Amino-substituted pyrimidine triazole derivatives, and preparation method and application thereof

Abstract

The invention discloses an amino-substituted pyrimidine bitriazole derivative shown as a general formula (A), wherein each substituent group of # imgabs0 # is shown in the specification. The invention also discloses a preparation method and application of the amino-substituted pyrimidine bitriazole derivative. The amino-substituted pyrimidine bitriazole derivative is especially suitable for preventing and treating insect pests of crops.

Description

Technical Field

[0001] The present invention belongs to the field of agricultural insecticides, and particularly relates to a class of amino-substituted pyrimidine-linked triazole derivatives, a preparation method thereof, and applications thereof. Technical Background

[0002] Due to the long-term use of existing pesticide varieties, diseases have developed resistance to existing pesticide varieties. Therefore, there is a continuous need to discover new pesticide varieties with different action mechanisms. At the same time, with the excessive use of existing insecticides, greater pressure has been brought to the environment. Thus, there is a demand to discover new pesticide varieties that are more efficient, low-toxic, environmentally compatible, and have new action mechanisms.

[0003] In existing patents such as WO2017 / 192385, WO2019 / 170626, WO2019 / 215198, WO2019 / 197468, WO2019 / 201835, WO2019 / 202077, WO2019 / 206799, WO2020 / 002563, WO2020 / 053364, WO2020 / 053365, WO2020 / 079198, WO 2020 / 094363, WO2020 / 169445, WO2020 / 182649, WO2020 / 188014, WO2020 / 188027, WO2020 / 193341, WO2021 / 013719, WO2021 / 013720, CN115996639, etc., heteroaryl-triazole compounds for controlling crop pests in the field of plant protection are disclosed.

[0004] Among them, CN115996639 discloses compounds with the following structure

[0005]

[0006] Although the above patents disclose heteroaryl-triazole compounds, they do not disclose the amino-substituted pyrimidine-linked triazole derivatives of the present invention. Different linking structures make the compounds exhibit different spectra of action and biological activities. Summary of the Invention

[0007] To solve the above technical problems, the present invention provides amino-substituted pyrimidine-linked triazole derivatives represented by the following formula (A):

[0008]

[0009] Wherein:

[0010] R1 and R2 are independently selected from hydrogen, halogen, cyano, C1-C 10 alkyl, C1-C 10 haloalkyl, C1-C10 Cyano-substituted alkyl, C3-C 10 Cycloalkyl, C3-C 10 Halocycloalkyl, C3-C 10 Cyano-substituted cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy, C1-C 10 Alkylthio, C1-C 10 Halogenated alkylthio, C1-C 10 Alkylsulfinyl, C1-C 10 Alkylsulfonyl, C1-C 10 Cycloalkylsulfonyl, carboxylic acid C1-C 10 Alkyl ester, carboxylic acid C1-C 10 Halogenated alkyl ester;

[0011] M is independently selected from CH, N;

[0012] R3 is independently selected from hydrogen, halogen, C1-C5 alkyl, C1-C5 halogenated alkyl, C3-C5 cycloalkyl, C3-C5 substituted cycloalkyl;

[0013] R4 is independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 halogenated alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, C3-C5 substituted cycloalkyl;

[0014] R5 is independently selected from hydrogen, halogen, C1-C5 alkyl, C3-C5 substituted cycloalkyl, which is substituted by hydrogen, halogen, cyano, C1-C 10 Alkyl, C1-C 10 Halogenated alkyl, C1-C 10 Cyano-substituted alkyl, C3-C 10 Cycloalkyl, C3-C 10 Halocycloalkyl, C3-C 10 Cyano-substituted cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy, C1-C 10 Alkylthio, C1-C 10 Halogenated alkylthio;

[0015] R6 is independently selected from hydrogen, halogen, cyano, nitro, C1-C5 alkyl, C1-C 10 Halogenated alkyl, C1-C 10 Cyano-substituted alkyl;

[0016] Q can be selected from hydrogen, C1-C 10 alkyl, C1-C 10 haloalkyl, C3-C 10 cycloalkyl, C3-C 10 halocycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C1-C 10 alkoxyalkyl, C1-C 10 substituted alkoxyalkyl, C1-C 10 alkylthioalkyl, C1-C 10 substituted alkylthioalkyl, C1-C 10 substituted alkylsulfinylalkyl, C1-C 10 substituted alkylsulfonylalkyl, substituted aryl, substituted heteroaryl. When Q is substituted aryl or substituted heteroaryl, it can adopt one of the following structures:

[0017]

[0018] Wherein: G1, G2, G3, G4, G5 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C1-C 10 haloalkyl, C1-C 10 alkoxy, C1-C 10 substituted alkoxy, C1-C 10 alkylthio, C1-C 10 substituted alkylthio, C1-C 10 alkylsulfinyl, C1-C 10 alkylsulfonyl, carboxylate ester;

[0019] T1 is independently selected from hydrogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C1-C 10 alkenyl, C1-C 10 alkynyl, C1-C 10 haloalkyl;

[0020] T2 and T3 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C1-C 10 haloalkyl;

[0021] Preferably, R1 and R2 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 cyano-substituted alkyl, C3-C5 cycloalkyl, C3-C5 halocycloalkyl, C3-C5 cyano-substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl, C1-C5 cycloalkylsulfonyl, C1-C5 alkyl carboxylate, C1-C5 haloalkyl carboxylate;

[0022] M is independently selected from CH, N;

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

[0024] R4 is independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 alkylthio, C3-C5 substituted cycloalkyl;

[0025] R5 is independently selected from hydrogen, halogen, C1-C5 alkyl, C3-C5 substituted cycloalkyl, aryl and heteroaryl substituted by hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 cyano-substituted alkyl, C3-C5 cycloalkyl, C3-C5 halocycloalkyl, C3-C5 cyano-substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl, C1-C5 cycloalkylsulfonyl, C1-C5 alkyl carboxylate, C1-C5 haloalkyl carboxylate;

[0026] R6 is independently selected from hydrogen, halogen, cyano, nitro, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 cyano-substituted alkyl;

[0027] Q may be selected from hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C5 cycloalkyl, C3-C5 halocycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 alkoxyalkyl, C1-C5 substituted alkoxyalkyl, C1-C5 alkylthioalkyl, C1-C5 substituted alkylthioalkyl, C1-C5 substituted alkylsulfinylalkyl, C1-C5 substituted alkylsulfonylalkyl, substituted aryl, substituted heteroaryl. When Q is substituted aryl or substituted heteroaryl, it may adopt one of the following structures:

[0028]

[0029] Wherein: G1, G2, G3, G4, G5 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 substituted alkoxy, C1-C5 alkylthio, C1-C5 substituted alkylthio, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl, carboxylic acid ester;

[0030] T1 is independently selected from hydrogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 haloalkyl;

[0031] T2 and T3 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 haloalkyl;

[0032] Further preferably, R1 and R2 are independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cyano-substituted alkyl, C3-C5 cycloalkyl, C3-C5 haloalkyl, C3-C5 cyano-substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 cycloalkylsulfonyl, carboxylic acid C1-C3 alkyl ester, carboxylic acid C1-C3 haloalkyl ester;

[0033] M is independently selected from CH, N;

[0034] R3 is independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, C3-C5 substituted cycloalkyl;

[0035] R4 is independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 alkylthio, C3-C3 substituted cycloalkyl;

