Nicotinic acid ester compound and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to a nicotinic acid ester compound and the use thereof. The compound is represented by general formula (I), wherein W represents O or S; M1, M2, M3, M4, and M5 each independently represent hydrogen, a halogen, an alkyl group, a haloalkyl group, etc.; R1, R2, R3, and R4 each independently represent hydrogen, a halogen, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, etc.; and X and Y each independently represent hydrogen, a halogen, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, etc. The present compound has good control activity on fungi, bacteria, and the like.

Description

Nicotinate compounds and their applications Technical Field

[0001] The present invention belongs to the technical field of pesticides, and in particular relates to a nicotinic acid ester compound and application thereof. Background Art

[0002] In recent years, due to the long-term use of pest control agents, such as insecticides or fungicides, pests and diseases have acquired drug resistance, making it difficult to control them with existing insecticides or fungicides. In addition, some known pest control agents are highly toxic, or some damage ecosystems through their long-term residual properties. In this situation, although a large number of fungicides are known, such as WO2016039459A1, which discloses nicotinic acid ester compounds and their use as fungicides, there is still a need to develop new pest control agents with low toxicity and low residual properties.

[0003] Summary of the Invention

[0004] To solve the above problems in the prior art, the present invention provides a nicotinic acid ester compound and its application. The compound has good control activity against fungi and bacteria.

[0005] The technical solution adopted in the present invention is as follows:

[0006] A nicotinic acid ester compound, as shown in the general formula I:

[0007] Among them, W represents O or S;

[0008] M1, M2, M3, M4, and M5 independently represent hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, or haloalkynyl;

[0009] R1, R2, R3, and R4 independently represent hydrogen, halogen, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, hydroxyl, mercapto, hydroxyalkyl, mercaptoalkyl, -NR5R6, -OR7, or -S(O). m R7, -alkylene-NR5R6, -alkylene-OR7, -alkylene-S(O) m R7; wherein the "alkyl", "alkenyl" or "alkynyl" is optionally substituted by halogen;

[0010] R5 represents H, optionally replaced by R 11 Substituted alkyl, alkenyl or alkynyl, aryl, heteroaryl, -COR 12 , nitro, -OR 13 , -SO2R 14 , -NR 15 R 16 , -N=CR 17 R18 , trialkylsilyl or dialkylphosphonyl; R6 represents H, optionally replaced by R 21 Substituted alkyl or -COR 22 ; or -NR5R6 represents -N=CR 31 NR 32 R 33 、-N=CR 34 OR 35 or a heterocyclic group wherein the 1-position is a nitrogen atom;

[0011] where R 11 、R 21 independently represents halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, alkoxycarbonyl, aryl or heteroaryl;

[0012] R 12 、R 22 independently represents H, alkyl, haloalkyl, alkylthio, alkylthioalkyl, alkoxy, alkoxyalkyl, -NR 15 R 16 , aryl, arylthio, aryloxy, arylalkyl, arylalkylthio or arylalkoxy;

[0013] R 13 represents H, alkyl, haloalkyl, phenyl, benzyl or -CHR 41 C(O)OR 42 ; R 41 represents H, alkyl or alkoxy; R 42 represents H, alkyl or benzyl;

[0014] R 14 represents alkyl and haloalkyl;

[0015] R 15 represents H, alkyl, formyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H, alkyl; or -NR 15 R 16 Each independently represents a heterocyclic group with a nitrogen atom at the 1-position;

[0016] R 17 represents H, alkyl, unsubstituted or substituted phenyl with at least one of halogen, alkyl, and alkoxy; R 18 represents H, alkyl; or -N=CR 17 R 18 represent

[0017] R 31 、R 34Each independently represents H or an alkyl group;

[0018] R 32 、R 33 Each independently represents H or alkyl; or -NR 32 R 33 represents a heterocyclic group wherein the 1-position is a nitrogen atom;

[0019] R 35 represents an alkyl group;

[0020] R7 independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, wherein the "alkyl group", "alkenyl group" or "alkynyl group" is optionally substituted by at least one group selected from halogen, cyano group, trialkylsilyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, -OR8, -SR8, -O(CO)R8, -(CO)R8, -(CO)OR8 or -O(CO)OR8;

[0021] R8 each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, alkylsulfonyl or phenoxy substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxy or haloalkoxy;

[0022] X and Y independently represent hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heterocyclic, arylalkyl, heterocyclicalkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2, -alkylene-OR 10 、-alkylene-SR 10 、-alkylene-(CO)OR 10 、-alkylene-(SO2)R 10 、-alkylene-N(R 10 )2 or -O-alkylene-(CO)OR 10 , or X and Y together form -CH=CH-CH=CH- which is unsubstituted or substituted by halogen;

[0023] The aforementioned "cycloalkyl", "cycloalkenyl", "heterocyclyl" or "aryl" is optionally selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, -OR10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-alkylene-(CO)OR 10 or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0024] R 10 Each independently represents hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy;

[0025] m represents 0, 1, or 2.

[0026] In one embodiment, M1, M2, M3, M4, and M5 independently represent hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, halogenated C2-C8 alkenyl, C2-C8 alkynyl, or halogenated C2-C8 alkynyl;

[0027] R1, R2, R3, and R4 independently represent hydrogen, halogen, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, hydroxyl, mercapto, hydroxyC1-C8 alkyl, mercaptoC1-C8 alkyl, -NR5R6, -OR7, or -S(O). m R7, -(C1-C8 alkylene)-NR5R6, -(C1-C8 alkylene)-OR7, -(C1-C8 alkylene)-S(O) m R7; wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally substituted by halogen;

[0028] R5 represents H, optionally replaced by R 11 Substituted C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl, aryl, heteroaryl, -COR 12 , nitro, -OR 13 , -SO2R 14 , -NR 15 R 16 , -N=CR 17 R 18 , tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphono; R6 represents H, optionally replaced by R 21 Substituted C1-C8 alkyl or -COR 22; or -NR5R6 represents -N=CR 31 NR 32 R 33 , -N=CR 34 OR 35 , unsubstituted or substituted by at least one group selected from oxo, halogen, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino or C1-C8 alkoxycarbonyl

[0029] where R 11 、R 21 independently represent halogen, hydroxy, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino, C1-C8 alkoxycarbonyl, aryl or heteroaryl;

[0030] R 12 、R 22 independently represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkylthio, C1-C8 alkylthioC1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkoxyC1-C8 alkyl, -NR 15 R 16 , aryl, arylthio, aryloxy, aryl C1-C8 alkyl, aryl C1-C8 alkylthio or aryl C1-C8 alkoxy;

[0031] R 13 represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or -CHR 41 C(O)OR 42 ; R 41 represents H, C1-C8 alkyl or C1-C8 alkoxy; R 42 represents H, C1-C8 alkyl or benzyl;

[0032] R 14 represents C1-C8 alkyl, halogenated C1-C8 alkyl;

[0033] R 15 represents H, C1-C8 alkyl, formyl, C1-C8 alkylcarbonyl, halogenated C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H, C1-C8 alkyl; or -NR 15 R 16Each independently represents an unsubstituted or substituted group selected from oxo, halogen, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino or C1-C8 alkoxycarbonyl.

[0034] R 17 represents H, C1-C8 alkyl, or phenyl which is unsubstituted or substituted by at least one of halogen, C1-C8 alkyl, and C1-C8 alkoxy; R 18 represents H, C1-C8 alkyl; or -N=CR 17 R 18 represent

[0035] R 31 、R 34 Each independently represents H or C1-C8 alkyl;

[0036] R 32 、R 33 Each independently represents H or C1-C8 alkyl; or -NR 32 R 33 represents an unsubstituted or substituted group selected from oxo, halogen, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino or C1-C8 alkoxycarbonyl

[0037] R 35 represents a C1-C8 alkyl group;

[0038] R7 each independently represents a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a C3-C8 cycloalkenyl group, an aryl group or a heterocyclic group, wherein the "C1-C8 alkyl group", "C2-C8 alkenyl group" or "C2-C8 alkynyl group" is optionally substituted by at least one group selected from halogen, cyano, tri-C1-C8 alkylsilyl group, C3-C8 cycloalkyl group, C3-C8 cycloalkenyl group, aryl group, heterocyclic group, -OR8, -SR8, -O(CO)R8, -(CO)R8, -(CO)OR8 or -O(CO)OR8;

[0039] R8 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl or phenoxy substituted by at least one group selected from the group consisting of halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy or halo-C1-C8 alkoxy;

[0040] X and Y independently represent hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, aryl, heterocyclic group, aryl C1-C8 alkyl, heterocyclic C1-C8 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2, -(C1-C8 alkylene)-OR 10 、-(C1-C8 alkylene)-SR 10 、-(C1-C8 alkylene)-(CO)OR 10 、-(C1-C8 alkylene)-(SO2)R 10 、-(C1-C8 alkylene)-N(R 10 )2 or -O-(C1-C8 alkylene)-(CO)OR 10 , or X and Y together form -CH=CH-CH=CH- which is unsubstituted or substituted by halogen;

[0041] The aforementioned “C3-C8 cycloalkyl”, “C3-C8 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C8 alkylene)-(CO)OR 10or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0042] R 10 Each independently represents hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy.

