A class of acyl imine derivatives containing trifluoromethyl oxadiazole, a preparation method thereof and applications

Abstract

The present invention discloses a class of acyl imine derivatives containing trifluoromethyl oxadiazole as shown in the following general formula (I): for each substituent, see the specification. The present invention also discloses a preparation method and uses of the acyl imine derivatives containing trifluoromethyl oxadiazole. The acyl imine derivatives containing trifluoromethyl oxadiazole are particularly suitable for preventing and controlling soybean rust, wheat rust, corn rust, crop anthracnose, etc.

Description

Technical Field

[0001] The present invention belongs to the field of agricultural fungicides, and particularly relates to a class of acyl imine derivatives containing trifluoromethyl oxadiazole, a preparation method thereof, and an application thereof. Background Art

[0002] In agriculture, long-term use of the same pesticide variety is likely to cause diseases to develop drug resistance. Therefore, it is necessary to continuously develop new varieties with different action mechanisms. With the improvement of fluorination technology, more and more polyfluoroalkyl groups are introduced into organic compounds. Due to the pseudo mimic effect, blocking effect of fluorine atoms, as well as the unique physical and chemical properties such as the high electronegativity of fluorine atoms and the liposolubility of fluorine-containing compounds, more and more new fluorine-containing pesticide varieties have been developed, and trifluoromethyl oxadiazole derivatives are one of them.

[0003] Patent CN110054596A discloses a trifluoromethyl oxadiazole derivative, including the compound structure shown in the following formula, and its connection structure with the trifluoromethyl oxadiazole-substituted phenyl is an alkylene group, and the specific molecular structure is as follows:

[0004]

[0005] Patent CN103781764A discloses an acyl imine compound, and the structural formula is as follows:

[0006]

[0007] Patent US5250498A discloses an acyl imine compound, and the structural formula is as follows:

[0008]

[0009] Although the above patents disclose trifluoromethyl oxadiazole and acyl imine derivatives, their connection structures with the compounds of the present invention are all different. Different connection structures make the compounds exhibit different biological activities. Summary of the Invention

[0010] In order to solve the above technical problems, the present invention provides a class of acyl imine derivatives containing trifluoromethyl oxadiazole, as shown in the following general formula (I):

[0011]

[0012] Wherein:

[0013] Ar is hydrogen, halogen, C1-C 10 alkyl, C3-C 10 cycloalkyl, C1-C 10 alkoxy, C1-C 10Halogenated alkoxy, C1-C 10 Alkenyl, C1-C 10 Alkynyl, C1-C 10 Alkylthio, C1-C 10 Halogenated alkylthio, C1-C 10 Halogenated alkyl, C1-C 10 Alkoxy-substituted alkyl, C1-C 10 Alkylthio-substituted alkyl, C1-C 10 Cyano-substituted alkyl, nitrile group, nitro group, C1-C 10 Alkylsulfonyl or C1-C 10 Phenyl, thiophenyl, naphthyl or pyridyl substituted by at least one substituent selected from alkylsulfinyl;

[0014] GR is selected from one of the structures shown by GR-1, GR-2 or GR-3:

[0015]

[0016] In the formula, R1, R2, R3, and R4 are independently selected from hydrogen, halogen, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy, C1-C 10 Alkenyl, C1-C 10 Alkynyl, C1-C 10 Alkylthio, C1-C 10 Halogenated alkylthio, C1-C 10 Halogenated alkyl, C1-C 10 Alkoxy-substituted alkyl, C1-C 10 Alkylthio-substituted alkyl, C1-C 10 Cyano-substituted alkyl, nitrile group, nitro group, C1-C 10 Alkylsulfonyl or C1-C 10 Alkylsulfinyl;

[0017] Q is selected from one of the structures shown by Q1, Q2, Q3 or Q4:

[0018]

[0019] Y is selected from hydrogen, C1-C 10 Alkyl, C1-C 10 Aryl-substituted alkyl, C3-C 10 Cycloalkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, C1-C 10 Halogenated alkoxy, C1-C 10 Halogenated alkylthio, C1-C10 haloalkyl, C1-C 10 alkoxy-substituted alkyl, C1-C 10 alkylthio-substituted alkyl, C1-C 10 cyano-substituted alkyl, C1-C 10 alkenyl, C1-C 10 alkynyl, or substituted by hydrogen, halogen, C1-C 10 alkyl, C3-C 10 cycloalkyl, C1-C 10 alkoxy, C1-C 10 alkylthio, C1-C 10 haloalkyl, C1-C 10 alkenyl, C1-C 10 alkynyl, C1-C 10 alkoxy-substituted alkyl, C1-C 10 alkylthio-substituted alkyl, C1-C 10 cyano-substituted alkyl, nitrile, nitro, C1-C 10 alkylsulfonyl, C1-C 10 alkylsulfinyl, carboxylate group, or an aryl or heteroaryl substituted by at least one substituent selected from the group consisting of these.

[0020] Preferably, Ar is selected from hydrogen, halogen, C1-C 10 alkyl, C3-C 10 cycloalkyl, C1-C 10 alkoxy, C1-C 10 haloalkoxy, C1-C 10 alkenyl, C1-C 10 alkynyl, C1-C 10 alkylthio, C1-C 10 haloalkylthio, C1-C 10 haloalkyl, C1-C 10 alkoxy-substituted alkyl, C1-C 10 alkylthio-substituted alkyl, C1-C 10 cyano-substituted alkyl, nitrile, nitro, C1-C 10 alkylsulfonyl, C1-C 10 alkylsulfinyl, or a phenyl or thiophenyl substituted by at least one substituent selected from the group consisting of these;

[0021] GR is selected from the structure shown in GR-1:

[0022]

[0023] That is, the compound represented by the general formula (I) of the present invention preferably contains the following two types of structures:

[0024]

[0025] Further preferably, Ar is a phenyl or thiophenyl group substituted by at least one substituent selected from hydrogen, halogen, C1-C5 alkyl, C3-C7 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkenyl, C1-C5 alkynyl, C1-C5 alkylthio, C1-C5 haloalkylthio, C1-C5 haloalkyl, C1-C5 alkoxy-substituted alkyl, C1-C5 alkylthio-substituted alkyl, C1-C5 cyano-substituted alkyl, nitrile group, nitro group, C1-C5 alkylsulfonyl, and C1-C5 alkylsulfinyl;

[0026] R1, R2, R3, and R4 are independently selected from hydrogen, halogen, C1-C5 alkyl, C3-C7 cycloalkyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkenyl, C1-C5 alkynyl, C1-C5 alkylthio, C1-C5 haloalkylthio, C1-C5 haloalkyl, C1-C5 alkoxy-substituted alkyl, C1-C5 alkylthio-substituted alkyl, C1-C5 cyano-substituted alkyl, nitrile group, nitro group, C1-C5 alkylsulfonyl, or C1-C5 alkylsulfinyl;

[0027] Q is selected from one of the structures shown by Q1 and Q3:

[0028]

[0029] Y is selected from hydrogen, C1-C5 alkyl, C1-C5 aryl-substituted alkyl, C3-C7 cycloalkyl, C1-C5 alkoxy, C1-C5 alkylthio, C1-C5 haloalkoxy, C1-C5 haloalkylthio, C1-C5 haloalkyl, C1-C5 alkoxyalkyl, C1-C5 alkylthioalkyl, C1-C5 cyano-substituted alkyl, C1-C5 alkenyl, C1-C5 alkynyl, or an aryl or heteroaryl group substituted by at least one substituent selected from hydrogen, halogen, C1-C5 alkyl, C3-C7 cycloalkyl, C1-C5 alkoxy, C1-C5 alkylthio, C1-C5 haloalkyl, C1-C5 alkenyl, C1-C5 alkynyl, C1-C5 alkoxy-substituted alkyl, C1-C5 alkylthio-substituted alkyl, C1-C5 cyano-substituted alkyl, nitrile group, nitro group, C1-C5 alkylsulfonyl, C1-C5 alkylsulfinyl, and carboxylate group.

[0030] More preferably, Ar is a phenyl or thiophenyl group substituted by at least one substituent selected from hydrogen, chlorine, fluorine, methyl, ethyl, cyclopropyl, methoxy, ethoxy, trifluoromethoxy, methylthio, ethylthio, trifluoromethyl, nitrile group, or nitro group;

[0031] R1, R2, R3, and R4 are independently selected from hydrogen, hydrogen, chlorine, fluorine, methyl, ethyl, cyclopropyl, methoxy, ethoxy, trifluoromethoxy, methylthio, ethylthio, trifluoromethyl, nitrile group, or nitro group;

[0032] Q is the structure shown by Q1

[0033]

[0034] Y is selected from hydrogen, methyl, ethyl, propyl, butyl, benzyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, propoxy, C1-C5 alkylthio, C1-C5 haloalkoxy, C1-C5 haloalkyl, cyanoethyl, cyanopropyl, allyl, or an aryl or heteroaryl substituted with at least one substituent selected from hydrogen, chlorine, fluorine, methyl, ethyl, cyclopropyl, methoxy, ethoxy, trifluoromethoxy, methylthio, ethylthio, trifluoromethyl, nitrile, nitro, carboxylate methyl ester or carboxylate ethyl ester.

[0035] Most preferably, the trifluoromethyl-containing oxadiazole acylimine derivatives are selected from at least one of the following structures:

[0036]

[0037]

[0038] Some compounds in the general formula (I) of the present invention can be illustrated by the following table of specific compounds, but these specific compounds do not limit the present invention.

[0039]

[0040]

[0041] Wherein: the general formula (I) can be stru-a:

[0042]

[0043] In the formula, R5, R6, R7, and R3 are hydrogen, and Q is a carbonyl group.

