.07(q,J C-F =270.1 Hz,-CF3),123.34,121.90,121.35,119.42,117.96,113.83,113.35,112.37,70.95,57.96,30.57,28.49,25.25,23.30.HRMS(DART)for C 30 H 30 F3N5S m / z:Calculated,550.2247,Found,550.2252[M+H] + .

[0065] Ⅱ1I: 1 H NMR(CDCl3,400 MHz)δ:10.66(s,1H,-NH),8.99(s,1H,-NH),8.15(s,1H,-CH),8.03-7.28(m,14H,Ph-H),7.08(d,J=7.2 Hz,2H,Ph-H),5.51(s,1H,-CH2),3.20-3.13(m,1H,-CH),1.29(d,J=6.8 Hz,6H,-CH3). 19 F NMR(CDCl3,376 MHz)δ:-60.74. 13C NMR(CDCl3,100 MHz)δ:177.28,155.05,144.72,142.53,141.89,138.09,135.49,135.18,134.87,131.02,129.71,129.30,128.34,128.19,127.70,126.15,126.05,125.79,125.27,124.12(q,J C-F =270.2 Hz,-CF3),123.33,120.25,117.78,111.00,109.99,48.67,28.47,23.32.HRMS(DART)for C 32 H 28 F3N5S m / z:Calculated,572.2090,Found,572.2095[M+H] + .

[0066] 20: 1 H NMR(CDCl3,400 MHz)δ:10.93(s,1H,-NH),9.05(s,1H,-NH),8.11(s,2H,-CH,Ph-H),7.90(d,J=8.4 Hz,2H,Ph-H),7.82(d,J=8.0 Hz,2H,Ph-H),7.60-7.28(m,6H,Ph-H),4.46(t,J=5.6 Hz 2H,-CH2),3.79(d,J=5.2 Hz,2H,-CH2),3.27(s,3H,-CH3),3.19-3.17(m,1H,-CH),1.32(d,J=6.8 Hz,6H,-CH3). 19 F NMR(CDCl3,376 MHz)δ:-60.72. 13 C NMR(CDCl3,100 MHz)δ:177.30,155.23,144.72,142.44,142.17,137.88,134.99,131.49,130.26,128.38,126.99,126.23,126.14,125.26,124.94,124.33(q,J C-F =265.5 Hz,-CF3),123.44,119.87,119.83,119.79,117.60,111.04,70.61,59.11,45.21,28.49,23.31.HRMS(DART)for C 28 H 28F3N5OS m / z:Calculated,540.2039,Found,540.2044[M+H] + .

[0067] 21 : 1 H NMR(CDCl3,400 MHz)δ:10.73(s,1H,-NH),9.04(s,1H,-NH),8.10(d,J=7.6Hz,2H,Ph-H,-CH),7.86(d,J=8.0 Hz,2H,Ph-H),7.79(d,J=8.4 Hz,2H,Ph-H),7.60-7.28(m,6H,Ph-H),4.66(t,J=7.6 Hz,2H,-CH2),3.62(s,3H,-CH3),3.24-3.17(m,1H,-CH),2.79(t,J=7.6 Hz,2H,-CH2),1.32(d,J=7.2 Hz,6H,-CH3). 19 FNMR(CDCl3,376 MHz)δ:-60.78.HRMS(DART)for C 29 H 28 F3N5O2S m / z:Calculated,568.1989,Found,568.1994[M+H] + .

[0068] 22: 1 H NMR(CDCl3,400 MHz)δ:10.89(s,1H,-NH),9.06(s,1H,-NH),8.70(s,1H,-CH),8.31(s,1H,pyridine-H),8.12(s,1H,Ph-H),7.94-7.86(m,4H,Ph-H,pyridine-H),7.61(d,J=7.6 Hz,1H,Ph-H),7.42-7.29(m,3H,Ph-H),4.06(s,3H,-CH3),3.24-3.17(m,1H,-CH),1.32(d,J=6.8 Hz,6H,-CH3). 19 F NMR(CDCl3,376MHz)δ:-60.17. 13C NMR(CDCl3,100 MHz)δ:177.50,155.93,151.06,151.02,144.70,141.67,141.45,135.67,135.02,134.37,131.02,129.96,129.87,128.41,128.30,127.86,126.42,126.32,125.76(q,J C-F =270.4 Hz,-CF3),124.80,124.28,124.12,123.06,122.84,122.50,122.17,121.58,31.14,28.66,23.44.HRMS(DART)for C 25 H 23 F3N6S m / z:Calculated,497.1730,Found,497.1735[M+H] + .