[0043] In another embodiment, M1, M2, M3, M4, and M5 independently represent hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, or halogenated C2-C6 alkynyl;

[0044] R1, R2, R3, and R4 independently represent hydrogen, halogen, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, hydroxyl, mercapto, hydroxyC1-C6 alkyl, mercaptoC1-C6 alkyl, -NR5R6, -OR7, or -S(O) m R7, -(C1-C6 alkylene)-NR5R6, -(C1-C6 alkylene)-OR7, -(C1-C6 alkylene)-S(O) m R7; wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally substituted by halogen;

[0045] R5 represents H, optionally replaced by R 11 Substituted C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, aryl, heteroaryl, -COR 12 , nitro, -OR 13 , -SO2R 14 , -NR 15 R 16 , -N=CR 17 R 18 , tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphono; R6 represents H, optionally replaced by R 21 Substituted C1-C6 alkyl or -COR 22 ; or -NR5R6 represents -N=CR 31 NR 32 R 33 , -N=CR 34 OR 35, unsubstituted or substituted by at least one group selected from oxo, halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino or C1-C6 alkoxycarbonyl

[0046] where R 11 、R 21 independently represent halogen, hydroxy, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino, C1-C6 alkoxycarbonyl, aryl or heteroaryl;

[0047] R 12 、R 22 independently represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkylthio, C1-C6 alkylthioC1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxyC1-C6 alkyl, -NR 15 R 16 , aryl, aryloxy, aryloxy, aryl C1-C6 alkyl, aryl C1-C6 alkoxy or aryl C1-C6 alkoxy;

[0048] R 13 represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or -CHR 41 C(O)OR 42 ; R 41 represents H, C1-C6 alkyl or C1-C6 alkoxy; R 42 represents H, C1-C6 alkyl or benzyl;

[0049] R 14 represents C1-C6 alkyl, halogenated C1-C6 alkyl;

[0050] R 15 represents H, C1-C6 alkyl, formyl, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H, C1-C6 alkyl; or -NR 15 R 16 Each independently represents an unsubstituted or substituted group selected from oxo, halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino or C1-C6 alkoxycarbonyl.

[0051] R17 represents H, C1-C6 alkyl, or phenyl which is unsubstituted or substituted by at least one of halogen, C1-C6 alkyl, and C1-C6 alkoxy; R 18 represents H, C1-C6 alkyl; or -N=CR 17 R 18 represent

[0052] R 31 、R 34 Each independently represents H or C1-C6 alkyl;

[0053] R 32 、R 33 Each independently represents H or C1-C6 alkyl; or -NR 32 R 33 represents an unsubstituted or substituted group selected from oxo, halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino or C1-C6 alkoxycarbonyl

[0054] R 35 represents a C1-C6 alkyl group;

[0055] R7 each independently represents a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkenyl group, an aryl group or a heterocyclic group, wherein the "C1-C6 alkyl group", "C2-C6 alkenyl group" or "C2-C6 alkynyl group" is optionally substituted by at least one group selected from halogen, cyano, tri-C1-C6 alkylsilyl group, C3-C6 cycloalkyl group, C3-C6 cycloalkenyl group, an aryl group, a heterocyclic group, -OR8, -SR8, -O(CO)R8, -(CO)R8, -(CO)OR8 or -O(CO)OR8;

[0056] R8 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl or phenoxy substituted by at least one group selected from the group consisting of halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy or halo-C1-C6 alkoxy;

[0057] X and Y independently represent hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, aryl, heterocyclic group, aryl C1-C6 alkyl, heterocyclic C1-C6 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2, -(C1-C6 alkylene)-OR 10 、-(C1-C6 alkylene)-SR 10 、-(C1-C6 alkylene)-(CO)OR 10 、-(C1-C6 alkylene)-(SO2)R 10 、-(C1-C6 alkylene)-N(R 10 )2 or -O-(C1-C6 alkylene)-(CO)OR 10 , or X and Y together form -CH=CH-CH=CH- which is unsubstituted or substituted by halogen;

[0058] The aforementioned “C3-C6 cycloalkyl”, “C3-C6 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C6 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0059] R 10 Each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

[0060] In another embodiment, M1, M2, M3, M4, and M5 each independently represent hydrogen.

[0061] In the definition of the compounds represented by the above general formula and in all the following structural formulas, the technical terms used, whether used alone or in compound words, represent the following substituents: Alkyl groups with more than two carbon atoms can be straight-chain or branched. For example, the compound word "-O-alkylene-(CO)OR 10 " " in which the alkylene group can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. The alkyl group is, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl. The term "cycloalkyl" refers to a group consisting of cyclopentyl, cyclohexyl, cyclopentenyl, cyclohex ...

[0062] Unless otherwise specified, the "aryl" mentioned in the present invention includes but is not limited to phenyl, naphthyl, The "heterocyclic group" includes but is not limited to saturated or unsaturated non-aromatic cyclic groups etc., and also include but are not limited to heteroaryl, i.e. an aromatic cyclic group containing, for example, 3 to 6 ring atoms and optionally fused to a benzo ring, wherein 1 to 4 (e.g. 1, 2, 3 or 4) heteroatoms in the ring atoms are selected from oxygen, nitrogen and sulfur, for example

[0063] If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different groups selected from the groups mentioned. Furthermore, identical or different substituent characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed from different atoms and units. At the same time, compounds known to those skilled in the art to be chemically unstable under standard conditions are excluded from the scope of the claims.

[0064] In addition, unless otherwise specified, the term "substituted by at least one group" as used herein refers to being substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without a specific connection position can be connected at any position, including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position as long as it complies with the chemical bond connection rules. For example, a heteroaryl group substituted by 1 methyl group Can represent wait.

[0065] The compounds of formula I in each case in free form or in salt form, and where appropriate their tautomers, may be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of the asymmetric carbon atoms present in the molecule, and / or on the configuration of the non-aromatic double bonds present in the molecule; the present invention relates to these pure isomers and also to all possible isomer mixtures and should be understood in this sense in each case above and below, even if no specific stereochemical details are mentioned in each case. The present invention therefore covers all such isomers and tautomers and their mixtures in all proportions, as well as isotopic forms, such as deuterated compounds.

[0066] In another embodiment, Formula I is also understood to include salts or hydrates thereof. Exemplary salts include, but are not limited to, hydrochlorides, hydrobromides, and hydroiodides.

[0067] It will also be understood by those skilled in the art that, unless otherwise indicated, additional substitutions are permissible as long as chemical bonding and strain energy rules are met and the product still exhibits fungicidal activity.

[0068] Another embodiment of the present application is a method for preparing the nicotinic acid ester compound, comprising the following steps:

[0069] The compound represented by general formula II is reacted with the compound represented by general formula III to obtain the compound represented by general formula I, and the reaction equation is as follows:

[0070] Wherein, W1 and W2 independently represent OH or halogen, and are not halogen at the same time, and the definitions of the substituents W, R1, R2, R3, R4, M1, M2, M3, M4, M5, X and Y are as described above.

[0071] In one embodiment, the reaction is carried out in the presence of a solvent.

[0072] In another embodiment, a condensing agent and / or a base is added during the reaction.

[0073] In one embodiment, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, THF, toluene, dichloromethane or ethyl acetate.

[0074] In a specific embodiment, the base is selected from at least one of an inorganic base (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, K3PO4, NaOH, KOH, etc.) or an organic base (such as DMAP, pyrazole, triethylamine, DIEA, MeONa, AcOK, AcONa, t-BuONa, EtONa, etc.).

[0075] In one embodiment, the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU or HATU.

[0076] The present application also discloses a fungicidal and / or bacterial composition, which comprises the aforementioned nicotinic acid ester compound (active ingredient A); preferably, further comprises other active ingredients.

[0077] In a specific embodiment, the other active ingredients (active ingredient B) are selected from at least one of the following compounds: fludioxonil (CAS No.: 131341-86-1), pyraclostrobin (CAS No.: 175013-18-0), Metconazole (CAS No.: 125116-23-6), Prothioconazole (CAS No.: 178928-70-6), Jinggangmycin (CAS No.: 37248-47-8), Iprodione (CAS No.: 36734-19-7), Mancozeb (CAS No.: 8018-01-7), Captan (CAS No.: 133-06-2), Difenoconazole (CAS No.: 119446-68-3), Tebuconazole (CAS No.: 107534-96-3), Metalaxyl-M (CAS No.: 70630-17-0), Trifloxystrobin (CAS No.: 141517-21-7), Flupyrosaccharide (CAS No.: 907204- 31-3), thiophanate-methyl (CAS No.: 130000-40-7), fluazinam (CAS No.: 79622-59-6), ethoxyconazole (CAS No.: 682-91-7), azoxystrobin (CAS No.: 131860-33-8), oxadiazine (CAS No.: 10004-44-1), trifluomethoxycarb (CAS No.: 911499-62-2), amino oligosaccharides (CAS No.: 6980-18-3) and dimethomorph (CAS No.: 110488-70-5).

[0078] In another specific embodiment, the weight ratio of active ingredients A and B in the composition is 1:20000-100:1, 1:15000-80:1, 1:10000-60:1, 1:6000-50:1, 1:3000-30:1, 1:100-20:1, 1:50-10:1, 1:30-5:1, 1:20-1:1 or 1:10-1:5.