[0044] Table 1

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061] The structure of the compound of general formula (I) can also be stru-b:

[0062]

[0063] wherein, R5, R6, and R3 are hydrogen, and Q is a carbonyl group.

[0064] Table 2

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073] The NMR data of some compounds are as follows:

[0074] 1: 1 H NMR(CDCl3,600MHz)δ:8.12 - 8.10(m,3H,Py - H,Ph - H),7.58 - 7.56(m,2H,Py - H),7.48 - 7.47(m,2H,Ph - H),6.58(s,1H,Py - H),5.54(s,2H,-CH2),2.20(s,3H,-CH3).

[0075] 3: 1 1H NMR (CDCl3, 600 MHz) δ: 8.53 (d, J = 9 Hz, 1H, Py-H), 8.12 (d, J = 8.4 Hz, 2H, Ph-H), 7.87 (d, J = 6.6 Hz, 1H, Py-H), 7.81 - 7.78 (m, 1H, Py-H), 7.56 (d, J = 8.4 Hz, 2H, Ph-H), 6.90 - 6.87 (m, 1H, Py-H), 5.63 (s, 2H, -CH2).

[0076] 4: 1 1H NMR (CDCl3, 600 MHz) δ: 8.12 - 8.08 (m, 3H, Py-H, Ph-H), 7.53 - 7.44 (m, 4H, Py-H, Ph-H), 6.64 (t, J = 12.6 Hz, 1H, Py-H), 5.47 (s, 2H, -CH2), 2.40 (t, J = 15 Hz, 2H, -CH2), 1.64 - 1.59 (m, 2H, -CH2), 1.36 - 1.30 (m, 2H, -CH2), 0.88 (t, J = 15 Hz, 3H, -CH3).

[0077] 19: 1 1H NMR (CDCl3, 600 MHz) δ: 8.38 (d, J = 9 Hz, 1H, Py-H), 8.15 - 8.13 (m, 2H, Ph-H), 8.11 - 8.10 (m, 2H, Ph-H), 7.60 - 7.58 (m, 1H, Py-H), 7.58 - 7.55 (m, 1H, Py-H), 7.49 (d, J = 8.4 Hz, 2H, Ph-H), 7.44 - 7.41 (m, 1H, Ph-H), 7.35 - 7.35 (m, 2H, Ph-H), 6.57 - 6.54 (m, 1H, Py-H), 5.63 (s, 2H, -CH2).

[0078] 8: 1 1H NMR (CDCl3, 600 MHz) δ: 8.55 (d, J = 9 Hz, 1H, Py-H), 8.12 - 8.11 (m, 2H, Ph-H), 7.84 - 7.82 (m, 1H, Py-H), 7.80 - 7.77 (m, 1H, Py-H), 7.55 - 7.54 (m, 2H, Ph-H), 6.88 - 6.85 (m, 1H, Py-H), 2.23 - 2.20 (m, 1H, -CH), 2.02 - 1.99 (m, 2H, -CH2), 0.89 - 0.86 (m, 2H, -CH2).

[0079] 5:1 1H NMR (CDCl3, 600 MHz) δ: 8.12 - 8.08 (m, 3H, Py-H, Ph-H), 7.51 - 7.45 (m, 4H, Py-H, Ph-H), 6.47 - 6.05 (m, 1H, Py-H), 5.47 (s, 2H, -CH2), 2.40 - 2.32 (m, 2H, -CH2), 1.30 - 1.25 (m, 8H, -CH2), 0.84 - 0.83 (m, 3H, -CH3).

[0080] 6: 1 1H NMR (CDCl3, 600 MHz) δ: 8.09 - 8.08 (m, 2H, Ph-H), 8.02 - 8.01 (m, 1H, Ar-H), 7.43 - 7.48 (m, 1H, Ar-H), 7.48 - 7.43 (m, 2H, Ph-H), 6.63 - 6.61 (m, 1H, Ar-H), 6.50 - 6.49 (m, 1H, Ar-H), 6.45 - 6.42 (m, 1H, Ar-H), 5.45 (s, 2H, -CH2), 2.30 (s, 2H, -CH2), 1.01 (s, 9H, -CH3).

[0081] 21: 1 1H NMR (CDCl3, 600 MHz) δ: 8.45 (d, J = 9 Hz, 1H, Py-H), 8.09 (d, J = 7.8 Hz, 2H, Ph-H), 7.95 - 7.92 (m, 1H, Py-H), 7.62 - 7.61 (m, 1H, Py-H), 7.60 - 7.59 (m, 1H, Ph-H), 7.50 (d, J = 7.8 Hz, 2H, Ph-H), 7.38 - 7.34 (m, 1H, Ph-H), 7.11 (t, J = 15.6 Hz, 1H, Ph-H), 7.07 - 7.04 (m, 1H, Ph-H), 6.60 (t, J = 13.2 Hz, 1H, Py-H), 5.64 (s, 2H, -CH2).

[0082] 2: 1 1H NMR (CDCl3, 600 MHz) δ: 8.14 (d, J = 9.6 Hz, 1H, Py-H), 8.10 - 8.09 (m, 2H, Ph-H), 7.52 - 7.64 (m, 4H, Py-H, Ph-H), 6.48 (s, 1H, Py-H), 5.49 (s, 2H, -CH2), 4.43 (q, J = 22.2 Hz, 2H, -CH2), 1.13 (t, J = 15 Hz, 3H, -CH3).

[0083] 7: 11H NMR (CDCl3, 600 MHz) δ: 8.33 (d, J = 9 Hz, 1H, Py-H), 8.10 (d, J = 7.8 Hz, 2H, Ph-H), 7.64 (d, J = 6.6 Hz, 1H, Py-H), 7.61 - 7.58 (m, 1H, Py-H), 7.50 (d, J = 8.4 Hz, 2H, Ph-H), 6.63 (t, J = 7.2 Hz, 1H, Py-H), 5.56 (s, 2H, -CH2), 4.52 - 4.48 (m, 2H, -CH2), 1.67 (d, J = 6.6 Hz, 3H, -CH3).

[0084] 24: 1 1H NMR (CDCl3, 600 MHz) δ: 8.42 (d, J = 9 Hz, 1H, Py-H), 8.11 - 8.10 (m, 2H, Ph-H), 7.93 - 7.92 (m, 1H, Ph-H), 7.80 - 7.78 (m, 1H, Ph-H), 7.65 - 7.63 (m, 1H, Py-H), 7.62 - 7.59 (m, 1H, Py-H), 7.46 (d, J = 8.4 Hz, 2H, Ph-H), 7.33 - 7.30 (m, 1H, Ph-H), 7.12 - 7.09 (m, 1H, Ph-H), 6.62 - 6.60 (m, 1H, Py-H), 5.63 (s, 2H, -CH2).

[0085] 100: 1 1H NMR (CDCl3, 600 MHz) δ: 8.10 (d, J = 9.6 Hz, 1H, Py-H), 8.08 - 8.06 (m, 2H, Ph-H), 7.51 - 7.50 (m, 1H, Py-H), 7.49 - 7.46 (m, 1H, Py-H), 7.40 ((d, J = 8.4 Hz, 2H, Ph-H), 7.24 - 7.19 (m, 4H, Ph-H), 7.14 - 7.12 (m, 1H, Ph-H), 6.49 - 6.47 (m, 1H, Py-H), 5.41 (s, 2H, -CH2), 2.97 (t, J = 15.6 Hz, 2H, -CH2) 2.73 (t, J = 15.6 Hz, 2H, -CH2).

[0086] 26: 11H NMR (CDCl3, 600 MHz) δ: 8.33 (d, J = 9 Hz, 1H, Py-H), 8.11 - 8.10 (m, 2H, Ph-H), 8.09 - 8.08 (m, 2H, Ph-H), 7.56 - 7.55 (m, 1H, Py-H), 7.53 - 7.50 (m, 1H, Py-H), 7.48 (d, J = 8.4 Hz, 2H, Ph-H), 6.86 - 6.84 (m, 2H, Ph-H), 6.51 - 6.48 (m, 1H, Py-H), 5.60 (s, 2H, -CH2), 3.82 (s, 3H, -CH3).

[0087] 27: 1 1H NMR (CDCl3, 600 MHz) δ: 8.38 (d, J = 9 Hz, 1H, Py-H), 8.08 (d, J = 8.4 Hz, 2H, Ph-H), 7.70 - 7.66 (m, 1H, Py-H), 7.56 - 7.53 (m, 2H, Ph-H, Py-H), 7.50 - 7.49 (m, 2H, Ph-H), 7.34 - 7.31 (m, 1H, Ph-H), 6.94 - 6.93 (m, 1H, Ph-H), 6.91 - 6.88 (m, 1H, Ph-H), 6.53 - 6.51 (m, 1H, Py-H), 5.57 (s, 2H, -CH2), 3.85 (s, 3H, -CH3).

[0088] 28: 1 1H NMR (CDCl3, 600 MHz) δ: 8.32 (d, J = 9 Hz, 1H, Py)-H), 8.11 (d, J = 7.8 Hz, 2H, Ph-H), 7.94 - 7.92 (m, 2H, Ph-H), 7.59 - 7.58 (m, 1H, Py-H), 7.55 - 7.52 (m, 1H, Py-H), 7.48 (d, J = 8.4 Hz, 2H, Ph-H), 7.24 - 7.23 (m, 2H, Ph-H), 7.54 - 7.52 (m, 1H, Py-H), 5.06 (s, 2H, -CH2), 2.34 (s, 3H, -CH3).