[0069] 116: 1 H NMR(CDCl3,400 MHz)δ:10.95(s,1H,-NH),9.04(s,1H,-NH),8.69(s,1H,-CH),8.30(s,1H,Ph-H),8.11(s,1H,Ph-H),7.86(s,4H,Ph-H),7.58(d,J=7.6 Hz,1H,Ph-H),7.41-7.29(m,3H,Ph-H),4.53(q,J=7.2 Hz,2H,-CH2),3.23-3.16(m,1H,-CH),1.52(t,J=7.2 Hz,3H,-CH3)1.31(d,J=6.8 Hz,6H,-CH3). 19 F NMR(CDCl3,376 MHz)δ:-60.19. 13 CNMR(CDCl3,100 MHz)δ:177.37,155.56,150.38,144.70,141.82,141.22,135.58,134.88,134.24,131.12,129.53,128.36,128.18,127.79,126.26,126.17,125.63(q,J C-F =270.5Hz,-CF3),124.68,124.64,124.60,124.08,124.03,122.92,122.26,121.94,121.31,39.26,28.50,23.30,15.28.HRMS(DART)for C26 H 25 F3N6S m / z:Calculated,511.1886,Found,511.1891[M+H] + .

[0070] 100: 1 H NMR(CDCl3,400 MHz)δ:10.51(s,1H,-NH),9.03(s,1H,-NH),8.68(s,1H,-CH),8.28(s,1H,pyridine-H),8.07(s,1H,Ph-H),7.87(d,J=8.4 Hz,2H,Ph-H),7.75(d,J=8.4 Hz,2H,Ph-H),7.60(d,J=8.0 Hz,1H,Ph-H),7.42-7.28(m,3H,Ph-H,pyridine-H),4.90-4.82(m,1H,-CH),3.23-3.16(m,1H,-CH),1.80(d,J=6.8Hz,6H,-CH3),1.32(d,J=6.8 Hz,6H,-CH3). 19 F NMR(CDCl3,376 MHz)δ:-60.33. 13 C NMR(CDCl3,100 MHz)δ:177.35,155.75,150.37,144.72,141.84,140.68,140.61,135.42,134.89,134.59,131.59,129.88,128.39,128.19,127.68,126.27,126.17,125.70(q,J C-F =270.6 Hz,-CF3),124.53,122.99,122.09,121.77,121.45,77.37,50.14,28.51,23.31,21.15.HRMS(DART)forC 27 H 27 F3N6S m / z:Calculated,525.2043,Found,525.2048[M+H] + .

[0071] 101: 1H NMR(CDCl3,400 MHz)δ:10.37(s,1H,-NH),9.03(s,1H,-NH),8.71(s,1H,-CH),8.27(s,1H,pyridine-H),8.09-8.04(m,3H,Ph-H,pyridine-H),7.84(d,J=8.4 Hz,2H,Ph-H),7.60(d,J=7.6 Hz,1H,Ph-H),7.41-7.29(m,3H,Ph-H),3.65-3.60(m,1H,cyclopropane-CH),3.22-3.15(m,1H,-CH),1.31(d,J=6.8 Hz,6H,-CH3),1.25(d,J=6.8Hz,2H,-CH2),0.93-0.88(m,2H,-CH2). 19 F NMR(CDCl3,376MHz)δ:-60.32. 13 C NMR(CDCl3,100MHz)δ:177.47,156.68,151.85,144.76,142.02,141.40,135.52,135.03,134.12,131.41,129.93,128.45,128.28,127.51,126.30,125.71(q,J C-F =270.3 Hz,-CF3),124.87,124.26,123.00,122.49,122.17,121.84,28.63,26.38,23.43,9.27.HRMS(DART)forC 27 H 25 F3N6S m / z:Calculated,523.1886,Found,523.1891[M+H] + .

[0072] 102: 1H NMR(CDCl3,400 MHz)δ:10.59(s,1H,-NH),9.03(s,1H,-NH),8.66(s,1H,-CH),8.28(s,1H,pyridine-H),8.08(s,1H,Ph-H),7.86(d,J=8.4 Hz,2H,Ph-H),7.73(d,J=8.4 Hz,2H,Ph-H),7.60(d,J=7.6 Hz,1H,Ph-H),7.42-7.30(m,3H,Ph-H,pyridine-H),4.57-4.48(m,1H,-CH),3.24-3.17(m,1H,-CH),2.55-1.98(m,2H,-CH2),1.82(d,J=6.8Hz,3H,-CH3),1.32(d,J=6.8 Hz,6H,-CH3)0.67(t,J=7.2Hz,3H,-CH3). 19 F NMR(CDCl3,376MHz)δ:-60.32. 13 C NMR(CDCl3,100 MHz)δ:177.42,156.72,150.28,144.83,142.00,140.67,135.46,134.99,134.52,131.73,130.01,129.05,128.49,128.24,127.74,126.31,125.76(q,J C-F =270.5 Hz,-CF3),124.62,123.05,121.85,121.52,121.20,76.84,56.26,28.56,27.55,23.37,19.60,11.15.HRMS(DART)for C 28 H 29 F3N6S m / z:Calculated,539.2199,Found,539.2204[M+H] + .

