WO2026016951A1 - Oxadiazole compound and use thereof - Google Patents

Abstract

Disclosed in the present invention is an oxadiazole compound having a novel structure, as represented by general formula I. See the description for the definition of each substituent in the formula. The compound of general formula I has excellent fungicidal activity, and has a good control effect on various diseases, especially on soybean rust, at low doses. As a result, the present invention covers the use of the compound of general formula I as a fungicide in agriculture and other fields.

Description

An oxadiazole compound and its application Technical Field

This invention belongs to the field of agricultural fungicides. Specifically, it relates to an oxadiazole compound and its applications.

Background Technology

Patent WO2017076935A1 relates to oxadiazole compounds and their use as bactericides; however, the activity of these compounds is still unsatisfactory, and new compounds with higher activity need to be continuously developed.

In the prior art, no oxadiazole compounds as shown in this invention and their bactericidal activities have been reported.

Summary of the Invention

The purpose of this invention is to provide an oxadiazole compound that can control a variety of plant fungal diseases, and its use in the preparation of drugs for the prevention and control of pathogens in agriculture and other fields.

To achieve the above objectives, the technical solution of the present invention is as follows:

An oxadiazole compound, as shown in general formula I:

In general formula I:

_A1 is selected from N or _CR1 , and _R1 is selected from hydrogen, halogen, _C1 - _C6 alkyl, halogenated _C1 - _C6 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C6 alkoxy or halogenated _C1 - _C6 alkoxy.

_A2 is selected from N or _CR2 , and _R2 is selected from hydrogen, halogen, _C1 - _C6 alkyl, halogenated _C1 - _C6 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C6 alkoxy or halogenated _C1 - _C6 alkoxy.

_A3 is selected from N or _CR3 , and _R3 is selected from hydrogen, halogen, _C1 - _C6 alkyl, halogenated _C1 - _C6 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C6 alkoxy or halogenated _C1 - _C6 alkoxy.

_A4 is selected from N or _CR4 , and _R4 is selected from hydrogen, halogen, _C1 - _C6 alkyl, halogenated _C1 - _C6 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C6 alkoxy or halogenated _C1 - _C6 alkoxy.

X is selected from hydrogen, halogen, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, _C1 - _C6 alkyl, halo- _C1 - _C6 alkyl, _C3 - _C8 cycloalkyl, _C1 - _C6 alkoxy, halo- _C1 - _C6 alkoxy, _C1 - _C6 alkylthio, _{halo-C1 - C6} alkylthio, _C2 - _C8 alkenyl, halo- _C2 - _C8 alkenyl, _C2 - _C8 ynyl, halo-C2- _C8 ynyl, _C1 - _C6 alkylamino, halo- _C1 - _C6 alkylamino, _C1 - _C6 dialkylamino, _C3 - _C8 cycloalkylamino, _C1 - _C6 alkylcarbonyl, _C1 - _C6 alkoxycarbonyl, _C1 - _C6 alkylsulfonyl, _C1 - _C6 alkylaminocarbonyl, _C1 -C ₆ alkylaminosulfonyl, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy carbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ alkyl carbonyloxy, C ₁ -C ₆ alkyl carbonylamino, C ₁ -C ₆ alkoxy carbonyloxy, C 1-C ₆ alkylamino carbonyloxy, C ₁ -C 6 alkylsulfonyloxy, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy, or C ₁ -C ₆ alkoxy carbonyl C ₁ -C ₆ alkoxy; m is selected from ₀ , 1, 2, 3, ₄ , or 5; when m is greater than 1, X can be the same or different;

Y is selected from O or S;

Z is selected from O or S;

n is selected from 0 or 1;

Or a salt of a compound of general formula I.

In one possible implementation, in general formula I,

_A1 is selected from N or _C1 , and _R1 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl;

_A2 is selected from N or _CR2 , and _R2 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl;

_A3 is selected from N or _CR3 , and _R3 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl;

_A4 is selected from N or _CR4 , and _R4 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl;

Furthermore, among _A1 , _A2 , _A3 , and _A4 , at most two are selected from N;

X is selected from hydrogen, halogen, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, _C1 - _C4 alkyl, halo- _C1 - _C4 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C4 alkoxy, halo- _C1 - _C4 alkoxy, _C1 - _C4 alkylthio, _{halo-C1 - C4} alkylthio, _C2 - _C4 alkenyl, halo- _C2 - _C4 alkenyl _{, C2-C4 alkynyl ,} halo- _C2 - _C4 alkynyl, _{C1-C4 alkylamino, halo-C1 -C4} alkylamino, _C1 - _C4 dialkylamino, _C3 - _C6 cycloalkylamino, _C1 - _C4 alkylcarbonyl, _C1 - _C4 alkoxycarbonyl, _C1 - _C4 alkylsulfonyl, _C1 - _C4 alkylaminocarbonyl, _{C1 -C4} alkylaminosulfonyl, _C1 -C4 alkoxyC1- _C4 alkyl, _C1 -C4 alkoxycarbonylC1- _C4 alkyl, _C1 - _C4 alkylcarbonyloxy, C1- _{C4 alkylcarbonylamino, C1-C4 alkoxycarbonyloxy, C1-C4 alkylaminocarbonyloxy , C1 - C4 alkylsulfonyloxy} , _C1 - _C4 alkoxyC1- _C4 alkoxy, halogenated _C1 - _C4 alkoxyC1- _C4 alkoxy, or _{C1 -} C4 alkoxycarbonylC1- _C4 alkoxy; m is selected from 0 _{, 1} , 2, _{3 , 4 ,} or ₅ ; when m is greater than ₁ , X can be the same or different;

Y is selected from O or S;

Z is selected from O or S;

n is selected from 0 or 1;

Salts formed by compounds of general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid, or citric acid.

In one possible implementation, in general formula I,

_A1 is selected from N or _C1 , and _R1 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl;

_A2 is selected from _CR2 , and _R2 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halo- _C1 - _C3 alkyl;

_A3 is selected from N or _CR3 , and _R3 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl;

_A4 is selected from _CR4 , and _R4 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl;

Furthermore, at most one of _A1 and _A3 can be selected from N;

X is selected from hydrogen, halogen, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, _C1 - _C4 alkyl, halo- _C1 - _C4 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C4 alkoxy, halo- _C1 - _C4 alkoxy, _C1 - _C4 alkylthio, _{halo-C1 - C4} alkylthio, _C2 - _C4 alkenyl, halo- _C2 - _C4 alkenyl _{, C2-C4 alkynyl ,} halo- _C2 - _C4 alkynyl, _{C1-C4 alkylamino, halo-C1 -C4} alkylamino, _C1 - _C4 dialkylamino, _C3 - _C6 cycloalkylamino, _C1 - _C4 alkylcarbonyl, _C1 - _C4 alkoxycarbonyl, _C1 - _C4 alkylsulfonyl, _C1 - _C4 alkylaminocarbonyl, _{C1 -C4} alkylaminosulfonyl, _C1 -C4 alkoxyC1- _C2 alkyl, _C1 -C4 alkoxycarbonylC1- _C2 alkyl, _C1 - _C4 alkylcarbonyloxy, C1- _{C4 alkylcarbonylamino, C1-C4 alkoxycarbonyloxy, C1-C4 alkylaminocarbonyloxy , C1 - C4 alkylsulfonyloxy} , _C1 - _C4 alkoxyC1- _C2 alkoxy, halogenated _C1 - _C4 alkoxyC1- _C2 alkoxy, or _{C1 -} C4 alkoxycarbonylC1- _C2 alkoxy; m is selected from 0 _{, 1 , 2, 3 , 4} , or ₅ ; when m is greater than _{1 ,} X can be the same or different;

Y is selected from O or S;

Z is selected from O or S;

n is selected from 0 or 1;

Salts formed by compounds of general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid, or citric acid.

In one possible implementation, in general formula I,

_A1 is selected from N or _CR1 , and _R1 is selected from hydrogen, fluorine, or methyl.

_A2 is selected from _CR2 , and _R2 is selected from hydrogen, fluorine, or methyl.

_A3 is selected from N or _CR3 , and _R3 is selected from hydrogen, fluorine, or methyl.

_A4 is selected from _CR4 , and _R4 is selected from hydrogen, fluorine, or methyl.

Furthermore, at most one of _A1 and _A3 can be selected from N;

X is selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethyl, trifluoromethyl, di ... Fluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, vinyl, 1-propenyl, 2-propenyl, ethynyl, 1-propynyl, methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, methylethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, or n-butoxycarbonyl; m is selected from 0, 1, 2, 3, 4, or 5; when m is greater than 1, X can be the same or different;

Y is selected from O or S;

Z is selected from O or S;

n is selected from 0 or 1;

Salts formed by compounds of general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid, or citric acid.

In one possible implementation, in general formula I,

_A1 is selected from _CR1 , and _R1 is selected from hydrogen or fluorine;

_A2 is selected from _CR2 , and _R2 is selected from hydrogen or fluorine;

_A3 is selected from _CR3 , and _R3 is selected from hydrogen or fluorine;

_A4 is selected from _CR4 , and _R4 is selected from hydrogen or fluorine;

X is selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethyl, trifluoromethyl, di ... Fluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, vinyl, 1-propenyl, 2-propenyl, ethynyl, 1-propynyl, methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, methylethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, or n-butoxycarbonyl; m is selected from 0, 1, 2, 3, 4, or 5; when m is greater than 1, X can be the same or different;

Y is selected from O or S;

Z is selected from O or S;

n is selected from 0 or 1;

Salts formed by compounds of general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid, or citric acid.

In the definitions of general formula compounds given above, the terms used in the compilation generally represent the following substituents:

Halogens: refer to fluorine, chlorine, bromine or iodine.

Alkyl: Straight-chain or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl or different butyl, pentyl or hexyl isomers.

Cycloalkyl: refers to substituted or unsubstituted cyclic alkyl groups, such as cyclopropyl, cyclopentyl, or cyclohexyl; substituents include methyl, halogen, etc.

Halogenated alkyl groups: straight-chain or branched alkyl groups in which hydrogen atoms may be partially or completely replaced by halogens, such as monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, etc.

Alkoxy groups: straight-chain or branched alkyl groups that are attached to the structure by oxygen atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc.

Halogenated alkoxy groups: The hydrogen atoms on the alkoxy group can be partially or completely replaced by halogens, such as monochloromethoxy, dichloromethoxy, trichloromethoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, 2,2,2-trifluoroethoxy, etc.

Alkylthio group: a straight-chain or branched alkyl group that is attached to the structure by a sulfur atom bond, such as methylthio and ethylthio.

Halogenated alkylthio groups: The hydrogen atoms on the alkylthio group can be partially or completely replaced by halogens, such as chloromethylthio, difluoromethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, etc.

Alkenyl groups include straight-chain or branched alkenes, such as vinyl, 1-propenyl, 2-propenyl and various butenyl, pentenyl and hexenyl isomers; alkenyl groups also include polyenes such as 1,2-propadienyl and 2,4-hexadienyl.

Haloalkenyl: An alkenyl group in which at least one or more hydrogen atoms can be replaced by halogen atoms.

Alkynyl groups include straight-chain or branched alkynes, such as ethynyl, 1-propynyl and various butynyl, penynyl and hexynyl isomers; alkynyl groups also include groups composed of multiple triple bonds, such as 2,5-hexadiynyl.

Halogenated alkynyl group: an alkynyl group in which at least one or more hydrogen atoms can be replaced by a halogen atom.

Alkylamino: Straight-chain or branched alkyl groups, linked to the structure by nitrogen bonds, such as methylamino, ethylamino, n-propylamino, isopropylamino, or isomeric butylamine.

Halogenated alkylamino groups: straight-chain or branched alkylamino groups in which hydrogen atoms may be partially or completely replaced by halogen atoms, such as chloromethylamino, dichloromethylamino, trichloromethylamino, fluoromethylamino, difluoromethylamino, trifluoromethylamino, chlorofluoromethylamino, or trifluoroethylamino.

Dialkylamino: Two identical or different straight-chain or branched alkyl groups are linked together in a structure by a nitrogen atom bond, such as dimethylamino, methylethylamino, etc.

Cycloalkylamino: cycloalkyl-NH-, for example, cyclopropylamino.

Alkyl carbonyl: alkyl-CO-, such as acetyl, propionyl, etc.

Alkoxycarbonyl: alkyl-O-CO-, such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl or n-butoxycarbonyl.

Alkyl sulfonyl: alkyl-S(O) _2- , for example, methyl sulfonyl.

Alkylaminocarbonyl: alkyl-NH-CO-, for example _CH3NHCO- .

Alkylaminosulfonyl: alkyl-NH-S(O) _2- , for example _CH3NHS (O) _2- .

Alkoxyalkyl: alkyl _- O-alkyl-, for example _CH3OCH2- .

Alkoxycarbonylalkyl: alkyl _- O-CO-alkyl-, for example _CH3OCOCH2- .

Alkyl carbonyloxy group: alkyl-CO-O-.

Alkyl carbonyl amino: alkyl-CO-NH-, such as: _CH3CONH- .

Alkoxycarbonyloxy: alkyl-O-CO-O-.

Alkylaminocarbonyloxy group: alkyl- _NH₂ -CO-O-.

Alkylsulfonyloxy: alkyl-S(O) ₂ -O-.

Alkoxy: Alkyl-O-alkyl _- O-, for example _CH3OCH2O- .

Halogenated alkoxyalkoxy groups: straight-chain or branched alkoxyalkoxy groups in which the hydrogen atoms may be partially or completely replaced by halogens.

Alkoxycarbonylalkoxy: alkyl-O-CO-alkyl-O-.

Some of the compounds of general formula I in this invention are shown below, but this invention is by no means limited to these compounds.

In general formula I, when _A1 = _A2 = _A3 = _A4 = CH, n = 0 and Y = Z = O, (X) _m represents different substituents as shown in Table 1, with the compounds numbered 1.1-1.321.

Table 1

In general formula I, when _A1 = CF, _A2 = _A3 = _A4 = CH, n = 0 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 2.1-2.321, which correspond to 1.1-1.321 in Table 1.

In general formula I, when _A3 = CF, _A1 = _A2 = _A4 = CH, n = 0 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 3.1-3.321, which correspond to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = CF, _A2 = _A4 = CH, n = 0 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 4.1-4.321, which correspond to 1.1-1.321 in Table 1.

In general formula I, when _A1 = C- _CH3 , _A2 = _A3 = _A4 = CH, n = 0 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 5.1-5.321, which correspond to 1.1-1.321 in Table 1.

In general formula I, when _A3 = C- _CH3 , _A1 = _A2 = _A4 = CH, n = 0 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 6.1-6.321, which correspond to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = C- _CH3 , _A2 = _A4 = CH, n = 0 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 7.1-7.321, which correspond to 1.1-1.321 in Table 1.

In general formula I, when _A1 = N, _A2 = _A3 = _A4 = CH, n = 0 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 8.1-8.321, which correspond to 1.1-1.321 in Table 1.

In general formula I, when _A3 = N, _A1 = _A2 = _A4 = CH, n = 0 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 9.1-9.321, which correspond to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = N, _A2 = _A4 = CH, n = 0 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 10.1-10.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A2 = _A3 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 11.1-11.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = CF, _A2 = _A3 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 12.1-12.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A3 = CF, _A1 = _A2 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 13.1-13.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = CF, _A2 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 14.1-14.321, which correspond to 1.1-1.321 in Table 1.