[0036] R5 is independently selected from hydrogen, halogen, C1-C3 alkyl, C3-C3 substituted cycloalkyl, aryl and heteroaryl substituted by hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cyano-substituted alkyl, C3-C5 cycloalkyl, C3-C5 haloalkyl, C3-C5 cyano-substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 cycloalkylsulfonyl, carboxylic acid C1-C3 alkyl ester, carboxylic acid C1-C3 haloalkyl ester;

[0037] R6 is independently selected from hydrogen, halogen, cyano, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cyano-substituted alkyl;

[0038] Q may be selected from hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, C3-C5 halocycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxyalkyl, C1-C3 substituted alkoxyalkyl, C1-C3 alkylthioalkyl, C1-C3 substituted alkylthioalkyl, C1-C3 substituted alkylsulfinylalkyl, C1-C3 substituted alkylsulfonylalkyl, substituted aryl, substituted heteroaryl. When Q is substituted aryl or substituted heteroaryl, it may adopt one of the following structures:

[0039]

[0040] wherein: G1, G2, G3, G4, G5 are independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C3-C5 substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 substituted alkoxy, C1-C3 alkylthio, C1-C3 substituted alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, carboxylic acid ester;

[0041] T1 is independently selected from hydrogen, cyano, C1-C3 alkyl, C3-C5 substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 haloalkyl;

[0042] T2 and T3 are independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C3-C5 substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 haloalkyl;

[0043] More preferably, R1 and R2 are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, trifluoromethyl, methylsulfonyl, isopropylsulfonyl, ethylsulfonyl, cyanocyclopropyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, cyclopropyl;

[0044] M is independently selected from CH, N;

[0045] R3 is independently selected from hydrogen, fluorine, methyl, ethyl, isopropyl, monofluoromethyl, trifluoromethyl, cyclopropyl;

[0046] R4 is independently selected from hydrogen, chlorine, fluorine, bromine, methyl, ethyl, methoxy, difluoromethyl, trifluoromethyl, cyclopropyl;

[0047] In the formula, R5 is independently selected from hydrogen, methyl, ethyl, cyclopropyl, and aryl and heteroaryl substituted by hydrogen, fluorine, chlorine, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methylsulfonyl;

[0048] R6 is independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl;

[0049] Q may be selected from hydrogen, methyl, ethyl, propyl, cyclopropyl, trifluoroethyl, difluoroethyl, cyanoethyl, substituted aryl, substituted heteroaryl. When Q is substituted aryl or substituted heteroaryl, one of the following structures may be selected:

[0050]

[0051] Wherein: G1, G2, G3, G4, G5 are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl, isopropyl, trifluoromethyl, methylsulfonyl, isopropylsulfonyl, ethylsulfonyl, cyanocyclopropyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, trifluoromethanesulfinyl, trifluoromethanesulfonyl, cyclopropyl;

[0052] T1 is independently selected from hydrogen, methyl, ethyl;

[0053] T2 and T3 are independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, difluoromethyl, trifluoromethyl, difluoromethoxy;

[0054] Most preferably, the amino-substituted pyrimidine-linked triazole derivative is selected from at least one of the following structures:

[0055]

[0056]

[0057] Some compounds in the general formula (A) of the present invention can be illustrated by the following table of specific compounds, but these specific compounds do not limit the present invention

[0058]

[0059] Wherein: R3 is methyl

[0060] Table 1

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] The NMR data of some compounds are as follows:

[0080] 179: 1 H NMR(CDCl3, 400 MHz) δ: 8.62 (d, J = 8.4 Hz, 1H, -NH), 8.55 (s, 1H, Py-H), 8.51 (s, 1H, -NH), 8.30 (s, 2H, Ph-H), 7.95 (s, 1H, Ph-H), 7.86 (s, 1H, Tr-H), 7.35 - 7.43 (m, 4H, Ph-H), 7.27 (s, 1H, Py-H), 7.22 (t, J = 7.2 Hz, 1H, Ph-H), 6.48 - 6.56 (m, 1H, -CH), 1.70 (d, J = 6.8 Hz, 3H, -CH3). 13 C NMR(DMSO-d6, 100 MHz) δ: 163.5, 162.4, 159.7, 158.5, 156.2, 151.8, 139.6, 136.3, 131.1 (q, J C-F = 34.3 Hz, -CF3), 129.3, 128.7, 124.9, 123.6, 122.1, 120.8, 110.5, 44.7, 19.4.

[0081] 619: 11H NMR (CDCl3, 400 MHz) δ: 8.62 (s, 1H, Py-H), 8.30 (s, 2H, Ph-H), 8.27 (s, 1H, -NH), 8.00 (s, 1H, -NH), 7.99 (s, 1H, Ph-H), 7.91 (s, 1H, Tr-H), 7.30 - 7.35 (m, 2H, Ph-H), 7.17 (d, J = 8.0 Hz, 1H, Ph-H), 7.16 (s, 1H, Py-H), 7.06 (d, J = 8.4 Hz, 1H, Ph-H), 6.45 - 6.52 (m, 1H, -CH), 2.39 (s, 3H, -CH3), 1.69 (d, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 162.5, 160.9, 159.6, 155.4, 151.5, 148.1, 143.1, 141.2, 140.9, 136.3, 130.7 (q, J C-F = 34.6 Hz, -CF3), 129.1, 125.5, 123.3, 122.2, 120.3, 116.5, 112.1, 48.7, 21.6, 14.6.

[0082] 620: 1 1H NMR (CDCl3, 400 MHz) δ: 8.60 (s, 1H, Py-H), 8.30 (d, J = 6.0 Hz, 1H, -NH), 8.30 (s, 2H, Ph-H), 7.99 (s, 1H, Ph-H), 7.89 (s, 1H, Tr-H, -NH), 7.34 - 7.40 (m, 4H, Ph-H), 7.19 (s, 1H, Py-H), 6.49 - 6.56 (m, 1H, -CH), 1.71 (d, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.5, 162.2, 159.7, 158.4, 156.2, 151.9, 138.7, 136.3, 131.0 (q, J C-F = 33.1 Hz, -CF3), 130.7, 129.1, 128.7, 127.0, 124.9, 122.1, 122.0, 110.0, 44.7, 19.4.

[0083] 621: 11H NMR (CDCl3, 400 MHz) δ: 8.72 (s, 1H, Py-H), 8.30 (s, 2H, Ph-H), 8.26 (s, J = 2.4 Hz, 1H, -NH), 8.24 (s, 1H, -NH), 7.96 (s, 1H, Ph-H), 7.92 (s, 1H, Tr-H), 7.62 (s, 1H, Ph-H), 7.35 (d, J = 8.4 Hz, 1H, Ph-H), 7.29 (s, 1H, Py-H), 7.08 (d, J = 8.4 Hz, 1H, Ph-H), 6.50 - 6.57 (m, 1H, -CH), 1.71 (d, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.6, 162.7, 159.6, 158.2, 156.6, 151.7, 136.9, 136.2, 132.0, 131.4, 131.0 (q, J C-F = 33.2 Hz, -CF3), 128.6, 126.2, 126.1, 126.0, 124.8, 122.0, 110.0, 44.7, 19.2.

[0084] 267: 1 1H NMR (CDCl3, 400 MHz) δ: 8.60 (s, 1H, Py-H), 8.29 (s, 2H, Ph-H), 8.26 (d, J = 8.4 Hz, 1H, -NH), 7.99 (s, 1H, Ph-H), 7.89 (s, 1H, Tr-H), 7.52 (s, 1H, -NH), 7.34 - 7.37 (m, 2H, Ph-H), 7.14 (s,1H,Py-H), 7.13 (t, J = 8.4 Hz, 1H, Ph-H). 6.45 - 6.52 (m, 1H, -CH), 1.70 (d, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.5, 163.0, 159.7, 158.3, 156.5, 154.1 (t, J C-F = 244.6 Hz, Ph-F), 151.8, 136.3, 131.0 (q, J C-F = 33.1 Hz, -CF3), 128.7, 126.6, 126.5, 126.0, 125.3, 125.0, 122.1, 116.2 (d, 2 J C-F = 19.2 Hz, Ph-F), 110.0, 44.7, 19.3.