[0073] 103: 1H NMR(CDCl3,400 MHz)δ:10.25(s,1H,-NH),9.03(s,1H,-NH),8.69(s,1H,-CH),8.31(s,1H,pyridine-H),8.04-7.86(m,5H,Ph-H,pyridine-H),7.61(d,J=7.60 Hz,1H,Ph-H),7.42-7.29(m,3H,Ph-H),4.35(d,J=7.6 Hz,2H,-CH2),3.23-3.16(m,1H,-CH),2.21-2.13(m,1H,-CH),1.32(d,J=6.8 Hz,6H,-CH3),0.76(d,J=6.8 Hz,6H,-CH3).

[0074] 104: 1 H NMR(CDCl3,400 MHz)δ:10.45(s,1H,-NH),9.01(s,1H,-NH),8.66(s,1H,-CH),8.28(s,1H,pyridine-H),8.05(s,1H,Ph-H),7.86(d,J=8.0 Hz,2H,Ph-H),7.77(d,J=8.4 Hz,2H,Ph-H),7.59(d,J=7.6 Hz,1H,Ph-H),7.41-7.29(m,3H,Ph-H,pyridine-H),4.88(t,J=8.4 Hz,1H,cyclopentane-CH),3.22-3.15(m,1H,-CH),2.68-1.68(m,8H,cyclopentane-CH2),1.31(d,J=6.8 Hz,6H,-CH3). 19 F NMR(DMSO-d6,376 MHz)δ:-58.54.HRMS(DART)for C 29 H 29 F3N6S m / z:Calculated,551.2199,Found,551.2204[M+H] + .

[0075] 105: 1H NMR(CDCl3,400 MHz)δ:10.44(s,1H,-NH),9.03(s,1H,-NH),8.68(s,1H,-CH),8.28(s,1H,pyridine-H),8.07(s,1H,Ph-H),7.87(d,J=8.4 Hz,2H,Ph-H),7.75(d,J=8.0 Hz,2H,Ph-H),7.59(d,J=7.6 Hz,1H,Ph-H),7.42-7.30(m,3H,Ph-H,pyridine-H),4.40(t,J=12.0 Hz,1H,cyclohexane-CH),3.24-3.16(m,1H,-CH),2.86-1.38(m,10H,cyclohexane-CH2),1.32(d,J=6.8 Hz,6H,-CH3). 19 F NMR(CDCl3,376 MHz)δ:-60.32. 13 CNMR(CDCl3,100 MHz)δ:177.40,155.91,150.45,141.84,140.48,135.38,134.90,134.46,131.66,129.86,128.99,128.39,128.19,127.70,126.27,125.69(q,J C-F =270.5 Hz,-CF3),124.49,122.99,121.74,121.41,58.04,30.86,28.51,25.95,24.87,23.31.HRMS(DART)for C 30 H 31 F3N6S m / z:Calculated,565.2356,Found,565.2361[M+H] + .

[0076] 106: 1H NMR(CDCl3,400 MHz)δ:10.26(s,1H,-NH),9.00(s,1H,-NH),8.72(s,1H,-CH),8.36(s,1H,pyridine-H),7.99(s,1H,pyridine-H),7.77(s,4H,Ph-H),7.58(d,J=8.0Hz,1H,Ph-H),7.41-7.29(m,5H,Ph-H),7.10(d,J=6.0 Hz,3H,Ph-H),5.66(s,2H,-CH2),3.21-3.14(m,1H,-CH),1.30(d,J=6.8 Hz,6H,-CH3). 19 FNMR(CDCl3,376 MHz)δ:-60.20.HRMS(DART)for C 31 H 27 F3N6S m / z:Calculated,573.2043,Found,573.2048[M+H] + .

[0077] 107: 1 H NMR(CDCl3,400 MHz)δ:10.46(s,1H,-NH),9.03(s,1H,-NH),8.69(s,1H,-CH),8.32(s,1H,pyridine-H),8.06-8.03(m,3H,Ph-H,pyridine-H),7.85(d,J=8.4 Hz,2H,Ph-H),7.60(d,J=7.6 Hz,1H,Ph-H),7.42-7.28(m,3H,Ph-H),4.61(t,J=5.2 Hz,2H,-CH2),3.93(t,J=5.6 Hz,2H,-CH2),3.26(s,3H,-CH3),3.23-3.16(m,1H,-CH),1.32(d,J=7.2 Hz,6H,-CH3). 19 F NMR(CDCl3,376 MHz)δ:-60.22. 13 CNMR(CDCl3,100 MHz)δ:177.29,156.63,150.58,144.74,142.09,141.09,135.43,134.95,134.15,130.98,130.25,128.38,128.09,127.58,126.20,126.11,125.62(q,J C-F=268.9 Hz,-CF3),124.62,122.91,122.24,121.92,69.91,58.92,44.23,28.46,23.29.HRMS(DART)for C 27 H 27 F3N6OS m / z:Calculated,541.1992,Found,541.1997[M+H] + .