In general formula I, when _A1 = C- _CH3 , _A2 = _A3 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 15.1-15.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A3 = C- _CH3 , _A1 = _A2 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 16.1-16.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = C- _CH3 , _A2 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 17.1-17.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = N, _A2 = _A3 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 18.1-18.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A3 = N, _A1 = _A2 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 19.1-19.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = N, _A2 = _A4 = CH, n = 0 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 20.1-20.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A2 = _A3 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 21.1-21.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = CF, _A2 = _A3 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 22.1-22.321, which correspond to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = CF, _A1 = _A2 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 23.1-23.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = CF, _A2 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 24.1-24.321, which correspond to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = C- _CH3 , _A2 = _A3 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 25.1-25.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = C- _CH3 , _A1 = _A2 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 26.1-26.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = C- _CH3 , _A2 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 27.1-27.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = N, _A2 = _A3 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 28.1-28.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A3 = N, _A1 = _A2 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 29.1-29.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = N, _A2 = _A4 = CH, n = 0, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 30.1-30.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A2 = _A3 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 31.1-31.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = CF, _A2 = _A3 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 32.1-32.321, which correspond to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = CF, _A1 = _A2 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 33.1-33.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = CF, _A2 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 34.1-34.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = C- _CH3 , _A2 = _A3 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 35.1-35.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = C- _CH3 , _A1 = _A2 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 36.1-36.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A3 = C- _CH3 , _A2 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 37.1-37.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = N, _A2 = _A3 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 38.1-38.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = N, _A1 = _A2 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 39.1-39.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A3 = N, _A2 = _A4 = CH, n = 0, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 40.1-40.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A2 = _A3 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 41.1-41.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = CF, _A2 = _A3 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 42.1-42.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A3 = CF, _A1 = _A2 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 43.1-43.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = CF, _A2 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 44.1-44.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = C- _CH3 , _A2 = _A3 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 45.1-45.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = C- _CH3 , _A1 = _A2 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 46.1-46.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = C- _CH3 , _A2 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 47.1-47.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = N, _A2 = _A3 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 48.1-48.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A3 = N, _A1 = _A2 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 49.1-49.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A3 = N, _A2 = _A4 = CH, n = 1 and Y = Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 50.1-50.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A2 = _A3 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 51.1-51.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = CF, _A2 = _A3 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 52.1-52.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A3 = CF, _A1 = _A2 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 53.1-53.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = CF, _A2 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 54.1-54.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = C- _CH3 , _A2 = _A3 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 55.1-55.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A3 = C- _CH3 , _A1 = _A2 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 56.1-56.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = C- _CH3 , _A2 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 57.1-57.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = N, _A2 = _A3 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 58.1-58.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A3 = N, _A1 = _A2 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 59.1-59.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A3 = N, _A2 = _A4 = CH, n = 1 and Y = Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 60.1-60.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A2 = _A3 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 61.1-61.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = CF, _A2 = _A3 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 62.1-62.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = CF, _A1 = _A2 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 63.1-63.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A3 = CF, _A2 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 64.1-64.321, which correspond to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = C- _CH3 , _A2 = _A3 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 65.1-65.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = C- _CH3 , _A1 = _A2 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 66.1-66.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = C- _CH3 , _A2 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 67.1-67.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = N, _A2 = _A3 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 68.1-68.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = N, _A1 = _A2 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 69.1-69.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A3 = N, _A2 = _A4 = CH, n = 1, Y = S and Z = O, the substituent (X) _m is consistent with Table 1, representing compounds numbered 70.1-70.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A2 = _A3 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 71.1-71.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = CF, _A2 = _A3 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 72.1-72.321, which correspond to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = CF, _A1 = _A2 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 73.1-73.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = CF, _A2 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 74.1-74.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = C- _CH3 , _A2 = _A3 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 75.1-75.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = C- _CH3 , _A1 = _A2 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 76.1-76.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = _A3 = C- _CH3 , _A2 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 77.1-77.321, corresponding to 1.1-1.321 in Table 1.

In general formula I, when _A1 = N, _A2 = _A3 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 78.1-78.321, corresponding to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A3 = N, _A1 = _A2 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 79.1-79.321, which correspond to 1.1-1.321 in Table 1 respectively.

In general formula I, when _A1 = _A3 = N, _A2 = _A4 = CH, n = 1, Y = O and Z = S, the substituent (X) _m is consistent with Table 1, representing compounds numbered 80.1-80.321, corresponding to 1.1-1.321 in Table 1 respectively.

The compounds of general formula I of the present invention include compounds of general formula I-1, general formula I-2, general formula I-3 and general formula I-4.

When the compound of general formula I of the present invention is a compound of general formula I-1 or a compound of general formula I-2, the compound of general formula I of the present invention can be prepared according to the following scheme (unless otherwise specified, each group is defined as before, wherein L is Br, Cl or I, and M is OH, Br, Cl or I):

Step (1): Preparation of compound IV from compound V

Compound of general formula V can be prepared by reacting N-hydroxyethyl phthalimide (CAS: 3891-07-4) with a suitable solvent in the presence of a base for 0.5-48 hours at a temperature ranging from -10°C to the boiling point of the solvent.

Step (2): Preparation of compound of general formula III from compound of general formula IV

Compounds of general formula IV can be reacted in a suitable solvent with hydrazine hydrate for 0.5-48 hours at temperatures ranging from -10°C to the solvent boiling point to obtain compounds of general formula III.

Step (3): Preparation of compound I-1 from compound III

Method 1 (when M is OH): Compound of general formula I-1 can be prepared by reacting compound of general formula III with compound of general formula II in the presence of a condensing agent in a suitable solvent at a temperature ranging from -10°C to the boiling point of the solvent for 0.5-48 hours. The reaction can be carried out in the presence or absence of a base. Condensing agents can be ethyl chloroformate, isobutyl ester, carbonyl diimidazole (CDI), methanesulfonyl chloride, p-toluenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, Boc anhydride, dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDCI), O-(7-azabenzotriazol-1-yl)-di(dimethylamino)carbodiium hexafluorophosphate (HATU), O-(benzotriazol-1-yl)-di(dimethylamino)carbodiium hexafluorophosphate (HBTU), O-(5-chlorobenzotriazol-1-yl)-di(dimethylamino)carbodiium tetrafluoroborate (TBTU), O-( N-Succinimide-Di(dimethylamino)carbomonium tetrafluoroborate (TSTU), O-(N-endo-5-norcamphene-2,3-dicarbomonimide)-Di(dimethylamino)carbomonium tetrafluoroborate (TNTU), Benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphate (BOP), Benzotriazol-1-yloxy-tris(tetrahydropyrrole)phosphonium hexafluorophosphate (PyBOP), Diphenylphosphine chloride (DPP-Cl), Diethyl cyanophosphate (DECP), Diphenyl phosphate azid (DPPA), Thiodimethylphosphoazide (MPTA), Di(2-oxo-3-azoloalkyl)phosphine chloride (BOP-Cl), Triphenylphosphine-polyhalomethane, Triphenylphosphine-hexachloroacetone, Triphenylphosphine-NBS, etc.

Method 2 (when M is Br, Cl, or I):

Compound of general formula I-1 can be prepared by reacting compound of general formula III with compound of general formula II in a suitable solvent at a temperature ranging from -10°C to the boiling point of the solvent for 0.5–48 hours. The reaction can be carried out in the presence or absence of a base.

Step (4): Preparation of compound I-2 from compound I-1

Compound of general formula I-1 can be reacted with a sulfiding agent in a suitable solvent at a temperature ranging from -10°C to the solvent's boiling point for 0.5–48 hours to prepare compound of general formula I-2. The sulfiding agent can be hydrogen sulfide, phosphorus pentasulfide, boron sulfide, phosphoryl bromide, or Lawesson's reagent, etc.

In steps (1) to (4) above: suitable solvents may be the same or different, such as aromatic hydrocarbons like benzene, toluene, and xylene; ketones like acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbons like chloroform and dichloromethane; esters like methyl acetate and ethyl acetate; ethers like tetrahydrofuran, 1,4-dioxane, diethyl ether, 1,2-dimethoxyethane, and 1,4-dioxane; polar solvents like water, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and hexamethylphosphoric acid triamine; or a mixture of the above solvents. Suitable bases, which may be the same or different, include organic bases such as trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine, and N,N-diisopropylethylamine; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate; and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, and sodium tert-butoxide.

When the compound of general formula I of the present invention is a compound of general formula I-3 or a compound of general formula I-4, the compound of general formula I of the present invention can be prepared according to the following scheme (unless otherwise specified, each group is defined as before, wherein L is Br, Cl or I, and M is OH, Br, Cl or I):

Step (1): Preparation of compound VI from compound V

Compound of general formula V can be prepared by reacting cysteine hydrochloride (CAS: 156-57-0) with a suitable solvent in the presence of a base at a temperature ranging from -10°C to the boiling point of the solvent for 0.5-48 hours.

Step (2): Preparation of compound I-3 from compound VI

Method 1 (when M is OH): Compounds of general formula I-3 can be prepared by reacting compounds of general formula VI and general formula II in the presence of a condensing agent in a suitable solvent at a temperature ranging from -10°C to the boiling point of the solvent for 0.5-48 hours. The reaction can be carried out in the presence or absence of a base. Condensing agents can be ethyl chloroformate, isobutyl ester, carbonyl diimidazole (CDI), methanesulfonyl chloride, p-toluenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, Boc anhydride, dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDCI), O-(7-azabenzotriazol-1-yl)-di(dimethylamino)carbodiium hexafluorophosphate (HATU), O-(benzotriazol-1-yl)-di(dimethylamino)carbodiium hexafluorophosphate (HBTU), O-(5-chlorobenzotriazol-1-yl)-di(dimethylamino)carbodiium tetrafluoroborate (TBTU), O-( N-Succinimide-Di(dimethylamino)carbomonium tetrafluoroborate (TSTU), O-(N-endo-5-norcamphene-2,3-dicarbomonimide)-Di(dimethylamino)carbomonium tetrafluoroborate (TNTU), Benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphate (BOP), Benzotriazol-1-yloxy-tris(tetrahydropyrrole)phosphonium hexafluorophosphate (PyBOP), Diphenylphosphine chloride (DPP-Cl), Diethyl cyanophosphate (DECP), Diphenyl phosphate azid (DPPA), Thiodimethylphosphoazide (MPTA), Di(2-oxo-3-azoloalkyl)phosphine chloride (BOP-Cl), Triphenylphosphine-polyhalomethane, Triphenylphosphine-hexachloroacetone, Triphenylphosphine-NBS, etc.

Method 2 (when M is Br, Cl, or I):

Compounds of general formula I-3 can be prepared by reacting compounds of general formula VI and general formula II in a suitable solvent at temperatures ranging from -10°C to the solvent's boiling point for 0.5–48 hours. The reaction can be carried out in the presence or absence of a base.

Step (3): Preparation of compound I-4 from compound I-3

Compounds of general formula I-3 can be prepared by reacting a compound with a sulfiding agent in a suitable solvent at a temperature ranging from -10°C to the solvent's boiling point for 0.5–48 hours. The sulfiding agent can be hydrogen sulfide, phosphorus pentasulfide, boron sulfide, phosphoryl bromide, or Lawesson's reagent, etc.

In steps (1) to (3) above: suitable solvents may be the same or different, such as aromatic hydrocarbons like benzene, toluene, and xylene; ketones like acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbons like chloroform and dichloromethane; esters like methyl acetate and ethyl acetate; ethers like tetrahydrofuran, 1,4-dioxane, diethyl ether, 1,2-dimethoxyethane, and 1,4-dioxane; polar solvents like water, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and hexamethylphosphoric acid triamine; or a mixture of the above solvents. Suitable bases, which may be the same or different, include organic bases such as trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine, and N,N-diisopropylethylamine; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate; and metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, and sodium tert-butoxide.

Compounds of general formula II can be prepared by known methods (e.g., methods reported for WO2019171234, WO2019150219, WO2013008162, WO2017076935, WO2013080120, WO2015185485, WO2016179554, WO2022174193, WO2013066835, WO2017198852, WO2017157962, etc.).

Compounds of general formula V and other conventional raw materials and reagents are usually commercially available, or they can be prepared in-house using conventional methods.

The compound represented by general formula I of this invention is used to control diseases caused by various fungi such as oomycetes, basidiomycetes, ascomycetes, and deuteromycetes on a variety of crops. For example, it has good control efficacy against diseases such as cucumber downy mildew, cucumber gray mold, cucumber anthracnose, cucumber powdery mildew, tomato early blight, tomato late blight, pepper blight, grape downy mildew, grape white rot, apple ring rot, apple leaf spot, rice sheath blight, rice blast, wheat rust, wheat leaf spot, wheat powdery mildew, rapeseed sclerotinia rot, corn leaf spot, and soybean rust at low doses.

Due to their positive properties, the above compounds can be advantageously used to protect important crops, livestock and breeding stock in agriculture and horticulture, as well as environments frequented by humans, from pathogens.

To achieve the desired effect, the amount of compound used varies depending on various factors, such as the compound used, the crop being protected, the type of pest, the degree of infection, climatic conditions, the application method, and the formulation used.

A compound dosage of 5 grams to 5 kilograms per hectare can provide adequate control.

The present invention also includes a fungicide using a compound of general formula I as the active ingredient. The fungicide contains an active ingredient at a weight percentage between 0.1% and 99%. The fungicide also includes agriculturally, forestryly, and health-acceptable carriers and adjuvants.

The bactericides of the present invention can be applied in formulation form. Compounds of general formula I are dissolved or dispersed as active components in a carrier and/or adjuvants, or formulated into preparations for easier dispersion when used as bactericides.

This invention uses a compound of general formula I as the active component and can prepare various formulations of the compound of general formula I in accordance with methods well known in the art, including aqueous solutions, soluble liquids, emulsifiable concentrates, microemulsions, water-in-oil emulsions, suspensions, suspension seed coatings, dispersible oil suspensions, ultra-low volume formulations, powders, wettable powders, soluble powders, emulsifiable powders, granules, water-dispersible granules, soluble granules, emulsifiable granules, dry suspensions, effervescent granules, floating granules, tablets, soluble tablets, effervescent tablets, microcapsule powders, and microcapsule suspensions. In any case, the selection of the formulation type depends on the physical, chemical, and biological properties of the compound of general formula I.

The bactericidal formulations of the compounds of general formula I of this invention can be prepared by conventional processing methods, namely, mixing the active substance with a liquid or solid carrier and adding one or more surfactants such as emulsifiers, dispersants, wetting agents, thickeners, stabilizers, and defoamers. Typically, the composition contains at least one carrier and at least one surfactant. In all cases, it should be ensured that the active components of the compositions of this invention are uniformly distributed.

Aqueous formulations are made by uniformly mixing a compound of general formula I, a surfactant, and water to form a homogeneous and transparent liquid. They typically contain 5–50% active ingredient, 5–20% emulsifier, 0–10% other additives such as penetrants, and the balance being water.

Soluble liquids are formed by uniformly mixing a compound of general formula I, a surfactant, and a non-aqueous polar solvent to form a homogeneous and transparent liquid. Soluble liquids typically contain 5–60% active ingredient, 5–20% emulsifier, 0–10% other additives such as penetrants, and the balance being a liquid carrier.