[0089] 25: 11H NMR (CDCl3, 600 MHz) δ: 8.38 (d, J = 9 Hz, 1H, Py-H), 8.15 - 8.10 (m, 4H, Ph-H), 7.61 - 7.57 (m, 2H, Py-H), 7.46 (d, J = 7.8 Hz, 2H, Ph-H), 7.01 (t, J = 17.4 Hz, 2H, Ph-H), 6.57 (t, J = 13.2 Hz, 1H, Py-H), 5.62 (s, 2H, -CH2).

[0090] 29: 1 1H NMR (CDCl3, 600 MHz) δ: 8.30 (d, J = 9.6 Hz, 1H, Py-H), 8.09 (d, J = 7.8 Hz, 2H, Ph-H), 7.78 (d, J = 7.8 Hz, 1H, Py-H), 7.56 (d, J = 7.2 Hz, 1H, Py-H), 7.44 (d, J = 7.8 Hz, 2H, Ph-H), 7.26 - 7.24 (m, 2H, Ph-H), 7.17 - 7.12 (m, 2H, Ph-H), 6.54 (t, J = 13.8 Hz, 1H, Py-H), 5.56 (s, 2H, -CH2). 2.57 (s, 3H, -CH3).

[0091] 23: 1 1H NMR (CDCl3, 600 MHz) δ: 8.41 (d, J = 9 Hz, 1H, Py-H), 8.11 (d, J = 8.4 Hz, 2H, Ph-H), 8.06 (d, J = 8.4 Hz, 2H, Ph-H), 7.61 - 7.58 (m, 2H, Py-H), 7.46 (d, J = 7.8 Hz, 2H, Ph-H), 7.31 (d, J = 8.4 Hz, 2H, Ph-H), 6.59 (t, J = 13.2 Hz, 1H, Py-H), 5.63 (s, 2H, -CH2).

[0092] 20: 1 1H NMR (CDCl3, 600 MHz) δ: 8.46 (d, J = 9.6 Hz, 1H, Py-H), 8.05 (d, J = 7.8 Hz, 2H, Ph-H), 7.82 (d, J = 7.2 Hz, 1H, Ph-H), 7.68 - 7.61 (m, 3H, Ph-H, Py-H), 7.56 (t, J = 15 Hz, 1H, Ph-H), 7.45 (t, J = 15.6 Hz, 1H, Ph-H), 7.38 (d, J = 7.8 Hz, 1H, Ph-H), 6.65 (t, J = 13.8 Hz, 1H, Py-H), 5.47 (s, 2H, -CH2).

[0093] 30: 1 1H NMR (CDCl3, 600 MHz) δ: 8.47 (d, J = 9 Hz, 1H, Py-H), 8.08 (d, J = 8.4 Hz, 2H, Ph-H), 7.67 - 7.64 (m, 2H, Py-H), 7.47 - 7.41 (m, 4H, Ph-H,), 7.17 (t, J = 15.6 Hz, 1H, Ph-H), 6.66 (t, J = 14.4 Hz, 1H, Py-H), 5.58 (s, 2H, -CH2).

[0094] 31: 1 1H NMR (CDCl3, 600 MHz) δ: 8.46 (d, J = 9 Hz, 1H, Py-H), 8.09 (d, J = 8.4 Hz, 2H, Ph-H), 7.66 - 7.62 (m, 3H, Py-H, Ph-H), 7.43 (d, J = 7.8 Hz, 2H, Ph-H), 7.33 - 7.38 (m, 1H, Ph-H), 7.21 - 7.19 (m, 1H, Ph-H), 6.66 - 6.64 (m, 1H, Py-H), 5.60 (s, 2H, -CH2).

[0095] 32: 1 1H NMR (CDCl3, 600 MHz) δ: 8.45 (d, J = 9 Hz, 1H, Py-H), 8.05 (d, J = 7.8 Hz, 2H, Ph-H), 7.81 (d, J = 7.8 Hz, 1H, Ph-H), 7.68 - 7.61 (m, 3H, Ph-H, Py-H), 7.55 (t, J = 15 Hz, 1H, Ph-H), 7.45 (t, J = 15 Hz, 1H, Ph-H), 7.38 (d, J = 8.4 Hz, 1H, Ph-H), 6.65 (t, J = 13.8 Hz, 1H, Py-H), 5.47 (s, 2H, -CH2).

[0096] 33: 1 1H NMR (CDCl3, 600 MHz) δ: 8.34 (d, J = 9.6 Hz, 1H, Py-H), 8.10 (d, J = 8.4 Hz, 2H, Ph-H), 7.60 - 7.57 (m, 2H, Py-H), 7.47 (d, J = 8.4 Hz, 1H, Ph-H), 7.44 (s, 2H, Ph-H), 6.57 (t, J = 13.8 Hz, 1H, Py-H), 5.63 (s, 2H, -CH2), 3.86 (s, 3H, -CH3), 3.77 (s, 6H, -CH3).

[0097] 34: 11H NMR (CDCl3, 600 MHz) δ: 8.55 (s, 2H, Py-H), 8.52 (d, J = 9 Hz, 1H, Py-H), 8.13 (d, J = 8.4 Hz, 2H, Ph-H), 7.89 (s, 1H, Ph-H), 7.75 - 7.71 (m, 2H, Py-H), 7.42 (d, J = 8.4 Hz, 2H, Ph-H), 6.76 - 6.74 (m, 1H, Py-H), 5.647 (s, 2H, -CH2).

[0098] 35: 1 1H NMR (CDCl3, 600 MHz) δ: 8.41 (d, J = 9 Hz, 1H, Py-H), 8.07 (d, J = 7.8 Hz, 2H, Ph-H), 7.66 - 7.58 (m, 4H, Ph-H, Py-H), 7.51 (t, J = 15 Hz, 1H, Ph-H), 7.44 - 7.41 (m, 3H, Ph-H), 6.63 (t, J = 13.8 Hz, 1H, Py-H), 5.56 (s, 2H, -CH2).

[0099] 36: 1 1H NMR (CDCl3, 600 MHz) δ: 8.70 (d, J = 1.8 Hz, 1H, Py-H), 8.49 (d, J = 8.4 Hz, 1H, Ph-H), 8.23 (dd, J = 1.8 Hz, J = 7.8 Hz, 1H, Py-H), 8.11 (d, J = 8.4 Hz, 2H, Ph-H), 7.72 (dd, J = 1.2 Hz, J = 6.6 Hz, 1H, Py-H), 7.68 - 7.65 (m, 1H, Ph-H), 7.46 (d, J = 8.4 Hz, 2H, Ph-H), 7.32 (d, J = 8.4 Hz, 1H, Ph-H), 6.70 - 6.67 m, 1H, Py-H), 5.65 (s, 2H, -CH2), 2.61 (s, 3H, -CH3).

[0100] 37: 11H NMR (CDCl3, 600 MHz) δ: 8.24 (d, J = 15 Hz, 1H, Py-H), 7.99 - 7.97 (m, 2H, Ph-H), 7.52 (d, J = 6.6 Hz, 1H, Py-H), 7.49 - 7.46 (m, 1H, Py-H), 7.27 - 7.23 (m, 3H, Ph-H, Py-H), 7.15 - 7.12 (m, 1H, Ph-H), 7.02 (t, J = 14.4 Hz, 1H, Ph-H), 6.95 (t, J = 18 Hz, 1H, Ph-H), 6.50 - 6.47 (m, 1H, Py-H), 5.32 (s, 2H, -CH2), 3.76 (s, 2H, -CH2).

[0101] 38: 1 1H NMR (CDCl3, 600 MHz) δ: 8.51 (d, J = 9 Hz, 1H, Py-H), 8.08 (d, J = 7.8 Hz, 2H, Ph-H), 7.67 - 7.63 (m, 2H, Py-H), 7.51 (d, J = 8.4 Hz, 2H, Ph-H), 7.24 - 7.21 (m, 1H, Ph-H), 6.91 - 6.86 (m, 2H, Ph-H), 6.67 - 6.65 (m, 1H, Py-H), 5.59 (s, 2H, -CH2).

[0102] 52: 1 1H NMR (CDCl3, 600 MHz) δ: 8.56 (d, J = 9 Hz, 1H, Py-H), 8.08 (t, J = 7.8 Hz, 1H, Ph-H), 7.88 (d, J = 6.6 Hz, 1H, Py-H), 7.83 - 7.80 (m, 1H, Py-H), 7.36 (d, J = 8.4 Hz, 1H, Ph-H), 7.33 (d, J = 10.2 Hz, 1H, Ph-H), 6.92 - 6.89 (m, 1H, Py-H), 5.61 (s, 2H, -CH2).

[0103] 39: 1 1H NMR (CDCl3, 600 MHz) δ: 8.22 (d, J = 9.6 Hz, 1H, Py-H), 8.03 (d, J = 8.4 Hz, 2H, Ph-H), 7.52 - 7.48 (m, 2H, Py-H), 7.28 (d, J = 8.4 Hz, 2H, Ph-H), 7.22 - 7.20 (m, 2H, Ph-H), 6.92 - 6.88 (m, 2H, Ph-H), 6.51 - 6.49 (m, 1H, Py-H), 5.38 (s, 2H, -CH2), 3.66 (s, 2H, -CH2).

[0104] 40: 1 1H NMR (CDCl3, 600 MHz) δ: 8.23 (d, J = 9 Hz, 1H, Py-H), 8.00 (d, J = 7.8 Hz, 2H, Ph-H), 7.58 - 7.54 (m, 2H, Py-H), 7.51 (d, J = 8.4 Hz, 2H, Ph-H), 6.97 - 6.91 (m, 3H, Ph-H), 6.59 (t, J = 12.6 Hz, 1H, Py-H), 5.37 (s, 2H, -CH2), 3.72 (s, 2H, -CH2).