[0078] 108: 1 H NMR(CDCl3,400 MHz)δ:11.19(s,1H,-NH),9.06(s,1H,-NH),8.69(s,1H,-CH),8.31(s,1H,pyridine-H),8.14(s,1H,pyridine-H),7.86(s,4H,ph-H),7.64(d,J=7.6Hz,1H,Ph-H),7.43-7.27(m,3H,Ph-H),4.76(t,J=7.2 Hz,2H,-CH2),3.61(s,3H,-CH3),3.25-3.18(m,1H,-CH),3.01(t,J=6.8 Hz,2H,-CH2),1.32(d,J=6.8 Hz,6H,-CH3). 19 FNMR(CDCl3,376 MHz)δ:-60.22.HRMS(DART)forC 28 H 27 F3N6O2S m / z:Calculated,569.1941,Found,569.1946[M+H] + .

[0079] 109: 1 H NMR(CDCl3,400 MHz)δ:10.99(s,1H,-NH),9.04(s,1H,-NH),8.74(s,1H,-CH),8.36(s,1H,pyridine-H),8.13-7.79(m,5H,Ph-H),7.58(d,J=7.6 Hz,1H,Ph-H),7.42-7.28(m,3H,Ph-H,pyridine-H),5.11(q,J=8.0 Hz,2H,-CH2),3.24-3.17(m,1H,-CH),1.32(d,J=6.8 Hz,6H,-CH3).HRMS(DART)for C 26 H 22F6N6Sm / z:Calculated,565.1604,Found,565.1609[M+H] + .

[0080] 52: 1 H NMR(CDCl3,400 MHz)δ:10.50(s,1H,-NH),9.04(s,1H,-NH),8.06(s,1H,-CH),7.81-7.93(m,5H,Ph-H),7.72(s,1H,Ph-H),7.57-7.61(m,2H,Ph-H),7.28-7.42(m,3H,Ph-H),4.39(q,J=7.2 Hz,2H,-CH2),3.16-3.2(m,1H,-CH),1.54(t,J=7.2 Hz,3H,-CH3),1.32(d,J=6.8 Hz,6H,isopropyl-CH3). 19 F NMR(DMSO-d6,376MHz)δ:-58.77. 13 C NMR(CDCl3,100 MHz)δ:177.34,154.79,145.10,144.65,141.94,135.18,134.92,134.84,131.37,129.71,128.34,128.13,127.70,126.76,126.25,126.15,126.08(q,J C-F =270.5Hz,-CF3),125.34,125.02,124.09,123.38,120.41,119.73,119.65,107.76,40.05,28.49,23.30,15.37.HRMS(DART)for C 27 H 26 F3N5S m / z:Calculated,510.1934,Found,510.1939[M+H] + .

[0081] 53: 1H NMR(CDCl3,400MHz)δ:10.79(s,1H,-NH),9.04(s,1H,-NH),8.10(s,1H,-CH),7.93-7.83(m,4H,Ph-H),7.70(d,J=8.4Hz,2H,Ph-H),7.61-7.30(m,5H,Ph-H),4.58-4.48(m,1H,-CH),3.24-3.17(m,1H,-CH),2.23-1.89(m,2H,-CH2),1.74(d,J=6.8Hz,3H,-CH3),1.32(d,J=6.8Hz,6H,-CH3),0.67(t,J=7.2Hz,3H,-CH3). 19 F NMR(CDCl3,376MHz)δ:-60.54. 13 C NMR(CDCl3,100MHz)δ:177.32,156.01,145.82,144.76,142.16,135.14,135.03,132.91,132.03,130.03,128.44,128.10,127.66,126.23,126.13,125.03,124.73,124.41,124.09(q,J C-F =276.1Hz,-CF3),123.45,121.33,120.75,119.32,109.74,55.51,28.49,28.20,23.32,19.98,11.02.HRMS(DART)for C 29 H 30 F3N5S m / z:Calculated,538.2247,Found,538.2252[M+H] + .

[0082] 54: 1H NMR(CDCl3,400MHz)δ:10.73(s,1H,-NH),9.04(s,1H,-NH),8.09(s,1H,-CH),7.84(d,J=8.4Hz,1H,Ph-H),7.84(d,J=8.4Hz,2H,Ph-H),7.78(d,J=8.4Hz,2H,Ph-H),7.69(s,1H,Ph-H),7.61-7.28(m,5H,Ph-H),4.16(d,J=7.6Hz,2H,-CH2),3.17-3.24(m,1H,-CH),2.18-2.15(m,1H,-CH),1.32(d,J=6.8Hz,6H,-CH3),0.77(d,J=6.4Hz,6H,-CH3). 19 F NMR(CDCl3,376MHz)δ:-60.59. 13 C NMR(CDCl3,100MHz)δ:177.32,155.57,145.05,144.72,142.23,135.30,135.10,131.92,129.86,128.42,128.06,127.70,126.21,125.46,125.13,124.81,124.48(q,J C-F =270.9Hz,-CF3),123.45,120.75,119.46,108.28,52.22,28.92,28.49,23.32,19.93.HRMS(DART)for C 29 H 30 F3N5S m / z:Calculated,538.2247,Found,538.2252[M+H] + .