Emulsifiable concentrates (ECs) are homogeneous oily liquids formed by uniformly mixing a compound of general formula I, a surfactant, and an organic solvent. Emulsifiable concentrates typically contain 1–70% of the active ingredient, 5–20% of the emulsifier, 0–10% of other additives such as penetrants and stabilizers, and the balance being a liquid carrier.

Microemulsions are formed by uniformly mixing a compound of general formula I, a surfactant, water, and an organic solvent to create a homogeneous, transparent liquid. Microemulsions typically contain 1–50% active ingredient, 5–30% emulsifier, 2–10% antifreeze, 0–10% other additives such as penetrants and stabilizers, and the balance being a liquid carrier.

A water-in-oil emulsion is prepared by uniformly mixing a compound of general formula I, a surfactant, and an organic solvent to form an oil phase; and by mixing water and antifreeze together to form an aqueous phase. The oil phase is then sheared at high speed using a high-shear emulsifier while the aqueous phase is slowly added to the oil phase, resulting in a uniformly dispersed water-in-oil emulsion. It typically contains 5–50% active ingredient, 5–20% emulsifier, 2–5% antifreeze, and the balance being a liquid carrier.

A suspending agent is produced by uniformly mixing a compound of general formula I, a dispersant, a wetting agent, an antifreeze, and water, followed by sand milling to obtain a stable, non-depositional, flowable liquid. Suspensions typically contain 5–50% active ingredient, 2–10% dispersant, 2–5% wetting agent, 2–5% antifreeze, 0–10% other additives such as defoamers, thickeners, and preservatives, with the balance being a liquid carrier.

Suspension seed coating agents are made by uniformly mixing a compound of general formula I, a dispersant, a wetting agent, a film-forming agent, and water, followed by sand milling to obtain a stable, non-depositional, flowable liquid. Suspension seed coating agents typically contain 1–50% active ingredient, 2–10% dispersant, 2–5% wetting agent, 2–5% antifreeze, 2–10% film-forming agent, 0–10% other additives such as defoamers, thickeners, preservatives, warning colors, and the balance being a liquid carrier.

Dispersible oil suspensions are produced by uniformly mixing a compound of general formula I, a surfactant, and an oil-based carrier, followed by sand milling to obtain a stable, non-depositing, flowable liquid. Dispersible oil suspensions typically contain 5–50% active ingredient, 5–30% surfactant, 0–10% other additives such as thickeners and stabilizers, and the balance being a liquid carrier.

Ultra-low capacity agents are produced by uniformly mixing a compound of general formula I, a surfactant, and an organic solvent to form a homogeneous and transparent oil phase. They typically contain 1–30% active ingredient, 5–30% emulsifier, 0–10% other additives such as stabilizers, and the remainder being a liquid carrier.

Powders are produced by mixing a compound of general formula I, additives, and a carrier, and then pulverizing the mixture to obtain a powder. Powders typically contain 5-85% active ingredient, 5-10% dispersant, 0-10% other additives such as stabilizers, and the balance being a solid carrier.

Wettable powders are made by mixing a compound of general formula I, a dispersant, a wetting agent, and a carrier, and then pulverizing the mixture to obtain a powder. Wettable powders typically contain 5-85% active ingredient, 5-10% dispersant, 1-10% wetting agent, 0-10% other additives such as stabilizers, and the balance being a solid carrier.

Soluble powders are produced by mixing a compound of general formula I, a dispersant, a wetting agent, and a carrier, and then pulverizing the mixture to obtain a powder. Soluble powders typically contain 5–80% active ingredient, 5–10% dispersant, 1–10% wetting agent, 0–10% other additives such as stabilizers, and the balance being a solid carrier.

Emulsifiable powders are made by mixing a compound of general formula I, a surfactant, and an organic solvent to form a homogeneous, transparent oil phase, which is then uniformly sprayed onto a pre-crushed carrier. Emulsifiable powders typically contain 5–50% active ingredient, 5–30% emulsifier, 5–10% wetting and dispersing agent, 0–15% organic solvent, and the balance being a solid carrier.

Granulations are made by mixing a compound of general formula I, additives, and a carrier, followed by kneading, granulation, drying, and coating. Granulations typically contain 0.5–20% active ingredient, 0.1–10% binder, 0–10% other additives such as stabilizers, and the balance being a solid carrier.

Water-dispersible granules are made by mixing a compound of general formula I, a dispersant, a wetting agent, a disintegrant, and a carrier, followed by kneading, granulation, and drying. Water-dispersible granules typically contain 5–85% active ingredient, 1–10% dispersant, 1–10% wetting agent, 0.1–10% binder, 0–10% other additives such as disintegrants and stabilizers, and the balance being a solid carrier.

Soluble granules are made by mixing a compound of general formula I, a dispersant, a wetting agent, a disintegrant, and a carrier, followed by kneading, granulation, and drying. Soluble granules typically contain 5–85% active ingredient, 1–10% dispersant, 1–10% wetting agent, 0.1–10% binder, 0–10% other additives such as disintegrants and stabilizers, and the balance being a solid carrier.

Emulsifiable granules are made by mixing a compound of general formula I, a surfactant, and an organic solvent to form a homogeneous, transparent oil phase. This oil phase is then uniformly sprayed onto a pre-crushed carrier, kneaded, granulated, and dried. Emulsifiable granules typically contain 5–50% active ingredient, 5–30% emulsifier, 5–10% wetting and dispersing agent, 0–15% organic solvent, 0–10% other additives such as disintegrants, stabilizers, and binders, with the balance being a solid carrier.

Dry suspensions are made by uniformly mixing a compound of general formula I, a dispersant, a wetting agent, a carrier, and water, then milling the mixture in a sand mill, followed by spray drying. Dry suspensions typically contain 5–80% active ingredient, 2–20% dispersant, 2–10% wetting agent, 0–10% other additives such as defoamers and thickeners, and the remainder being a solid carrier.

Effervescent granules are made by mixing a compound of general formula I, a wetting and dispersing agent, an effervescent disintegrant, and a carrier, and then kneading and granulating the mixture. Effervescent granules typically contain 0.5–30% of the active ingredient, 2–20% of the wetting and dispersing agent, 2–20% of the effervescent disintegrant, 0–10% of other additives such as stabilizers and binders, and the balance being a solid carrier.

Floating granules are made by mixing a compound of general formula I, a wetting and dispersing agent, cenospheres, and a carrier, followed by kneading and granulation. Floating granules typically contain 0.5–30% active ingredient, 2–20% wetting and dispersing agent, 5–20% cenospheres, 0–10% other additives such as stabilizers, binders, and disintegrants, with the balance being a solid carrier.

Tablets are made by mixing a compound of general formula I, a dispersant, a wetting agent, a disintegrant, and a carrier, then kneading, compressing, and drying. Tablets typically contain 5–50% of the active ingredient, 1–10% of the dispersant, 1–10% of the wetting agent, 0.1–10% of the binder, 0–10% of other additives such as disintegrants and stabilizers, and the balance being a solid carrier.

Soluble tablets are made by mixing a compound of general formula I, a dispersant, a wetting agent, a disintegrant, and a carrier, then kneading, compressing, and drying the mixture. Soluble tablets typically contain 5–50% of the active ingredient, 1–10% of the dispersant, 1–10% of the wetting agent, 0.1–10% of the binder, 0–10% of other additives such as disintegrants and stabilizers, and the balance being a solid carrier.

Effervescent tablets are made by mixing a compound of general formula I, a wetting and dispersing agent, an effervescent disintegrant, and a carrier, then kneading and compressing the mixture. Effervescent tablets typically contain 0.5–30% of the active ingredient, 2–20% of the wetting and dispersing agent, 2–20% of the effervescent disintegrant, 0–10% of other additives such as stabilizers and binders, and the balance being a solid carrier.

Microcapsule powder is produced by dissolving a compound of general formula I in a solvent, adding an emulsifier and wall material, and stirring until homogeneous to obtain an oil phase; adding a dispersant to water to obtain an aqueous phase; adding the oil phase to the aqueous phase under high-speed stirring to form an oil-in-water emulsion; adding a curing agent to the emulsion under stirring conditions, heating and maintaining the temperature to form capsules, and then filtering and drying. Microcapsule powder typically contains 0.5–30% active ingredient, 2–10% emulsifier, 2–10% wetting and dispersing agent, 5–30% other additives such as wall material, defoamer, curing agent, stabilizer, and the balance being a solid carrier.

Microcapsule suspensions are prepared by dissolving a compound of general formula I in a solvent, adding an emulsifier and wall material, and stirring until homogeneous to obtain an oil phase; adding a dispersant to water to obtain an aqueous phase; adding the oil phase to the aqueous phase under high-speed stirring to form an oil-in-water emulsion; adding a curing agent to the emulsion under stirring conditions, heating and maintaining the temperature to form microcapsules, thus forming a microcapsule suspension. Microcapsule suspensions typically contain 0.5–30% active ingredient, 2–10% emulsifier, 2–10% wetting and dispersing agent, 5–30% other additives such as wall material, defoamer, preservative, thickener, curing agent, stabilizer, and the balance being a liquid carrier.

The bactericidal formulation of the compound of general formula I of this invention can be prepared using (liquid or solid) carriers and various adjuvants known to those skilled in the art. Examples include, but are not limited to, the following substances.

Suitable surfactants in the bactericidal formulations of the compounds of general formula I of this invention can be emulsifiers, dispersants, or wetting agents; they can be one or more of nonionic or ionic surfactants. Ionic surfactants are selected from sulfonates, sulfates, carboxylates, phosphate esters, succinates, lignin sulfonates, acrylamide-acrylic acid copolymers, etc. Nonionic surfactants are selected from fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty amine polyoxyethylene ethers, fatty acid polyoxyethylene ethers, acid alcohol esters and their polyoxyethylene ethers, alkyl polyethylene glycol ethers, alkyl phenyl polyethylene glycol ethers, fatty amides and their polyoxyethylene ethers, alkanolamides and their polyoxyethylene ethers, polyoxyethylene polyoxypropylene ether block copolymers, sodium alkylnaphthalene sulfonate fatty alcohol polyoxyethylene ethers, sorbitan fatty acid ester polyoxyethylene ethers, etc.

The surfactants mentioned above can be selected from one or more of the surfactants shown, such as: sodium or calcium lignin sulfonate, polyoxyethylene (n20) phenylethylphenol oleate, alkyl aryl polyoxyethylene polyoxypropylene ether, tristyrylphenol polyoxyethylene (n20) ether phosphorylated triethanolamine, agricultural emulsion 0201B, agricultural emulsion 0203B, agricultural emulsion 100#, agricultural emulsion 600#, agricultural emulsion 700#, agricultural emulsion 1601#, agricultural emulsion AEO-3, agricultural emulsion AEO-5, agricultural emulsion AEO-7, agricultural emulsion T-20, agricultural emulsion T-80, agricultural emulsion T-85, agricultural emulsion S-80, agricultural emulsion S-85, agricultural emulsion NP-7, agricultural emulsion NP-10, agricultural emulsion NP-15, agricultural emulsion OX-2681, agricultural emulsion OX-8686, agricultural emulsion OX-690, agricultural emulsion 2201#, and polycarboxylate dispersant GY-D8. 00, Polycarboxylate Dispersant GY-D04, Polycarboxylate Dispersant GY-D02, Alkyl Naphthalene Sulfonate Formaldehyde Condensate (NNO), Naphthol Sulfonate Formaldehyde Condensate Sodium Salt, Alkylphenol Polyoxyethylene Polyoxypropylene Ether, Styrene Maleic Anhydride, Methyl Naphthalene Sulfonate Formaldehyde Condensate, Castor Oil Ethyl Oxide Additive, Alkylphenol Polyoxyethylene Polyoxypropylene Ether, Alkyl-Diethylene Glycol Ether-Sulfonate Sodium, N-Methyl-Oleoyl-Taurate Sodium, Detergent LS, Methylene Naphthalene Sulfonate Sodium, Oleate Methylaminoethyl Sulfonate Sodium, Dispersant SP-28F, Dispersant SP-SC3, Darun Dispersant D909S, Alkyl Aryl Polyoxyethylene Ether, Dodecyl Polyoxyethylene Ether Phosphate, Alkylphenol Polyoxyethylene Ether Formaldehyde Condensate, Dibutyl Naphthalene Sulfonate Sodium (Spreading Powder BX), Dibutyl Naphthalene Sulfonate Formaldehyde Condensate, Dispersant SD-81 1. Dispersants SD815, SK-24, SK-20TX, SK-5218, SK-33H, SK-10LX, SK-551, Atlox 4913, EL-20, EL-40, EL-90, YUS-NV1203, YUS-NV1420, YUS-WG4, YUS-TG285, YUS-WP1, YUS-110, YUS-EP60P, YUS-CH1100, SP-OF3468, SP-OF3472, SP-2728, SP-SC29, Suprag IL MNS/90, dispersant Soprophor FD, dispersant YUS-FS1, dispersant YUS-PQ100, dispersant YUS-WG5, YUS-D935, octylphenol polyoxyethylene ether sulfate, Morwet EFW, wetting agent Igepal BC/10, wetting agent GEROPONL-WET/P, wetting agent Rhodasurf860/p, wetting agent SP-SC3266, wetting agent PICO-SW2, wetting agent PICO-SW3, wetting agent YUS-LXC, wetting agent YUS-204, alkyl alcohol polyoxyethylene ether sodium sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkyl succinate sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, calcium dodecylbenzene sulfonate, etc.

In the bactericidal formulation of the compound of general formula I of this invention, a suitable liquid carrier can be one or more of water, organic solvents, and oily media. Suitable organic solvents are selected from aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, alcohols and their ethers, esters, ketones, etc., such as benzene, xylene, toluene, alkylbenzene, alkylnaphthalene, chlorinated benzene, vinyl chloride, trichloroethane, dichloromethane, chloroform, carbon tetrachloride, polychloroethane, petroleum fractions, cyclohexane, methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, glycerol, sorbitol, benzyl alcohol, furfuryl alcohol, cyclohexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, tributyl phosphate, dimethylformamide, and dimethyl sulfoxide, etc. Suitable oily media are selected from soybean oil, methyl oleate, light mineral oil, liquid paraffin, kerosene, turpentine, etc.

Suitable solid carriers for the bactericidal formulations of the compounds of general formula I of this invention include natural or synthetic ones. They may be selected from, but are not limited to, clay, rock powder, chalk, quartz, montmorillonite, sodium sulfate, silica, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, attapulgite, light calcium carbonate, kaolin, montmorillonite, magnesium aluminum silicate, activated clay, white carbon black, ammonium sulfate, benzofuran resin, superphosphate, alumina, calcite, marble, pumice, etc. Suitable particulate carriers include crushed and graded natural rocks such as sepiolite and dolomite, and synthetic particles made from organic and inorganic powders.

Suitable binders and thickeners include synthetic or natural water-soluble polymers. These may be selected from, but are not limited to, carbonyl methyl alcohol, polyvinyl alcohol, polyvinyl acetate, xanthan gum, gelatin, gum arabic, polyvinylpyrrolidone, magnesium aluminum silicate, polyvinyl alcohol, polyethylene glycol, phenolic resin, shellac, methylcellulose, soluble starch, carboxymethyl cellulose, and sodium alginate, and added to the formulation in powder, granule, or latex form.

Suitable defoamers can be selected from, but are not limited to, defoamer SAG1522, silicones, C8-10 fatty alcohols, phosphate esters, C10-20 saturated fatty acids (such as decanoic acid), and amides.