[0079] Another embodiment of the present application is the use of a compound of formula I for protecting plants from attack by phytopathogenic microorganisms or for treating plants attacked by phytopathogenic microorganisms, comprising applying a compound of formula I or a composition containing the compound to soil, plants, parts of plants, leaves, and / or roots.

[0080] In addition, another embodiment of the present application is a composition for protecting plants from phytopathogenic microorganisms and / or treating plants attacked by phytopathogenic microorganisms, the composition comprising a compound of formula I and a phytologically acceptable carrier substance.

[0081] The present invention further relates to crop protection compositions for controlling unwanted microorganisms, in particular unwanted fungi and bacteria, comprising an effective and non-phytotoxic amount of the active ingredients according to the invention. These are preferably fungicidal compositions comprising agriculturally suitable adjuvants, solvents, carriers, surfactants or extenders.

[0082] In the context of the present invention, "control of harmful microorganisms" means a reduction in the infestation of harmful microorganisms compared to untreated plants, measured as fungicidal efficacy, preferably a reduction of 25-50% compared to untreated plants (100%), more preferably a reduction of 40-79% compared to untreated plants (100%), even more preferably a complete inhibition of infestation by harmful microorganisms (70-100%). The control can be curative, i.e. for treating infected plants, or protective, for protecting plants that have not yet been infected.

[0083] An "effective but non-phytotoxic amount" is an amount of the composition of the present invention sufficient to control fungal diseases of plants in a satisfactory manner or to completely eliminate them, without causing any significant symptoms of phytotoxicity. In general, this application rate can vary within a relatively wide range. It depends on several factors, for example, on the fungi to be controlled, the plant, climatic conditions, and the ingredients of the composition of the present invention.

[0084] Suitable organic solvents include all polar and nonpolar organic solvents commonly used for formulation purposes. Preferably, the solvent is selected from ketones, such as methyl isobutyl ketone and cyclohexanone, amides, such as dimethylformamide and alkanecarboxylic acid amides, such as N, N-dimethyldecylamide and N, N-dimethyloctanamide, as well as cyclic solvents, such as N-methyl-pyrrolidone, N-octyl-pyrrolidone, N-dodecyl-pyrrolidone, N-octyl-caprolactam, N-dodecyl-caprolactam and butyrolactone, as well as strongly polar solvents, such as dimethyl sulfoxide, as well as aromatic hydrocarbons, such as xylene, mineral oils, such as white spirit, petroleum oil, alkylbenzenes and spindle oil, as well as esters, such as propylene glycol monomethyl ether acetate, dibutyl adipate, hexyl acetate, heptyl acetate, tri-n-butyl citrate and di-n-butyl phthalate, and also alcohols, such as benzyl alcohol and 1-methoxy-2-propanol.

[0085] According to the present invention, the carrier is a natural or synthetic, organic or inorganic substance with which the active ingredient is mixed or combined to achieve better suitability, in particular for application to plants or plant parts or seeds. The carrier, which can be solid or liquid, is generally inert and should be suitable for use in agriculture.

[0086] Useful solid or liquid carriers include, for example, ammonium salts and natural rock dusts, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock dusts, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils, and derivatives thereof. Mixtures of the aforementioned carriers can likewise be used.

[0087] Suitable solid fillers and carriers include inorganic particles having an average particle size of 0.005 to 20 μm, preferably 0.02 to 10 μm, such as carbonates, silicates, sulfates and oxides, for example ammonium sulfate, ammonium phosphate, urea, calcium carbonate, calcium sulfate, magnesium sulfate, magnesium oxide, aluminum oxide, silicon dioxide, so-called fine-particle silicon dioxide, silica gel, natural or synthetic silicates, and aluminosilicates and plant products, such as cereal flour, wood flour / sawdust and cellulose powder.

[0088] Useful solid carriers for granules include, for example, crushed and classified natural rocks, such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic flours, and also granules of organic matter, such as sawdust, coconut shells, corn cobs and tobacco stalks.

[0089] Useful liquefied gas extenders or carriers are those liquids which are gases at standard temperature and standard pressure, for example aerosol propellants such as halogenated hydrocarbons, and also butane, propane, nitrogen and carbon dioxide.

[0090] In the formulation, thickeners such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, for example gum arabic, polyvinyl alcohol and polyvinyl acetate, or other natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used. Further additives can be mineral oils and vegetable oils.

[0091] If the extender used is water, organic solvents, for example, can also be used as auxiliary solvents. Useful liquid solvents are, inter alia, aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes; chlorinated aromatic and aliphatic hydrocarbons such as chlorobenzenes, vinyl chlorides or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffins; mineral oil fractions, mineral oils and vegetable oils; alcohols such as butanol or glycols and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; highly polar solvents such as dimethylformamide and dimethyl sulfoxide; and also water.

[0092] Suitable surfactants (auxiliaries, emulsifiers, dispersants, protective colloids, wetting agents and binders) include all customary ionic and nonionic substances, for example ethoxylated nonylphenols, polyalkylene glycol ethers of linear or branched alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, reaction products of fatty acid amines with ethylene oxide and / or propylene oxide, also fatty acid esters, alkylsulfonates, alkyl sulfates, alkyl ether sulfates, alkyl ether phosphates, aryl sulfates, ethoxylated arylalkylphenols, for example tristyrylphenol ethoxylate, and ethoxylated and propoxylated arylalkylphenols, such as sulfated or phosphated arylalkylphenol ethoxylates and ethoxy- and propoxylates. Further examples are natural and synthetic water-soluble polymers, such as ligninsulfonates, gelatin, gum arabic, phospholipids, starch, hydrophobically modified starch and cellulose derivatives, in particular cellulose esters and cellulose ethers, further polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid and copolymers of (meth)acrylic acid and (meth)acrylic esters, and further copolymers of methacrylic acid and methacrylic esters neutralized with alkali metal hydroxides, and also condensation products of optionally substituted naphthalenesulfonates with formaldehyde. If one of the active ingredients and / or one of the inert carriers is insoluble in water and when application is carried out in water, the presence of a surfactant is essential. The proportion of surfactant is 5 to 40% by weight, based on the weight of the composition according to the invention.

[0093] Dyes such as inorganic pigments, for example, iron oxide, titanium oxide and Prussian blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as iron salts, manganese salts, boron salts, copper salts, cobalt salts, molybdenum salts and zinc salts can also be used.

[0094] Antifoaming agents that may be present in the formulation include, for example, silicone emulsions, long-chain alcohols, fatty acids and their salts, and fluorinated organic substances and mixtures thereof.

[0095] Examples of thickeners are polysaccharides, such as xanthan gum or veegum, silicates, such as attapulgite, bentonite, and finely divided silica.

[0096] If appropriate, other auxiliary ingredients may also be present, such as protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, stabilizers, chelating agents, complexing agents. In general, the active ingredients can be combined with any solid or liquid additives usually used for formulation purposes.

[0097] The active ingredients or compositions according to the invention can be used as such or, depending on their specific physical and / or chemical properties, in the form of their formulations or use forms prepared therefrom, such as, for example, aerosols, capsule suspensions, cold mist concentrates, warm mist concentrates, encapsulated granules, fine granules, flowable concentrates for seed treatment, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, large granules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, gases ( under pressure), gas-generating products, foams, pastes, pesticide-coated seeds, suspension concentrates, suspoemulsion concentrates, soluble concentrates, suspension concentrates, wettable powders, soluble powders, dusts and granules, water-soluble and water-dispersible granules or tablets, water-soluble and water-dispersible powders for seed treatment, wettable powders, natural products and synthetic substances impregnated with active ingredients, and also microcapsules in polymeric substances and in coating materials for seeds, and also ULV cold mist and warm mist formulations.

[0098] The compositions according to the invention include both ready-to-use formulations which can be applied to plants or seeds using suitable equipment, and commercial concentrates which must be diluted with water before use. Conventional applications are, for example, dilution in water and subsequent spraying of the resulting spray liquor, application after dilution in oil, direct application without dilution, seed treatment or soil application of granules.

[0099] The compositions and formulations of the present invention generally contain 0.05-99% by weight, 0.01-98% by weight, preferably 0.1-95% by weight, more preferably 0.5-90% by weight, and most preferably 10-70% by weight of the active ingredient. For special applications, such as protecting wood and derived timber products, the compositions and formulations of the present invention generally contain 0.0001-95% by weight, preferably 0.001-60% by weight of the active ingredient.

[0100] The content of active ingredient in the application forms prepared from commercially available preparations can vary within wide ranges. The concentration of active ingredient in the application forms is generally 0.000001 to 95% by weight, preferably 0.0001 to 2% by weight.

[0101] The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredient with at least one customary extender, solvent or diluent, adjuvant, emulsifier, dispersant, and / or binder or fixative, wetting agent, water repellent, if appropriate, drying agent and UV stabilizer, and if appropriate, dyes and pigments, defoamers, preservatives, inorganic and organic thickeners, adhesives, gibberellins and further processing aids and also water. Depending on the type of formulation to be prepared, further processing steps may be necessary, such as wet grinding, dry grinding and granulation.

[0102] The active ingredients of the present invention may be present as such or as a mixture with other (known) active ingredients, such as fungicides, bactericides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners and / or semiochemicals, in their (commercial) formulations and in use forms prepared from these formulations. Examples of known fungicides, insecticides, acaricides, nematicides and bactericides are disclosed in the Pesticide Manual, 17th edition.