[0083] 55: 1 H NMR(CDCl3,400MHz)δ:11.24(s,1H,-NH),9.06(s,1H,-NH),8.15(s,1H,-CH),7.91(d,J=8.8Hz,1H,Ph-H),7.84(d,J=8.4Hz,2H,Ph-H),7.78(s,1H,Ph-H),7.73(d,J=8.0Hz,2H,Ph-H),7.59-7.30(m,5H,Ph-H),5.00-4.91(m,1H,Cyclopentane-H),3.24-3.17(m,1H,-CH),2.35-1.77(m,8H,Cyclopentane-H),1.31(d,J=6.8Hz,6H,-CH3).19 F NMR(CDCl3,376MHz)δ:-60.54.HRMS(DART)for C 30 H 30 F3N5S m / z:Calculated,550.2247,Found,550.2252[M+H] + .

[0084] 56: 1 H NMR (CDCl3, 400MHz) δ: 10.48 (s, 1H, -NH), 9.02 (s, 1H, -NH), 8.04 (s, 1H, -CH), 7.93-7.77 (m, 6H, Ph-H), 7.58 (t, J=7.6Hz, 2H, Ph-H), 7.40-7.27 (m,3H,Ph-H),4.66(t,J=5.2Hz,2H,-CH2),3.80(t,J=5.2Hz,2H,-CH2),3.28(s,3H,-CH3),3.22-3.15(m,1H,-CH),1.30(d,J=6.8Hz,6H,-CH3). 19 F NMR (CDCl3, 376MHz) δ: -60.59. 13 C NMR(CDCl3,100MHz)δ:177.27,155.76,145.13,144.75,142.17,135.37,135.05 ,131.43,130.30,128.41,127.58,126.25,126.15,125.52,125.21,124.89(q,J C-F =272.7Hz,-CF3),124.57,123.44,120.33,119.67,108.36,70.62,59.12,45.25,28.49,23.33.HRMS(DART)forC 28 H 28 F3N5OS m / z:Calculated,540.2039,Found,540.2044[M+H] + .

[0085] This invention also provides a method for preparing the above-mentioned ureahydrazone derivative, the method comprising the following steps:

[0086] Type 1:

[0087]

[0088] Z represents oxygen and sulfur.

[0089] Type Two:

[0090]

[0091] In the formula: X, Y, Q, M, R5, R4, R3, L, J, G, G1, and G2 are defined as described above; the base is selected from organic and / or inorganic bases; the solvent is selected from at least one of dichloromethane, 1,2-dichloroethane, toluene, and tetrahydrofuran.

[0092] The present invention also provides the application of any of the above-described ureahydrazone derivatives, wherein the ureahydrazone derivatives are used for agricultural insecticides, preferably for the prevention and control of at least one disease among crop mites, lepidopterans, homoptera, hemiptera, coleopterans or sanitary pests, and more preferably for the prevention and control of at least one disease among crop armyworms, diamondback moths, rice stem borers, rice leaf rollers, aphids or spider mites.

[0093] This invention also provides a pesticide formulation containing 1%-99% by mass of a ureahydrazone derivative represented by general formula (I). The pesticide formulation can be formulated into various liquids, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, water-in-oil emulsions, powders, wettable powders, soluble powders, granules, water-dispersible granules, or capsules.

[0094] The pesticide formulation provided by the present invention, in addition to containing 1%-99% by mass of the urea-hydrazone derivative represented by general formula (I), may further contain an agriculturally acceptable carrier.

[0095] The carrier comprises at least two components, at least one of which is a surfactant. The carrier can be solid or liquid. Suitable solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as kaolinite, montmorillonite, and mica; silica, calcium carbonate, and light calcium carbonate; calcium sulfate; limestone; sodium sulfate; and amine salts such as ammonium sulfate and hexamethylenediamine. Liquid carriers include water and organic solvents. When water is used as a solvent or diluent, organic solvents can also be used as auxiliaries or antifreeze additives. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, and toluene; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, and dichloromethane; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, and light mineral oils; alcohols such as isopropanol, butanol, ethylene glycol, glycerol, and cyclohexanol; their ethers and esters; and ketones such as acetone, cyclohexanone, dimethylformamide, and N-methylpyrrolidone.