Suitable antifreeze agents can be selected from, but are not limited to, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, ethylene glycol butyl ether, propylene glycol butyl ether, ethylene glycol butyl ether acetate, urea, etc.

Suitable penetrants can be selected from, but are not limited to, organosilicon, penetrant T, penetrant JFC, etc.

Suitable film-forming agents include natural products and their modified forms, as well as synthetic polymers. These can be selected from, but are not limited to, sodium carboxymethyl starch, soluble starch, phosphorylated starch, oxidized starch, chitosan and its derivatives, polypropylene graft copolymers, xanthan gum, sodium alginate, agar, gelatin, gum arabic, polyethylene glycol, polyvinyl alcohol, polyvinyl acetate, polyacrylamide, polyvinylpyrrolidone, polyacrylic acid, etc.

Suitable preservatives can be selected from, but are not limited to, sodium benzoate, Kathon, potassium sorbate, etc.

Suitable disintegrants may be selected from, but are not limited to, sodium carboxymethyl starch, croscarmellose sodium, croscarmellose sodium, modified starch, croscarmellose polyvinylpyrrolidone, ammonium sulfate, sodium sulfate, sodium chloride, ammonium chloride, etc.

Effervescent disintegrants may be acidic and/or basic components. Acidic components may be selected from organic acids or inorganic acids, such as tartaric acid, citric acid, salicylic acid, phosphoric acid, etc.; basic components may be selected from basic carbonates or carbonates, such as sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, etc.

Suitable warning colors can be selected from, but are not limited to, inorganic pigments such as iron oxide, titanium dioxide, or Prussian blue; and organic dyes such as aliasalin, Acid Red G, Basic Rose, azo dyes, and metallic phthalocyanines.

Suitable wall materials include one or more of the following: natural polymers, semi-synthetic polymers, and fully synthetic polymers. Natural polymers can be selected from, but are not limited to, gelatin, gum arabic, agar, alginate, chitosan, fibroin, corn gluten, etc.; semi-synthetic polymers can be selected from, but are not limited to, methyl (ethyl) cellulose, carboxymethyl cellulose (sodium), cellulose acetate and its esters and some glycerides, etc.; fully synthetic polymers can be selected from, but are not limited to, polyacrylate resin, urea-formaldehyde resin, polyamide, polyester, polymethyl methacrylate, polyurea, polyurethane, etc.

Suitable curing agents include one or more of polyols and polyamines. Polyols may be selected from, but are not limited to, ethylene glycol, glycerol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, etc.; polyamines may be selected from, but are not limited to, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, diethanolamine, triethanolamine, hexamethylenetetramine, isophorone diamine, etc.

The bactericidal preparations of the compound of general formula I of this invention can be diluted by the user or directly sprayed with water before use, or they can be used directly.

The technical solution of the present invention also includes a method for controlling pathogens: applying the fungicide of the present invention to the pathogens or their growth medium. A generally suitable effective amount is 10 to 1000 grams per hectare, preferably 10 to 500 grams per hectare.

It should be clearly stated that various modifications and alterations can be made within the scope defined by the claims of this invention.

Detailed Implementation

The following specific embodiments are used to further illustrate the present invention, but the present invention is by no means limited to these examples. (Unless otherwise noted, all raw materials used are commercially available.)

Synthesis Examples

Following the synthetic route described above, compounds of general formula I of this invention can be prepared by using different starting materials, as further described in detail below:

Example 1: Preparation of compounds 1.2 and 31.2

(1) Preparation of intermediate IV-1

N-hydroxyethyl phthalimide (0.98 g, 6.14 mmol) and DMF (20 mL) were added to the reaction flask; stirring was started, and sodium hydride (0.21 g, 60 wt%, 5.25 mmol) was added in portions to the reaction mixture, and the mixture was stirred at room temperature for 15 minutes. Benzyl bromide (1.00 g, 4.90 mmol) was added, and the reaction was continued with stirring. After the reaction was monitored by TLC until complete, residual sodium hydride was quenched with water. The mixture was extracted with ethyl acetate and water, and the organic layer was collected. After desolvation under reduced pressure, 1.30 g of a yellow oily substance, namely intermediate IV-1, was obtained.

(2) Preparation of intermediate III-1

Intermediate IV-1 (1.30 g, 4.13 mmol), ethanol (40 mL), and hydrazine hydrate (5 mL, 80 wt%) were added sequentially to a reaction flask, and the mixture was heated to 85 °C and refluxed. The reaction was stopped when intermediate IV-1 was no longer detected by TLC. The mixture was filtered under reduced pressure, and the filtrate was concentrated under reduced pressure to remove ethanol. The residue was extracted with ethyl acetate and water, and the organic layer was collected. After desolvation under reduced pressure, 0.65 g of a pale yellow oil, namely compound III-1, was obtained.

(3) Preparation of compound 1.2

Intermediate II-1 (0.91 g, 3.53 mmol), carbonyl diimidazole (0.63 g, 3.89 mmol), N,N-diisopropylethylamine (0.45 g, 3.48 mmol), and tetrahydrofuran (25 mL) were added sequentially to the reaction flask, and the mixture was stirred at room temperature for 40 minutes. Intermediate III-1 (0.65 g, 3.51 mmol) was then added to the reaction mixture, and the reaction was continued with stirring. After the reaction was complete as monitored by TLC, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to give 1.25 g of a white solid, namely compound 1.2. ¹ H NMR (600MHz, DMSO-d ₆ )δ8.83(t,1H),8.17(d,2H),8.07(d,2H),7.53(dd,1H),7.44(dd,1H),7.34-7.3 0(m,2H),4.60(s,2H),3.67(t,2H),3.53(dt,2H).LC-MS(m/z,ESI):426.25[M+H] ⁺ .

(4) Preparation of compound 31.2

Compound 1.2 (1.00 g, 2.35 mmol), Lawstson's reagent (1.05 g, 2.60 mmol), and toluene (20 mL) were added sequentially to the reaction flask, and the mixture was heated to 90 °C and refluxed. After the reaction was completed as monitored by TLC, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to give 0.85 g of a yellow solid, namely compound 31.2. ^¹H NMR (600 MHz, DMSO-d6) δ 10.62 (t, 1H), 8.12 (d, 2H), 7.93 (d, 2H), 7.54 (dd, 1H), 7.45 (dd, 1H), 7.38–7.30 (m, 2H), 4.62 (s, 2H), 3.98 (dt, 2H), 3.84 (t, 2H). LC-MS (m/z, ESI): 442.26 [M+H] ⁺ .

Following the synthesis method described in Example 1, the present invention also yielded the following compounds:

Compound 1.1:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.81 (t, ¹H), 8.16 (d, 2H), 8.06 (d, 2H), 7.47 (m, ¹H), 7.40–7.30 (m, ¹H), 7.17 (d, 2H), 4.57 (s, 2H), 3.61 (t, 2H), 3.50 (dt, 2H). LC-MS (m/z, ESI): 410.03 [M+H] ^⁺ .

Compound 1.3:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.82 (t, ¹H), 8.17 (d, 2H), 8.07 (d, 2H), 7.60 (dd, ¹H), 7.52 (dd, 1H), 7.36 (m, ¹H), 7.24 (m, 1H), 4.56 (s, 2H), 3.66 (t, 2H), 3.54 (dt, 2H). LC-MS (m/z, ESI): 470.23 [M+H] ^⁺ .

Compound 1.4:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.83 (t, ¹H), 8.16 (d, 2H), 8.07 (d, 2H), 7.37 (m, ¹H), 7.20–7.14 (m, 2H), 7.12–7.04 (m, ¹H), 4.54 (s, 2H), 3.60 (t, 2H), 3.51 (dt, 2H). LC-MS (m/z, ESI): 410.03 [M+H] ^⁺ .

Compound 1.5:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.83 (t, ¹H), 8.16 (d, 2H), 8.07 (d, 2H), 7.40 (s, ¹H), 7.37–7.28 (m, 3H), 4.53 (s, 2H), 3.60 (t, 2H), 3.51 (dt, 2H). LC-MS (m/z, ESI): 426.27 [M+H] ^⁺ .

Compound 1.6:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.83 (t, ¹H), 8.17 (d, 2H), 8.07 (d, 2H), 7.55 (s, ¹H), 7.48–7.45 (m, ¹H), 7.34 (dt, ¹H), 7.29 (t, ¹H), 4.53 (s, 2H), 3.60 (t, 2H), 3.51 (dt, 2H). LC-MS (m/z, ESI): 470.17 [M+H] ^⁺ .

Compound 1.7:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.80 (t, ¹H), 8.16 (d, 2H), 8.06 (d, 2H), 7.39–7.36 (m, 2H), 7.17–7.14 (m, 2H), 4.50 (s, 2H), 3.58 (t, 2H), 3.50 (dt, 2H). LC-MS (m/z, ESI): 410.25 [M+H] ^⁺ .

Compound 1.8:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.81 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.48–7.29 (m, 4H), 4.51 (s, 2H), 3.59 (t, 2H), 3.50 (dt, 2H). LC-MS (m/z, ESI): 426.26 [M+H] ^⁺ .

Compound 1.9:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.81 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.52 (d, 2H), 7.30 (d, 2H), 4.49 (s, 2H), 3.59 (t, 2H), 3.50 (dt, 2H). LC-MS (m/z, ESI): 470.11 [M+H] ^⁺ .

Compound 1.10:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.83 (t, ¹H), 8.17 (d, 2H), 8.07 (d, 2H), 7.84 (dd, ¹H), 7.46 (dd, 1H), 7.37 (m, ¹H), 7.05 (m, 1H), 4.48 (s, 2H), 3.67 (t, 2H), 3.54 (dt, 2H). LC-MS (m/z, ESI): 518.14 [M+H] ^⁺ .

Compound 1.13:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.83 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.80 (d, 2H), 7.58–7.52 (m, 2H), 4.62 (s, 2H), 3.63 (t, 2H), 3.52 (dt, 2H). LC-MS (m/z, ESI): 518.13 [M+H] ^⁺ .

Compound 1.16:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.80 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.69 (d, 2H), 7.15 (d, 2H), 4.47 (s, 2H), 3.58 (t, 2H), 3.49 (dt, 2H). LC-MS (m/z, ESI): 518.14 [M+H] ^⁺ .

Compound 1.17:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.83 (t, ¹H), 8.17 (d, 2H), 8.07 (d, 2H), 7.84 (dd, ¹H), 7.46 (dd, 1H), 7.37 (dd, 1H), 7.05 (dd, 1H), 4.48 (s, 2H), 3.67 (t, 2H), 3.54 (dt, 2H). LC-MS (m/z, ESI): 417.32 [M+H] ^⁺ .

Compound 1.19:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.81 (t, ¹H), 8.16 (d, 2H), 8.06 (d, 2H), 7.33–7.29 (m, ¹H), 7.20–7.11 (m, 3H), 4.50 (s, 2H), 3.61 (t, 2H), 3.51 (dt, 2H), 2.26 (s, 3H). LC-MS (m/z, ESI): 428.32 [M+Na] ^⁺ .

Compound 1.22:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.81 (t, ¹H), 8.16 (d, 2H), 8.07 (d, 2H), 7.20 (t, ¹H), 7.14 (s, ¹H), 7.11 (d, 1H), 7.07 (d, 1H), 4.48 (s, 2H), 3.57 (t, 2H), 3.50 (dt, 2H), 2.26 (s, 3H). LC-MS (m/z, ESI): 428.07 [M+Na] ^⁺ .

Compound 1.25:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.81 (t, ¹H), 8.16 (d, 2H), 8.05 (d, 2H), 7.22 (d, 2H), 7.13 (d, 2H), 4.6 (s, 2H), 3.5 (t, 2H), 3.49 (dt, 2H), 2.27 (s, 3H). LC-MS (m/z, ESI): 428.23 [M+Na] ^⁺ .

Compound 1.37:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.82 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.69 (d, 2H), 7.57 (d, 2H), 4.63 (s, 2H), 3.63 (t, 2H), 3.52 (dt, 2H). LC-MS (m/z, ESI): 482.21 [M+Na] ^⁺

Compound 1.42:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.81 (t, ¹H), 8.16 (d, 2H), 8.07 (d, 2H), 7.23 (t, ¹H), 6.90 (d, 2H), 6.83 (dd, ¹H), 4.49 (s, 2H), 3.71 (s, 3H), 3.58 (t, 2H), 3.50 (dt, 2H). LC-MS (m/z, ESI): 444.21 [M+Na] ^⁺ .

Compound 1.43:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.83(t, ¹H), 8.17(d, 2H), 8.07(d, 2H), 7.76–7.70(m, 2H), 7.65(t ¹H), 7.50(t, ¹H), 4.69(s, 2H), 3.66(t, 2H), 3.53(dt, 2H). LC-MS (m/z, ESI): 482.23 [M+Na] ^⁺ .

Compound 1.45:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.79 (t, ¹H), 8.16 (d, 2H), 8.06 (d, 2H), 7.26 (d, 2H), 6.88 (d, 2H), 4.43 (s, 2H), 3.73 (s, 3H), 3.54 (t, 2H), 3.48 (dt, 2H). LC-MS (m/z, ESI): 444.26 [M+Na] ^⁺ .

Compound 1.54:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.81 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.39 (d, 2H), 7.27 (t, ¹H), 7.13 (d, 2H), 4.51 (s, 2H), 3.58 (t, 2H), 3.50 (dt, 2H). LC-MS (m/z, ESI): 458.27 [M+H] ^⁺ .

Compound 1.64:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.81 (t, ¹H), 8.16 (d, 2H), 8.06 (d, 2H), 7.39–7.36 (m, ¹H), 7.31–7.26 (m, ¹H), 7.22–7.15 (m, ¹H), 4.62 (s, 2H), 3.62 (t, 2H), 3.50 (dt, 2H). LC-MS (m/z, ESI): 428.29 [M+H] ^⁺ .

Compound 1.65:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.83(t, ¹H), 8.16(d, 2H), 8.07(d, 2H), 7.58–7.55(m, ¹H), 7.53–7.49(m, ¹H), 7.37–7.34(m, ¹H), 4.63(s, 2H), 3.68(t, 2H), 3.54(dt, 2H). LC-MS (m/z, ESI): 460.17 [M+H] ^⁺ .

Compound 1.67:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.82 (t, ¹H), 8.16 (d, 2H), 8.06 (d, 2H), 7.55–7.48 (m, ¹H), 7.26–7.19 (m, ¹H), 7.10–7.03 (m, ¹H), 4.53 (s, 2H), 3.62 (t, 2H), 3.52 (dt, 2H). LC-MS (m/z, ESI): 450.24 [M+Na] ^⁺ .

Compound 1.68:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.82 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.60 (d, ¹H), 7.54 (d, ¹H), 7.42 (dd, ¹H), 4.58 (s, 2H), 3.66 (t, 2H), 3.52 (dt, 2H). LC-MS (m/z, ESI): 460.23 [M+H] ^⁺ .

Compound 1.71:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.86 (t, ¹H), 8.16 (d, 2H), 8.08 (d, 2H), 7.56 (d, ¹H), 7.47 (d, 1H), 7.39–7.36 (m, ¹H), 4.58 (s, 2H), 3.69 (t, 2H), 3.55 (dt, 2H). LC-MS (m/z, ESI): 460.16 [M+H] ^⁺ .