[0105] 41: 1 1H NMR (CDCl3, 600 MHz) δ: 8.28 (dd, J = 1.2 Hz, J = 9.6 Hz, 1H, Py-H), 8.04 (d, J = 8.4 Hz, 2H, Ph-H), 7.57 - 7.54 (m, 2H, Py-H), 7.26 - 7.25 (m, 2H, Ph-H), 7.05 - 7.01 (m, 1H, Ph-H), 6.79 - 6.74 (m, 1H, Ph-H), 6.58 - 6.55 (m, 1H, Py-H), 5.38 (s, 2H, -CH2), 3.65 (s, 2H, -CH2).

[0106] 42: 1 1H NMR (CDCl3, 600 MHz) δ: 8.20 (d, J = 9 Hz, 1H, Py-H), 8.00 (d, J = 8.4 Hz, 2H, Ph-H), 7.50 (dd, J = 1.2 Hz, J = 6.6 Hz, 1H, Py-H), 7.47 - 7.44 (m, 1H, Py-H), 7.28 (d, J = 8.4 Hz, 2H, Ph-H), 7.15 - 7.12 (m, 2H, Ph-H), 7.08 (d, J = 7.8 Hz, 1H, Ph-H), 6.99 (d, J = 7.2 Hz, 1H, Ph-H), 6.48 - 6.45 (m, 1H, Py-H), 5.37 (s, 2H, -CH2), 3.67 (s, 2H, -CH2) 2.27 (s, 3H, -CH3).

[0107] 97: 11H NMR (CDCl3, 600 MHz) δ: 8.43 (d, J = 9.6 Hz, 1H, Py-H), 8.09 (t, J = 7.8 Hz, 1H, Ph-H), 7.73 (s, 1H, -CH), 7.62 - 7.57 (m, 2H, Py-H), 7.22 (d, J = 9.6 Hz, 1H, Ph-H), 7.16 (d, J = 12.6 Hz, 1H, Ph-H), 6.63 - 6.61 (m, 1H, Py-H), 5.59 (s, 2H, -CH2), 3.90 (s, 3H, -CH3).

[0108] 51: 1 1H NMR (CDCl3, 600 MHz) δ: 8.13 (d, J = 9.6 Hz, 1H, Py-H), 8.06 (t, J = 15 Hz, 1H, Ph-H), 7.52 (d, J = 6.6 Hz, 1H, Py-H), 7.48 - 7.46 (m, 1H, Py-H), 7.27 - 7.24 (m, 2H, Ph-H), 6.49 - 6.46 (m, 1H, Ph-H), 5.45 (s, 2H, -CH2), 2.41 (q, J = 7.8 Hz, 2H, -CH2), 1.12 (t, J = 15 Hz, 3H, -CH3).

[0109] 56: 1 1H NMR (CDCl3, 600 MHz) δ: 8.34 (d, J = 9 Hz, 1H, Py-H), 8.08 (t, J = 15.6 Hz, 1H, Ph-H), 7.67 - 7.64 (m, 2H, Py-H), 7.30 (t, J = 21.6 Hz, 2H, Ph-H), 6.69 (t, J = 12.6 Hz, 1H, Py-H), 5.58 (s, 2H, -CH2), 4.51 (q, J = 7.2 Hz, 1H, -CH), 1.16 (d, J = 6.6 Hz, 3H, -CH3).

[0110] 101: 1 1H NMR (CDCl3, 600 MHz) δ: 8.21 (d, J = 9 Hz, 1H, Py-H), 7.93 (d, J = 8.4 Hz, 2H, Ph-H), 7.49 - 7.45 (m, 2H, Py-H), 7.21 - 7.19 (m, 1H, Ph-H), 7.18 (d, J = 8.4 Hz, 1H, Ph-H), 7.11 - 7.09 (m, 3H, Ph-H), 6.48 - 6.45 (m, 1H, Py-H), 5.28 (s, 2H, -CH2), 3.37 (s, 2H, -CH2), 2.28 (s, 3H, -CH3).

[0111] 105: 1 1H NMR (CDCl3, 600 MHz) δ: 8.21 (d, J = 9.6 Hz, 1H, Py-H), 7.99 (d, J = 8.4 Hz, 2H, Ph-H), 7.50 (d, J = 7.8 Hz, 1H, Py-H), 7.48 - 7.45 (m, 1H, Py-H), 7.20 (d, J = 8.4 Hz, 1H, Ph-H), 7.03 (s, 1H, Ph-H), 7.00 (d, J = 7.8 Hz, 1H, Ph-H), 6.92 (d, J = 7.8 Hz, 1H, Ph-H), 6.48 - 6.46 (m, 1H, Py-H), 5.30 (s, 2H, -CH2), 3.69 (s, 2H, -CH2), 2.24 (d, J = 5.4 Hz, 6H, -CH6).

[0112] 53: 1 1H NMR (CDCl3, 600 MHz) δ: 8.11 (d, J = 9 Hz, 1H, Py-H), 8.06 (t, J = 15.6 Hz, 1H, Ph-H), 7.50 - 7.45 (m, 2H, Py-H), 7.26 - 7.23 (m, 2H, Ph-H), 6.47 - 6.45 (m, 1H, Py-H), 5.44 (s, 2H, -CH2), 2.39 (t, J = 15 Hz, 2H, -CH2), 1.63 - 1.58 (m, 2H, -CH2), 1.35 - 1.29 (m, 2H, -CH2), 0.88 (t, J = 15 Hz, 3H, -CH3).

[0113] 54: 1 1H NMR (CDCl3, 600 MHz) δ: 8.12 (d, J = 9.6 Hz, 1H, Py-H), 8.06 (t, J = 7.2 Hz, 1H, Ph-H), 7.50 (d, J = 6.6 Hz, 1H, Py-H), 7.48 - 7.45 (m, 1H, Py-H), 7.26 - 7.22 (m, 2H, Ph-H), 6.48 - 6.46 (m, 1H, Py-H), 5.44 (s, 2H, -CH2), 2.38 (t, J = 7.2 Hz, 2H, -CH2), 1.63 - 1.58 (m, 2H, -CH2), 1.31 - 1.23 (m, 6H, -CH6), 0.83 (t, J = 7.2 Hz, 3H, -CH3).

[0114] 55: 11H NMR (CDCl3, 600 MHz) δ: 8.09 - 8.05 (m, 2H, Py-H, Ph-H), 7.49 - 7.46 (m, 2H, Py-H), 7.24 - 7.22 (m, 2H, Ph-H), 6.48 - 6.46 (m, 1H, Py-H), 5.44 (s, 2H, -CH2), 2.29 (s, 3H, -CH3), 1.00 (s, 9H, -CH9).

[0115] 78: 1 1H NMR (CDCl3, 600 MHz) δ: 8.32 (d, J = 9 Hz, 1H, Py-H), 8.08 (t, J = 7.2 Hz, 1H, Ph-H), 7.90 - 7.29 (m, 2H, Ph-H), 7.59 (d, J = 6.6 Hz, 1H, Py-H), 7.57 - 7.54 (m, 1H, Py-H), 7.29 - 7.24 (m, 4H, Ph-H), 6.56 - 6.54 (m, 1H, Py-H), 5.57 (s, 2H, -CH2), 2.34 (s, 3H, -CH3).

[0116] 74: 1 1H NMR (CDCl3, 600 MHz) δ: 8.37 (d, J = 9 Hz, 1H, Py-H), 8.11 - 8.10 (m, 2H, Ph-H), 8.08 (t, J = 7.8 Hz, 1H, Ph-H), 7.60 - 7.56 (m, 2H, Py-H), 7.44 - 7.42 (m 1H, Ph-H), 7.36 (d, J = 7.8 Hz, 2H, Ph-H), 7.29 (d, J = 7.8 Hz, 1H, Ph-H), 7.25 (d, J = 10.8 Hz, 1H, Ph-H), 6.58 - 6.56 (m, 1H, Py-H), 5.61 (s, 2H, -CH2).

[0117] 84: 1 1H NMR (CDCl3, 600 MHz) δ: 8.42 (d, J = 9 Hz, 1H, Py-H), 8.03 (t, J = 7.2 Hz, 1H, Ph-H), 7.66 - 7.60 (m, 4H, Ph-H, Py-H), 7.51 (t, J = 7.2 Hz, 1H, Ph-H), 7.43 (t, J = 7.8 Hz, 1H, Ph-H), 7.21 - 7.17 (m, 2H, Ph-H), 6.66 - 6.64 (m, 1H, Py-H), 5.53 (s, 2H, -CH2).

[0118] 83: 11H NMR (CDCl3, 600 MHz) δ: 8.54 - 8.55 (m, 2H, Py-H, Ph-H), 8.11 (t, J = 7.8 Hz, 1H, Ph-H), 7.89 (s, 1H, Ph-H), 7.77 - 7.74 (m, 2H, Py-H), 7.25 (d, J = 8.4 Hz, 1H, Ph-H), 7.14 (d, J = 10.8 Hz, 1H, Ph-H), 6.79 - 6.77 (m, 1H, Py-H), 5.63 (s, 2H, -CH2).

[0119] 70: 1 1H NMR (CDCl3, 600 MHz) δ: 8.45 (d, J = 10.2 Hz, 1H, Py-H), 8.06 (t, J = 7.8 Hz, 1H, Ph-H), 7.93 - 7.90 (m, 1H, Ph-H), 7.63 - 7.60 (m, 2H, Py-H), 7.38 - 7.34 (m, 1H, Ph-H), 7.30 (d, J = 9.6 Hz, 2H, Ph-H), 7.13 - 7.10 (m, 1H, Ph-H), 7.07 - 7.04 (m, 1H, Ph-H), 6.63 - 6.60 (m, 1H, Py-H), 5.62 (s, 2H, -CH2).