[0096] Surfactants can be emulsifiers, dispersants, or wetting agents; they can be ionic or nonionic. Examples of nonionic emulsifiers include polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amines, and commercially available emulsifiers such as Agricultural Emulsion 2201B, Agricultural Emulsion 0203B, and Agricultural Emulsion 100.# 500g of agricultural dairy products # 600g of agricultural dairy products # 600-2 Agricultural Milk # Agricultural Milk 1601, Agricultural Milk 2201, Agricultural Milk NP-10, Agricultural Milk NP-15, Agricultural Milk 507 # Agricultural Milk OX-635, Agricultural Milk OX-622, Agricultural Milk OX-653, Agricultural Milk OX-667, Ningru 36 # Dispersants include sodium lignosulfonate, dispersing agents, calcium lignosulfonate, and methylnaphthalenesulfonic acid formaldehyde condensate. Wetting agents include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium alkylnaphthalenesulfonate.

[0097] These formulations can be prepared using common methods. For example, the active substance can be mixed with a liquid solvent and / or a solid carrier, while surfactants such as emulsifiers, dispersants, stabilizers, and wetting agents are added, as well as other additives such as binders, defoamers, and oxidants.

[0098] Compared with the prior art, the ureahydrazone derivatives represented by general formula (I) provided by the present invention have the following advantages:

[0099] The urea-hydrazone derivatives of the present invention have high insecticidal activity, and at a concentration of 50 pm, they control more than 80% of pests such as armyworms and diamondback moths. Detailed Implementation

[0100] The present invention will be further described below with reference to specific embodiments, but the invention is not limited to these specific embodiments. Those skilled in the art should recognize that the present invention covers all alternatives, improvements, and equivalents that may be included within the scope of the claims.

[0101] (I) Compound preparation:

[0102] Synthetic route of the target compound:

[0103]

[0104] R4 represents the methyl synthesis route:

[0105]

[0106] Example 1: inter-1 synthesis

[0107] 0.1 mol of 2-chloro-3-nitro-5-trifluoromethylpyridine was dissolved in 100 mL of LDMAC. Three molar amounts of methylammonium aqueous solution were added at room temperature. The mixture was stirred at room temperature for 5 h. Thin-layer chromatography was used to monitor the reaction until it was complete. The reaction mixture was then poured into 200 mL of saturated saline solution and extracted twice with 100 mL of ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain the product. 1 H NMR (CDCl3, 400MHz) δ: 8.47 (s, 1H, -NH), 8.44 (s, 1H, Ph-H), 7.62 (d, J = 10.8Hz, 1H, Ph-H), 6.97 (d ,J=9.2Hz,1H,Ph-H),3.70(t,J=5.2Hz,2H,-CH2),3.54(q,J=5.2Hz,2H,-CH2),3.44(s,3H,-CH3). 19 F NMR (CDCl3, 376MHz) δ: -61.94.

[0108] Example 2: inter-2 synthesis

[0109] In a 100 mL round-bottom flask, intermediate inter-2 (2.21 g, 1 mmol) and palladium on carbon (0.1 g) were dissolved in EA (40 mL). The system was evacuated with nitrogen and then purged with hydrogen. The mixture was stirred at room temperature for 4 h. The reaction was completed by TLC monitoring. The mixture was filtered, dried over MgSO4, filtered again, and the solvent was evaporated to obtain 1.9 g of intermediate product, with a yield of 98.5%. 1 H NMR (CDCl3, 400MHz) δ: 8.03 (s, 1H, pyridine-H), 6.98 (s, 1H, pyridine-H), 4.64 (s, 1H, -NH), 3.30 (s, 2H, -NH), 3.06 (d, J = 4.8Hz, 3H, -CH3). 19 F NMR (CDCl3, 376MHz) δ: -61.15.

[0110] Example 3: inter-3 synthesis

[0111] Intermediate inter-2 (1.91 g, 1 mmol) was dissolved in dichloroethane (30 mL), and 1.2 times the amount of triethylamine was added. Under ice bath conditions, dichloroethane (10 mL) was added dropwise to dissolve p-formylbenzoyl chloride (2.01 g, 1.2 mmol). The mixture was stirred overnight, and the reaction was monitored by TLC until it was complete. Sodium bicarbonate aqueous solution was added and stirred for 1 h. The lower layer of the solution was dried over MgSO4, filtered, and the solvent was evaporated. The intermediate product inter-3 (2.72 g) was purified by plate chromatography.

[0112] Example 4: Inter-4 Synthesis

[0113] Dissolve 2.72 g of inter-3 in 20 mL of acetic acid, heat under reflux and stir for 5 h. The reaction was monitored by TLC until it was complete. Water was added, and the mixture was extracted three times with EA. The product was dried over MgSO4 and purified by column chromatography to obtain 2.23 g of the intermediate product inter-5. 1 H NMR(CDCl3,400MHz)δ:10.15(s,1H,-CH),8.73(s,1H,pyridine-H),8.34(s,1H,pyridine-H),8.12-8.05(m,4H,Ph-H),4.08(s,3H,-CH3). 19 F NMR (CDCl3, 376MHz) δ: -60.21.