Compound 1.73:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.83 (t, ¹H), 8.15 (d, 2H), 8.04 (d, 2H), 7.49–7.41 (m, ¹H), 7.15–7.07 (m, 2H), 4.56 (t, 2H), 3.58 (t, 2H), 3.44 (dt, 2H). LC-MS (m/z, ESI): 450.22 [M+Na] ^⁺ .

Compound 1.74:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.76 (t, ¹H), 8.15 (d, 2H), 8.05 (d, 2H), 7.48 (d, 2H), 7.39–7.35 (m, ¹H), 4.72 (s, 2H), 3.65 (t, 2H), 3.48 (dt, 2H). LC-MS (m/z, ESI): 460.18 [M+H] ^⁺ .

Compound 1.76:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.82 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.59 (d, 2H), 7.33 (m, ¹H), 4.52 (s, 2H), 3.60 (t, 2H), 3.51 (dt, 2H). LC-MS (m/z, ESI): 428.27 [M+H] ^⁺ .

Compound 1.77:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.82 (t, ¹H), 8.16 (d, 2H), 8.06 (d, 2H), 7.62–7.56 (m, 2H), 7.33 (m, ¹H), 4.52 (s, 2H), 3.60 (t, 2H), 3.51 (dt, 2H). LC-MS (m/z, ESI): 460.18 [M+H] ^⁺ .

Compound 1.80:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.84 (t, ¹H), 8.16 (d, 2H), 8.07 (d, 2H), 7.49 (t, ¹H), 7.39 (d, 2H), 4.54 (s, 2H), 3.61 (t, 2H), 3.52 (dt, 2H). LC-MS (m/z, ESI): 482.28 [M+Na] ^⁺ .

Compound 1.256:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.81 (t, ¹H), 8.16 (d, 2H), 8.06 (d⁻¹⁰²H), 7.54 (m, 2H), 4.53 (s, 2H), 3.62 (t, 2H), 3.50 (dt, 2H). LC-MS (m/z, ESI): 446.22 [M+H] ^⁺ .

Compound 1.315:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.79 (t, ¹H), 8.15 (d, 2H), 8.03 (d, 2H), 7.86 (m, ¹H), 4.64 (s, 2H), 3.62 (t, 2H), 3.44 (dt, 2H). LC-MS (m/z, ESI): 464.19 [M+H] ^⁺ .

Compound 1.321:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.81 (t, ¹H), 8.16 (d, 2H), 8.07 (d, 2H), 7.36–7.31 (m, 4H), 7.29–7.25 (m, ¹H), 4.52 (s, 2H), 3.59 (t, 2H), 3.52–3.49 (m, 2H). LC-MS (m/z, ESI): 414.04 [M+Na] ^⁺ .

Compound 31.1:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 10.60 (t, ¹H), 8.11 (d, 2H), 7.91 (d, 2H), 7.48 (td, ¹H), 7.40–7.33 (m, ¹H), 7.22–7.17 (m, 2H), 4.60 (s, 2H), 3.94 (dt, 2H), 3.79 (t, 2H). LC-MS (m/z, ESI): 426.24 [M+H] ^⁺ .

Compound 31.3:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.62 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.61 (dd, ¹H), 7.53 (dd, 1H), 7.39 (td, 1H), 7.25 (td, 1H), 4.59 (s, 2H), 3.98 (dt, 2H), 3.85 (t, 2H). LC-MS (m/z, ESI): 486.07 [M+H] ^⁺ .

Compound 31.4:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.62 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.42–7.36 (m, ¹H), 7.19 (d, 2H), 7.14–7.07 (m, ¹H), 4.56 (s, 2H), 3.96 (dt, 2H), 3.78 (t, 2H). LC-MS (m/z, ESI): 426.30 [M+H] ^⁺ .

Compound 31.5:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.63 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.42 (s, ¹H), 7.40–7.36 (m, ¹H), 7.35–7.33 (m, ¹H), 7.31 (dd, ¹H), 4.55 (s, 2H), 3.96 (dt, 2H), 3.78 (t, 2H). LC-MS (m/z, ESI): 442.18 [M+H] ^⁺ .

Compound 31.6:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.62 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.57 (s, ¹H), 7.50–7.46 (m, ¹H), 7.36 (dt, 1H), 7.31 (t, 1H), 4.55 (s, 2H), 3.96 (dt, 2H), 3.78 (t, 2H). LC-MS (m/z, ESI): 486.12 [M+H] ^⁺ .

Compound 31.7:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (t, ¹H), 8.12 (d, 2H), 7.91 (d, 2H), 7.41–7.38 (m, 2H), 7.20–7.15 (m, 2H), 4.52 (s, 2H), 3.94 (dt, 2H), 3.76 (t, 2H). LC-MS (m/z, ESI): 426.26 [M+H] ^⁺ .

Compound 31.8:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (t, ¹H), 8.12 (d, 2H), 7.91 (d, 2H), 7.41 (d, 2H), 7.38 (d, 2H), 4.53 (s, 2H), 3.95 (dt, 2H), 3.77 (t, 2H). LC-MS (m/z, ESI): 442.19 [M+H] ^⁺ .

Compound 31.9:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (t, ¹H), 8.12 (d, 2H), 7.91 (d, 2H), 7.54 (d, 2H), 7.32 (d, 2H), 4.52 (s, 2H), 3.94 (dt, 2H), 3.76 (t, 2H). LC-MS (m/z, ESI): 486.07 [M+H] ^⁺ .

Compound 31.10:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.62 (t, ¹H), 8.12 (d, 2H), 7.94 (d, 2H), 7.85 (dd, ¹H), 7.47 (dd, 1H), 7.40 (td, 1H), 7.06 (td, 1H), 4.50 (s, 2H), 3.98 (dt, 2H), 3.85 (t, 2H). LC-MS (m/z, ESI): 534.09 [M+H] ^⁺ .

Compound 31.13:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 10.62 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.74 (s, ¹H), 7.66–7.64 (m, ¹H), 7.38–7.35 (m, 1H), 7.16 (t, ¹H), 4.51 (s, 2H), 3.95 (dt, 2H), 3.77 (t, 2H). LC-MS (m/z, ESI): 534.08 [M+H] ^⁺ .

Compound 31.16:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.62 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.74 (d, ¹H), 7.65 (d, 1H), 7.37 (d, 1H), 7.19–7.14 (m, ¹H), 4.51 (s, 2H), 3.95 (dt, 2H), 3.77 (t, 2H). LC-MS (m/z, ESI): 534.03 [M+H] ^⁺ .

Compound 31.19:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (t, ¹H), 8.11 (d, 2H), 7.92 (d, 2H), 7.35–7.30 (m, ¹H), 7.17 (m, 3H), 4.53 (s, 2H), 3.96 (dt, 2H), 3.79 (t, 2H), 2.28 (s, 3H). LC-MS (m/z, ESI): 422.27 [M+H] ^⁺ .

Compound 31.22:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (t, ¹H), 8.11 (d, 2H), 7.94 (d, 2H), 7.22 (t, ¹H), 7.16 (s, ¹H), 7.13 (d, 1H), 7.08 (d, 1H), 4.50 (s, 2H), 3.96 (dt, 2H), 3.76 (t, 2H), 2.28 (s, 3H). LC-MS (m/z, ESI): 422.28 [M+H] ^⁺ .

Compound 31.25:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.60 (t, ¹H), 8.12 (d, 2H), 7.91 (d, 2H), 7.23 (d, 2H), 7.15 (d, 2H), 4.49 (s, 2H), 3.93 (dt, 2H), 3.73 (t, 2H), 2.29 (s, 3H). LC-MS (m/z, ESI): 422.26 [M+H] ^⁺ .

Compound 31.37:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.63 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.39 (td, ¹H), 7.19 (d, 2H), 7.10 (td, ¹H), 4.56 (s, 2H), 3.96 (dt, 2H), 3.78 (t, 2H). LC-MS (m/z, ESI): 476.23 [M+H] ^⁺ .

Compound 31.42:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (t, ¹H), 8.11 (d, 2H), 7.92 (d, 2H), 7.26 (t, ¹H), 6.91 (dd, 2H), 6.84 (dd, 1H), 4.52 (s, 2H), 3.95 (dt, 2H), 3.76 (t, 2H), 3.72 (s, 3H). LC-MS (m/z, ESI): 438.24 [M+H] ^⁺ .

Compound 31.43:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.63 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.71 (d, 2H), 7.58 (d, 2H), 4.65 (s, 2H), 3.97 (dt, 2H), 3.77 (t, 2H). LC-MS (m/z, ESI): 476.14 [M+H] ^⁺ .

Compound 31.45:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.59 (t, ¹H), 8.11 (d, 2H), 7.91 (d, 2H), 7.27 (d, 2H), 6.90 (d, 2H), 4.45 (s, 2H), 3.92 (dt, 2H), 3.74 (s, 3H), 3.72 (d, 2H). LC-MS (m/z, ESI): 438.30 [M+H] ^⁺ .

Compound 31.54:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 10.61 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.41 (d, 2H), 7.28 (t, ¹H), 7.16 (d, 2H), 4.53 (s, 2H), 3.95 (dt, 2H), 3.76 (t, 2H). LC-MS (m/z, ESI): 474.21 [M+H] ^⁺ .

Compound 31.64:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.60 (t, ¹H), 8.11 (d, 2H), 7.91 (d, 2H), 7.42–7.35 (m, ¹H), 7.33–7.27 (m, 1H), 7.24–7.18 (m, 1H), 4.64 (s, 2H), 3.94 (dt, 2H), 3.80 (t, 2H). LC-MS (m/z, ESI): 444.29 [M+H] ^⁺ .

Compound 31.65:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.62 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.58 (dd, ¹H), 7.52 (dd, 1H), 7.37 (t, ¹H), 4.65 (s, 2H), 3.98 (dt, 2H), 3.86 (t, 2H). LC-MS (m/z, ESI): 476.13 [M+H] ^⁺ .

Compound 31.67:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.59 (t, ¹H), 8.12 (d, 2H), 7.91 (d, 2H), 7.53 (td, ¹H), 7.24 (td, 1H), 7.09 (td, 1H), 4.56 (s, 2H), 3.93 (dt, 2H), 3.78 (t, 2H). LC-MS (m/z, ESI): 444.27 [M+H] ^⁺ .

Compound 31.68:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.61 (d, ¹H), 7.56 (d, 1H), 7.44 (dd, ¹H), 4.60 (s, 2H), 3.97 (dt, 2H), 3.84 (t, 2H). LC-MS (m/z, ESI): 476.15 [M+H] ^⁺ .

Compound 31.71:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.64 (t, ¹H), 8.11 (d, 2H), 7.93 (d, 2H), 7.59 (d, ¹H), 7.48 (d, 1H), 7.40 (dd, 1H), 4.61 (s, 2H), 3.99 (dt, 2H), 3.86 (t, 2H). LC-MS (m/z, ESI): 476.13 [M+H] ^⁺ .

Compound 31.73:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.56 (t, ¹H), 8.11 (d, 2H), 7.89 (d, 2H), 7.46 (m, ¹H), 7.16–7.09 (m, 2H), 4.59 (s, 2H), 3.91–3.88 (m, 2H), 3.77 (t, 2H). LC-MS (m/z, ESI): 444.24 [M+H] ^⁺ .

Compound 31.74:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.55 (t, ¹H), 8.11 (d, 2H), 7.91 (d, 2H), 7.49 (d, 2H), 7.39 (dd, ¹H), 4.74 (s, 2H), 3.92 (dt, 2H), 3.84 (t, 2H). LC-MS (m/z, ESI): 476.15 [M+H] ^⁺ .

Compound 31.77:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.62 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.63–7.60 (m, 2H), 7.35 (dd, ¹H), 4.55 (s, 2H), 3.95 (dt, 2H), 3.81–3.76 (t, 2H). LC-MS (m/z, ESI): 476.14 [M+H] ^⁺ .

Compound 31.321:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.37–7.32 (m, 4H), 7.29 (m, ¹H), 4.54 (s, 4H), 3.95 (dt, 2H), 3.76 (t 2H). LC-MS (m/z, ESI): 408.28 [M+H] ^⁺ .

Example 2: Preparation of compounds 41.321 and 71.321

(1) Preparation of compound 41.321

Intermediate II-2 (2.01 g, 7.40 mmol), carbonyl diimidazole (1.32 g, 8.14 mmol), N,N-diisopropylethylamine (0.96 g, 7.40 mmol), and tetrahydrofuran (25 mL) were added sequentially to the reaction flask, and the mixture was stirred at room temperature for 40 minutes. Intermediate III-1 (1.12 g, 7.40 mmol) was then added to the reaction mixture, and the reaction was continued with stirring. After the reaction was complete as monitored by TLC, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to give 2.10 g of a white solid, namely compound 41.321. ¹ H NMR (600MHz, DMSO-d ₆ )δ8.27(t,1H),7.98(d,2H),7.50(d,2H),7.35-7.30(m,4H),7.29-7.26(m,1H),4. 47(s,2H),3.55(s,2H),3.45(t,2H),3.28(dt,2H).LC-MS(m/z,ESI):406.32[M+H] ⁺ .

(2) Preparation of compound 71.321

Compound 41.321 (1.00 g, 2.47 mmol), Lawesson reagent (1.00 g, 2.47 mmol), and toluene (15 mL) were added sequentially to the reaction flask, and the mixture was heated to 90 °C and refluxed. After the reaction was completed by TLC monitoring, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to obtain 0.85 g of white solid, namely compound 71.321. ¹ H NMR (600MHz, DMSO-d ₆ )δ10.49(t,1H),7.98(d,2H),7.55(d,2H),7.37-7.29(m,4H),7.31-7.25(m,1H ),4.49(s,2H),4.03(s,2H),3.75(dt,2H),3.65(t,2H).LC-MS(m/z,ESI):[M+H] ^+422.32 .

Following the synthesis method described in Example 2, the present invention also yielded the following compounds:

Compound 41.1:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.28(t,¹H), 7.98(d,²H), 7.49(d,²H), 7.45–7.42(m,¹H), 7.39–7.32(m,¹H), 7.20–7.16(m,²H), 4.53(s,²H), 3.54(s,²H), 3.48(t,²H), 3.31–3.25(m,²H). LC-MS (m/z, ESI): [M+H] ⁺ 424.37.

Compound 41.2:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.28(t,¹H), 7.97(d,¹H), 7.53–7.48(m,³H), 7.45–7.41(m,¹H), 7.34–7.30(m,¹H), 4.55(s,²H), 3.56(s,²H), 3.54(t,³H), 3.34–3.28(m,³H). LC-MS (m/z, ESI): [M+H] ⁺ 440.24.

Compound 41.3:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.29(t,¹H), 7.97(d,²H), 7.60(dd,¹H), 7.50(d,²H), 7.48(d,¹H), 7.37(td,¹H), 7.24(td,¹H), 4.51(s,²H), 3.56(s,²H), 3.54(t,²H), 3.31(dt,²H). LC-MS (m/z, ESI): [M+H] ⁺ 484.26.

Compound 41.4:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.29 (t, ¹H), 7.98 (d, 2H), 7.50 (d, 2H), 7.40–7.35 (m, ¹H), 7.15 (d, 1H), 7.13–7.06 (m, 1H), 4.49 (s, 2H), 3.55 (s, 2H), 3.47 (t, 2H), 3.31–3.27 (m, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 424.39.