[0085] 622: 11H NMR (DMSO-d6, 400 MHz) δ: 10.02 (s, 1H, Py-H), 9.58 (d, J = 6.4 Hz, 1H, -NH), 8.64 (s, 1H, -NH), 8.47 (s, 2H, Ph-H), 8.27 (s, 1H, Ph-H), 8.16 (s, 1H, Tr-H), 7.59 (s, 1H, Ph-H), 7.54 (d, J = 8.8 Hz, 1H, Ph-H), 7.35 (d, J = 8.8 Hz, 1H, Ph-H), 7.20 (s, 1H, Py-H), 6.19 - 6.26 (m, 1H, -CH), 2.30 (s, 3H, -CH3), 1.62 (d, J = 7.2 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.5, 162.2, 159.6, 158.4, 156.2, 151.8, 136.2, 136.1, 131.0 (q, J C-F = 33.1 Hz, -CF3), 129.4, 128.6, 127.4, 125.3, 124.8, 122.9, 122.1, 119.7, 110.0, 44.7, 20.2, 19.3.

[0086] 623: 1 1H NMR (DMSO-d6, 400 MHz) δ: 10.51 (s, 1H, Py-H), 9.58 (d, J = 7.2 Hz, 1H, -NH), 8.73 (s, 2H, Ph-H, -NH), 8.47 (s, 2H, Ph-H), 8.23 (s, 1H, Ph-H), 8.17 (s, 1H, Tr-H), 7.35 (d, J = 8.8 Hz, 1H, Ph-H), 7.96 (d, J = 8.8 Hz, 1H, Ph-H), 7.83 (d, J = 8.8 Hz, 1H, Ph-H), 7.58 (d, J = 8.0 Hz, 1H, Ph-H), 7.27 (s, 1H, Py-H), 6.20 - 6.26 (m, 1H, -CH), 1.63 (d, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.5, 162.0, 159.8, 158.4, 156.3, 151.9, 148.4, 141.0, 136.2, 131.0 (q, J C-F = 33.2 Hz, -CF3), 130.5, 128.7, 126.0, 124.8, 122.1, 117.4, 114.0, 97.0, 44.7, 19.3.

[0087] 624:1 1H NMR (in DMSO-d6, 400 MHz) δ: 9.81 (singlet, 1H, Py-H), 9.59 (doublet, J = 6.8 Hz, 1H, -NH), 8.59 (singlet, 1H, -NH), 8.48 (singlet, 2H, Ph-H), 8.27 (singlet, 1H, Ph-H), 8.14 (singlet, 1H, Tr-H), 7.33 (singlet, 1H, Ph-H), 7.14 (singlet, 1H, Py-H), 7.09 (doublet, J = 8.8 Hz, 1H, Ph-H), 6.20 - 6.27 (multiplet, 1H, -CH), 2.19 (singlet, 3H, -CH3), 2.17 (singlet, 3H, -CH3), 1.63 (doublet, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (in DMSO-d6, 100 MHz) δ: 163.5, 162.6, 159.6, 158.5, 156.2, 151.8, 137.9, 137.1, 136.3, 131.0 (quartet, J C-F = 33.2 Hz, -CF3), 130.2, 130.1, 128.7, 125.4, 124.9 122.4, 122.2, 118.8, 44.6, 20.0, 19.4, 19.2.

[0088] 626: 1 1H NMR (in DMSO-d6, 400 MHz) δ: 9.81 (singlet, 1H, Py-H), 9.59 (doublet, J = 6.8 Hz, 1H, -NH), 8.70 (singlet, 1H, -NH), 8.48 (singlet, 2H, Ph-H), 8.27 (singlet, 1H, Ph-H), 8.18 (singlet, 1H, Tr-H), 8.08 (singlet, 1H, Ph-H), 7.55 (doublet, J = 8.4 Hz, 1H, Ph-H), 7.29 (triplet, J = 8.0 Hz, 1H, Ph-H), 7.24 (singlet, 1H, Py-H), 7.22 (triplet, J = 8.0 Hz, 1H, Ph-H), 6.21 - 6.28 (multiplet, 1H, -CH), 1.64 (doublet, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (in DMSO-d6, 100 MHz) δ: 163.5, 162.1, 159.7, 158.5, 156.3, 151.9, 141.4, 136.3, 131.2, 131.1 (quartet, J C-F = 33.1 Hz, -CF3), 128.7, 125.8, 125.5, 125.4 124.8, 122.6, 122.1, 119.1, 96.6, 44.7, 19.4.

[0089] 625:1 1H NMR (in DMSO-d6, 400 MHz) δ: 10.11 (singlet, 1H, Py-H), 9.59 (doublet, J = 7.2 Hz, 1H, -NH), 8.66 (singlet, 1H, -NH), 8.48 (singlet, 2H, Ph-H), 8.29 (singlet, 1H, Ph-H), 8.17 (singlet, 1H, Tr-H), 7.65 (doublet, J = 8.8 Hz, 2H, Ph-H), 7.51 (doublet, J = 8.8 Hz, 2H, Ph-H), 7.23 (singlet, 1H, Py-H), 6.20 - 6.27 (multiplet, 1H, -CH), 1.63 (doublet, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (in DMSO-d6, 100 MHz) δ: 163.5, 162.1, 159.7, 158.4, 156.2, 151.9, 139.1, 136.3, 132.0, 131.0 (quartet, J C-F = 33.1 Hz, -CF3), 128.7, 125.5, 124.9, 122.4, 122.1 115.0, 44.7, 19.4.

[0090] 627: 1 1H NMR (in DMSO-d6, 400 MHz) δ: 10.15 (singlet, 1H, Py-H), 9.59 (doublet, J = 6.8 Hz, 1H, -NH), 8.70 (singlet, 1H, -NH), 8.48 (singlet, 2H, Ph-H), 8.25 (singlet, 1H, Ph-H), 8.17 (singlet, 1H, Tr-H), 7.95 (singlet, 1H, Ph-H), 7.49 (doublet, J = 8.8 Hz, 1H, Ph-H), 7.34 (triplet, J = 8.8 Hz, 2H, Ph-H), 7.25 (singlet, 1H, Py-H), 7.07 (doublet, J = 8.8 Hz, 1H, Ph-H), 6.21 - 6.28 (multiplet, 1H, -CH), 1.65 (doublet, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (in DMSO-d6, 100 MHz) δ: 163.5, 162.1, 159.7, 158.4, 156.3, 151.9, 141.2, 136.3, 133.6, 131.0 (quartet, J C-F = 33.2 Hz, -CF3), 130.8, 128.7, 124.9, 122.8, 122.1 119.7, 118.7, 96.6, 44.7, 19.4.