[0103] The other fungicides may include: 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxy quinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, QST713), benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Borgundy mixture, boscalid, bromuconazole, bupirimate, calcium sulfur polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium Minitans, copper hydroxide, copper tanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid,Cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammoniumethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion), diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine,

[0104] (diphenylamine), dithianon, dodemorph, dodemorph acetate, dodine, dodine free base freebase), edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, and triphenyltin hydroxide. hydroxide), ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol fol), fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminum, fuberidazole, furaxyl, furametpyr, guazatine, guazatine acetate, sodium tetrasulfate (GY-81), hexachlorobenzene, hexaconazole, hymexazol, imazalil,Imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprethiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate), kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofuramide, oleic acid (fatty acid), orysastrobin,Oxadixyl, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercuryacetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroquinoline sulfate sulfate), probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenolate 2-phenyl phenoxide), sodium bicarbonate,Sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oil, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol imenol, triazoxide, tricyclazole, triridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate hydrate), 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,2-(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenylthiocyanate, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394), benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate). bis(3-phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate,Cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944), hexylthiofos, procyclidine (ICIA0858), isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride anhydride), myclozolin, N-3,5-dichlorophenylsuccinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide,Nickel bis(dimethyldithiocarbamate), octachloroketone (OCH), phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, 5-acetyl-8-hydroxyquinoline (quinacetol); 5-acetyl-8-hydroxyquinoline sulfate (quinacetolsulfate), quinazamid, quinconazole, rabenzazole, salicylanilide, pyraclostrobinol (SSF-109), pentyl sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combination thereof.

[0105] The treatment according to the invention of plants and plant parts with the active ingredients or compositions is carried out directly or by acting on their surroundings, habitat or storage space by customary treatment methods, for example by dipping, spraying, atomizing, irrigation, evaporation, dusting, spraying, sowing, foaming, spraying, spreading, watering (dip), drip irrigation, and in the case of propagation materials, in particular seeds, also by dry seed treatment, wet seed treatment, slurry treatment, encrustation, coating with one or more coatings, etc. This also makes it possible to deploy the active ingredients by ultra-low volume methods or to inject the active ingredient preparation or the active ingredient itself into the soil.

[0106] The active ingredients or compositions according to the invention have strong microbicidal activity in crop protection and material protection and can be used for controlling unwanted microorganisms, such as fungi and bacteria.

[0107] The invention furthermore relates to a method for controlling unwanted microorganisms, characterized in that the active ingredients according to the invention are applied to the phytopathogenic fungi, phytopathogenic bacteria and / or their habitats.

[0108] Fungicides can be used in crop protection for controlling phytopathogenic fungi. They are characterized by excellent efficacy against a broad spectrum of phytopathogenic fungi, including soil-borne pathogens, particularly members of the following classes: Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes. Some fungicides are systemically active and can be used in plant protection as foliar, seed dressing, or soil fungicides. Furthermore, they are suitable for controlling fungi that infect, in particular, wood or plant roots.

[0109] Fungicides can be used in crop protection for the control of Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae, and Streptomycetaceae.

[0110] Non-limiting examples of pathogens of fungal diseases that can be treated according to the present invention include:

[0111] Diseases caused by powdery mildew pathogens, such as Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator;

[0112] Diseases caused by rust pathogens, for example Gymnosporangium species, such as Gymnosporangium sabinae; Hemileia species, such as Hemileia vastatrix; Phakopsora species, such as Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, such as Puccinia recondite, P. triticina, P. graminis or P. striiformis; Uromyces species, such as Uromyces appendiculatus;

[0113] Diseases caused by Oomycete pathogens, for example Albugo species, such as Algubo candida; Bremia species, such as Bremia lactucae; Peronospora species, such as Peronospora pisi or P. brassicae; Phytophthora species, such as Phytophthora infestans; Plasmopara species, such as Plasmopara viticola; Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, such as Pythium ultimum;

[0114] Leaf spot and leaf blight caused by pathogens such as Alternaria species, for example Alternaria solani; Cercospora species, for example Cercospora beticola; Cladiosporum species, for example Cladiosporium cucumerinum; Cochliobolus species, for example Cochliobolus sativus (conidial form: Drechslera, synonyms: Helminthosporium, Cochliobolus miyabeanus); Colletotrichum species, for example Colletotrichum lindemuthanium; Cycloconium species, for example Cycloconium oleiferum. oleaginum; Diaporthe species, such as Diaporthe citri; Elsinoe species, such as Elsinoe fawcettii; Gloeosporium species, such as Gloeosporium laeticolor; Glomerella species, such as Glomerella cingulata; Guignardia species, such as Guignardia bidwelli; Leptosphaeria species, such as Leptosphaeria maculans and Leptosphaeria nodorum; Magnaporthe species, such as Magnaporthe oryzae. grisea); Microdochium species, such as Microdochium nivale; Mycosphaerella species, such as Mycosphaerella graminicola, M.arachidicola and M.fijiensi; Phaeosphaeria species, such as Phaeosphaeria nodorum; Pyrenophora species, such as Pyrenophora teres, Pyrenophora tritici repentis; Ramularia species, such as Ramularia collo-cygni, Ramularia areola; Rhynchosporium species, such as Rhynchosporium secalis; Septoria species, such as Septoria apii, Septoria lycopersii; Typhula species, such as Typhula incarnata; Venturia species, such as Venturia spp. inaequalis);.

[0115] Root and stem diseases caused by pathogens such as Corticium species, for example Corticium graminearum; Fusarium species, for example Fusarium oxysporum; Gaeumannomyces species, for example Gaeumannomyces graminis; Rhizoctonia species, such as for example Rhizoctonia solani; rice sheath rot disease, for example caused by Sarocladium oryzae; Sclerotium disease, for example caused by Sclerotium oryzae; Tapesia species, for example Tapesia acuformis; Thielaviopsis species, for example Thielaviopsis basicola;

[0116] Ear and inflorescence diseases (including corn cobs) caused by pathogens such as Alternaria species, for example, Alternaria spp.; Aspergillus species, for example, Aspergillus flavus; Cladosporium species, for example, Cladosporium cladosporioides; Claviceps species, for example, Claviceps purpurea; Fusarium species, for example, Fusarium culmorum; Gibberella species, for example, Gibberella zeae; Monographella species, for example, Monographella nivalis; Septoria species, for example, Septoria nodorum;

[0117] Diseases caused by smut pathogens, such as Sphacelotheca species, such as Sphacelotheca reiliana; Tilletia species, such as Tilletia caries, T.controversa; Urocystis species, such as Urocystis occulta; Ustilago species, such as Ustilago nuda, U. nuda tritici;

[0118] Fruit rot caused by pathogens such as Aspergillus species, for example, Aspergillus flavus; Botrytis species, for example, Botrytis cinerea; Penicillium species, for example, Penicillium expansum and P. purpurogenum; Sclerotinia species, for example, Sclerotinia sclerotiorum; Verticilium species, for example, Verticilium alboatrum;

[0119] Seed- and soil-borne rots, mildews, blights, rots and damping-offs caused by pathogens such as Alternaria species, such as Alternaria brassicicola; Aphanomyces species, such as Aphanomyces euteiches; Ascochyta species, such as Ascochyta lentis; Aspergillus species, such as Aspergillus flavus; Cladosporium species, such as Cladosporium herbarum; Cochliobolus species, such as Cochliobolus graminis. sativus (conidial forms: Drechslera, Bipolaris; synonym: Helminthosporium); Colletotrichum species, for example caused by Colletotrichum coccodes; Fusarium species, for example caused by Fusarium culmorum; Gibberella species, for example caused by Gibberella zeae; Macrophomina species, for example caused by Macrophomina phaseolina; Monographella species, for example caused by Monographella nivalis; Penicillium species, for example caused by Penicillium expansum; Phoma species, for example caused by Phoma nigra lingam); Phomopsis species, such as Phomopsis sojae; Phytophthora species, such as Phytophthora cactorum; Pyrenophora species, such as Pyrenophora graminea; Pyricularia species, such as Pyricularia oryzae;Pythium species, such as those caused by Pythium ultimum; Rhizoctonia species, such as those caused by Rhizoctonia solani; Rhizopus species, such as those caused by Rhizopus oryzae; Sclerotium species, such as those caused by Sclerotium rolfsii; Septoria species, such as those caused by Septoria nodorum; Typhula species, such as those caused by Typhula incarnata; Verticillium species, such as those caused by Verticillium dahliae;

[0120] Cancer, gall and witches'-broom diseases caused by pathogens such as Nectria species, for example Nectria galligena;

[0121] blight caused by Monilinia species, such as Monilinia laxa;

[0122] Leaf blisters or leaf curls caused by, for example, Exobasidium species, such as Exobasidium vexans; Taphrina species, such as Taphrina deformans;

[0123] Decline diseases of woody plants caused by the following pathogens: for example, Esca caused by Phaemoniella clamydospora, Phaeoacremonium aleophilum and Fomitiporia mediterranea; for example, Eutypa dyeback caused by Eutypa lata; for example, Ganoderma diseases caused by Ganoderma boninense; for example, Rigidoporus diseases caused by Rigidoporus lignosus;

[0124] Flower and seed diseases, such as those caused by Botrytis spp., e.g., Botrytis cinerea;

[0125] Root and stem diseases caused by pathogens such as Rhizoctonia species, for example Rhizoctonia solani; Helminthosporium species, for example Helminthosporium solani.