Compound 41.5:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.30 (t, ¹H), 7.98 (d, 2H), 7.50 (d, 2H), 7.38 (s, ¹H), 7.37–7.32 (m, 2H), 7.28–7.26 (m, ¹H), 4.48 (s, 2H), 3.56 (s, 2H), 3.47 (t, 2H), 3.29 (dt, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 440.32.

Compound 41.6:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.29 (t, ¹H), 7.98 (d, ¹H), 7.53 (s, ¹H), 7.50 (d, 2H), 7.47 (dt, ¹H), 7.34–7.27 (m, 2H), 4.47 (s, 2H), 3.55 (s, 2H), 3.47 (t, 2H), 3.29 (dt, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 484.25.

Compound 41.7:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.26(t,¹H), 7.98(d,¹H), 7.49(d,²H), 7.36–7.33(m,²H), 7.17–7.12(m,¹H), 4.44(s,²H), 3.55(s,²H), 3.45(t,²H), 3.29–3.26(m,²H). LC-MS (m/z, ESI): [M+H] ⁺ 424.37.

Compound 41.8:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.27 (t, ¹H), 7.98 (d, ¹H), 7.49 (d, 2H), 7.40–7.34 (m, 2H), 7.32 (d, 2H), 4.45 (s, 2H), 3.55 (s, 2H), 3.45 (t, 2H), 3.28 (dt, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 440.35.

Compound 41.9:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.27 (t, ¹H), 7.98 (d, 2H), 7.52–7.47 (m, 4H), 7.25 (d, 2H), 4.44 (s, 2H), 3.54 (s, 2H), 3.45 (t, 2H), 3.28 (dt, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 484.25.

Compound 41.10:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.29 (t, ¹H), 7.98 (d, 2H), 7.84 (dd, ¹H), 7.50 (d, 2H), 7.43 (dd, 1H), 7.38 (td, 1H), 7.06 (td, 1H), 4.43 (s, 2H), 3.56 (s, 2H), 3.54 (t, 2H), 3.32–3.28 (m, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 532.20.

Compound 41.13:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.29(t,¹H), 7.98(d,²H), 7.70(s,¹H), 7.66–7.62(m,¹H), 7.50(d,²H), 7.35–7.31(m,¹H), 7.14(td,¹H), 4.44(s,²H), 3.56(s,²H), 3.46(t,²H), 3.28(dt,²H). LC-MS (m/z, ESI): [M+H] ⁺ 532.17.

Compound 41.16:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶) δ 8.27 (t, ¹H), 7.99 (d, 2H), 7.66 (d, 2H), 7.50 (d, 2H), 7.10 (d, ¹H), 4.42 (s, 2H), 3.54 (s, 2H), 3.44 (t, 2H), 3.27 (dt, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 532.13.

Compound 41.19:

White solid. ^¹H NMR (600 MHz, DMSO): δ 8.26 (t, ¹H), 7.98 (d, ¹H), 7.49 (d, 2H), 7.29 (dd, ¹H), 7.23–7.10 (m, 3H), 4.46 (s, 2H), 3.54 (s, 2H), 3.47 (t, 2H), 3.29 (dt, 2H), 2.25 (s, 3H). LC-MS (m/z, ESI): [M+H] ⁺ 420.33.

Compound 41.22:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.27 (t, ¹H), 7.98 (d, 2H), 7.49 (d, 2H), 7.22 (t, ¹H), 7.13 (s, ¹H), 7.09 (t, 2H), 4.43 (s, 2H), 3.55 (s, 2H), 3.45 (t, 2H), 3.28 (dt, 2H), 2.29 (s, 3H). LC-MS (m/z, ESI): [M+H] ⁺ 420.43.

Compound 41.25:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.26 (t, ¹H), 7.98 (d, 2H), 7.49 (d, 2H), 7.19 (d, 2H), 7.13 (d, 2H), 4.41 (s, 2H), 3.54 (s, 2H), 3.42 (t, 2H), 3.26 (dt, ¹H), 2.28 (s, 3H). LC-MS (m/z, ESI): [M+H] ⁺ 420.35.

Compound 41.37:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 7.96(d,²H), 7.68–7.65(m,¹H), 7.65–7.61(m,²H), 7.57(t,¹H), 7.49(d,²H), 4.56(s,²H), 3.55(s,²H), 3.50(t,²H), 3.31(dt,²H). LC-MS (m/z, ESI): [M+H] ⁺ 474.31.

Compound 41.40:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 7.96(d,²H), 7.66(s,¹H), 7.65–7.61(m,²H), 7.58(t,¹H), 7.49(d,²H), 4.57(s,²H), 3.55(s,²H), 3.50(t,²H), 3.30(dt,²H). LC-MS (m/z, ESI): [M+H] ⁺ 474.29.

Compound 41.42:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.28 (t, 1), 7.98 (d, 2H), 7.49 (d, 2H), 7.25 (t, 1H), 6.88 (dd, 2H), 6.86–6.82 (m, 1H), 4.45 (s, 2H), 3.74 (s, 2H), 3.55 (s, 2H), 3.45 (t, 2H), 3.28 (dt, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 436.38.

Compound 41.43:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.29 (t, ¹H), 7.98 (d, 2H), 7.65 (d, 2H), 7.53–7.47 (m, 4H), 4.56 (s, 2H), 3.55 (s, 2H), 3.49 (t, 2H), 3.32–3.29 (m, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 474.33.

Compound 41.45:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.25(t,¹H), 7.98(d,²H), 7.49(d,²H), 7.22(d,²H), 6.88(d,²H), 4.38(s,²H), 3.73(s,²H), 3.54(s,²H), 3.41(t,²H), 3.26(dt,²H). LC-MS (m/z, ESI): [M+H] ⁺ 436.35.

Compound 71.1:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 10.49 (t, ¹H), 7.97 (d, ¹²), 7.55 (d, ²), 7.44 (td, ¹H), 7.40–7.33 (m, ¹H), 7.23–7.16 (m, 2H), 4.55 (s, 2H), 4.02 (s, 2H), 3.75 (dt, 2H), 3.68 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 440.23.

Compound 71.2:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 10.49 (t, ¹H), 7.96 (d, 2H), 7.55 (d, 2H), 7.49 (dd, ¹H), 7.46–7.42 (m, ¹H), 7.36–7.30 (m, 2H), 4.57 (s, 2H), 4.03 (s, 2H), 3.78 (dt, 2H), 3.72 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 456.29.

Compound 71.3:

Yellow solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 10.50(t,¹H), 7.96(d,²H), 7.61–7.59(m,¹H), 7.56(d,²H), 7.48(dd,¹H), 7.39–7.35(m,¹H), 7.24(td,¹H), 4.53(s,²H), 4.04(s,²H), 3.79(dd,²H), 3.73(t,²H). LC-MS (m/z, ESI): [M+H] ⁺ 500.04.

Compound 71.4:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 10.49 (t, ¹H), 7.97 (d, 2H), 7.56 (d, 2H), 7.41–7.34 (m, ¹H), 7.15 (d, 2H), 7.12–7.06 (m, ¹H), 4.51 (s, 2H), 4.04 (s, 2H), 3.77 (dt, 2H), 3.67 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 440.19.

Compound 71.5:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 10.50 (t, ¹H), 7.97 (d, 2H), 7.56 (d, 2H), 7.39 (s, ¹H), 7.35 (d, 1H), 7.33 (d, 1H), 7.28–7.25 (m, ¹H), 4.49 (s, 2H), 4.04 (s, 2H), 3.77 (dt, 2H), 3.67 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 456.15.

Compound 71.6:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.49 (t, ¹H), 7.97 (d, 2H), 7.56 (d, 2H), 7.53 (s, ¹H), 7.47 (d, 1H), 7.30 (t, 2H), 4.49 (s, 2H), 4.04 (s, 2H), 3.76 (dt, 2H), 3.67 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 500.03.

Compound 71.7:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶) δ 10.47 (t, ¹H), 7.97 (d, 2H), 7.55 (d, 2H), 7.35 (dd, 2H), 7.15 (t, 2H), 4.46 (s, 2H), 4.03 (s, 2H), 3.75 (dt, 2H), 3.64 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 440.20.

Compound 71.8:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶) δ 10.47 (t, ¹H), 7.97 (d, 2H), 7.56 (d, 2H), 7.37 (d, 2H), 7.31 (d, 2H), 4.47 (s, 2H), 4.03 (s, 2H), 3.75 (dt, 2H), 3.65 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 456.20.

Compound 71.19:

Yellow solid. ^¹H NMR (400 MHz, DMSO): δ 10.49 (t, ¹H), 7.98 (d, ¹H), 7.56 (d, 2H), 7.26 (dd, ¹H), 7.23–7.10 (m, 3H), 4.45 (s, 2H), 4.03 (s, 2H), 3.75 (t, 2H), 3.61 (dt, 2H), 2.28 (s, 3H). LC-MS (m/z, ESI): [M+H] ⁺ 436.25.

Compound 71.22:

Yellow solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 10.49(t, ¹H), 7.97(d, 2H), 7.55(d, 2H), 7.22(t, ¹H), 7.13(s, ¹H), 7.10(dd, 2H), 4.45(s, 2H), 4.03(s, 2H), 3.75(dt, 2H), 3.64(t, 2H), 2.29(s, 3H). LC-MS (m/z, ESI): [M+H] ⁺ 436.25.

Compound 71.25:

Yellow solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 10.48 (t, ¹H), 7.96 (d, 2H), 7.55 (d, 2H), 7.19 (d, 2H), 7.13 (d, 2H), 4.43 (s, 2H), 4.03 (s, 2H), 3.74 (dt, 2H), 3.62 (t, 2H), 2.28 (s, 3H). LC-MS (m/z, ESI): [M+H] ⁺ 436.25.

Example 3: Preparation of compounds 21.2 and 11.2

(1) Preparation of intermediate VI-1

Lithium hydroxide (0.25 g, 10.42 mmol) and water (10 mL) were added to a reaction flask and dissolved completely. Cysteine hydrochloride (0.67 g, 5.90 mmol) and anhydrous ethanol (15 mL) were then added. The mixture was stirred at room temperature for 10 minutes, and then benzyl bromide (1.00 g, 4.90 mmol) was slowly added dropwise. The reaction was stopped when no benzyl bromide was detected by TLC. The mixture was extracted with ethyl acetate and water, and the organic layer was collected. After desolvation under reduced pressure, 0.85 g of a yellow oily substance, namely compound VI-1, was obtained.

(2) Preparation of compound 21.2

Intermediate II-1 (1.00 g, 3.88 mmol), HATU (1.77 g, 4.65 mmol), N,N-diisopropylethylamine (1.00 g, 7.74 mmol), and tetrahydrofuran (25 mL) were added sequentially to the reaction flask, and the mixture was stirred at room temperature for 40 minutes. Intermediate VI-1 (0.78 g, 3.88 mmol) was then added to the reaction mixture, and the reaction was continued with stirring. After the reaction was complete as monitored by TLC, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to give 1.45 g of a white solid, namely compound 21.2. ¹ H NMR (600MHz, DMSO-d ₆ )δ8.87(t,1H),8.17(d,2H),8.06(d,2H),7.49(dd,1H),7.45(dd,1H),7.34-7.26 (m,2H),3.88(s,2H),3.50(dt,2H),2.67(dd,2H).LC-MS(m/z,ESI):442.00[M+H] ⁺ .

(3) Preparation of compound 11.2

Compound 21.2 (1.00 g, 2.27 mmol), Lawstøy reagent (0.92 g, 2.27 mmol), and toluene (20 mL) were added sequentially to the reaction flask, and the mixture was heated to 90 °C and refluxed. After the reaction was completed as monitored by TLC, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to give 0.93 g of a white solid, namely compound 11.2. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.62 (t, 1H), 8.13 (d, 2H), 7.94 (d, 2H), 7.51 (dd, 1H), 7.46 (dd, 1H), 7.33–7.28 (m, 2H), 3.96 (dt, 2H), 3.92 (s, 2H), 2.84 (dd, 2H). LC-MS (m/z, ESI): 458.19 [M+H]⁺.

Following the synthesis method described in Example 3, the present invention also yielded the following compounds:

Compound 21.1:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.87 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.44 (td, ¹H), 7.35–7.27 (m, ¹H), 7.23–7.07 (m, 2H), 3.82 (s, 2H), 3.49 (dt, 2H), 2.66 (dd, 2H). LC-MS (m/z, ESI): 426.07 [M+H] ^⁺ .

Compound 21.4:

White solid. ^¹H NMR (600 MHz, _CDCl₃ ) δ 8.20 (d, 2H), 7.90 (d, 2H), 7.30–7.26 (m, 1H), 7.13–7.05 (m, 2H), 6.97–6.91 (m, 1H), 6.52 (t, 1H), 3.75 (s, 2H), 3.63 (dt, 2H), 2.73 (dd, 2H). LC-MS (m/z, ESI): 426.29 [M+H] ^⁺ .

Compound 21.5:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.86 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.43 (s, ¹H), 7.35 (dd, ¹H), 7.34–7.28 (m, 2H), 3.81 (s, 2H), 3.48 (dt, 2H), 2.61 (dd, 2H). LC-MS (m/z, ESI): 442.25 [M+H] ^⁺ .

Compound 21.7:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.85 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.38 (dd, 2H), 7.17–7.11 (m, 2H), 3.79 (s, 2H), 3.47 (dt, 2H), 2.60 (dd, 2H). LC-MS (m/z, ESI): 426.05 [M+H] ^⁺ .

Compound 21.8:

White solid ^{, ¹H} NMR (600 MHz, DMSO- _d⁶ ): δ 8.85 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.38 (s, 4H), 3.79 (s, 2H), 3.46 (dt, 2H), 2.60 (dd, 2H). LC-MS (m/z, ESI): 442.23 [M+H] ^⁺ .

Compound 21.9:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.84 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.51 (d, 2H), 7.32 (d, 2H), 3.78 (s, 2H), 3.46 (dt, 2H), 2.59 (dd, 2H). LC-MS (m/z, ESI): 486.17 [M+H] ^⁺ .

Compound 21.17:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.85 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.79 (d, 2H), 7.56 (d, 2H), 3.88 (s, 2H), 3.46 (dt, 2H), 2.60 (t, 2H). LC-MS (m/z, ESI): 433.27 [M+H] ^⁺ .

Compound 21.19:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.87 (t ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.25 (dd, ¹H), 7.19–7.10 (m, 3H), 3.79 (s, 2H), 3.50 (dt, 2H), 2.65 (dd, 2H), 2.34 (s, 3H). LC-MS (m/z, ESI): 422.32 [M+H] ^⁺ .

Compound 21.22:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.85 (t ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.20 (t, 1H), 7.16 (s, 1H), 7.12 (d, 1H), 7.05 (d, 1H), 3.75 (s, 2H), 3.48 (dt, 2H), 2.60 (dd, 2H), 2.28 (s, 3H). LC-MS (m/z, ESI): 422.07 [M+H] ^⁺ .

Compound 21.25:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.85 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.22 (d, 2H), 7.12 (d, 2H), 3.75 (s, 2H), 3.47 (dt, 2H), 2.61 (t, 2H), 2.27 (s, 3H). LC-MS (m/z, ESI): 422.08 [M+H] ^⁺ .