[0120] 73: 1 1H NMR (CDCl3, 600 MHz) δ: 8.42 (d, J = 8.4 Hz, 1H, Py-H), 8.09 (t, J = 7.8 Hz, 1H, Ph-H), 7.89 (d, J = 7.8 Hz, 1H, Ph-H), 7.76 - 7.73 (m, 1H, Ph-H), 7.63 - 7.61 (m, 2H, Ph-H), 7.33 - 7.30 (m, 1H, Py-H), 7.28 (d, J = 8.4 Hz, 1H, Py-H), 7.22 (d, J = 10.2 Hz, 1H, Ph-H), 7.12 - 7.09 (m, 1H, Ph-H), 6.64 - 6.61 (m, 1H, Py-H), 5.61 (s, 2H, -CH2).

[0121] 87: 11H NMR (CDCl3, 600 MHz) δ: 8.53 (d, J = 8.4 Hz, 1H, Py-H), 8.04 (t, J = 7.8 Hz, 1H, Ph-H), 7.69 - 7.65 (m, 2H, Py-H), 7.29 (d, J = 9 Hz, 2H, Ph-H), 7.25 - 7.22 (m, 1H, Ph-H), 6.88 (t, J = 7.2 Hz, 2H, Ph-H), 6.71 - 6.68 (m, 1H, Py-H), 5.56 (s, 2H, -CH2).

[0122] 75: 1 1H NMR (CDCl3, 600 MHz) δ: 8.32 (d, J = 9 Hz, 1H, Py-H), 8.09 - 8.05 (m, 2H, Ph-H), 7.56 - 7.52 (m, 2H, Py-H), 7.29 (d, J = 7.4 Hz, 1H, Ph-H), 7.25 (d, J = 10.8 Hz, 1H, Ph-H), 6.86 (d, J = 9 Hz,, 2H, Ph-H), 6.53 - 6.51 (m, 1H, Py-H), 5.58 (s, 2H, -CH2), 3.83 (s, 3H, -CH3).

[0123] 103: 1 1H NMR (CDCl3, 600 MHz) δ: 8.32 (d, J = 9 Hz, 1H, Py-H), 8.07 (t, J = 7.8 Hz, 1H, Ph-H), 7.73 (d, J = 8.4 Hz, 1H, Ph-H), 7.70 - 7.69 (m, 1H, Ph-H), 7.57 - 7.54 (m, 2H, Py-H), 7.29 (d, J = 7.8 Hz, 1H, Ph-H), 7.26 (d, J = 10.8 Hz, 1H, Ph-H), 6.83 (d, J = 8.4 Hz,, 1H, Ph-H), 6.55 - 6.53 (m, 1H, Py-H), 5.59 (s, 2H, -CH2), 3.90 (s, 3H, -CH3), 3.85 (s, 3H, -CH3).

[0124] 104: 11H NMR (CDCl3, 600 MHz) δ: 8.50 (d, J = 9 Hz, 1H, Py-H), 8.03 (t, J = 7.8 Hz, 1H, Ph-H), 7.82 (d, J = 7.8 Hz, 1H, Ph-H), 7.69 - 7.66 (m, 2H, Ph-H), 7.61 (d, J = 6.6 Hz, 1H, Py-H), 7.58 - 7.55 (m, 1H, Py-H), 7.48 - 7.45 (m, 1H, Ph-H), 7.18 (d, J = 8.4 Hz, 1H, Ph-H), 7.14 (d, J = 7.2 Hz, 1H, Ph-H), 6.72 - 6.67 (m, 1H, Py-H), 5.45 (s, 2H, -CH2).

[0125] 88: 1 1H NMR (CDCl3, 600 MHz) δ: 8.23 (d, J = 9.6 Hz, 1H, Py-H), 8.00 (t, J = 7.8 Hz, 1H, Ph-H), 7.53 - 7.50 (m, 2H, Py-H), 7.21 - 7.18 (m, 2H, Ph-H), 7.07 (d, J = 8.4 Hz, 1H, Ph-H), 7.03 (d, J = 10.8 Hz, 1H, Ph-H), 6.90 (t, J = 8.4 Hz, 1H, Ph-H), 6.53 - 6.51 (m, 1H, Py-H), 5.34 (s, 2H, -CH2), 3.65 (s, 2H, -CH2).

[0126] 90: 1 1H NMR (CDCl3, 600 MHz) δ: 8.30 (d, J = 9 Hz, 1H, Py-H), 8.02 (t, J = 7.8 Hz, 1H, Ph-H), 7.59 - 7.54 (m, 2H, Py-H), 7.08 - 6.99 (m, 3H, Ph-H), 6.86 - 6.76 (m, 1H, Ph-H), 6.60 - 6.57 (m, 1H, Py-H), 5.36 (s, 2H, -CH2), 3.65 (s, 2H, -CH2).

[0127] 91: 11H NMR (CDCl3, 600 MHz) δ: 8.22 (d, J = 9.6 Hz, 1H, Py-H), 7.97 (t, J = 7.2 Hz, 1H, Ph-H), 7.49 - 7.46 (m, 2H, Py-H), 7.14 - 7.10 (m, 2H, Ph-H), 7.08 - 7.06 (m, 2H, Ph-H), 7.04 (d, J = 11.4 Hz, 1H, Ph-H), 6.98 (d, J = 7.8 Hz, 1H, Ph-H), 6.50 - 6.47 (m, 1H, Py-H), 5.34 (s, 2H, -CH2), 3.66 (s, 2H, -CH2), 2.27 (s, 3H, -CH3).

[0128] 105: 1 1H NMR (CDCl3, 600 MHz) δ: 8.23 (d, J = 9 Hz, 1H, Py-H), 7.95 (t, J = 7.2 Hz, 1H, Ph-H), 7.50 - 7.48 (m, 2H, Py-H), 7.17 - 7.16 (m, 1H, Ph-H), 7.08 - 7.07 (m, 2H, Ph-H), 6.96 (d, J = 8.7 Hz, 1H, Ph-H), 6.92 (d, J = 10.8 Hz, 1H, Ph-H), 6.50 - 6.48 (m, 1H, Py-H), 5.25 (s, 2H, -CH2), 3.71 (s, 2H, -CH2), 2.26 (s, 3H, -CH3).

[0129] 106: 1 1H NMR (CDCl3, 600 MHz) δ: 8.23 (d, J = 9.6 Hz, 1H, Py-H), 7.94 (t, J = 7.8 Hz, 1H, Ph-H), 7.50 - 7.47 (m, 2H, Py-H), 6.98 (d, J = 7.2 Hz, 1H, Ph-H), 6.95 (d, J = 10.8 Hz, 1H, Ph-H), 6.89 (d, J = 7.2 Hz, 1H, Ph-H), 6.50 - 6.47 (m, 1H, Py-H), 5.27 (s, 2H, -CH2), 3.68 (s, 2H, -CH2), 2.23 (d, J = 9 Hz, 6H, -CH3).

[0130] 107: 11H NMR (CDCl3, 600 MHz) δ: 8.46 (d, J = 9 Hz, 1H, Py-H), 8.38 (s, 1H, Ph-H), 8.32 (d, J = 7.8 Hz, 1H, Ph-H), 8.13 (d, J = 8.4 Hz, 2H, Ph-H), 7.68 - 7.64 (m, 3H, Ph-H, Py-H), 7.49 - 7.45 (m, 3H, Ph-H), 6.67 - 6.65 (m, 1H, Py-H), 5.64 (s, 2H, -CH2).

[0131] 108: 1 1H NMR (CDCl3, 600 MHz) δ: 8.34 (d, J = 9 Hz, 1H, Py-H), 8.11 (d, J = 8.4 Hz, 2H, Ph-H), 7.77 (d, J = 8.4 Hz, 1H, Ph-H), 7.77 (d, J = 1.8 Hz, 1H, Ph-H), 7.58 (d, J = 6.6 Hz, 1H, Py-H), 7.55 - 7.52 (m, 1H, Py-H), 7.49 (d, J = 8.4 Hz, 1H, Ph-H), 6.83 (d, J = 9 Hz, 1H, Ph-H), 6.54 - 6.51 (m, 1H, Py-H), 5.61 (s, 2H, -CH2), 3.90 (s, 3H, -CH3), 3.83 (s, 3H, -CH3).

[0132] 78: 1 1H NMR (CDCl3, 600 MHz) δ: 8.30 (d, J = 9.6 Hz, 1H, Py-H), 8.06 (t, J = 7.2 Hz, 1H, Ph-H), 7.75 (d, J = 7.8 Hz, 1H, Ph-H), 7.57 - 7.55 (m, 2H, Py-H), 7.25 - 7.23 (m, 2H, Ph-H), 7.22 (d, J = 10.8 Hz, 1H, Ph-H), 7.18 (d, J = 7.8 Hz, 1H, Ph-H), 7.13 (t, J = 7.8 Hz, 1H, Ph-H), 6.55 - 6.54 (m, 1H, Py-H), 5.53 (s, 2H, -CH2), 2.56 (s, 3H, -CH3).

[0133] 109: 11H NMR (CDCl3, 600 MHz) δ: 8.12 (d, J = 9 Hz, 1H, Py-H), 8.04 (t, J = 7.2 Hz, 1H, Ph-H), 7.50 - 7.46 (m, 2H, Py-H), 7.24 - 7.18 (m, 6H, Ph-H), 7.13 (t, J = 7.2 Hz, 1H, Ph-H), 6.50 - 6.48 (m, 1H, Py-H), 5.38 (s, 2H, -CH2), 2.96 (t, J = 7.8 Hz, 2H, -CH2), 2.72 (t, J = 8.4 Hz, 2H, -CH2).