[0114] Example 5: Synthesis of target compound 99

[0115] Anhydrous ethanol (15 mL), 2.23 g of intermediate-4, and equimolar amounts of 1-amino-3-(2-isopropylphenyl)thiourea were added to a 50 mL round-bottom flask. After stirring and heating under reflux for 1 h, the solid in the flask was completely dissolved. The reaction was monitored by TLC until it was complete. After cooling, a solid was observed to precipitate. The solid was filtered and dried to obtain 3.11 g of solid. 1 H NMR(CDCl3,400MHz)δ:10.89(s,1H,-NH),9.06(s,1H,-NH),8.70(s,1H,-CH),8.31(s,1H,pyridine-H),8.12(s,1H,Ph-H),7.94-7.86(m,4H,Ph -H,pyridine-H),7.61(d,J=7.6Hz,1H,Ph-H),7.42-7.29(m,3H,Ph-H),4.06(s,3H,-CH3),3.24-3.17(m,1H,-CH),1.32(d,J=6.8Hz,6H,-CH3). 19 F NMR (CDCl3, 376MHz) δ: -60.17.

[0116] (II) Formulation

[0117] The following examples are prepared according to the mass ratio.

[0118] Example 6: 20% oil suspension

[0119]

[0120]

[0121] Compound 99 and other components are premixed evenly, then added to a sand mill for grinding. After filtration, a suspension mother liquor is obtained. Then, a prepared xanthan gum (0.1%) aqueous solution is added and sheared and mixed evenly.

[0122] Example 7: 30% aqueous suspension

[0123]

[0124] Compound 99, along with 80% of the required amount of water and sodium dodecyl sulfonate, was pulverized together in a ball mill. Hemicellulose and propylene oxide were dissolved in the remaining 20% ​​of water, and then the above components were added with stirring.

[0125] Example 8: 10% emulsifiable concentrate

[0126]

[0127] Phosphorous acid was dissolved in DMSO, compound 99 and ethoxylated triglyceride were added, and the mixture was heated and stirred to obtain a clear solution.

[0128] Example 9: 50% wettable powder

[0129]

[0130] Compound 99 sodium dodecyl naphthalene sulfonate, sodium lignosulfonate, and diatomaceous earth are mixed together and pulverized in a pulverizer until the particles meet the standard.

[0131] (III) Bioactivity Testing

[0132] Example 10: Insecticidal activity against armyworms

[0133] After thoroughly soaking an appropriate amount of corn leaves in the prepared pesticide solution, allow them to air dry naturally. Place them in a petri dish lined with filter paper, and inoculate 10 mid-3rd instar larvae per dish. Incubate the dish in an observation room at 24–27°C and investigate the results after 48 hours. Touch the insects with a paintbrush; if there is no reaction, the insects are considered dead.

[0134] The results showed that compounds 2,3,5,23,24,26,30,31,33,44,45,47,52,57,59,70,71,73,99,110,112 exhibited over 90% efficacy at the tested concentration of 50 mg / L.

[0135] Example 11: Insecticidal activity against diamondback moth

[0136] After thoroughly soaking a suitable amount of cabbage leaves in the prepared solution, allow them to air dry naturally. Place them in a petri dish lined with filter paper, and inoculate each dish with 10 mid-second instar larvae of the diamondback moth. Incubate the dish in an observation room at 24–27°C and examine the results after 48 hours. Touch the insects with a paintbrush; if there is no reaction, the insects are considered dead.

[0137] The results showed that compounds 2,3,5,23,24,26,30,31,33,44,45,47,52,57,59,70,71,73,99,110,112 exhibited a control efficacy of over 80% at the tested concentration of 50 mg / L.

[0138] Example 12: Comparative test of insecticidal activity against armyworms

[0139] After thoroughly soaking an appropriate amount of corn leaves in the prepared pesticide solution, allow them to air dry naturally. Place them in a petri dish lined with filter paper, and inoculate 10 mid-3rd instar larvae per dish. Incubate the dish in an observation room at 24–27°C and investigate the results after 48 hours. Touch the insects with a paintbrush; if there is no reaction, the insects are considered dead.

[0140] test compounds Concentration (mg / L) mortality rate(%) 23 0.5 90 24 0.5 83 26 0.5 75 99 0.5 70 110 0.5 80 112 0.5 84 P31 0.5 45 P32 0.5 40 P33 0.5 50 P34 0.5 55

Claims

1. A class of ureahydrazone derivatives, such as those of general formula (Ⅰ) In the formula: X, Y, Q, and M are independently selected from nitrogen, C-R5, where R5 can be selected from hydrogen, halogen, cyano, C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C3-C 10 cycloalkyl, C1-C 10 Alkoxyalkyl, C1-C 10 Haloalkoxyalkyl, C1-C 10 Alkyl thioalkyl, C1-C 10 Haloalkanes and thioalkyl groups; Z is independently selected from oxygen, sulfur, and NR4, where R4 can be selected from hydrogen, C1-C 10 Alkyl, C1-C 10 Halogenated alkyl groups; R3 is independently selected from hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C5 cycloalkyl, and C3-C5 substituted cycloalkyl; L and J are independently selected from nitrogen and CR6, where R6 can be selected from hydrogen, halogens, and C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C3-C 10 cycloalkyl; G is selected from oxygen and sulfur; G1 and G2 are independently selected from hydrogen, halogen, cyano, and C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, C3-C 10 Substituted cycloalkyl groups.