[0126] For example, clubroot caused by Plasmodiophora species, such as Plamodiophora brassicae;

[0127] Diseases caused by bacterial pathogens such as Xanthomonas species, for example Xanthomonas campestris pv. oryzae; Pseudomonas species, for example Pseudomonas syringae pv. lachrymans; and Erwinia species, for example Erwinia amylovora.

[0128] The following soybean diseases can be preferably controlled:

[0129] Fungal diseases on leaves, stems, pods and seeds caused by, for example, Alternaria leaf spot (Alternaria spec. atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cercospora leaf spot and blight (Cercospora kikuchii), Choanephora leaf blight (Choanephora infundibulifera trispora (Syn.), Dactuliophora leaf spot (Dactuliophora glycines), soybean downy mildew (Peronospora manshurica), Drechslera glycini, frog eye (Cercospora sojina), bean leaf spot (Leptosphaerulina trifolii), phyllosporic leaf spot (Phyllosticta sojaecola), pod and stem blight (Phomopsis sojae); powdery mildew (Microsphaera diffusa), acanthosporium leaf spot (Pyrenochaeta glycines), Rhizoctonia aerial part, leaf blight, and damping-off (Rhizoctonia solani), rust (Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphaceloma glycines), Stemphylium leaf blight (Stemphylium botryosum), target spot (Corynespora solani), cassiicola)).

[0130] Fungal diseases on the roots and base of the stems caused by, for example, black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), Fusarium wilt or wilt, root rot, and pod and crown rot ((Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var. caulivora), Phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), Pythium diseases (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), Rhizoctonia root rot, stem rot, and damping-off (Rhizoctonia solani), Sclerotinia stem rot (Sclerotinia sclerotiorum), Sclerotinia white rot (Sclerotinia rolfsii), Thielaviopsis root rot (Thielaviopsis basicola).

[0131] The fungicidal compositions according to the invention can be used for the therapeutic or protective / preventive control of phytopathogenic fungi. The present invention therefore also relates to a method for the therapeutic and protective control of phytopathogenic fungi by using the active ingredients or compositions according to the invention, which are applied to seeds, plants or plant parts, fruits or the soil in which the plants are growing.

[0132] The fact that the active ingredients are well tolerated by plants at the concentrations required for controlling plant diseases allows the treatment of aerial parts of plants, propagation stems and seeds, as well as the soil.

[0133] According to the present invention, can process all plants and plant parts.Plant refers to all plants and plant colonies, for example desired (desirable) and undesirable (undesirable) wild plants, cultivation plants and plant varieties (no matter whether protected by plant varieties or plant breeder's rights).Cultivation plants and plant varieties can be the plants obtained by conventional breeding and breeding methods, and described method can be assisted or supplemented by one or more following biotechnology methods, for example: by using double haploid, protoplast fusion, random and directed mutagenesis, molecule or genetic marker or utilize bioengineering and genetic engineering method.Plant parts refer to the organ of all above-ground and underground parts and plant, for example bud, leaf, flower and root, wherein lists for example leaf, needle-shaped leaf, stem, trunk, flower, fruit body, fruit and seed and root, bulb and rhizome.Crop and asexual and sexual propagation material, for example cutting, bulb, rhizome, long runner and seed also belong to plant parts.

[0134] The active ingredients of the present invention, when well tolerated by plants, have favorable toxicity to warm-blooded animals and good environmental tolerance and are suitable for protecting plants and plant organs, for increasing harvest yields, and for improving the quality of harvested material. They can preferably be used as crop protection compositions. They are active against normally sensitive and resistant species and against all or some developmental stages.

[0135] Plants that can be treated according to the invention include the following major crop plants: corn, soybean, alfalfa, cotton, sunflower, Brassica oil seeds, such as Brassica napus (e.g., corn, rape), Brassica rapa, B. juncea (e.g., (field) mustard) and Brassica carinata, Arecaceae sp. (e.g., oil palm, coconut), rice, wheat, sugar beets, sugar cane, oats, rye, barley, millet and sorghum, triticale, flax, nuts, grapes and vines and various fruits and vegetables from various plant groups, such as Rosaceae sp. (e.g., pome fruits, such as apples and pears, but also nut fruits, such as apricots, cherries, almonds, plums and peaches, and berry fruits, such as strawberries, trichoderma, red and black currants and gooseberries), Ribesioidae sp. sp.), Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp. (e.g., olive trees), Actinidaceae sp., Lauraceae sp. (e.g., avocado, cinnamon, camphor), Musaceae sp. (e.g., banana trees and species), Rubiaceae sp. (e.g., coffee), Theaceae sp. (e.g., tea), Sterculiaceae sp., Rutaceae sp. (e.g., lemon, orange, tangerine, and grapefruit); Solanaceae sp. (e.g., tomato, potato, pepper, chili pepper, eggplant, tobacco), Liliaceae sp., Compositae sp. sp.) (such as lettuce, artichokes, and endive—including root endive, chicory, or common endive), Umbelliferae sp. (such as carrots, cilantro, celery, and celeriac), Cucurbitaceae sp. (such as cucumbers—including cucumbers, pumpkins, watermelons, gourds, and honeydew melons), Alliaceae sp. (such as onions and leeks), Cruciferae sp. (such as white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, bok choy, kohlrabi, radish, wasabi, watercress, and Chinese cabbage), Leguminosae sp.) (e.g. peanuts, peas, lentils and pulses - such as common beans and broad beans), Chenopodiaceae sp. (e.g. Swiss chard, fodder beets, spinach, beetroot); Linaceae sp. (e.g. hemp), Cannabeacea sp. (e.g. hemp), Malvaceae sp. (e.g. okra, cocoa), Papaveraceae (e.g. poppy), Asparagaceae (e.g. asparagus); useful plants and ornamental plants for gardens and woods including turf, lawn, grass and Stevia rebaudiana, and in each case genetically modified versions of these plants.

[0136] When using the active ingredient according to the invention as a fungicide, the application rate can vary within a relatively wide range, depending on the type of application. The application rate of the active ingredient according to the invention is:

[0137] in the case of the treatment of plant parts, such as leaves: 0.1-10 000 g / ha, preferably 10-1000 g / ha, more preferably 10-800 g / ha, even more preferably 50-300 g / ha (in the case of application by watering or dripping, the application rate can even be reduced, in particular when using inert substrates such as rock wool or perlite);

[0138] in the case of seed treatment: 2-200 g / 100 kg of seeds, preferably 3-150 g / 100 kg of seeds, more preferably 2.5-25 g / 100 kg of seeds, even more preferably 2.5-12.5 g / 100 kg of seeds;

[0139] In the case of soil treatment: 0.1-10000 g / hectare, preferably 1-5000 g / hectare.

[0140] The active ingredients or compositions of the present invention can therefore be used to protect plants from attack by the above-mentioned pathogens for a period of time after treatment. The period of protection generally extends to 1-28 days, preferably 1-14 days, more preferably 1-10 days, most preferably 1-7 days after treatment of the plants with the active ingredients, or up to 200 days after seed treatment.

[0141] It will be apparent to the skilled artisan understanding the teachings herein that any range or desired value given herein can be expanded or altered without losing the effect sought. DETAILED DESCRIPTION

[0142] The following examples are provided to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights claimed in the present invention is described in the claims.

[0143] Given the economical efficiency and diversity of the compounds, we have selected and synthesized a number of compounds. A selection of these compounds is listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are intended to better illustrate the present invention but are not intended to limit the present invention. Those skilled in the art should not interpret this as limiting the scope of the present invention to the following compounds.

[0144] Table 1 Compound structures and their 1 H NMR

[0145] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as described in detail. It will be understood by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific starting materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar starting materials and conditions, and these modifications or variations of the preparation methods of the present invention that result in various isomerizations of the compounds are included within the scope of the present invention. In addition, the preparation methods described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups can be protected during the reaction, etc.

[0146] The following process examples are provided to facilitate a further understanding of the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthesis of the compounds shown in the table below are either commercially available or can be readily prepared by one of ordinary skill in the art.

[0147] Examples of representative compounds are shown below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0148] 1. Synthesis of compound 5

[0149] Add substrate 5-1 (1 eq) to a single-necked flask and dissolve in methanol. Then, add sodium borohydride in batches at 0°C. Stir for one hour and sample for liquid chromatography-mass spectrometry. The reaction is complete. Quench with water, remove the methanol, and extract with EA. Dry and spin dry to obtain product 5-2, which is used directly in the next step.

[0150] Substrate 5-2 (1 eq) and DCM were added to a single-necked bottle, and thionyl chloride (1.5 eq) was added dropwise at 0°C. The mixture was reacted at room temperature for 5 hours. The reaction was completed by liquid chromatography-mass spectrometry. After drying, 5-3 was obtained and used directly in the next step.

[0151] Substrate 5-3 (1 eq) was added to acetonitrile in a single-necked flask and stirred evenly. Potassium carbonate (2 eq) and 5-4 (1.2 eq) were added and reacted at room temperature for 5 hours. The reaction was almost complete by liquid chromatography-mass spectrometry. The sample was directly mixed and passed through a column to obtain a solid product 5 (40 mg, 91% purity).