[0134] 69: 1 1H NMR (CDCl3, 600 MHz) δ: 8.44 (d, J = 9 Hz, 1H, Py-H), 8.04 (t, J = 7.2 Hz, 1H, Ph-H), 7.66 - 7.61 (m, 3H, Py-H, Ph-H), 7.46 - 7.41 (m, 1H, Ph-H), 7.37 - 7.36 (m, 1H, Ph-H), 7.25 - 7.22 (m, 3H, Ph-H), 6.66 - 6.63 (m, 1H, Py-H), 5.57 (s, 2H, -CH2).

[0135] 80: 1 1H NMR (CDCl3, 600 MHz) δ: 8.43 (d, J = 9 Hz, 1H, Py-H), 8.05 (t, J = 7.8 Hz,, 1H, Ph-H), 7.70 - 7.67 (m, 1H, Py-H), 7.65 - 7.64 (m, 1H, Py-H), 7.46 - 7.41 (m, 2H, Ph-H), 7.123 - 7.16 (m, 3H, Ph-H), 6.70 - 6.68 (m, 1H, Py-H), 5.56 (s, 2H, -CH2).

[0136] 81: 1 1H NMR (CDCl3, 600 MHz) δ: 8.47 (d, J = 9.6 Hz, 1H, Py-H), 8.06 (t, J = 7.2 Hz,, 1H, Ph-H), 7.68 - 7.61 (m, 3H, Py-H, Ph-H), 7.38 (d, J = 1.8 Hz, 1H, Ph-H), 7.24 (d, J = 8.4 Hz, 1H, Ph-H), 7.21 (d, J = 10.8 Hz, 2H, Ph-H), 6.67 (t, J = 6.6 Hz, 1H, Py-H), 5.57 (s, 2H, -CH2).

[0137] 83: 11H NMR (CDCl3, 600 MHz) δ: 8.33 (d, J = 10.2 Hz, 1H, Py-H), 8.08 (t, J = 7.8 Hz, 1H, Ph-H), 7.61 - 7.58 (m, 2H, Py-H), 7.28 - 7.24 (m, 3H, Ph-H), 6.60 - 6.58 (m, 1H, Ph-H), 5.60 (s, 2H, -CH2), 3.86 (s, 2H, -CH2), 3.79 (s, 6H, -CH3).

[0138] 87: 1 1H NMR (CDCl3, 600 MHz) δ: 8.26 (d, J = 9 Hz, 1H, Py-H), 7.96 (t, J = 8.4 Hz, 1H, Ph-H), 7.52 - 7.49 (m, 2H, Py-H), 7.23 (t, J = 7.2 Hz, 1H, Ph-H), 7.13 - 7.10 (m, 1H, Ph-H), 7.03 - 6.99 (m, 2H, Ph-H), 6.96 - 6.92 (m, 2H, Ph-H), 6.53 - 6.50 (m, 1H, Ph-H), 5.30 (s, 2H, -CH2), 3.73 (s, 2H, -CH2).

[0139] 88: 1 1H NMR (CDCl3, 600 MHz) δ: 8.30 (d, J = 9.6 Hz, 1H, Py-H), 7.98 (t, J = 7.8 Hz, 1H, Ph-H), 7.56 - 7.53 (m, 1H, Py-H), 7.52 (d, J = 6.6 Hz, 1H, Py-H), 7.03 (d, J = 7.8 Hz, 1H, Ph-H), 6.99 - 6.96 (m, 1H, Ph-H), 6.95 - 6.91 (m, 3H, Ph-H), 6.57 - 6.54 (m, 1H, Ph-H), 5.33 (s, 2H, -CH2), 3.75 (s, 2H, -CH2).

[0140] 50: 1 1H NMR (CDCl3, 600 MHz) δ: 8.11 (d, J = 9 Hz, 1H, Py-H), 8.07 (t, J = 15 Hz, 1H, Ph-H), 7.51 - 7.47 (m, 2H, Py-H), 7.26 (t, J = 20.4 Hz, 2H, Ph-H), 6.49 (t, J = 13.2 Hz, 1H, Py-H), 5.45 (s, 2H, -CH2), 2.17 (s, 3H, -CH3).

[0141] 48: 11H NMR (CDCl3, 600 MHz) δ: 8.43 (d, J = 9.6 Hz, 1H, Py-H), 8.12 (d, J = 8.4 Hz, 2H, Ph-H), 7.75 (s, 1H, Ar-H), 7.61 - 7.56 (m, 2H, Py-H), 7.40 (d, J = 8.4 Hz, 2H, Ph-H), 7.24 (d, J = 54.6 Hz, 1H, -CHF2), 6.62 - 6.59 (m, 1H, Py-H), 5.60 (s, 2H, -CH2), 3.90 (s, 3H, -CH3).

[0142] 110: 1 1H NMR (CDCl3, 600 MHz) δ: 8.31 (d, J = 9 Hz, 1H, Py-H), 8.09 (d, J = 8.4 Hz, 2H, Ph-H), 7.67 (d, J = 6.6 Hz, 1H, Py-H), 7.60 - 7.57 (m, 1H, Py-H), 7.52 (d, J = 8.4 Hz, 2H, Ph-H), 6.62 - 6.60 (m, 1H, Py-H), 5.54 (s, 2H, -CH2), 2.96 - 2.92 (m, 2H, -CH2), 2.62 - 2.57 (m, 2H, -CH2), 2.17 - 2.11 (m, 1H, -CH2), 1.77 - 1.71 (m, 1H, -CH2), 1.25 (s, 1H, -CH).

[0143] 111: 1 1H NMR (CDCl3, 600 MHz) δ: 8.31 (d, J = 9 Hz, 1H, Py-H), 8.06 (d, J = 7.2 Hz, 1H, Ph-H), 7.67 (d, J = 6.6 Hz, 1H, Py-H), 7.62 - 7.59 (m, 1H, Py-H), 7.32 - 7.30 (m, 2H, Ph-H), 6.64 - 6.62 (m, 1H, Py-H), 5.52 (s, 2H, -CH2), 2.94 - 2.89 (m, 2H, -CH2), 2.61 - 2.56 (m, 2H, -CH2), 2.20 - 2.13 (m, 1H, -CH2), 1.77 - 1.72 (m, 1H, -CH).

[0144] 112: 11H NMR (CDCl3, 600 MHz) δ: 8.16 - 8.13 (m, 1H, Py-H), 8.10 - 8.07 (m, 2H, Ph-H), 7.71 - 7.69 (m, 1H, Py-H), 7.56 - 7.52 (m, 1H, Py-H), 7.48 - 7.46 (m, 2H, Ph-H), 6.60 - 6.57 (m, 1H, Py-H), 5.55 (d, J = 7.2 Hz, 2H, -CH2), 3.52 - 3.48 (m, 2H, -CH2), 2.45 - 2.41 (m, 2H, -CH2), 1.80 - 1.77 (m, 4H, -CH2).

[0145] 113: 1 1H NMR (CDCl3, 600 MHz) δ: 8.14 (t, J = 9 Hz, 1H, Py-H), 8.06 (q, J = 7.8 Hz, 1H, Ph-H), 7.70 (t, J = 6.6 Hz, 1H, Py-H), 7.56 - 7.52 (m, 1H, Py-H), 7.28 - 7.26 (m, 1H, Ph-H), 7.24 - 7.22 (m, 1H, Ph-H), 6.59 - 6.57 (m, 1H, Py-H), 5.52 (d, J = 3 Hz, 2H, -CH2), 3.51 - 3.48 (m, 2H, -CH2), 2.42 (t, J = 6.6 Hz, 2H, -CH2), 1.78 - 1.75 (m, 4H, -CH2).

[0146] The present invention also provides a preparation method of the above-mentioned acyl imine derivatives containing trifluoromethyl oxadiazole, and the preparation method includes the following steps:

[0147]

[0148] Wherein:

[0149] R8 is selected from hydrogen, halogen, C1-C 10 alkyl, C3-C 10 cycloalkyl, C1-C 10 alkoxy, C1-C 10 haloalkoxy, C1-C 10 alkenyl, C1-C 10 alkynyl, C1-C 10 alkylthio, C1-C 10 haloalkylthio, C1-C 10 haloalkyl, C1-C 10 alkoxy-substituted alkyl, C1-C 10 alkylthio-substituted alkyl, C1-C 10 cyano-substituted alkyl, nitrile, nitro, C1-C 10At least one of alkylsulfonyl or C1-C 10 alkylsulfinyl;

[0150] Y is selected from hydrogen, C1-C 10 alkyl, C1-C 10 aryl-substituted alkyl, C3-C 10 cycloalkyl, C1-C 10 alkoxy, C1-C 10 alkylthio, C1-C 10 haloalkoxy, C1-C 10 haloalkylthio, C1-C 10 haloalkyl, C1-C 10 alkoxy-substituted alkyl, C1-C 10 alkylthio-substituted alkyl, C1-C 10 cyano-substituted alkyl, C1-C 10 alkenyl, C1-C 10 alkynyl, or aryl or heteroaryl substituted by at least one substituent selected from hydrogen, halogen, C1-C 10 alkyl, C3-C 10 cycloalkyl, C1-C 10 alkoxy, C1-C 10 alkylthio, C1-C 10 haloalkyl, C1-C 10 alkenyl, C1-C 10 alkynyl, C1-C 10 alkoxy-substituted alkyl, C1-C 10 alkylthio-substituted alkyl, C1-C 10 cyano-substituted alkyl, nitrile, nitro, C1-C 10 alkylsulfonyl, C1-C 10 alkylsulfinyl, carboxylate group.