[0091] 628: 11H NMR (DMSO-d6, 400 MHz) δ: 9.73 (s, 1H, Py-H), 9.58 (d, J = 6.8 Hz, 1H, -NH), 8.53 (s, 1H, -NH), 8.48 (s, 2H, Ph-H), 8.29 (s, 1H, Ph-H), 8.16 (s, 1H, Tr-H), 7.95 (s, 1H, Ph-H), 7.49 (d, J = 8.8 Hz, 1H, Ph-H), 7.34 - 7.42 (m, 1H, Ph-H), 7.21 (t, J = 8.0 Hz, 1H, Ph-H), 7.13 (s, 1H, Py-H), 6.18 - 6.25 (m, 1H, -CH), 1.62 (d, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.5, 163.3, 159.8, 158.5, 157.2 (d, J C-F = 5.0 Hz, Ph-F), 156.6, 151.9, 136.2, 131.1 (q, J C-F = 33.2 Hz, -CF3), 128.7, 125.5, 124.9, 122.1, 115.3, 112.7, 112.4, 44.7, 19.3.

[0092] 629: 1 1H NMR (DMSO-d6, 400 MHz) δ: 9.93 (s, 1H, Py-H), 9.59 (d, J = 6.8 Hz, 1H, -NH), 8.62 (s, 1H, -NH), 8.49 (s, 2H, Ph-H), 8.24 (s, 1H, Ph-H), 8.15 (s, 1H, Tr-H), 7.51 (d, J = 7.6 Hz, 1H, Ph-H), 7.42 (s, 2H, Ph-H), 7.24 (t, J = 7.6 Hz, 1H, Ph-H), 7.21 (s, 1H, Py-H), 6.92 (t, J = 8.0 Hz, 1H, Ph-H), 6.22 - 6.29 (m, 1H, -CH), 2.80 - 2.87 (m, 1H, -CH), 1.64 (d, J = 7.2 Hz, 3H, -CH3), 1.18 (s, 3H, -CH3), 1.16 (s, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.5, 162.5, 159.7, 158.5, 156.2, 151.8, 149.6, 139.5, 136.3, 131.1 (q, J C-F= 34.9 Hz, -CF3), 129.2, 128.7, 125.3, 124.8, 122.1, 121.7, 118.9, 118.6, 44.7, 33.9, 24.2, 19.4.

[0093] 632: 1 1H NMR (DMSO-d6, 400 MHz) δ: 9.90 (s, 1H, Py-H), 9.58 (d, J = 7.2 Hz, 1H, -NH), 8.59 (s, 1H, -NH), 8.48 (s, 2H, Ph-H), 8.28 (s, 1H, Ph-H), 8.15 (s, 1H, Tr-H), 7.50 (d, J = 8.0 Hz, 1H, Ph-H), 7.18 (d, J = 7.6 Hz, 1H, Ph-H), 7.16 (s, 1H, Py-H), 6.20 - 6.27 (m, 1H, -CH), 2.55 (q, J = 7.6 Hz, 2H, -CH2), 1.63 (d, J = 7.2 Hz, 3H, -CH3), 1.15 (t, J = 7.6 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.5, 162.5, 159.6, 158.5, 156.2, 151.8, 137.1, 136.3, 135.4, 131.0 (q, J C-F = 34.1 Hz, -CF3), 128.7, 128.6, 125.5, 124.9, 122.2, 121.2, 44.6, 28.1, 19.4, 16.1.

[0094] 487: 1 1H NMR (DMSO-d6, 400 MHz) δ: 10.28 (s, 1H, Py-H), 9.58 (d, J = 6.8 Hz, 1H, -NH), 8.70 (s, 1H, -NH), 8.47 (s, 2H, Ph-H), 8.24 (s, 1H, Ph-H), 8.18 (s, 1H, Tr-H), 8.16 (s, 1H, Ph-H), 7.86 (d, J = 8.8 Hz, 1H, Ph-H), 7.55 (t, J = 8.0 Hz, 1H, Ph-H), 7.35 (d, J = 8.0 Hz, 1H, Ph-H), 7.16 (s, 1H, Py-H), 6.20 - 6.26 (m, 1H, -CH), 1.63 (d, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.5, 162.2, 159.7, 158.4, 156.3, 151.9, 140.6, 136.3, 131.0 (q, JC-F = 32.9 Hz, -CF3), 130.7 (q, J C-F = 30.3 Hz, -CF3), 129.8, 128.7, 125.4, 124.8, 123.8, 122.1, 119.4, 116.3, 96.8, 44.7, 19.4.

[0095] 630: 1 1H NMR (DMSO-d6, 400 MHz) δ: 9.66 (s, 1H, Py-H), 9.59 (d, J = 6.8 Hz, 1H, -NH), 8.52 (s, 1H, -NH), 8.49 (s, 2H, Ph-H), 8.25 (s, 1H, Ph-H), 8.13 (s, 1H, Tr-H), 7.37 (d, J = 8.0 Hz, 1H, Ph-H), 7.31 (t, J = 8.0 Hz, 1H, Ph-H), 7.22 (t, J = 8.0 Hz, 1H, Ph-H), 7.03 (s, 1H, Py-H), 6.20 - 6.27 (m, 1H, -CH), 2.21 (s, 3H, -CH3), 1.63 (d, J = 6.8 Hz, 3H, -CH3). 13 13C NMR (DMSO-d6, 100 MHz) δ: 163.5, 163.4, 159.7, 158.5, 156.5, 151.8, 138.5, 136.3, 134.6, 132.0, 131.0 (q, J C-F = 33.1 Hz, -CF3), 128.7, 127.6, 127.0, 125.5, 124.8, 122.1, 44.7, 19.4, 15.5.

[0096] 631: 1 1H NMR (DMSO-d6, 400 MHz) δ: 9.79 (s, 1H, Py-H), 9.58 (d, J = 7.2 Hz, 1H, -NH), 8.56 (s, 1H, -NH), 8.48 (s, 2H, Ph-H), 8.27 (s, 1H, Ph-H), 8.13 (s, 1H, Tr-H), 7.46 (s, 2H, Ph-H), 7.08 (s, 1H, Py-H), 6.90 (d, J = 8.8 Hz, 1H, Ph-H), 6.20 - 6.27 (m, 1H, -CH), 3.97 (q, J = 7.2 Hz, 2H, -CH2), 1.62 (d, J = 6.8 Hz, 3H, -CH3), 1.29 (t, J = 7.2 Hz, 3H, -CH3). 1313C NMR (DMSO-d6, 100 MHz) δ: 163.5, 159.6, 158.5, 156.2, 154.1, 151.7, 136.3, 131.1, 131.0 (q, J C-F = 33.2 Hz, -CF3), 128.7, 127.6, 125.5, 124.9, 122.1, 119.4, 115.1, 63.6, 44.6, 19.4, 15.1.

[0097] 1H NMR (DMSO-d6, 400 MHz) δ: 10.01 (s, 1H, Py-H), 9.39 (d, J = 7.2 Hz, 1H, -NH), 8.66 (s, 1H, -NH), 8.27 (s, 2H, Ph-H), 8.12 (s, 1H, Ph-H), 8.07 (s, 1H, Tr-H), 7.17 (s, 1H, Py-H), 6.15 - 6.27 (m, 1H, -CH), 2.91 (s, 3H, -NCH3), 1.63 (d, J = 6.8 Hz, 3H, -CH3).

[0098] The present invention also provides a preparation method of the above-mentioned amino-substituted pyrimidine-linked triazole derivatives, and the preparation method includes the following steps

[0099] Preparation method one:

[0100]

[0101] Wherein R1, R2, M, R3, R4, R5, R6, Q are the same as described above, X is selected from chlorine, bromine, iodine, and R7 is selected from methyl, ethyl, isopropyl, 2,2,2-trifluoroethyl, 2,2,2-difluoroethyl.

[0102] Preparation method two:

[0103]

[0104] Wherein R1, R2, M, R3, R4, R5, R6, Q are the same as described above, X is selected from chlorine, bromine, iodine, and R7 is selected from methyl, ethyl, isopropyl, 2,2,2-trifluoroethyl, 2,2,2-difluoroethyl.