[0152] 2. Synthesis of Compound 65

[0153] Substrate 65-1 (1 eq) and DCM were added to a single-necked bottle, and thionyl chloride (1.5 eq) was added dropwise at 0°C. The mixture was reacted at room temperature for 5 hours. The reaction was completed by liquid chromatography-mass spectrometry to obtain 65-2.

[0154] Substrate 65-2 (1 eq) was added to acetonitrile in a single-necked flask and stirred evenly. Potassium carbonate (2 eq) and 65-3 (1.2 eq) were added and allowed to react at room temperature for 5 hours. The reaction was essentially complete by liquid chromatography-mass spectrometry. The sample was mixed and passed through a column to obtain a solid product 65 (70 mg).

[0155] 3. Synthesis of compound 39

[0156] In a 50 mL round-bottom flask, compound 5-3 (0.77 g, 1.1 eq, 3.21 mmol) was added to 10 mL of DMF, followed by 39-1 (1.0 eq, 2.92 mmol) and potassium carbonate (1.21 g, 3.0 eq, 8.76 mmol). The reaction was allowed to react at room temperature overnight. The reaction was monitored until the starting material disappeared. The reaction solution was poured into 80 mL of saturated brine and extracted with 20 mL of ethyl acetate x 2. The organic phase was collected, concentrated under reduced pressure, and silica gel was added to the sample. The product was separated by normal phase column chromatography. This afforded compound 39 (0.04 g, 4% yield) as a white oil.

[0157] 4. Synthesis of Compound 40

[0158] In a 50 mL single-necked flask, compound 5 (0.1 g, 1.0 eq, 0.28 mmol) was added to 5 mL of toluene. TEA (0.086 g, 3.0 eq, 0.85 mmol) and acetyl chloride (0.026 g, 1.2 eq, 0.34 mmol) were also added, and the mixture was allowed to react at 70°C overnight. After completion, the reaction solution was poured into 50 mL of water and extracted with 30 mL of ethyl acetate twice. The organic phase was collected, concentrated under reduced pressure, and silica gel was added to the sample for mixing. The product 40 (0.047 g, 95% purity, 42% yield) was obtained.

[0159] 5. Synthesis of Compound 43

[0160] In a 50 mL single-necked flask, compound 5 (0.3 g, 1.0 eq, 0.85 mmol) and methoxyacetic anhydride (0.273 g, 2.0 eq, 1.69 mmol) were added to 5 mL of THF. DMAP (0.021 g, 0.2 eq, 0.17 mmol) was added and the mixture was allowed to react at 70°C overnight. After completion, the reaction solution was poured into 50 mL of water and extracted with 30 mL of ethyl acetate twice. The organic phase was collected, concentrated under reduced pressure, and silica gel was added to the sample for mixing. The product 43 was separated by normal phase column chromatography to obtain product 43 (0.093 g, 98% purity, 24% yield).

[0161] 6. Synthesis of Compound 45

[0162] In a 50 mL single-necked flask, compound 5 (0.2 g, 1.0 eq, 0.56 mmol) was dissolved in 3 mL of dichloromethane. Triethylamine (0.17 g, 3.0 eq, 1.68 mmol) was added, the temperature was cooled to 0°C with stirring, and triphosgene (0.18 g, 1.1 eq, 0.61 mmol) was added. The temperature was raised to 30°C and the reaction was allowed to react for 5 min. The disappearance of the starting material was monitored with methanol. The resulting solution of compound 45-1 was used directly in the next step without post-treatment. The yield was calculated as 100%.

[0163] In a 50 mL flask, add dichloromethane (10 mL), dimethylamine hydrochloride (0.45 g, 10.0 eq, 5.6 mmol), and triethylamine (0.23 g, 20.0 eq, 11.2 mmol). Cool to 0°C and stir. Slowly add the freshly prepared solution of compound 45-1 dropwise to the dichloromethane system, monitoring the reaction until the starting material disappears. The reaction solution is concentrated and passed through a silica gel column to obtain compound 45 (0.15 g, 60% yield) as a white solid.

[0164] 7. Synthesis of Compound 70

[0165] In a 50 mL flask, add 10 mL of ethanol and stir at room temperature. Slowly add the solution of 45-1, prepared as above, dropwise to the ethanolic system, monitoring the reaction until the starting material disappears. The reaction solution is concentrated and passed through a silica gel column to yield 70 (0.05 g, 20% yield over two steps) as a light yellow oil.

[0166] 8. Synthesis of Compound 71

[0167] In a 50 mL flask, add dichloromethane (5 mL), 1-octanethiol (0.1 g, 1.2 eq, 0.56 mmol), and triethylamine (0.17 g, 3.0 eq, 1.68 mmol). Cool to 0°C and stir. The reaction mixture of 45-1, prepared as above, was slowly added dropwise to the dichloromethane system. Monitor the reaction until the starting material disappears. The reaction mixture was concentrated and passed through a silica gel column to obtain 71 (0.09 g, 30% yield) as a white solid.

[0168] 1. Evaluation of compound biological activity:

[0169] (1) Plate method: The drug is dissolved in acetone and diluted with sterile water, and different mass concentrations are set according to its activity. Under aseptic operating conditions, according to the test treatment, the pre-melted sterilized culture medium is quantitatively added to the sterile conical flask, and the drug solution is quantitatively drawn from low concentration to high concentration, and added to the above conical flask respectively, and shaken thoroughly. Then, an equal amount is poured into three culture dishes with a diameter of 9 cm to make drug-containing plates of corresponding concentrations. The test sets the treatment without drug as a blank control, and each treatment is repeated 3 times. The cultured pathogens are cut from the edge of the colony with a sterile punch of 5 mm diameter under aseptic conditions. The bacterial cake is inoculated with an inoculator in the center of the drug-containing plate with the mycelium facing up, covered, and placed in a 25°C incubator for incubation. After the corresponding number of days, the growth of pathogen mycelium is investigated based on the growth of bacteria in the blank control culture dish. The colony diameter is measured with a caliper in millimeters (mm). The diameter of each colony is measured vertically once using the cross-cross method, and the average value is taken. According to the survey results, the mycelial growth inhibition rate of each treatment concentration on the target bacteria was calculated according to formula (1) (2), and the unit is percentage (%). D = D1-D2………………………………………………(1)

[0170] Where: D is the diameter of colony growth; D1 is the diameter of colony; D2 is the diameter of bacterial cake.

[0171] Where: I——hyphae growth inhibition rate; D0——blank control colony growth diameter; D t ——The growth diameter of the colony after treatment with chemicals.

[0172] Table 2 Representative test results of fungicide inhibition of pathogenic fungal hyphae growth by plate method Note: N stands for no data.

[0173] Table 3 The results of the control test on the inhibition of pathogenic fungi hyphae growth by the plate method

[0174] Note: Control compound A: Control compound B: N stands for no data.

[0175] (2) Bactericidal activity test - potting method:

[0176] The agent was dissolved in dimethyl sulfoxide and diluted to varying concentrations with a 0.1% Tween 80 solution. The solution was evenly sprayed onto the leaf surface until completely wet. Allowed to air-dry, the solution was then used. A blank control was established with no agent. Three controls were established for each agent.

[0177] Cucumber and wheat powdery mildew inoculation: The test targets were Sphaerotheca cucurbitae (Jacz.) ZYZhao, cultured on live cucumber plants or detached leaves, and Blumeria graminis, cultured on live wheat plants or detached leaves. Diseased and spore-forming cucumber or wheat leaves were removed, and the powdery mildew was shaken off. The leaves were then gently tapped with a glass rod to evenly distribute the powdery mildew spores across the test leaves. Protective tests were performed 24 hours after treatment. After inoculation, the plants were incubated at approximately 25°C, with alternating periods of light and darkness (12 hours each). Results were assessed 10 days later, and the efficacy of each treatment was calculated.

[0178] Cucumber gray mold inoculation: Protective test was carried out 24 hours after the treatment. In a culture dish full of cucumber gray mold fungus (Botritis cinerea) spores, culture medium was added, and the surface spores were gently scraped and filtered through 4 layers of gauze to make a concentration of 5×10 6 ~6×10 6 The inoculated test materials were moved to an incubator or artificial climate chamber without light for incubation. The control effect was evaluated after 2 days.

[0179] Inoculation of rice sheath blight, tomato gray mold, cucumber anthracnose, and wheat scab: Select tomato gray mold, cucumber anthracnose, and wheat scab that have produced spores in a culture dish, wash off the spores on the surface of the culture medium with a 0.1% Tween 80 aqueous solution, and prepare a suspension (concentration of 4×10 per ml). 5 1x10 6spores) and stored at 4°C until needed. Spray inoculate the leaf surface with a fresh spore suspension. For rice sheath blight, inoculate cucumber leaves with a 5mm cake of bacteria. Protective tests were performed 24 hours after treatment. After inoculation, place the leaves in a dark environment with a relative humidity above 90% and a temperature around 25°C. After 24 hours, alternate 12-hour light / dark cycles.