[0151] The present invention also provides the use of the acyl imine derivatives containing trifluoromethyl oxadiazole as described in any one of the above. The acyl imine derivatives containing trifluoromethyl oxadiazole are used for agricultural sterilization, and are particularly suitable for preventing and treating one, two or more combinations of soybean rust, wheat rust, corn rust, and crop anthracnose. When used for formulating agricultural chemical fungicides, the mass percentage content of the acyl imine derivatives containing trifluoromethyl oxadiazole in the fungicides is 1-99%, and can be formulated into various liquid agents, emulsifiable concentrates, suspension concentrates, aqueous suspension concentrates, 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 isopropyl alcohol, 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.

[0152] 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: Nongru 2201B, Nongru 0203B, Nongru 100 # 、Nongru 500 # 、Nongru 600 # 、Nongru 600-2 # 、Nongru 1601, Nongru 2201, Nongru NP-10, Nongru NP-15, Nongru 507 # 、Nongru OX-635, Nongru OX-622, Nongru OX-653, Nongru OX-667, Ningru 36 # 。The dispersants include sodium lignin sulfonate, Nekal, calcium lignin sulfonate, methylnaphthalene sulfonic acid formaldehyde condensate, etc. The wetting agents are: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, etc.

[0153] These preparations can be prepared by common 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 binders, defoamers, oxidants, etc. can also be added.

[0154] Compared with the prior art, the acyl imine derivatives containing trifluoromethyl oxadiazole represented by the general formula (I) provided by the present invention have the following advantages:

[0155] The acyl imine derivatives containing trifluoromethyl oxadiazole of the present invention have high bactericidal activity, can prevent and control soybean rust 100% at a concentration of 5 ppm, and the control effect on wheat rust is more than 90% at a concentration of 100 ppm. Detailed implementation manners

[0156] 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.

[0157] (1). Compound preparation

[0158]

[0159] In the formula, R8 = H, F.

[0160] Example 1: Synthesis of intermediate B

[0161] The raw material A p-tolunitrile (55 g, 0.45 mol), hydroxylamine hydrochloride (97 g, 1.35 mol) and triethylamine (145 g, 1.35 mol) were added to a 1000 mL round-bottom flask, and then 500 mL of absolute ethanol was added. After stirring until completely dissolved, the mixture was heated to reflux for 10 h. After the reaction was completed, it was cooled to room temperature, the excess solvent ethanol was rotary evaporated, and then water (500 mL) was added and stirred for 15 min. The white solid was filtered, dried, and intermediate B (54 g, 0.30 mol) was obtained, with a yield of 80.0%. R1 = H: 1 H NMR(CDCl3,600MHz)δ:7.46(d,2H,J = 7.2Hz,Ph-H),7.12(s,2H,N-H),7.06(d,2H,J = 7.2Hz,Ph-H),2.51(s,3H,Ph-CH3). 13 C NMR(CDCl3,150MHz)δ:163.3,139.8,130.3,129.1,125.6,21.3.; R1 = F: 11H NMR (CDCl3, 600 MHz) δ: 7.56 (t, 1H, J = 7.8 Hz, Ph-H), 6.98 (d, 1H, J = 7.8 Hz, Ph-H), 6.94 (d, 1H, J = 12.6 Hz, Ph-H), 5.12 (s, 2H, -NH2), 2.36 (s, 3H, -CH3). 13 13C NMR (CDCl3, 150 MHz) δ: 163.1, 156.4, 139.9, 127.6, 124.7, 116.9, 116.1, 21.3.

[0162] Example 2: Synthesis of Intermediate C

[0163] Add intermediate B (50 g, 0.33 mol) to a 1000 mL round-bottom flask, dissolve it in 500 mL of tetrahydrofuran, stir until completely dissolved, then add trifluoroacetic anhydride (84 g, 0.40 mol) under an ice bath, and stir at room temperature for 12 h. After the reaction is completed, spin-dry the excess tetrahydrofuran solvent, add 200 mL of water and stir. While stirring, add sodium bicarbonate to neutralize until the solution is weakly alkaline, extract with ethyl acetate (150 mL × 3), and separate by dry column chromatography to obtain intermediate C (61 g, 0.27 mol), with a yield of 84.0%. R1 = H: 1 1H NMR (CDCl3, 600 MHz) δ: 8.00 (d, 2H, J = 7.8 Hz, Ph-H), 7.32 (d, 2H, J = 7.8 Hz, Ph-H), 2.43 (s, 3H, Ph-CH3). 13 13C NMR (CDCl3, 150 MHz) δ: 169.1, 165.7 (q, 2 J C-F = 43.9 Hz), 142.8, 129.8, 127.6, 122.1, 116.9 (q, J C-F = 272.0 Hz, -CF3), 21.6. R1 = F: 1 1H NMR (CDCl3, 600 MHz) δ: 7.95 (t, 1H, J = 7.8 Hz, Ph-H), 7.12 (d, 1H, J = 7.8 Hz, Ph-H), 7.08 (d, 1H, J = 11.4 Hz, Ph-H), 2.43 (s, 3H, Ph-CH3). 13 13C NMR (CDCl3, 150 MHz) δ: 166.0, 165.4 (q, 2 J C-F = 44.2 Hz), 161.5, 145.4, 130.4, 125.5, 117.3, 116.9 (q, J C-F= 272.0 Hz, -CF3), 110.4, 21.4.

[0164] Example 3: Synthesis of Intermediate D

[0165] Add intermediate C (49 g, 0.21 mol) to a 1000 mL round-bottom flask, add 400 mL of carbon tetrachloride, stir to dissolve, then add N-bromosuccinimide (38 g, 0.21 mol) and azobisisobutyronitrile (3 g, 0.02 mol), heat and stir to reflux for 4 h. After the reaction is completed, spin-dry the excess carbon tetrachloride solvent, and separate by column chromatography to obtain intermediate D (45 g, 0.15 mol), with a yield of 71.4%. R1 = H: 1 H NMR (CDCl3, 600 MHz) δ: 8.08 (d, 2H, J = 8.4 Hz, Ph-H), 7.54 (d, 2H, J = 8.4 Hz, Ph-H), 4.52 (s, 2H, -CH2). 13 C NMR (CDCl3, 150 MHz) δ: 169.5, 165.8 (q, 2 J C-F = 43.9 Hz), 142.9, 129.8, 127.5, 122.0, 117.0 (q, J C-F = 272.0 Hz, -CF3), 33.6. R1 = F: 1 H NMR (CDCl3, 600 MHz) δ: 8.06 (t, 1H, J = 11.4 Hz, Ph-H), 7.33 (t, 2H, J = 11.4 Hz, Ph-H), 4.48 (s, 2H, -CH2). 13 C NMR (CDCl3, 150 MHz) δ: 165.7, 165.6 (q, 2 J C-F = 44.5 Hz), 161.4, 144.3, 131.2, 125.2, 117.5 (q, J C-F = 272.0 Hz, -CF3), 113.3, 30.9.

[0166] Example 4: Synthesis of Intermediate E

[0167] Add intermediate D (45 g, 0.15 mol) to a 1000 mL round-bottom flask, add 500 mL of xylene and 2-aminopyridine (28 g, 0.30 mol), heat and stir to reflux for 8 h. After the reaction is completed, obvious solid precipitates, filter out the yellow solid, and dry to obtain the crude product intermediate E.

[0168] Example 5: Synthesis of Intermediate F

[0169] Add intermediate E (40 g, 0.13 mol) into a 1000 mL round-bottom flask, add 500 mL of anhydrous methanol and stir to dissolve. Then add 30% sodium ethoxide solution (21 g, 0.39 mol), heat and stir to reflux for 3 h. After the reaction is completed, rotary evaporate the excess anhydrous methanol solvent, then add water (200 mL) and dichloromethane (150 mL * 3) for extraction, and separate by column chromatography to obtain intermediate F (25 g, 0.08 mol), with a yield of 61.5%. R1 = H: 1 H NMR (CDCl3, 600 MHz) δ: 8.56 (d, 1H, J = 9.0 Hz, Py-H), 8.13 (d, 2H, J = 8.4 Hz, Ph-H), 7.85 (d, 1H, J = 6.6 Hz, Py-H), 7.80 (t, 1H, J = 9.0 Hz, Py-H), 7.56 (d, 2H, J = 8.4 Hz, Ph-H), 6.88 (t, 1H, J = 6.6 Hz, Py-H), 5.64 (s, 2H, -CH2).

[0170] Example 6: Synthesis of Compound 1

[0171] Add intermediate F (0.1 g, 0.30 mmol) into a 50 mL round-bottom flask, add 10 mL of dichloromethane and stir to dissolve. Then add acetyl chloride and stir at room temperature for 1 h. After the reaction is completed, obtain Compound 1 by thin-layer chromatography, 1 H NMR (CDCl3, 600 MHz) δ: 8.12 - 8.10 (m, 3H, Py-H, Ph-H), 7.58 - 7.56 (m, 2H, Py-H), 7.48 - 7.47 (m, 2H, Ph-H), 6.58 (s, 1H, Py-H), 5.54 (s, 2H, -CH2), 2.20 (s, 3H, -CH3). 13 C NMR (CDCl3, 150 MHz) 168.6, 166.0 (q, 2 J C-F = 44.2 Hz), 156.1, 139.5, 137.8, 128.9, 128.2, 121.7, 116.8 (q, J C-F = 272.0 Hz, -CF3), 109.1, 54.9, 29.3.

[0172] (II) Formulation Preparation

[0173] The following examples are prepared according to the mass ratio.

[0174] Example 7 30% Suspension Concentrate

[0175]

[0176] Compound 8 and other components are fully mixed, and the resulting suspending agent can be diluted with water to obtain a dilution of any desired concentration.