Compound 21.37:

White solid. ^¹H NMR (600 MHz, _CDCl₃ ) δ 8.20 (d, 2H), 7.90 (d, 2H), 7.66–7.61 (m, 2H), 7.52 (t, 1H), 7.36 (t, 1H), 6.59 (t, 1H), 3.95 (s, 2H), 3.67 (dt, 2H), 2.82 (t, 2H). LC-MS (m/z, ESI): 476.23 [M+H] ^⁺ .

Compound 21.42:

White solid, ^¹H NMR (600 MHz, DMSO- _d⁶ ): δ 8.86 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.23 (t, ¹H), 6.93–6.91 (m, ¹H), 6.91 (s, ¹H), 6.83–6.78 (m, ¹H), 3.76 (s, 2H), 3.74 (s, 3H), 3.48 (dt, 2H), 2.61 (dd, 2H). LC-MS (m/z, ESI): 438.08 [M+H] ^⁺ .

Compound 21.45:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.85 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.26 (d, 2H), 6.87 (d, 2H), 3.74 (s, 2H), 3.73 (s, 3H), 3.47 (dt, 2H), 2.61–2.57 (m, 2H). LC-MS (m/z, ESI): 436.22 [MH] ^- .

Compound 21.54:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.86 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.40 (d, 2H), 7.27 (t, ¹H), 7.12 (d, 2H), 3.80 (s, ¹H), 3.48 (dt, 2H), 2.63–2.58 (m, 2H). LC-MS (m/z, ESI): 474.18 [M+H] ^⁺ .

Compound 21.64:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.85 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.45–7.40 (m, ¹H), 7.40–7.35 (m, ¹H), 7.22–7.18 (m, ¹H), 3.80 (s, 2H), 3.46 (dt, 2H), 2.61 (dd, 2H). LC-MS (m/z, ESI): 444.21 [M+H] ^⁺ .

Compound 21.67:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.86 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.49 (td, ¹H), 7.23 (td, 1H), 7.06 (td, 1H), 3.80 (s, 2H), 3.48 (dt, 2H), 2.65 (dd, 2H). LC-MS (m/z, ESI): 444.24 [M+H] ^⁺ .

Compound 21.73:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.86 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.42–7.33 (m, ¹H), 7.11 (t, 2H), 3.82 (s, 2H), 3.54–3.48 (m, 2H), 2.72 (t, 2H). LC-MS (m/z, ESI): 444.04 [M+H] ^⁺ .

Compound 21.74:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.86 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.41–7.33 (m, ¹H), 7.11 (t, 2H), 3.82 (s, 2H), 3.51 (dt, 2H), 2.72 (t, 2H). LC-MS (m/z, ESI): 474.28 [MH] ^⁻

Compound 21.175:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.85 (t, ¹H), 8.17 (d, 2H), 8.05 (d, 2H), 7.84 (dd, ¹H), 7.69–7.64 (m, 2H), 3.88 (s, 2H), 3.47 (dt, 2H), 2.66 (dd, 2H). LC-MS (m/z, ESI): 451.22 [M+H] ^⁺ .

Compound 21.321:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.86 (t, ¹H), 8.17 (d, 2H), 8.06 (d, 2H), 7.36–7.34 (m, 2H), 7.34–7.30 (m, 2H), 7.26–7.22 (m, ¹H), 3.79 (s, 2H), 3.48 (dt, 2H), 2.61 (dd, 2H). LC-MS (m/z, ESI): 408.05 [M+H]⁺.

Compound 11.1:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (s, ¹H), 8.13 (d, 2H), 7.93 (d, 2H), 7.48–7.43 (m, ¹H), 7.35–7.29 (m, ¹H), 7.22–7.14 (m, 2H), 3.94 (dt, 2H), 3.85 (s, 2H), 2.83 (t, 2H). LC-MS (m/z, ESI): 442.23 [M+H] ^⁺ .

Compound 11.4:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.60 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.39–7.35 (m, ¹H), 7.22–7.19 (m, 2H), 7.10–7.06 (m, ¹H), 3.92 (dt, 2H), 3.85 (s, 2H), 2.78 (t, 2H). LC-MS (m/z, ESI): 442.24 [M+H] ^⁺ .

Compound 11.5:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.60 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.45 (s, ¹H), 7.38–7.33 (m, 2H), 7.33–7.30 (m, ¹H), 3.92 (dt, 2H), 3.84 (s, 2H), 2.78 (t, 2H). LC-MS (m/z, ESI): 458.18 [M+H] ^⁺ .

Compound 11.7:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.60 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.42–7.38 (m, 2H), 7.17–7.13 (m, 2H), 3.91 (dt, 2H), 3.83 (s, 2H), 2.77 (t, 2H). LC-MS (m/z, ESI): 442.25 [M+H] ^⁺ .

Compound 11.8:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.59 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.39 (s, 4H), 3.92 (dt, 2H), 3.83 (s, 2H), 2.77 (t, 2H). LC-MS (m/z, ESI): 458.20 [M+H] ^⁺ .

Compound 11.17:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.59 (t, ¹H), 8.12 (d, 2H), 7.92 (d, 2H), 7.80 (d, 2H), 7.57 (d, 2H), 3.94–3.87 (m, 4H), 2.78 (t, 2H). LC-MS (m/z, ESI): 449.21 [M+H] ^⁺ .

Compound 11.22:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.60 (t, ¹H), 8.12 (d, 2H), 7.94 (d, 2H), 7.20 (t, ¹H), 7.17 (s, ¹H), 7.14 (d, 1H), 7.06–7.03 (d, 1H), 3.93 (dt, 2H), 3.79 (s, 2H), 2.79–2.75 (m, 2H), 2.29 (s, 3H). LC-MS (m/z, ESI): 438.32 [M+H] ^⁺ .

Compound 11.25:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.60 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.26–7.22 (m, 2H), 7.13 (d, 2H), 3.92 (dt, 2H), 3.78 (s, 2H), 2.76 (t, 2H), 2.28 (s, 3H). LC-MS (m/z, ESI): 438.24 [M+H] ^⁺ .

Compound 11.37:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.62 (t, ¹H), 8.13 (d, 2H), 7.94 (d, 2H), 7.70 (t, 2H), 7.66 (t, ¹H), 7.48 (t, ¹H), 4.00 (s, 2H), 3.95 (dt, 2H), 2.92 (t, 2H). LC-MS (m/z, ESI): 492.14 [M+H] ^⁺ .

Compound 11.45:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.60 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.27 (d, 2H), 6.88 (d, 2H), 3.95–3.89 (dt, 2H), 3.77 (s, 2H), 3.73 (s, 3H), 2.76 (t, 2H). LC-MS (m/z, ESI): 454.27 [M+H] ^⁺ .

Compound 11.54:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.61 (t, ¹H), 8.13 (d, 2H), 7.93 (d, 2H), 7.41 (d, 2H), 7.27 (t, ¹H), 7.13 (d, 2H), 3.93 (dt, 2H), 3.83 (s, 2H), 2.78 (t, 2H). LC-MS (m/z, ESI): 490.19 [M+H] ^⁺ .

Compound 11.321:

Yellow solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 10.60 (t, ¹H), 8.12 (d, 2H), 7.93 (d, 2H), 7.36 (d, 2H), 7.33 (t, 2H), 7.28–7.22 (m, ¹H), 3.93 (dt, 2H), 3.83 (s, 2H), 2.78 (dd, 2H). LC-MS (m/z, ESI): 424.30 [M+H] ^⁺ .

Example 4: Preparation of compounds 61.321 and 51.321

(1) Preparation of compound 61.321

Intermediate II-2 (2.01 g, 7.40 mmol), carbonyl diimidazole (1.32 g, 8.14 mmol), N,N-diisopropylethylamine (0.96 g, 7.40 mmol), and tetrahydrofuran (25 mL) were added sequentially to the reaction flask, and the mixture was stirred at room temperature for 40 minutes. Intermediate VI-1 (1.24 g, 7.40 mmol) was then added to the reaction mixture, and the reaction was continued with stirring. After the reaction was complete as monitored by TLC, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to give 2.34 g of a white solid, namely compound 62.321. ¹ H NMR(400MHz,DMSO)δ8.29(t,1H),7.99(d,2H),7.50(d,2H),7.35-7.25(m,4H),7.26-7.1 9(m,1H),3.73(s,2H),3.54(s,2H),3.25(dt,2H),2.47(dd,2H).LC-MS(m/z,ESI):[M+H] ^+422.32 .

(2) Preparation of compound 51.321

Compound 61.321 (1.00 g, 2.37 mmol), Lawstson's reagent (1.06 g, 2.61 mmol), and toluene (20 mL) were added sequentially to the reaction flask, and the mixture was heated to 90 °C and refluxed. After the reaction was completed as monitored by TLC, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to give 0.98 g of a white solid, namely compound 51.321. ¹ H NMR (600MHz, DMSO-d ₆ )δ10.45(t,1H),8.00(d,2H),7.56(d,2H),7.34-7.27(m,4H),7.25-7.21(m,1H) ,4.01(s,2H),3.76(s,2H),3.73(dt,2H),2.65(dd,2H).LC-MS(m/z,ESI):[M+H] ^+438.32 .

Following the synthesis method described in Example 4, the present invention also yielded the following compounds:

Compound 61.1:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.32 (t, ¹H), 7.99 (d, 2H), 7.50 (d, 2H), 7.46–7.40 (m, 2H), 7.31–7.25 (m, 2H), 3.82 (s, 2H), 3.54 (s, 2H), 3.28 (dt, 2H), 2.53 (dd, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 456.16.

Compound 61.2:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.32 (t, ¹H), 7.99 (d, 2H), 7.50 (d, 2H), 7.46–7.40 (m, 2H), 7.31–7.25 (m, 2H), 3.82 (s, 2H), 3.54 (s, 2H), 3.28 (dt, 2H), 2.53 (dd, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 456.16.

Compound 61.3:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.32(t, ¹H), 7.99(d, 2H), 7.62–7.59(m, ¹H), 7.50(d, 2H), 7.42(dd, ¹H), 7.32(td, ¹H), 7.19(td, 1H), 3.81(s, 2H), 3.54(s, 2H), 3.28(dt, 2H), 2.53(t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 500.24.

Compound 61.4:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 7.99(d,²H), 7.50(d,²H), 7.37–7.31(m,¹H), 7.15(s,¹H), 7.13(d,¹H), 7.09–7.03(m,²H), 3.75(s,²H), 3.54(s,²H), 3.25(dt,²H), 2.48(t,²H). LC-MS (m/z, ESI): [M+H] ⁺ 440.37.

Compound 61.5:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 7.99(d,²H), 7.50(d,²H), 7.37(s,¹H), 7.34–7.31(m,¹H), 7.31–7.26(m,¹H), 7.29–7.24(m,¹H), 3.74(s,²H), 3.54(s,²H), 3.25(dt,²H), 2.47(t,²H). LC-MS (m/z, ESI): [M+H] ⁺ 456.33.

Compound 61.6:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.30 (t, ¹H), 7.99 (d, 2H), 7.51 (d, 2H), 7.50 (s, ¹H), 7.43 (dt, 1H), 7.31 (dt, 1H), 7.26 (t, 1H), 3.73 (s, 2H), 3.54 (s, 2H), 3.25 (dt, 2H), 2.47 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 500.25.

Compound 61.7:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.29(t,¹H), 7.99(d,²H), 7.50(d,²H), 7.36–7.30(m,²H), 7.14–7.08(m,²H), 3.73(s,²H), 3.53(s,²H), 3.24(dt,²H), 2.46(t,²H). LC-MS (m/z, ESI): [M+H] ⁺ 440.38.

Compound 61.8:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.29 (t, ¹H), 7.99 (d, 2H), 7.50 (d, 2H), 7.34 (d, 2H), 7.31 (d, 2H), 3.72 (s, 2H), 3.53 (s, 2H), 3.24 (dt, 2H), 2.45 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 456.35.

Compound 61.9:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.29 (t, ¹H), 7.99 (d, 2H), 7.50 (d, 2H), 7.47 (d, 2H), 7.25 (d, 2H), 3.71 (s, 2H), 3.53 (s, 2H), 3.24 (dt, 2H), 2.45 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 500.23.

Compound 61.10:

White solid. ^¹H NMR (600 MHz, DMSO-d⁶): δ 8.32 (t, ¹H), 8.00 (d, 2H), 7.85 (dd, ¹H), 7.50 (d, 2H), 7.39 (dd, ¹H), 7.33 (td, ¹H), 6.99 (td, 1H), 3.79 (s, 2H), 3.54 (s, 2H), 3.31–3.26 (m, 2H), 2.53 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 548.14.

Compound 61.11:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.32 (t, ¹H), 7.99 (d, 2H), 7.82 (dd, ¹H), 7.64 (td, ¹H), 7.54 (dd, 1H), 7.50 (d, 2H), 7.45 (td, 1H), 3.90 (s, 2H), 3.54 (s, 2H), 3.27 (dt, 2H), 2.53 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 447.32.

Compound 61.12:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.29 (t, ¹H), 8.01–7.98 (m, ³H), 7.69–7.63 (m, ¹H), 7.57 (dd, ¹H), 7.56–7.50 (m, ¹H), 7.49 (d, ²H), 4.04 (s, ²H), 3.53 (s, ²H), 3.21 (dt, ²H), 2.48 (dd, ²H). LC-MS (m/z, ESI): [M+H] ⁺ 467.31.

Compound 61.13:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 8.00(d,²H), 7.69(s,¹H), 7.59(dd,¹H), 7.50(d,²H), 7.32(dt,¹H), 7.11(t,¹H), 3.70(s,²H), 3.54(s,²H), 3.25(dt,²H), 2.47(t,²H). LC-MS (m/z, ESI): [M+H] ⁺ 548.15.

Compound 61.16:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.29 (t, ¹H), 8.00 (d, 2H), 7.64 (d, 2H), 7.50 (d, 2H), 7.10 (d, 2H), 3.68 (s, 2H), 3.53 (s, 2H), 3.24 (dt, 2H), 2.45 (dd, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 548.14.

Compound 61.17:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 7.99(d,²H), 7.75(d,²H), 7.50(d,²H), 7.49(d,²H), 3.81(s,²H), 3.53(s,²H), 3.24(dt,²H), 2.46(t,²H). LC-MS (m/z, ESI): [M+H] ⁺ 447.35.

Compound 61.18:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 8.15(d,²H), 7.99(d,²H), 7.56(d,²H), 7.50(d,²H), 3.87(s,²H), 3.53(s,²H), 3.25(dt,²H), 2.48(dd,²H). LC-MS (m/z, ESI): [M+H] ⁺ 467.31.

Compound 61.19:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t, ¹H), 7.99(d, 2H), 7.50(d, 2H), 7.19(dd, ¹H), 7.18–7.07(m, 3H), 3.73(s, 2H), 3.54(s, 2H), 3.27(dt, 2H), 2.54–2.49(m, 2H), 2.32(s, 3H). LC-MS (m/z, ESI): [M+H] ⁺ 436.39.

Compound 61.22:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 7.99(d,²H), 7.50(d,²H), 7.17(t,¹H), 7.11(s,¹H), 7.08(d,¹H), 7.03(d,¹H), 3.68(s,²H), 3.54(s,²H), 3.25(dt,²H), 2.47(t,²H), 2.27(s,³H). LC-MS (m/z, ESI): [M+H] ⁺ 436.39.