[0105] Preparation method three:

[0106]

[0107] Wherein R1, R2, M, R3, R4, R5, R6, Q are the same as described above, X is selected from chlorine, bromine, iodine, and R7 is selected from methyl, ethyl, isopropyl, 2,2,2-trifluoroethyl, 2,2,2-difluoroethyl.

[0108] The present invention also provides the use of any of the above-mentioned amino-substituted pyrimidine-linked triazole derivatives, which are used for agricultural insecticidal purposes, particularly suitable for controlling crop mites, Lepidoptera, Homoptera, Hemiptera, Coleoptera, and hygienic pests. When used for formulating agricultural chemical insecticides, the mass percentage content of the amino-substituted pyrimidine-linked triazole derivatives of the present invention in the insecticide is 1-99%, and can be formulated into various liquid agents, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, water-in-oil emulsions, powders, wettable powders, soluble powders, granules, water-dispersible granules or capsules. The carriers include at least two kinds, and at least one of them is a surfactant. The carriers can be solid or liquid. Suitable solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicate such as talc; magnesium aluminum silicate such as kaolinite, kaolin, montmorillonite and mica; silica white, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylenediamine. Liquid carriers include water and organic solvents. When water is used as a solvent or diluent, organic solvents can also be used as adjuvants or antifreeze additives. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, etc.; chlorinated hydrocarbons, such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, etc.; aliphatic hydrocarbons, such as petroleum fractions, cyclohexane, light mineral oil; alcohols, such as isopropanol, butanol, ethylene glycol, glycerol and cyclohexanol, etc.; and their ethers and esters; and ketones, such as acetone, cyclohexanone, as well as dimethylformamide and N-methyl-pyrrolidone.

[0109] The surfactant can be an emulsifier, a dispersant or a wetting agent; it can be ionic or non-ionic. Non-ionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amines, and commercially available emulsifiers: agricultural emulsion 2201B, agricultural emulsion 0203B, agricultural emulsion 100 # , agricultural emulsion 500 # , agricultural emulsion 600 # , agricultural emulsion 600-2 # , agricultural emulsion 1601, agricultural emulsion 2201, agricultural emulsion NP-10, agricultural emulsion NP-15, agricultural emulsion 507 # , agricultural emulsion OX-635, agricultural emulsion OX-622, agricultural emulsion OX-653, agricultural emulsion OX-667, Ning emulsion 36 # . Dispersants include sodium lignosulfonate, Nekal, calcium lignosulfonate, methylnaphthalenesulfonic acid formaldehyde condensate, etc. Wetting agents are: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonate, etc.

[0110] These preparations can be prepared by general methods. For example, the active substance is mixed with a liquid solvent and / or a solid carrier, and at the same time, surfactants such as emulsifiers, dispersants, stabilizers, wetting agents are added, and other auxiliaries such as adhesives, defoamers, oxidants, etc. can also be added.

[0111] Compared with the prior art, the amino-substituted pyrimidine bi-triazole derivatives represented by the general formula (A) provided by the present invention have the following advantages:

[0112] The amino-substituted pyrimidine bi-triazole derivatives of the present invention have high insecticidal activity. At a concentration of 150 ppm, the control effect on pests such as Mythimna separata and Plutella xylostella is greater than 85%, and for some compounds, the control effect on Tetranychus cinnabarinus is greater than 75% at a concentration of 200 ppm. Detailed implementation manners

[0113] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to these specific implementation manners. Those skilled in the art should recognize that the present invention covers all alternative solutions, improvement solutions, and equivalent solutions that may be included within the scope of the claims.

[0114] (1) Compound preparation:

[0115] Synthesis of amino-substituted pyrimidine hydrazine:

[0116]

[0117] Example 1: Synthesis of 4-methylamino-6-hydrazinylpyrimidine

[0118] Dissolve 0.1 mol of 4,6-dichloropyrimidine in 50 mL of dimethyl sulfoxide. Add 3 times the molar mass of aqueous methylamine at room temperature, stir the reaction at room temperature for 5 h, monitor the reaction by thin-layer chromatography. After the reaction is complete, pour the reaction system into 200 mL of saturated brine, extract twice with 100 mL of ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate, evaporate the solvent, and use the product directly in the next step without purification; dissolve the above-obtained product in 100 mL of ethanol, then add 0.2 mL of 80% hydrazine hydrate to the system, heat under reflux for 6 h, monitor the reaction to completion by analysis, evaporate the solvent, add 50 mL of water to the residue, and filter to obtain a white solid.

[0119] Example 2: Synthesis of 4-phenylamino-6-hydrazinylpyrimidine

[0120] Dissolve 0.03 mol of 4,6-dichloropyrimidine in 40 mL of ethanol, add 0.04 mol of aniline to the solution, then dropwise add 0.5 mL of concentrated hydrochloric acid, and heat under reflux for 5 h. After the reaction is completed, evaporate the solvent by rotary evaporation, wash with NaHCO3 solution multiple times, and then extract with ethyl acetate (3 × 20 mL), dry and evaporate the ethyl acetate by rotary evaporation. Column chromatography separation (eluent is ethyl acetate and petroleum ether) to obtain a white solid. 11H NMR (CDCl3, 400 MHz) δ: 8.43 (s, 1H, Py-H), 7.64 (s, 1H, -NH), 7.44 (t, J = 7.6 Hz, 2H, Ph-H), 7.30 (t, J = 7.6 Hz, 2H, Ph-H), 7.22 (t, J = 7.2 Hz, 1H, Ph-H), 6.70 (s, 1H, Py-H).

[0121] Synthesis of the target compound:

[0122]

[0123] Example 3: Synthesis of Intermediate WU-1

[0124] Dissolve 3,5-trifluoromethylbenzoic acid (46.35 g, 0.18 mol) in dichloromethane (80 mL). Add 30 mL of SOCl2 under an ice-water bath, protect it from moisture, absorb the tail gas, and heat under reflux for 3 h. After the reaction is completed, distill it under reduced pressure to obtain the colorless liquid Intermediate WU-1.

[0125] Example 4: Synthesis of Intermediate WU-2

[0126] At 0 °C, add 2-aminopropionamide (1.33 g, 10.70 mmol) to a solution of Intermediate WU-1 (1.65 g, 6.00 mmol) and 1 mL of triethylamine in dichloromethane (20 mL). Stir the reaction mixture at room temperature for 16 h. After the reaction is completed, remove the solvent to obtain the white solid Intermediate WU-2. 1 1H NMR (DMSO-d6, 400 MHz) δ: 9.04 (d, J = 7.2 Hz, 1H, -NH), 8.53 (s, 2H, Ph-H), 8.27 (s, 1H, Ph-H), 7.49 (s, 1H, -NH2), 7.02 (s, 1H, -NH2), 4.38 - 4.46 (m, 1H, -CH), 1.34 (d, J = 7.2 Hz, 3H, -CH3).

[0127] Example 5: Synthesis of Intermediate WU-3

[0128] Add Intermediate WU-2 (0.85 g, 2.60 mmol) to dichloromethane (10 mL) to form a white suspension. At room temperature, add N,N-dimethylformamide dimethyl acetal (0.55 g, 4.60 mmol), and the solution turns yellow. Heat under reflux for 2 h. When the reaction is completed as detected by TLC and the solution becomes a yellow clear solution; rotary evaporate to remove the solvent to obtain a yellow oily substance, which solidifies at room temperature to obtain the crude yellow solid Intermediate WU-3. 11H NMR (DMSO-d6, 400 MHz) δ: 9.04 (d, J = 7.6 Hz, 1H, -NH), 8.52 (s, 2H, Ph-H), 8.39 (s, 1H, -CH), 8.27 (s, 1H, Ph-H), 4.48 - 4.55 (m, 1H, -CH), 3.11 (s, 3H, -CH3), 1.34 (s, 3H, -CH3), 1.38 (d, J = 7.2 Hz, 3H, -CH3).