[0180] According to the disease situation of the blank control (when the disease reaches level 9), the inoculated leaves are graded. The following grading method is used:

[0181] Level 0: no disease;

[0182] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0183] Level 3: The lesion area accounts for 6% to 10% of the entire leaf area;

[0184] Level 5: The lesion area accounts for 11% to 25% of the entire leaf area;

[0185] Level 7: The lesion area accounts for 26% to 50% of the entire leaf area;

[0186] Level 9: The area of ​​lesions accounts for more than 50% of the entire leaf area.

[0187] Based on the survey data, the disease index and prevention and control effect of each treatment were calculated.

[0188] The disease index is calculated according to formula (1), and the result is rounded to two decimal places: X = {(∑(Ni xi)) / (N x 9)} x 100…………………………………………(1)

[0189] In the formula: X is the disease index; Ni is the number of diseased leaves at each level; i is the relative level value; N is the total number of leaves surveyed.

[0190] The control effect is calculated according to the formula:

[0191] In the formula: P is the control effect, the unit is percentage (%); CK is the disease index of blank control; PT is the disease index of drug treatment.

[0192] Table 4 Representative bactericidal activity test results Note: N stands for no data.

[0193] (3) Bactericidal activity test - turbidity method

[0194] Dissolve the compound in DMSO and dilute with 0.1% Tween-20 solution. Based on the drug's activity, set different concentrations, with three replicates per treatment. Maintain an equal amount of DMSO at each concentration, and establish a DMSO blank control at the highest dose. Additionally, establish a blank control and a DMSO inoculation control, with three replicates per control group. Under aseptic conditions, add sterile NB culture medium to a sterile shaker tube as needed. Aspirate the drug solution, starting from the lowest concentration and working up to the highest, into each shaker tube and shake thoroughly. Treat the control group in the same manner.

[0195] Inoculation of rice bacterial leaf blight and wheat bacterial leaf blight: Under sterile conditions, quantitatively aspirate the cultured bacterial solution and add it to the above-mentioned shaking tubes containing the agent, and place them in a constant temperature shaking incubator at 30°C and 180 rpm for shaking culture.

[0196] The bacterial solution in the control shake tube was cultured to the logarithmic growth phase (OD = 0.6-0.8), and the OD values ​​of each treatment and the control were investigated. Based on the investigation results, the inhibition rate of each treatment concentration on the target bacteria was calculated according to formula (1) (2), and the unit is percentage (%). D = D1-D2………………………………………………(1)

[0197] Where:

[0198] D——OD value of the treated bacterial solution after correction;

[0199] D1——OD value of bacterial solution treated with chemical;

[0200] D2——blank reagent control OD value.

[0201] Where:

[0202] I——inhibition rate;

[0203] D0——OD value of control bacterial solution after correction;

[0204] D t ——OD value of the treated bacterial solution after correction.

[0205] Table 5 Representative bactericidal activity test results

[0206] 2. Evaluation of the biological activity of the composition:

[0207] 1) In vitro

[0208] After 4 days, the growth of pathogenic mycelia was assessed using the aforementioned plate method, based on the growth of bacteria in the blank control plate. The colony diameters were measured using a caliper in millimeters (mm). Each colony was measured vertically once using the cross-hatch method, and the average value was taken.

[0209] Observation efficacy (%) = (control colony growth diameter - treated colony growth diameter) / control colony growth diameter × 100

[0210] An efficacy of "0" means that the growth level of the treated pathogen is the same as the growth level of the untreated pathogen; an efficacy of "100" means that the treated crop is not infected.

[0211] 2) Living

[0212] The agent was dissolved in dimethyl sulfoxide and diluted to different concentrations with 0.1% Tween 80 aqueous solution. Each concentration treatment was repeated three times. A solvent control without the agent and a water treatment were used as blank controls. The agent was applied using a walking sprayer and the solution was allowed to air dry before use.

[0213] Select cucumber anthracnose fungi that produce spores in a culture dish. Wash the spores on the surface of the culture medium with a 0.1% Tween 80 aqueous solution and prepare a suspension (concentration of 4x10 per ml). 5 1x10 6 spores) and store at 4°C until use. Spray inoculate the leaf surface with a fresh spore suspension. For protective tests, inoculate 24 hours after treatment. After inoculation, place the leaves in a dark environment with a relative humidity above 90% and a temperature of approximately 25°C. After 24 hours, alternate 12-hour light / dark cycles.

[0214] A graded survey was conducted according to the aforementioned method, and the disease index of each treatment was calculated.

[0215] Observation efficacy (%) = (control disease index - treatment disease index) / control disease index × 100

[0216] An efficacy of "0" means that the level of infection in the treated crop is the same as the level of infection in the untreated control crop; an efficacy of "100" means that the treated crop is not infected.

[0217] 3) Evaluation method

[0218] The expected efficacy (Cexp) of the composition was determined using the Abbott method (see Liu Xuemin et al., Synergistic Effects of Fungicide Combinations, Pesticide Science and Management, 2002, 23(5), 12-15). Cexp = X + Y – XY / 100

[0219] Wherein, X: the efficacy of active ingredient A at concentration a;

[0220] Y: Efficacy of active ingredient B at concentration b.

[0221] The synergistic effect of the combination was evaluated by the ratio of the observed efficacy (Cobs) to the expected efficacy (Cexp). When the ratio (synergistic ratio) > 1, the combination exhibited synergistic effects; when the ratio (synergistic ratio) = 1, the combination exhibited additive effects; and when the ratio (synergistic ratio) < 1, the combination exhibited antagonistic effects.

[0222] Table 6 Qualitative evaluation test results of composition synergism (active ingredient A is compound 5 in Table 1)

[0223] At the same time, after many tests, it was found that many of the compounds and compositions of the present invention have good control activity against different types of fungi and bacteria such as Ascomycetes, Basidiomycetes, Deuteromycetes, and Oomycetes, and have certain commercial value.

Claims

1. A nicotinic acid ester compound, as shown in the general formula I: in, W stands for O or S; M1, M2, M3, M4, and M5 independently represent hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, or haloalkynyl; R1, R2, R3, and R4 independently represent hydrogen, halogen, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, hydroxyl, mercapto, hydroxyalkyl, mercaptoalkyl, -NR5R6, -OR7, or -S(O). m R7, -alkylene-NR5R6, -alkylene-OR7, -alkylene-S(O) m R7; wherein the "alkyl", "alkenyl" or "alkynyl" is optionally substituted by halogen; R5 represents H, optionally replaced by R 11 Substituted alkyl, alkenyl or alkynyl, aryl, heteroaryl, -COR 12 , nitro, -OR 13 , -SO2R 14 , -NR 15 R 16 , -N=CR 17 R 18 , trialkylsilyl or dialkylphosphonyl; R6 represents H, optionally replaced by R 21 Substituted alkyl or -COR 22 ; or -NR5R6 represents -N=CR 31 NR 32 R 33 、-N=CR 34 OR 35 or a heterocyclic group with a nitrogen atom at the 1-position; Where R 11 , R 21 independently represent halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, alkoxycarbonyl, aryl or heteroaryl; R 12 , R 22 independently represent H, alkyl, haloalkyl, alkylthio, alkylthioalkyl, alkoxy, alkoxyalkyl, -NR 15 R 16 , aryl, arylthio, aryloxy, arylalkyl, arylalkylthio or arylalkoxy; R 13 represents H, alkyl, haloalkyl, phenyl, benzyl or -CHR 41 C(O)OR 42 ; R 41 represents H, alkyl or alkoxy; R 42 represents H, alkyl or benzyl; R 14 represents alkyl and halogenated alkyl; R 15 represents H, alkyl, formyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H, alkyl; or -NR 15 R 16 Each independently represents a heterocyclic group with a nitrogen atom at the 1-position; R 17 represents H, alkyl, unsubstituted or substituted phenyl with at least one of halogen, alkyl, and alkoxy; R 18 represents H, alkyl; or -N=CR 17 R 18 represent R 31 , R 34 Each independently represents H or an alkyl group; R 32 , R 33 Each independently represents H or alkyl; or -NR 32 R 33 represents a heterocyclic group with a nitrogen atom at the 1-position; R 35 represents an alkyl group; R7 independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, wherein the "alkyl group", "alkenyl group" or "alkynyl group" is optionally substituted by at least one group selected from halogen, cyano, trialkylsilyl, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, -OR8, -SR8, -O(CO)R8, -(CO)R8, -(CO)OR8 or -O(CO)OR8; R8 independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl or phenyl substituted by at least one group selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, alkoxy alkyl, haloalkoxy, alkoxycarbonyl, alkylthio, alkylsulfonyl or phenoxy substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxy or haloalkoxy; X and Y independently represent hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, heterocyclic, arylalkyl, heterocyclicalkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2, -alkylene-OR 10 、-Alkylene-SR 10 、-Alkylene-(CO)OR 10 、-Alkylene-(SO2)R 10 , -alkylene-N(R 10 )2 or -O-alkylene-(CO)OR 10 , or X and Y together form -CH=CH-CH=CH- which is unsubstituted or substituted by halogen; The aforementioned "cycloalkyl", "cycloalkenyl", "heterocyclyl" or "aryl" is optionally selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-alkylene-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 Each independently represents hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy; m represents 0, 1 or 2.