Compound 61.25:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.29(t,¹H), 7.99(d,²H), 7.50(d,²H), 7.17(d,²H), 7.09(d,²H), 3.68(s,²H), 3.53(s,²H), 3.27–3.21(m,³H), 2.45(dd,²H), 2.26(s,³H). LC-MS (m/z, ESI): [M+H] ⁺ 436.40.

Compound 61.37:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.32 (t, ¹H), 7.99 (d, 2H), 7.69 (d, ¹H), 7.65–7.58 (m, 2H), 7.50 (d, 2H), 7.49–7.43 (m, ¹H), 3.88 (s, ¹H), 3.54 (s, 2H), 3.31–3.24 (m, 3H), 2.60 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 490.17.

Compound 61.40:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.31(t,¹H), 7.99(d,²H), 7.66(s,¹H), 7.61(d,¹H), 7.59(d,¹H), 7.54(t,¹H), 7.50(d,²H), 3.84(s,²H), 3.53(s,²H), 3.26(dt,²H), 2.48(t,²H). LC-MS (m/z, ESI): [M+H] ⁺ 490.17.

Compound 61.41:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 7.99(d,¹H), 7.76(s,¹H), 7.71(dt,¹H), 7.66(dt,¹H), 7.53(d,¹H), 7.50(d,²H), 3.79(s,²H), 3.54(s,²H), 3.24(dt,²H), 2.46(dd,²H). LC-MS (m/z, ESI): [M+H] ⁺ 447.31.

Compound 61.42:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 7.99(d,²H), 7.50(d,²H), 7.21(t,¹H), 6.88–6.83(m,²H), 6.81–6.77(m,¹H), 3.72(s,³H), 3.70(s,²H), 3.54(s,²H), 3.25(dt,²H), 2.47(dd,²H). LC-MS (m/z, ESI): [M+H] ⁺ 452.39.

Compound 61.43:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.30 (t, ¹H), 7.99 (d, 2H), 7.64 (d, 2H), 7.50 (d, 4H), 3.81 (s, 2H), 3.53 (s, 2H), 3.26 (dt, 2H), 2.47 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 490.17.

Compound 61.45:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ) δ 8.29 (t, ¹H), 7.99 (d, ¹H), 7.50 (d, 2H), 7.20 (d, 2H), 6.85 (d, ¹H), 3.72 (s, 3H), 3.67 (s, 2H), 3.53 (s, 2H), 3.27–3.21 (m, 2H), 2.45 (t, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 452.39.

Compound 61.54:

White solid. ^¹H NMR (600MHz, DMSO- _d⁶ ) δ 8.30(t,¹H), 8.00(d,²H), 7.50(d,²H), 7.33(d,²H), 7.25(t,¹H), 7.08(d,²H), 3.73(s,²H), 3.54(s,²H), 3.25(dt,²H), 2.46(t,²H). LC-MS (m/z, ESI): [M+H] ⁺ 488.19.

Compound 51.2:

White solid. ^¹H NMR (600 MHz, DMSO- _d⁶ ): δ 10.47 (t, ¹H), 7.99 (d, 2H), 7.56 (d, 2H), 7.47–7.42 (m, 2H), 7.30–7.27 (m, 2H), 4.01 (s, 2H), 3.85 (s, 2H), 3.78–3.73 (m, 2H), 2.72 (dd, 6.4 Hz, 2H). LC-MS (m/z, ESI): [M+H] ⁺ 472.05.

Other compounds of the present invention can be prepared according to the description in the embodiments of the present invention.

Bioactivity assay

Example 5: Determination of fungicidal activity against soybean rust

Protective activity testing method: A live pot test method was used. The sample of the test compound was dissolved in a small amount of solvent (the type of solvent, such as acetone, methanol, DMF, etc., selected based on its solubility in the sample; the volume ratio of solvent to spray volume was equal to or less than 0.05), diluted with water containing 0.1% Tween 80, to prepare the test solution of the required concentration. A separate aqueous solution of the solvent was used as a blank control. The test solution was sprayed onto the diseased host plants (standard potted seedlings cultivated in a greenhouse) using a crop sprayer. Disease inoculation was performed 24 hours later. Based on the characteristics of the disease, diseased plants requiring temperature and humidity control were inoculated and placed in an artificial climate chamber for cultivation. After the disease had fully infected the plants, they were transferred to a greenhouse for further cultivation. Diseased plants not requiring humidity control were directly inoculated and cultivated in the greenhouse. The disease control effect of the compound was evaluated after the control group had fully developed the disease (usually one week).

The in vivo protective activity against soybean rust is as follows:

When the drug concentration is 1.56 mg/L, the compounds 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.13, 1.16, 1.17, 1.19, 1.22, 1.25, 1.37, 1.42, 1.43, 1.45, 1.54, 1.64, 1.65, 1.67, 1.68, 1.71, 1.73, 1.74, 1.76, 1.77, 1.80, 1.256, 1.315, 1.321, 11.2, 11.1, 11.4, 11.5, 11.7, 11.8, 11.17, 11.22, 11 .25, 11.37, 11.45, 11.54, 11.321, 21.1, 21.2, 21.4, 21.5, 21.7, 21.8, 21.9, 21.17, 21.19, 21.22, 21.25, 21.37, 21.42, 21.45, 21.54, 21.64, 21.67, 21.73, 21.74, 21.175, 21.321, 31.1, 31.2, 31.3, 31.4, 31.5, 31.6, 31.7, 31.8, 31.9, 31.10, 31.13, 31.16, 31.19, 31.22, 3 1.25, 31.37, 31.42, 31.43, 31.45, 31.54, 31.64, 31.65, 31.67, 31.68, 31.71, 31.73, 31.74, 31.77, 31.321, 41.1, 41.2, 41.3, 41.4, 41.5, 41.6, 41.7, 41.8, 41.9, 41.10, 41.13, 41.16, 41.19, 41.22, 41.25, 41.37, 41.40, 41.42, 41.43, 41.45, 41.321, 51.2, 51.321, 61.1, 6 Varieties 1.2, 61.3, 61.4, 61.5, 61.6, 61.7, 61.8, 61.9, 61.10, 61.11, 61.12, 61.13, 61.16, 61.17, 61.18, 61.19, 61.22, 61.25, 61.37, 61.40, 61.41, 61.42, 61.43, 61.45, 61.54, 61.321, 71.1, 71.2, 71.3, 71.4, 71.5, 71.6, 71.7, 71.8, 71.19, 71.22, 71.25, and 71.321 exhibit a control efficacy of no less than 90% against soybean rust.

Claims (8)

An oxadiazole compound, characterized in that the compound is as shown in general formula I:
In general formula I: _A1 is selected from N or _CR1 , and _R1 is selected from hydrogen, halogen, _C1 - _C6 alkyl, halogenated _C1 - _C6 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C6 alkoxy or halogenated _C1 - _C6 alkoxy. _A2 is selected from N or _CR2 , and _R2 is selected from hydrogen, halogen, _C1 - _C6 alkyl, halogenated _C1 - _C6 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C6 alkoxy or halogenated _C1 - _C6 alkoxy. _A3 is selected from N or _CR3 , and _R3 is selected from hydrogen, halogen, _C1 - _C6 alkyl, halogenated _C1 - _C6 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C6 alkoxy or halogenated _C1 - _C6 alkoxy. _A4 is selected from N or _CR4 , and _R4 is selected from hydrogen, halogen, _C1 - _C6 alkyl, halogenated _C1 - _C6 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C6 alkoxy or halogenated _C1 - _C6 alkoxy. X is selected from hydrogen, halogen, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, _C1 - _C6 alkyl, halo- _C1 - _C6 alkyl, _C3 - _C8 cycloalkyl, _C1 - _C6 alkoxy, halo- _C1 - _C6 alkoxy, _C1 - _C6 alkylthio, _{halo-C1 - C6} alkylthio, _C2 - _C8 alkenyl, halo- _C2 - _C8 alkenyl, _C2 - _C8 ynyl, halo-C2- _C8 ynyl, _C1 - _C6 alkylamino, halo- _C1 - _C6 alkylamino, _C1 - _C6 dialkylamino, _C3 - _C8 cycloalkylamino, _C1 - _C6 alkylcarbonyl, _C1 - _C6 alkoxycarbonyl, _C1 - _C6 alkylsulfonyl, _C1 - _C6 alkylaminocarbonyl, _C1 -C ₆ alkylaminosulfonyl, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy carbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ alkyl carbonyloxy, C ₁ -C ₆ alkyl carbonylamino, C ₁ -C ₆ alkoxy carbonyloxy, C 1-C ₆ alkylamino carbonyloxy, C ₁ -C 6 alkylsulfonyloxy, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy, or C ₁ -C ₆ alkoxy carbonyl C ₁ -C ₆ alkoxy; m is selected from ₀ , 1, 2, 3, ₄ , or 5; when m is greater than 1, X can be the same or different; Y is selected from O or S; Z is selected from O or S; n is selected from 0 or 1; Or a salt of a compound of general formula I. The compound according to claim 1, characterized in that, in general formula I: _A1 is selected from N or _C1 , and _R1 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl; _A2 is selected from N or _CR2 , and _R2 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl; _A3 is selected from N or _CR3 , and _R3 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl; _A4 is selected from N or _CR4 , and _R4 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl; Furthermore, among _A1 , _A2 , _A3 , and _A4 , at most two are selected from N; X is selected from hydrogen, halogen, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, _C1 - _C4 alkyl, halo- _C1 - _C4 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C4 alkoxy, halo- _C1 - _C4 alkoxy, _C1 - _C4 alkylthio, _{halo-C1 - C4} alkylthio, _C2 - _C4 alkenyl, halo- _C2 - _C4 alkenyl _{, C2-C4 alkynyl ,} halo- _C2 - _C4 alkynyl, _{C1-C4 alkylamino, halo-C1 -C4} alkylamino, _C1 - _C4 dialkylamino, _C3 - _C6 cycloalkylamino, _C1 - _C4 alkylcarbonyl, _C1 - _C4 alkoxycarbonyl, _C1 - _C4 alkylsulfonyl, _C1 - _C4 alkylaminocarbonyl, _{C1 -C4} alkylaminosulfonyl, _C1 -C4 alkoxyC1- _C4 alkyl, _C1 -C4 alkoxycarbonylC1- _C4 alkyl, _C1 - _C4 alkylcarbonyloxy, C1- _{C4 alkylcarbonylamino, C1-C4 alkoxycarbonyloxy, C1-C4 alkylaminocarbonyloxy , C1 - C4 alkylsulfonyloxy} , _C1 - _C4 alkoxyC1- _C4 alkoxy, halogenated _C1 - _C4 alkoxyC1- _C4 alkoxy, or _{C1 -} C4 alkoxycarbonylC1- _C4 alkoxy; m is selected from 0 _{, 1} , 2, _{3 , 4 ,} or ₅ ; when m is greater than ₁ , X can be the same or different; Y is selected from O or S; Z is selected from O or S; n is selected from 0 or 1; Salts formed by compounds of general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid, or citric acid. The compound according to claim 2, characterized in that, in general formula I: _A1 is selected from N or _C1 , and _R1 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl; _A2 is selected from _CR2 , and _R2 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halo- _C1 - _C3 alkyl; _A3 is selected from N or _CR3 , and _R3 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl; _A4 is selected from _CR4 , and _R4 is selected from hydrogen, halogen, _C1 - _C3 alkyl or halogenated _C1 - _C3 alkyl; Furthermore, at most one of _A1 and _A3 can be selected from N; X is selected from hydrogen, halogen, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, _C1 - _C4 alkyl, halo- _C1 - _C4 alkyl, _C3 - _C6 cycloalkyl, _C1 - _C4 alkoxy, halo- _C1 - _C4 alkoxy, _C1 - _C4 alkylthio, _{halo-C1 - C4} alkylthio, _C2 - _C4 alkenyl, halo- _C2 - _C4 alkenyl _{, C2-C4 alkynyl ,} halo- _C2 - _C4 alkynyl, _{C1-C4 alkylamino, halo-C1 -C4} alkylamino, _C1 - _C4 dialkylamino, _C3 - _C6 cycloalkylamino, _C1 - _C4 alkylcarbonyl, _C1 - _C4 alkoxycarbonyl, _C1 - _C4 alkylsulfonyl, _C1 - _C4 alkylaminocarbonyl, _{C1 -C4} alkylaminosulfonyl, _C1 -C4 alkoxyC1- _C2 alkyl, _C1 -C4 alkoxycarbonylC1- _C2 alkyl, _C1 - _C4 alkylcarbonyloxy, C1- _{C4 alkylcarbonylamino, C1-C4 alkoxycarbonyloxy, C1-C4 alkylaminocarbonyloxy , C1 - C4 alkylsulfonyloxy} , _C1 - _C4 alkoxyC1- _C2 alkoxy, halogenated _C1 - _C4 alkoxyC1- _C2 alkoxy, or _{C1 -} C4 alkoxycarbonylC1- _C2 alkoxy; m is selected from 0 _{, 1 , 2, 3 , 4} , or ₅ ; when m is greater than _{1 ,} X can be the same or different; Y is selected from O or S; Z is selected from O or S; n is selected from 0 or 1; Salts formed by compounds of general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid, or citric acid. The compound according to claim 3, characterized in that, in general formula I: _A1 is selected from N or _CR1 , and _R1 is selected from hydrogen, fluorine, or methyl. _A2 is selected from _CR2 , and _R2 is selected from hydrogen, fluorine, or methyl. _A3 is selected from N or _CR3 , and _R3 is selected from hydrogen, fluorine, or methyl. _A4 is selected from _CR4 , and _R4 is selected from hydrogen, fluorine, or methyl. Furthermore, at most one of _A1 and _A3 can be selected from N; X is selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethyl, trifluoromethyl, di ... Fluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, vinyl, 1-propenyl, 2-propenyl, ethynyl, 1-propynyl, methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, methylethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, or n-butoxycarbonyl; m is selected from 0, 1, 2, 3, 4, or 5; when m is greater than 1, X can be the same or different; Y is selected from O or S; Z is selected from O or S; n is selected from 0 or 1; Salts formed by compounds of general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid, or citric acid. The compound according to claim 4, characterized in that, in general formula I: _A1 is selected from _CR1 , and _R1 is selected from hydrogen or fluorine; _A2 is selected from _CR2 , and _R2 is selected from hydrogen or fluorine; _A3 is selected from _CR3 , and _R3 is selected from hydrogen or fluorine; _A4 is selected from _CR4 , and _R4 is selected from hydrogen or fluorine; X is selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxyl, mercapto, amino, _CONH2 , COOH, CHO, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethyl, trifluoromethyl, di ... Fluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, vinyl, 1-propenyl, 2-propenyl, ethynyl, 1-propynyl, methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, methylethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, or n-butoxycarbonyl; m is selected from 0, 1, 2, 3, 4, or 5; when m is greater than 1, X can be the same or different; Y is selected from O or S; Z is selected from O or S; n is selected from 0 or 1; Salts formed by compounds of general formula I with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid, or citric acid. The use of a compound of general formula I according to claim 1 as a fungicide in agriculture or forestry. A bactericidal composition, characterized in that: the composition contains a compound of general formula I as described in claim 1 and an agriculturally acceptable carrier, and the weight percentage of the active component in the composition is 0.1-99%. A method for preventing and controlling pathogens, characterized in that: applying an effective dose of the bactericidal composition as described in claim 7 to the crop or the crop's growing medium or location.