[0129] Example 6: Synthesis of Target Compound 179

[0130] Add glacial acetic acid (10 mL) and 1,2-dioxane (10 mL) to intermediate 4-phenylamino-6-hydrazinylpyrimidine (0.21 g, 1.00 mmol) and intermediate WU-3 (0.39 g, 1.00 mmol), heat and stir under reflux for 7 h. After detecting the end of the reaction by TLC, remove the solvent by rotary evaporation, wash it with NaHCO3 multiple times, extract it with ethyl acetate (3×20 mL), dry and filter, and then remove the ethyl acetate by rotary evaporation. Separate by column chromatography (ethyl acetate and petroleum ether) to obtain a white solid.

[0131] Example 7: Synthesis of Target Compound 1

[0132] Add glacial acetic acid (10 mL) and 1,2-dioxane (10 mL) to intermediate 4-methylamino-6-hydrazinylpyrimidine (0.14 g, 1.00 mmol) and intermediate WU-3 (0.39 g, 1.00 mmol), heat and stir under reflux for 7 h. After detecting the end of the reaction by TLC, remove the solvent by rotary evaporation, wash it with NaHCO3 multiple times, extract it with ethyl acetate (3×20 mL), dry and filter, and then remove the ethyl acetate by rotary evaporation. Separate by column chromatography (ethyl acetate and petroleum ether) to obtain a white solid.

[0133]

[0134] Example 8: Synthesis of Intermediate XU-2

[0135] Dissolve 0.05 mol of XU-1 in 100 mL of dichloroethane, stir and add 20 mL of thionyl chloride, stir at room temperature for 1 h, heat the reaction system to reflux for 5 h, analyze that the reaction is complete, distill off the solvent under reduced pressure, and directly use the residue for the next reaction without purification. Add 150 mL of dichloromethane and 0.075 mol of triethylamine to the system, cool the reaction system with ice water, and then add 0.062 mol of intermediate M in batches over 0.5 h. Continue the reaction for 1 h under cooling, and then react at room temperature for 3 h. Analyze that the reaction is complete, add 100 ml of saturated brine to the system, separate the organic phase, dry the organic phase with anhydrous sodium sulfate, distill off the solvent, and separate by column chromatography to obtain a solid.

[0136] Example 9: Synthesis of Intermediate XU-3

[0137] Dissolve 0.03 mol of XU-2 in 50 mL of acetic acid, add an equimolar amount of 4-methylamino-6-hydrazinylpyrimidine, heat under reflux for 4.5 h. After analyzing that the reaction is complete, distill off the solvent under reduced pressure, and obtain a white solid by column chromatography.

[0138] Example 10: Synthesis of Intermediate XU-4

[0139] Dissolve 0.02 mol of Intermediate XU-3 in 60 mL of ethanol, then add 0.04 mol of hydrazine hydrate. Heat the system under reflux for 5 h. After analyzing that the reaction is complete, cool to room temperature, filter, distill off the solvent from the filtrate under reduced pressure, and obtain a solid by column chromatography.

[0140] Example 11: Synthesis of Intermediate XU-5

[0141] Dissolve 0.015 mol of Intermediate XU-4 in 50 mL of dichloromethane, add 1.5 times the amount of triethylamine, cool with ice, and slowly add a 20 mL dichloromethane solution of 0.01 mol of 3,5-bis(trifluoromethyl)benzoyl chloride dropwise. The addition is completed in 0.5 h, and the reaction is carried out at room temperature for 4 h. After analyzing that it is complete, add 50 mL of saturated brine, separate the organic phase, dry it over anhydrous sodium sulfate, and separate the product by column chromatography to obtain a white solid.

[0142] Example 12: Synthesis of Intermediate XU-7

[0143] Dissolve 0.01 mol of Intermediate XU-5 in 50 mL of dichloromethane, add 5 mL of trifluoroacetic acid, heat under reflux for 1 h. After analyzing that the reaction is complete, distill off the solvent, neutralize it to neutral with saturated NaHCO3, extract with dichloromethane, dry the organic phase over anhydrous sodium sulfate, distill off the solvent, and use it directly in the next step without purification.

[0144] Example 13: Synthesis of Target Compound 5

[0145] Add 0.005 mol of XU-7 to 30 mL of acetonitrile, add 0.010 mol of anhydrous copper chloride, and then add 0.015 mol of propyl nitrite dropwise within 1 h. React the reaction system at 50 °C for 3 h. After analyzing that the reaction is complete, cool to room temperature, add 100 mL of water, extract twice with 50 mL of ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate, distill off the solvent, and obtain the target product by column chromatography of the residue.

[0146] (II) Formulation Preparation

[0147] The following examples are prepared according to mass ratios.

[0148] Example 14: 20% Oil Suspension Concentrate

[0149]

[0150] Compound 1 and other components are fully mixed. The resulting suspending agent can be diluted with water to obtain a dilution of any desired concentration.

[0151] Example 15: 30% aqueous suspension

[0152]

[0153] All the above components (except 0.1% xanthan gum) are premixed in a shear mixer, then added to a sand mill and ground to the desired particle size. After filtration, the mother suspension is obtained, and then the prepared 0.1% aqueous xanthan gum solution is added and sheared and mixed evenly.

[0154] Example 16: 10% emulsifiable concentrate

[0155]

[0156] Phosphorous acid is dissolved in DMSO, and compound 1 and ethoxylated triglyceride are added. After heating and stirring, a transparent solution is obtained.

[0157] Example 17: 50% wettable powder

[0158]

[0159]

[0160] Compound 1, sodium dodecylnaphthalenesulfonate, sodium lignosulfonate and diatomaceous earth are mixed together and ground in a pulverizer until the particles reach the standard.

[0161] (III) Biological activity test

[0162] Example 18, Insecticidal activity against Mythimna separata

[0163] An appropriate amount of corn leaves are fully soaked in the prepared liquid medicine and then air-dried naturally. They are placed in a petri dish lined with filter paper, and 10 mid-instar larvae of Mythimna separata are inoculated per dish. They are cultured in an observation room at 24 - 27°C, and the results are investigated after 48 h. Using a writing brush to touch the insect body, those with no response are regarded as dead insects.

[0164] The results showed that compounds 1, 2, 4, 5, 10, 18, 26, 30, 34, 38, 42, 90, 92, 93, 94, 135, 137, 138, 139, 179, 181, 182, 183, 223, 225, 227, 226, 267, 355, 443, 487, 619, 620, 621, 622, 623, 624, 625, 626, 627, 628, 629, 630, 631, 632, 633, 635 showed a control efficacy of over 90% at the test concentration of 150 mg / L.

[0165] Example 19, Insecticidal Activity Against Plutella xylostella

[0166] Appropriately amount of Chinese cabbage leaves were fully soaked in the prepared liquid medicine and then air-dried naturally. They were placed in a petri dish lined with filter paper, and 10 mid-second-instar larvae of Plutella xylostella were inoculated per dish. The dish was placed in an observation chamber at 24 - 27 °C for cultivation. The results were investigated after 48 h. When the body of the insect was touched with a writing brush and showed no reaction, it was regarded as a dead insect.