[0177] Example 8 30% Aqueous Suspension

[0178]

[0179] Compound 57 is ground together with 80% of the water to be added and sodium dodecyl sulfonate in a ball mill. Half-fiber and propylene oxide are dissolved in the remaining 20% of the water, and then the above components are added with stirring.

[0180] Example 9 30% Emulsifiable Concentrate

[0181]

[0182] Phosphorous acid is dissolved in toluene, and compound 605 and ethoxylated triglyceride are added to obtain a clear solution.

[0183] Example 10 60% Wettable Powder

[0184]

[0185] Compound 134, sodium dodecylnaphthalene sulfonate, sodium lignin sulfonate and diatomaceous earth are mixed together and ground in a grinder until the particles reach the standard.

[0186] (II) Biological Activity Test

[0187] Example 11: Preventive Effect on Soybean Rust Caused by Phakopsora pachyrhizi on Soybeans

[0188] The test compound is dissolved in a small amount of N,N-dimethylformamide and then diluted with water containing 0.1% Tween 80 to the concentration to be tested. The leaves of potted soybean seedlings are sprayed with an aqueous suspension containing the active ingredient or its mixture at the concentration described below until dripping. Allow the plants to air dry. The test plants are cultured in a greenhouse at 23 - 27°C and 60 - 80% relative humidity for 2 days. Then the plants are inoculated with the spores of Phakopsora pachyrhizi. To ensure successful artificial inoculation, the plants are transferred to a humid chamber at a relative humidity of about 95% and 20 - 24°C and kept for 24 hours. The test plants are cultured in a greenhouse at 23 - 27°C and 60 - 80% relative humidity for 14 days. The degree of fungal invasion on the leaves is evaluated visually as the percentage of diseased leaf area.

[0189] In this test, at 10 ppm, compounds 1, 2, 3, 4, 5, 6, 7, 8, 19, 20, 21, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 51, 50, 53, 54, 55, 56, 69, 70, 73, 74, 75, 78, 80, 81, 83, 84, 85, 87, 88, 90, 91, 97, 101, 105, 106, 107, 108, 110, 111, 112, 113, 134, 605 had a control effect of over 85%.

[0190] Example 12: Therapeutic effect on soybean rust caused by Phakopsora pachyrhizi on soybeans

[0191] The leaves of potted soybean seedlings were inoculated with spores of Phakopsora pachyrhizi. To ensure successful artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and a temperature of 20 - 24 °C and kept for 24 hours. The next day, the plants were sprayed to runoff with an aqueous suspension containing the active ingredient or its mixture at the concentrations described below. The plants were air-dried. Then, the test plants were cultivated in a greenhouse at 23 - 27 °C and a relative humidity of 60 - 80% for 14 days. The degree of fungal infestation on the leaves was evaluated visually as the percentage of diseased leaf area.

[0192] In this test, at 50 ppm, compounds 1, 2, 3, 4, 5, 6, 7, 8, 19, 20, 21, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 51, 50, 53, 54, 55, 56, 69, 70, 73, 74, 75, 78, 80, 81, 83, 84, 85, 87, 88, 90, 91, 97, 101, 105, 106, 107, 108, 110, 111, 112, 113, 134, 605, 611, 624 had a control effect of over 85%.

[0193] Example 13: Therapeutic effect on brown rust caused by Puccinia recondita on wheat

[0194] The first two developed leaves of potted wheat seedlings were inoculated with spores of Puccinia triticina. To ensure successful artificial inoculation, the plants were transferred to a humid chamber without light with a relative humidity of 95 - 99% and a temperature of 20 - 24 °C and kept for 24 hours. The next day, the plants were cultivated in a greenhouse at 20 - 24 °C and a relative humidity of 65 - 70% for 3 days. Then, the plants were sprayed to runoff with an aqueous suspension containing the active ingredient or its mixture at the concentration described below. The plants were air-dried. Then, the test plants were cultivated in a greenhouse at 20 - 24 °C and a relative humidity of 65 - 70% for 8 days. The degree of fungal infestation on the leaves was evaluated visually as the percentage of diseased leaf area.

[0195] In this test, at 200 ppm g, compounds 1, 2, 3, 4, 5, 6, 7, 8, 19, 20, 21, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 51, 50, 53, 54, 55, 56, 69, 70, 73, 74, 75, 78, 80, 81, 83, 84, 85, 87, 88, 90, 91, 97, 101, 105, 106, 107, 108, 110, 111, 112, 113, 134, 605, 611, 624 had a control effect of over 90%.

[0196] Example 14: Preventive effect against brown rust on wheat caused by Puccinia recondita.

[0197] The first two developed leaves of potted wheat seedlings were sprayed to runoff with an aqueous suspension containing the active ingredient or its mixture at the concentration described below. The next day, the plants were inoculated with spores of Puccinia triticina. To ensure successful artificial inoculation, the plants were transferred to a humid chamber without light with a relative humidity of 95 - 99% and a temperature of 20 - 24 °C and kept for 24 hours. Then, the test plants were cultivated in a greenhouse at 20 - 24 °C and a relative humidity of 65 - 70% for 6 days. The degree of fungal infestation on the leaves was evaluated visually as the percentage of diseased leaf area.

[0198] In this test, compounds 1, 2, 3, 4, 5, 6, 7, 8, 19, 20, 21, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 51, 50, 53, 54, 55, 56, 69, 70, 73, 74, 75, 78, 80, 81, 83, 84, 85, 87, 88, 90, 91, 97, 101, 105, 106, 107, 108, 110, 111, 112, 113, 134, 605, 611, 624 at 100 ppm had a control effect of over 90%.

[0199] Example 15: Comparative test of some compounds in the present invention against Phakopsora pachyrhizi on soybeans and compounds in the prior art:

[0200] The leaves of potted soybean seedlings were inoculated with spores of Phakopsora pachyrhizi. To ensure successful artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and a temperature of 20 - 24 °C and kept for 24 hours. The next day, the plants were sprayed to runoff with an aqueous suspension containing different concentrations of the active ingredient or its mixture as described in Table 2 below. The plants were air-dried. Then, the test plants were cultivated in a greenhouse at 23 - 27 °C and a relative humidity of 60 - 80% for 14 days. The degree of fungal infestation on the leaves was evaluated visually as the percentage of diseased leaf area.

[0201] A comparative test was conducted on compounds 2, 8, 21, 51, 57, 605, 611, 624 of the present invention and compounds mentioned in the prior art. Two different concentrations of 10 ppm and 5 ppm were prepared respectively, and each test was repeated 3 times and the average value was taken. The results of the comparative test are shown in Table 3:

[0202] Table 3: Results of the comparative test

[0203]

[0204] According to the results of the comparative test, it can be seen that the compounds of the present invention have significantly better activity against soybean rust than the compounds disclosed in the prior art.

Claims

1. A class of acyl imine derivatives containing trifluoromethyl oxadiazole, as shown in the following general formula (I): Wherein: Ar is a phenyl group substituted by hydrogen and / or halogen, or a thiophenyl group substituted by hydrogen; GR is selected from the structure shown in GR-1: In the formula, R1, R2, R3, and R4 are independently selected from hydrogen, halogen, C1-C2 alkyl; Q is selected from Q1: Y is selected from C1-C5 alkyl, C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C5 haloalkyl, C1-C2 cyano-substituted alkyl, or a phenyl group substituted by at least one substituent selected from hydrogen, halogen, C1-C5 alkyl, C1-C2 alkoxy, C1-C5 haloalkyl, and nitro.

2. The acyl imine derivative containing trifluoromethyl oxadiazole according to claim 1, characterized in that: Ar is a phenyl group substituted by hydrogen and / or fluorine, or a thiophenyl group substituted by hydrogen; GR is selected from the structure shown in GR-1: R1, R2, R3, and R4 are independently selected from hydrogen, chlorine, fluorine, methyl, or ethyl; Q is the structure shown in Q1: Y is selected from methyl, ethyl, propyl, butyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, halomethyl, cyanomethyl, or cyanoethyl, or a phenyl group substituted by at least one substituent selected from hydrogen, chlorine, fluorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, and nitro.

3. The acyl imine derivatives containing trifluoromethyl oxadiazole according to claim 2, characterized in that: The acyl imine derivative containing trifluoromethyl oxadiazole is selected from at least one of the following structures: 。 4. The preparation method of the acyl imine derivatives containing trifluoromethyl oxadiazole according to any one of claims 1-3, characterized in that: The preparation method shown includes the following steps: In the formula: R8 is selected from hydrogen or halogen; Y is selected from C1-C5 alkyl, C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C5 haloalkyl, C1-C2 cyano-substituted alkyl, or a phenyl group substituted by at least one substituent selected from hydrogen, halogen, C1-C5 alkyl, C1-C2 alkoxy, C1-C5 haloalkyl, and nitro.

5. Use of the acyl imine derivatives containing trifluoromethyl oxadiazole according to any one of claims 1 to 3, characterized in that: The acyl imine derivative containing trifluoromethyl oxadiazole is used for agricultural sterilization.

6. Use of the acyl imine derivative containing trifluoromethyl oxadiazole according to claim 5, characterized in that: The acyl imine derivative containing trifluoromethyl oxadiazole is used for preventing and treating crop rust, anthracnose, and brown rust.

7. Use of the acyl imine derivatives containing trifluoromethyl oxadiazole according to claim 6, characterized in that: The acyl imine derivative containing trifluoromethyl oxadiazole is used for preventing and treating soybean rust, wheat rust, corn rust, and crop anthracnose.

8. An agrochemical fungicide, characterized in that: The agricultural chemical fungicide contains 1-99% by mass of the acyl imine derivative containing trifluoromethyl oxadiazole according to any one of claims 1-3, and the rest is an agriculturally acceptable carrier.

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