Nicotinic acid ester compound and application thereof

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a nicotinate compound and application thereof. The compound is shown as a general formula I: # imgabs0 #, wherein W represents O or S; m1, M2, M3, M4, and M5 each independently represent hydrogen, halogen, alkyl, haloalkyl, or the like; r1, R2, R3, and R4 each independently represent hydrogen, halogen, nitro, alkyl, alkenyl, alkynyl, or the like; x and Y independently represent hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl and the like. The compound has good prevention and treatment activity on fungi, bacteria and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides, and specifically 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 and become difficult to control with the existing insecticides or fungicides. In addition, some of the known pest control agents are highly toxic, or some of them damage the ecosystem through their long-term residual properties. In this case, although a large number of fungicides are known, such as WO2016039459A1 discloses nicotinic acid ester compounds and their use as fungicides, it is still necessary to develop new pest control agents with low toxicity and low residual properties. Summary of the invention

[0003] In order to solve the above problems existing 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.

[0004] The technical solution adopted by the present invention is as follows:

[0005] A nicotinic acid ester compound, as shown in the general formula I:

[0006]

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

[0008] M 1 、M 2 、M 3 、M 4 、M 5 Each independently represents hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl;

[0009] R 1 , R 2 , R 3 , R 4 Each independently represents hydrogen, halogen, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, hydroxyl, mercapto, hydroxyalkyl, mercaptoalkyl, -NR 5 R 6 、-OR 7 、-S(O) m R 7 、-Alkylene-NR 5 R 6 、-alkylene-OR 7 , -Alkylene-S(O) m R 7; wherein the "alkyl", "alkenyl" or "alkynyl" is optionally substituted by halogen;

[0010] R 5 represents H, optionally replaced by R 11 Substituted alkyl, alkenyl or alkynyl, aryl, heteroaryl, -COR 12 , nitro, -OR 13 , -SO 2 R 14 , -NR 15 R 16 , -N=CR 17 R 18 , trialkylsilyl or dialkylphosphonyl; R 6 represents H, optionally replaced by R 21 Substituted alkyl or -COR 22 ; or -NR 5 R 6 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;

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

[0012] R 12 , R 22 independently represent 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 halogenated alkyl;

[0015] R 15 represents H, alkyl, formyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16represents 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 34 Each 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 with a nitrogen atom at the 1-position;

[0019] R 35 represents an alkyl group;

[0020] R 7 Each independently represents an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heterocyclic group, wherein the "alkyl", "alkenyl" or "alkynyl" is optionally selected from halogen, cyano, trialkylsilyl, cycloalkyl, cycloalkenyl, aryl, heterocyclic group, -OR 8 、-SR 8 、-O(CO)R 8 、-(CO)R 8 、-(CO)OR 8 OR-O(CO)OR 8 is substituted by at least one group in;

[0021] R 8 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 the following: 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 、-(SO 2 )R 10 、-N(R 10 ) 2 、-alkylene-OR 10 、-Alkylene-SR 10 、-Alkylene-(CO)OR 10 、-alkylene-(SO 2 )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, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO 2 )R 10 、-N(R 10 ) 2 or -O-alkylene-(CO)OR 10 or two adjacent carbon atoms on the ring are substituted with -OCH 2 CH 2 -or-OCH 2 O- forms a fused ring;

[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 a specific embodiment, M 1 、M 2 、M 3 、M 4 、M 5 Each independently represents 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 , R 2 , R 3 , R 4 Each independently represents 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, -NR 5 R 6 、-OR 7 、-S(O) m R 7 、-(C1-C8 alkylene)-NR 5 R 6 、-(C1-C8 alkylene)-OR 7 、-(C1-C8 alkylene)-S(O) m R 7 ; wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally substituted by halogen;

[0028] R 5 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 , -SO 2 R 14 , -NR 15 R 16 , -N=CR 17 R 18 , tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphonyl; R 6 represents H, optionally replaced by R 21 Substituted C1-C8 alkyl or -COR 22 ; or -NR 5 R 6 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 21independently 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 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.

[0034] 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

[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] R 7 Each independently represents a C1-C8 alkyl, a C2-C8 alkenyl, a C2-C8 alkynyl, a C3-C8 cycloalkyl, a C3-C8 cycloalkenyl, an aryl or a heterocyclic group, wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally selected from halogen, cyano, tri-C1-C8 alkylsilyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclic group, -OR 8 、-SR 8 、-O(CO)R 8 、-(CO)R 8 、-(CO)OR 8 OR-O(CO)OR 8 is substituted by at least one group in;

[0039] R 8 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;

[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 、-(SO 2 )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)-(SO 2 )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 、-(SO 2 )R 10 、-N(R 10 ) 2 or -O-(C1-C8 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring are substituted with -OCH 2 CH 2 -or-OCH 2 O- forms a fused ring;

[0042] R 10They 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.