[0167] The results showed that compounds 1, 2, 4, 5, 10, 18, 26, 30, 34, 38, 42, 90, 92, 93, 94, 135, 137, 138, 139, 179,, 181, 182, 183, 223, 225, 227, 226, 267, 355, 443, 487, 619, 620, 621, 622, 623, 624, 625, 626, 627, 628, 629, 630, 631, 632, 633, 635 showed a control efficacy of over 85% at the test concentration of 250 mg / L.

[0168] Example 20, Insecticidal Activity Against Aphis medicaginis

[0169] The broad bean leaf seedlings with Aphis medicaginis were spray-treated under a Potter spray tower. After treatment, the Aphis medicaginis were placed in an observation chamber at 20 - 22 °C for cultivation. The results were investigated after 48 h. When the body of the insect was touched with a writing brush and showed no reaction, it was regarded as a dead insect.

[0170] The results showed that compounds 1, 2, 4, 5, 10, 18, 26, 30, 34, 38, 42, 90, 92, 93, 94, 135, 137, 138, 139, 179, 181, 182, 183, 223, 225, 227, 226, 267, 355, 443, 487, 619, 620, 621, 622, 623, 624, 625, 626, 627, 628, 629, 630, 631, 632, 633, 635 showed a control efficacy of over 90% at the test concentration of 150 mg / L.

[0171] Example 21, Insecticidal Activity Against Nilaparvata lugens

[0172] The rice plants were sprayed with the active ingredient preparation at the required concentration and then infested with Nilaparvata lugens. Four days later, the control efficacy was investigated.

[0173] In this test, Compounds 1, 2, 4, 5, 10, 18, 26, 30, 34, 38, 42, 90, 92, 93, 94, 135, 137, 138, 139, 179, 181, 182, 183, 223, 225, 227, 226, 267, 355, 443, 487, 619, 620, 621, 622, 623, 624, 625, 626, 627, 628, 629, 630, 631, 632, 633, 635 showed a control efficacy of over 90% at the test concentration of 500 mg / L.

[0174] Example 22, Insecticidal Activity Against Spodoptera frugiperda

[0175] The leaf surface part of corn was sprayed with the active ingredient preparation at the required concentration. After drying, the leaf surface part was infested with Spodoptera frugiperda. Seven days later, the control efficacy was investigated.

[0176] In this test, Compounds 1, 2, 4, 5, 10, 18, 26, 30, 34, 38, 42, 90, 92, 93, 94, 135, 137, 138, 139, 179, 181, 182, 183, 223, 225, 227, 226, 267, 355, 443, 487, 619, 620, 621, 622, 623, 624, 625, 626, 627, 628, 629, 630, 631, 632, 633, 635 showed a control efficacy of over 85% at the test concentration of 250 mg / L.

[0177] Example 23, Determination of Activity Against Tetranychus cinnabarinus Adult Mites

[0178] According to the solubility of the compound to be tested, the original drug was dissolved in N, N-dimethylformamide and then formulated into the test solution with the required concentration using an aqueous solution containing 1‰ Tween 80. The content of N, N-dimethylformamide in the solution did not exceed 10%. After taking two true leaf kidney bean seedlings, inoculating Tetranychus cinnabarinus adult mites and investigating the base number, the whole plant was sprayed with a hand-held sprayer. Each treatment had 3 replicates. After treatment, it was placed in a standard observation room. After 48 h, the number of surviving mites was investigated and the mortality rate was calculated.

[0179] In this test, Compounds 1, 2, 4, 5, 10, 18, 26, 30, 34, 38, 42, 90, 92, 93, 94, 135, 137, 138, 139, 179, 181, 182, 183, 223, 225, 227, 226, 267, 355, 443, 487, 619, 620, 621, 622, 623, 624, 625, 626, 627, 628, 629, 630, 631, 632, 633, 635 showed a control efficacy of over 75% at the test concentration of 200 mg / L. However, the compounds disclosed in Patent CN115996639 did not show activity against Tetranychus cinnabarinus.

Claims

1. A class of amino-substituted pyrimidine-linked triazole derivatives, such as general formula (A) Wherein: R1 and R2 are independently selected from hydrogen, halogen, cyano, C1-C 10 alkyl, C1-C 10 haloalkyl, C1-C 10 cyano-substituted alkyl, C3-C 10 cycloalkyl, C3-C 10 halocycloalkyl, C3-C 10 cyano-substituted cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C1-C 10 alkoxy, C1-C 10 haloalkoxy, C1-C 10 alkylthio, C1-C 10 haloalkylthio, C1-C 10 alkylsulfinyl, C1-C 10 alkylsulfonyl, C1-C 10 cycloalkylsulfonyl, C1-C carboxylic acid 10 alkyl ester, C1-C carboxylic acid 10 haloalkyl ester; M is independently selected from CH, N; R3 is independently selected from hydrogen, halogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C5 cycloalkyl, C3-C5 substituted cycloalkyl; R4 is independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C 10 alkoxy, C1-C 10 alkylthio, C3-C5 substituted cycloalkyl; R5 is independently selected from hydrogen, halogen, C1-C5 alkyl, C3-C5 substituted cycloalkyl, which is substituted by hydrogen, halogen, cyano, C1-C 10 alkyl, C1-C 10 haloalkyl, C1-C 10 cyano-substituted alkyl, C3-C 10 cycloalkyl, C3-C 10 halocycloalkyl, C3-C 10 cyano-substituted cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C1-C 10 alkoxy, C1-C 10 haloalkoxy, C1-C 10 alkylthio, C1-C 10 haloalkylthio; R6 is independently selected from hydrogen, halogen, cyano, nitro, C1-C5 alkyl, C1-C 10 haloalkyl, C1-C 10 cyano-substituted alkyl; Q can be selected from hydrogen, C1-C 10 alkyl, C1-C 10 haloalkyl, C3-C 10 cycloalkyl, C3-C 10 halocycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C1-C 10 alkoxyalkyl, C1-C 10 substituted alkoxyalkyl, C1-C 10 alkylthioalkyl, C1-C 10 substituted alkylthioalkyl, C1-C 10 substituted alkylsulfinylalkyl, C1-C 10 substituted alkylsulfonylalkyl, substituted aryl, substituted heteroaryl. When Q is substituted aryl or substituted heteroaryl, one of the following structures can be selected: Wherein: G1, G2, G3, G4, G5 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C1-C 10 haloalkyl, C1-C 10 alkoxy, C1-C 10 substituted alkoxy, C1-C 10 alkylthio, C1-C 10 substituted alkylthio, C1-C 10 alkylsulfinyl, C1-C 10 alkylsulfonyl, carboxylate ester; T1 is independently selected from hydrogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C1-C 10 alkenyl, C1-C 10 alkynyl, C1-C 10 haloalkyl; T2 and T3 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C 10 alkenyl, C2-C 10 alkynyl, C1-C 10 haloalkyl.