2. The nicotinic acid ester compound according to claim 1, characterized in that M1, M2, M3, M4, and M5 independently represent hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, halogenated C2-C8 alkenyl, C2-C8 alkynyl, or halogenated C2-C8 alkynyl; R1, R2, R3, and R4 independently represent hydrogen, halogen, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, hydroxyl, mercapto, hydroxyC1-C8 alkyl, mercaptoC1-C8 alkyl, -NR5R6, -OR7, or -S(O) m R7, -(C1-C8 alkylene)-NR5R6, -(C1-C8 alkylene)-OR7, -(C1-C8 alkylene)-S(O) m R7; wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally substituted by halogen; R5 represents H, optionally replaced by R 11 Substituted C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl, aryl, heteroaryl, -COR 12 , nitro, -OR 13 , -SO2R 14 , -NR 15 R 16 , -N=CR 17 R 18 , tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphonyl; R6 represents H, optionally replaced by R 21 Substituted C1-C8 alkyl or -COR 22 ; or -NR5R6 represents -N=CR 31 NR 32 R 33 , -N=CR 34 OR 35 , unsubstituted or substituted by at least one group selected from oxo, halogen, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino or C1-C8 alkoxycarbonyl Where R 11 , R 21 independently represent halogen, hydroxy, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino, C1-C8 alkoxycarbonyl, aryl or heteroaryl; R 12 , R 22 independently represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkylthio, C1-C8 alkylthioC1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkoxyC1-C8 alkyl, -NR 15 R 16 , aryl, arylthio, aryloxy, aryl C1-C8 alkyl, aryl C1-C8 alkylthio or aryl C1-C8 alkoxy; R 13 represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or -CHR 41 C(O)OR 42 ; R 41 represent H, C1-C8 alkyl or C1-C8 alkoxy; R 42 represents H, C1-C8 alkyl or benzyl; R 14 represents C1-C8 alkyl, halogenated C1-C8 alkyl; R 15 represents H, C1-C8 alkyl, formyl, C1-C8 alkylcarbonyl, halogenated C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H, C1-C8 alkyl; or -NR 15 R 16 Each independently represents an unsubstituted or substituted group selected from oxo, halogen, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino or C1-C8 alkoxycarbonyl. R 17 represents H, C1-C8 alkyl, unsubstituted or substituted phenyl with at least one of halogen, C1-C8 alkyl, and C1-C8 alkoxy; R 18 represents H, C1-C8 alkyl; or -N=CR 17 R 18 represent R 31 , R 34 Each independently represents H or C1-C8 alkyl; R 32 , R 33 Each independently represents H or C1-C8 alkyl; or -NR 32 R 33 represents an unsubstituted or substituted group selected from oxo, halogen, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino or C1-C8 alkoxycarbonyl. R 35 represents a C1-C8 alkyl group; R7 independently represents C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl or heterocyclyl, wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally substituted by at least one group selected from halogen, cyano, tri-C1-C8 alkylsilyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclyl, -OR8, -SR8, -O(CO)R8, -(CO)R8, -(CO)OR8 or -O(CO)OR8; R8 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy; X and Y independently represent hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, aryl, heterocyclic group, aryl C1-C8 alkyl, heterocyclic C1-C8 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2, -(C1-C8 alkylene)-OR 10 、-(C1-C8 alkylene)-SR 10 、-(C1-C8 alkylene)-(CO)OR 10 、-(C1-C8 alkylene)-(SO2)R 10 、-(C1-C8 alkylene)-N(R 10 )2 or -O-(C1-C8 alkylene)-(CO)OR 10 , or X and Y together form -CH=CH-CH=CH- which is unsubstituted or substituted by halogen; The aforementioned "C3-C8 cycloalkyl", "C3-C8 cycloalkenyl", "heterocyclyl" or "aryl" is optionally selected from oxo, halogen, cyano alkyl, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C8 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 They independently represent hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy.

3. The nicotinic acid ester compound according to claim 1 or 2, characterized in that M1, M2, M3, M4, and M5 independently represent hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, or halogenated C2-C6 alkynyl; R1, R2, R3, and R4 independently represent hydrogen, halogen, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, hydroxyl, mercapto, hydroxyC1-C6 alkyl, mercaptoC1-C6 alkyl, -NR5R6, -OR7, or -S(O) m R7, -(C1-C6 alkylene)-NR5R6, -(C1-C6 alkylene)-OR7, -(C1-C6 alkylene)-S(O) m R7; wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally substituted by halogen; R5 represents H, optionally replaced by R 11 Substituted C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, aryl, heteroaryl, -COR 12 , nitro, -OR 13 , -SO2R 14 , -NR 15 R 16 , -N=CR 17 R 18 , tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphonyl; R6 represents H, optionally replaced by R 21 Substituted C1-C6 alkyl or -COR 22 ; or -NR5R6 represents -N=CR 31 NR 32 R 33 , -N=CR 34 OR 35 , unsubstituted or substituted by at least one group selected from oxo, halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino or C1-C6 alkoxycarbonyl Where R 11 , R 21 independently represent halogen, hydroxy, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino, C1-C6 alkoxycarbonyl, aryl or heteroaryl; R 12 , R 22 independently represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkylthio, C1-C6 alkylthioC1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxyC1-C6 alkyl, -NR 15 R 16 , aryl, aryloxy, aryloxy, aryl C1-C6 alkyl, aryl C1-C6 alkoxy or aryl C1-C6 alkoxy; R 13 represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or -CHR 41 C(O)OR 42 ; R 41 represents H, C1-C6 alkyl or C1-C6 alkoxy; R 42 represents H, C1-C6 alkyl or benzyl; R 14 represents C1-C6 alkyl, halogenated C1-C6 alkyl; R 15 represents H, C1-C6 alkyl, formyl, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H, C1-C6 alkyl; or -NR 15 R 16 Each independently represents unsubstituted or selected from oxo, halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino or C1-C6 alkoxycarbonyl. substituted by at least one group R 17 represents H, C1-C6 alkyl, unsubstituted or substituted phenyl with at least one of halogen, C1-C6 alkyl, and C1-C6 alkoxy; R 18 represents H, C1-C6 alkyl; or -N=CR 17 R 18 represent R 31 , R 34 Each independently represents H or C1-C6 alkyl; R 32 , R 33 Each independently represents H or C1-C6 alkyl; or -NR 32 R 33 represents an unsubstituted or substituted group selected from oxo, halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino or C1-C6 alkoxycarbonyl. R 35 represents a C1-C6 alkyl group; R7 independently represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl or heterocyclyl, wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally substituted by at least one group selected from halogen, cyano, tri-C1-C6 alkylsilyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclyl, -OR8, -SR8, -O(CO)R8, -(CO)R8, -(CO)OR8 or -O(CO)OR8; R8 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl or phenoxy substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy; X and Y independently represent hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, aryl, heterocyclic group, aryl C1-C6 alkyl, heterocyclic C1-C6 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2, -(C1-C6 alkylene)-OR 10 、-(C1-C6 alkylene)-SR 10 、-(C1-C6 alkylene)-(CO)OR 10 、-(C1-C6 alkylene)-(SO2)R 10 、-(C1-C6 alkylene)-N(R 10 )2 or -O-(C1-C6 alkylene)-(CO)OR 10 , or X and Y together form -CH=CH-CH=CH- which is unsubstituted or substituted by halogen; The aforementioned "C3-C6 cycloalkyl", "C3-C6 cycloalkenyl", "heterocyclyl" or "aryl" is optionally selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C6 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 Each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, or is selected from halogen, cyano, Phenyl substituted with at least one of nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy; Preferably, the compound is selected from any one of Table 1 in the specification.

4. The method for preparing a nicotinic acid ester compound according to any one of claims 1 to 3, comprising the following steps: The compound represented by the general formula II is reacted with the compound represented by the general formula III to obtain the compound represented by the general formula I, and the reaction equation is as follows: Wherein, W1 and W2 independently represent OH or halogen, and are not halogens at the same time, and the definitions of substituents W, R1, R2, R3, R4, M1, M2, M3, M4, M5, X and Y are as shown in any one of claims 1-3; Preferably, the reaction is carried out in the presence of a solvent; More preferably, a condensing agent and / or a base is added during the reaction; Further preferably, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, THF, toluene, dichloromethane or ethyl acetate, the base is selected from at least one of an inorganic base or an organic base, and / or the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU or HATU.

5. A fungicidal and / or bacterial composition comprising the nicotinic acid ester compound according to any one of claims 1 to 3; preferably, further comprising other active ingredients.

6. A fungicidal and / or bacterial composition according to claim 5, characterized in that: The other active ingredients are selected from at least one of the following compounds: fludioxonil, pyraclostrobin, Metconazole, prothioconazole, jinggangmycin, iprodione, mancozeb, captan, fenpropimorph, tebuconazole, metalaxyl-M, trifloxystrobin, fluopicolide, thiophanate-methyl, fluazinam, ethidium bromide, azoxystrobin, oxadiazine, trifloxystrobin, triflumuron, amino oligosaccharides and oxadiazine.

7. Use of the nicotinic acid ester compound according to any one of claims 1 to 3, or the composition according to claim 5 or 6, in controlling plant pathogenic fungi and / or bacteria.

8. A method for controlling harmful fungi and / or bacteria, comprising treating fungi and / or bacteria or materials, plants, soil or seeds to be protected from fungi and / or bacteria with an effective amount of a nicotinic acid ester compound according to any one of claims 1 to 3, or a composition according to claim 5 or 6.

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