2. The ureahydrazone derivative represented by general formula (I) according to claim 1, characterized in that: In the general formula (I): X, Y, Q, and M are independently selected from nitrogen and C-R5, where R5 can be selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, C3-C5 cycloalkyl, C1-C5 alkoxyalkyl, C1-C5 haloalkoxyalkyl, C1-C5 alkylthioalkyl, and C1-C5 haloalkylthioalkyl. Z is independently selected from oxygen, sulfur, and N-R4, where R4 can be selected from hydrogen, C1-C5 alkyl, and C1-C5 haloalkyl; R3 is independently selected from hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C5 cycloalkyl, and C3-C5 substituted cycloalkyl; L and J are independently selected from nitrogen and C-R6, where R6 can be selected from hydrogen, halogen, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, and C3-C5 cycloalkyl. G is selected from oxygen and sulfur; G1 and G2 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 alkylthio, and C3-C5 substituted cycloalkyl.

3. The ureahydrazone derivative represented by general formula (I) according to claim 2, characterized in that: In the general formula (I): X, Y, Q, and M are independently selected from nitrogen and C-R5, where R5 can be selected from hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, C3-C5 cycloalkyl, C1-C3 alkoxyalkyl, C1-C3 haloalkoxyalkyl, C1-C3 alkylthioalkyl, and C1-C3 haloalkylthioalkyl. Z is independently selected from oxygen, sulfur, and N-R4, where R4 can be selected from hydrogen, C1-C3 alkyl, and C1-C3 haloalkyl; R3 is independently selected from hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, and C3-C5 substituted cycloalkyl; L and J are independently selected from nitrogen and C-R6, where R6 can be selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, and C3-C5 cycloalkyl. G is selected from oxygen and sulfur; G1 and G2 are independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 alkylthio, and C3-C5 substituted cycloalkyl.

4. The ureahydrazone derivative represented by general formula (I) according to claim 3, characterized in that: In the general formula (I): X, Y, Q, and M are independently selected from nitrogen and C-R5, where R5 can be selected from hydrogen, fluorine, chlorine, cyano, methyl, ethyl, isopropyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, methoxy, ethoxy, methylthio, ethylthio, trifluoromethylthio, cyclopropane, and C1-C3 alkoxyalkyl. Z is independently selected from oxygen, sulfur, and N-R4, where R4 can be selected from hydrogen, methyl, ethyl, and 2,2,2-trifluoroethyl; R3 is independently selected from hydrogen, trifluoromethyl, methyl, and ethyl. L and J are independently selected from nitrogen and C-R6, where R6 can be selected from hydrogen, fluorine, chlorine, methyl, trifluoromethyl, methoxy, and trifluoromethoxy. G is selected from oxygen and sulfur; G1 and G2 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, heptafluoroisopropyl, methoxy, ethoxy, trifluoromethoxy, methylthio, and trifluoromethylthio.

5. The ureahydrazone derivative of general formula (I) according to claim 4, characterized in that: The ureahydrazone derivatives are selected from at least one of the compounds shown in the following structures:

6. A ureahydrazone derivative according to any one of the general formula (I) of claims 1-5, characterized in that: The preparation method of the ureahydrazone derivative includes the following steps: Type 1: Z represents oxygen and sulfur. Type Two: In the formula: X, Y, Q, M, R5, R4, R3, L, J, G, G1, and G2 are defined as described in claims 1-4; the base is selected from organic bases and / or inorganic bases; the solvent is selected from at least one of dichloromethane, 1,2-dichloroethane, toluene, and tetrahydrofuran.

7. The application of the ureahydrazone derivatives represented by any one of the general formulas (I) according to claims 1-5, characterized in that: The ureahydrazone derivatives represented by general formula (I) are used for agricultural insecticides.

8. The application of the ureahydrazone derivatives represented by general formula (I) according to claim 7, characterized in that: The urea-hydrazone derivatives represented by general formula (I) are used to control at least one of the following pests: crop mites, lepidopterans, homoptera, hemiptera, coleopterans, or sanitary pests.

9. The application of the ureahydrazone derivatives represented by general formula (I) according to claim 8, characterized in that: The urea-hydrazone derivatives represented by general formula (I) are used to control at least one of the following pests: armyworm, diamondback moth, rice stem borer, rice leaf roller, aphid, and spider mite.

10. A pesticide formulation, characterized in that: The pesticide formulation contains 1 to 99% by weight of the urea-hydrazone derivative of any one of claims 1-5 as represented by general formula (I), with the remainder being an agriculturally acceptable carrier.

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