2. The amino-substituted pyrimidine-linked triazole derivative according to claim 1, characterized in that: R1 and R2 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 cyano-substituted alkyl, C3-C5 cycloalkyl, C3-C5 halocycloalkyl, C3-C5 cyano-substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl, C1-C5 cycloalkylsulfonyl, C1-C5 alkyl carboxylate, C1-C5 haloalkyl carboxylate; M is independently selected from CH, N; R3 is independently selected from hydrogen, halogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C5 cycloalkyl, C3-C5 substituted cycloalkyl; R4 is independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 alkylthio, C3-C5 substituted cycloalkyl; R5 is independently selected from hydrogen, halogen, C1-C5 alkyl, C3-C5 substituted cycloalkyl, and is substituted by hydrogen, halogen, cyano, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 cyano-substituted alkyl, C3-C5 cycloalkyl, C3-C5 halocycloalkyl, C3-C5 cyano-substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl, C1-C5 cycloalkylsulfonyl, C1-C5 alkyl carboxylate, C1-C5 haloalkyl carboxylate-substituted aryl and heteroaryl; R6 is independently selected from hydrogen, halogen, cyano, nitro, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 cyano-substituted alkyl; Q can be selected from hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C5 cycloalkyl, C3-C5 halocycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 alkoxyalkyl, C1-C5 substituted alkoxyalkyl, C1-C5 alkylthioalkyl, C1-C5 substituted alkylthioalkyl, C1-C5 substituted alkylsulfinylalkyl, C1-C5 substituted alkylsulfonylalkyl, substituted aryl, substituted heteroaryl. When Q is substituted aryl or substituted heteroaryl, the following one structure can be selected: Wherein: G1, G2, G3, G4, G5 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 haloalkyl, C1-C5 alkoxy, C1-C5 substituted alkoxy, C1-C5 alkylthio, C1-C5 substituted alkylthio, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl, carboxylic acid ester; T1 is independently selected from hydrogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 haloalkyl; T2 and T3 are independently selected from hydrogen, halogen, cyano, C1-C5 alkyl, C3-C5 substituted cycloalkyl, C2-C5 alkenyl, C2-C5 alkynyl, C1-C5 haloalkyl.

3. The amino-substituted pyrimidine-linked triazole derivative according to claim 2, wherein: R1 and R2 are independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cyano-substituted alkyl, C3-C5 cycloalkyl, C3-C5 haloalkyl, C3-C5 cyano-substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 cycloalkylsulfonyl, C1-C3 alkyl carboxylate, C1-C3 haloalkyl carboxylate; M is independently selected from CH, N; R3 is independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, C3-C5 substituted cycloalkyl; R4 is independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 alkylthio, C3-C3 substituted cycloalkyl; R5 is independently selected from hydrogen, halogen, C1-C3 alkyl, C3-C3 substituted cycloalkyl, and is substituted by hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cyano-substituted alkyl, C3-C5 cycloalkyl, C3-C5 haloalkyl, C3-C5 cyano-substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C1-C3 alkylthio, C1-C3 haloalkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 cycloalkylsulfonyl, C1-C3 alkyl carboxylate, C1-C3 haloalkyl carboxylate-substituted aryl and heteroaryl; R6 is independently selected from hydrogen, halogen, cyano, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cyano-substituted alkyl; Q may be selected from hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, C3-C5 haloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 alkoxyalkyl, C1-C3 substituted alkoxyalkyl, C1-C3 alkylthioalkyl, C1-C3 substituted alkylthioalkyl, C1-C3 substituted alkylsulfinylalkyl, C1-C3 substituted alkylsulfonylalkyl, substituted aryl, substituted heteroaryl. When Q is substituted aryl or substituted heteroaryl, the following one structure can be selected: Wherein: G1, G2, G3, G4, G5 are independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C3-C5 substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 substituted alkoxy, C1-C3 alkylthio, C1-C3 substituted alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, carboxylic acid ester; T1 is independently selected from hydrogen, cyano, C1-C3 alkyl, C3-C s substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 haloalkyl; T2, T3 are independently selected from hydrogen, halogen, cyano, C1-C3 alkyl, C3-C5 substituted cycloalkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 haloalkyl.

4. The amino-substituted pyrimidine-linked triazole derivative according to claim 3, characterized in that: R1, R2 are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, trifluoromethyl, methylsulfonyl, isopropylsulfonyl, ethylsulfonyl, cyanocyclopropyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, cyclopropyl; M is independently selected from CH, N; R3 is independently selected from hydrogen, fluorine, methyl, ethyl, isopropyl, monofluoromethyl, trifluoromethyl, cyclopropyl; R4 is independently selected from hydrogen, chlorine, fluorine, bromine, methyl, ethyl, methoxy, difluoromethyl, trifluoromethyl, cyclopropyl; R5 is independently selected from hydrogen, methyl, ethyl, cyclopropyl, aryl and heteroaryl substituted by hydrogen, fluorine, chlorine, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methylsulfonyl; R6 is independently selected from hydrogen, fluorine, fluorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl; Q is optionally selected from hydrogen, methyl, ethyl, propyl, cyclopropyl, trifluoroethyl, difluoroethyl, cyanoethyl, substituted aryl, substituted heteroaryl. When Q is substituted aryl or substituted heteroaryl, the following structure can be selected: G1, G2, G3, G4, G5 are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl, isopropyl, trifluoromethyl, methylsulfonyl, isopropylsulfonyl, ethylsulfonyl, cyanocyclopropyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, cyclopropyl; T1 is independently selected from hydrogen, methyl, ethyl; T2, T3 are independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, difluoromethyl, trifluoromethyl, difluoromethoxy.

5. The amino-substituted pyrimidine-linked triazole derivative according to claim 4, wherein: The amino-substituted pyrimidine-linked triazole derivative is selected from at least one of the following structures:

6. The biological preparation method of amino-substituted pyrimidine-linked triazole according to any one of claims 1-5, characterized in that: The shown preparation method comprises the following steps: Wherein: R1, R2, M, R3, R4, R5, R6, Q are the same as those described in claims 1-4, X is selected from chlorine, bromine, iodine, and R7 is selected from methyl, ethyl, isopropyl, 2,2,2-trifluoroethyl, 2,2,2-difluoroethyl.

7. The biological preparation method of amino-substituted pyrimidine-linked triazole according to any one of claims 1-5, characterized in that: The shown preparation method comprises the following steps: Wherein: R1, R2, M, R3, R4, R5, R6, Q are the same as those described in claims 1-4, X is selected from chlorine, bromine, iodine, and R7 is selected from methyl, ethyl, isopropyl, 2,2,2-trifluoroethyl, 2,2,2-difluoroethyl.

8. The biological preparation method of amino-substituted pyrimidine-linked triazole according to any one of claims 1-5, characterized in that: The shown preparation method comprises the following steps: Wherein: R1, R2, M, R3, R4, R5, R6, Q are the same as those described in Claims 1-4, X is selected from chlorine, bromine, iodine, and R7 is selected from methyl, ethyl, isopropyl, 2,2,2-trifluoroethyl, 2,2,2-difluoroethyl.

9. Use of the amino-substituted pyrimidine-linked triazole derivative according to any one of claims 1-5, characterized in that: The said substituted pyrimidine-linked triazole derivative is used for agricultural insecticidal purposes.

10. Use of the amino-substituted pyrimidine-linked triazole derivative according to claim 9, characterized in that: The said amino-substituted pyrimidine-linked triazole derivative is used for controlling crop mites, Lepidoptera, Homoptera, Hemiptera, Coleoptera and pests in hygiene, etc.

11. Use of the amino-substituted pyrimidine-linked triazole derivative according to claim 10, characterized in that: The said substituted pyrimidine-linked triazole derivative is used for controlling any one of the following crop diseases: armyworms, diamondback moths, alfalfa aphids, brown planthoppers, Spodoptera frugiperda, Chilo suppressalis, Cnaphalocrocis medinalis, aphids, spider mites.

12. An agrochemical insecticide, characterized in that: The said agricultural chemical insecticide contains 1-99% by mass of the amino-substituted pyrimidine-linked triazole derivative according to any one of Claims 1-5, and the remainder is an agriculturally acceptable carrier.

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