[0043] In another specific embodiment, M 1 、M 2 、M 3 、M 4 、M 5 Each independently represents 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] R 1 , R 2 , R 3 , R 4 Each independently represents 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, -NR 5 R 6 、-OR 7 、-S(O) m R 7 、-(C1-C6 alkylene)-NR 5 R 6 、-(C1-C6 alkylene)-OR 7 、-(C1-C6 alkylene)-S(O) m R 7 ; wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally substituted by halogen;

[0045] R 5 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 , -SO 2 R 14 , -NR 15 R 16 , -N=CR 17 R 18 , tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphonyl; R 6 represents H, optionally replaced by R21 Substituted C1-C6 alkyl or -COR 22 ; or -NR 5 R 6 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 16Each 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] 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

[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] R 7 Each independently represents a C1-C6 alkyl, a C2-C6 alkenyl, a C2-C6 alkynyl, a C3-C6 cycloalkyl, a C3-C6 cycloalkenyl, an aryl or a heterocyclic group, wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally selected from halogen, cyano, tri-C1-C6 alkylsilyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclic group, -OR 8 、-SR 8 、-O(CO)R 8 、-(CO)R 8 、-(CO)OR 8 OR-O(CO)OR 8 is substituted by at least one group in;

[0056] R 8Each 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 following: 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 、-(SO 2 )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)-(SO 2 )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 、-(SO 2 )R 10、-N(R 10 ) 2 or -O-(C1-C6 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring are substituted with -OCH 2 CH 2 -or-OCH 2 O- forms a fused ring;

[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 specific embodiment, M 1 、M 2 、M 3 、M 4 、M 5 Each independently represents hydrogen.

[0061] In the definition of the compounds represented by the above general formula and in all the following structural formulae, 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 "The alkylene group can be -CH 2 -、-CH 2 CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2- etc. Alkyl groups are, 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-ene-1-yl, 2-methylprop-2-ene-1-yl, but-2-ene-1-yl, but-3-ene-1-yl, 1-methylbut-3-ene-1-yl and 1-methylbut-2-ene-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Multiple bonds can be at any position of each unsaturated group. Cycloalkyl is a carbocyclic saturated ring system with, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is a monocyclic alkenyl with, for example, three to six carbocyclic ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein the double bond can be in any position. Halogen is fluorine, chlorine, bromine or iodine.

[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

[0063]

[0064] etc., also including but not limited to heteroaryl, i.e. aromatic cyclic groups 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 among the ring atoms are selected from oxygen, nitrogen and sulfur, for example

[0065] 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 those mentioned. In addition, identical or different substitution characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed by different atoms and units. At the same time, the scope of the claims will exclude compounds that are known to the person skilled in the art to be chemically unstable under standard conditions.

[0066] In addition, unless otherwise specified, the term "substituted by at least one group" in the present invention means substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without specific connection positions 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.

[0067] 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 mention is made of stereochemical details in each case. The present invention therefore encompasses all such isomers and tautomers and their mixtures in all proportions, together with isotopic forms, such as deuterated compounds.

[0068] In another embodiment, Formula I is also understood to include their salts or hydrates. Exemplary salts include, but are not limited to, hydrochlorides, hydrobromides, and hydroiodides.

[0069] It will also be understood by those skilled in the art that, unless otherwise specified, additional substitutions are permissible as long as chemical bonding and strain energy rules are met and the product still exhibits fungicidal activity.

[0070] Another embodiment of the present application is a method for preparing the nicotinic acid ester compound, comprising the following steps:

[0071] 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:

[0072]

[0073] Among them, W 1 , W 2 Each independently represents OH or halogen, and they are not halogen at the same time, and the substituents W, R 1 , R 2 , R 3 , R 4 、M1 、M 2 、M 3 、M 4 、M 5 , X and Y are defined as above.

[0074] In one embodiment, the reaction is carried out in the presence of a solvent.

[0075] In another embodiment, a condensing agent and / or a base is added during the reaction.

[0076] In a specific embodiment, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, THF, toluene, dichloromethane or ethyl acetate.

[0077] In one embodiment, the base is selected from an inorganic base (such as K 2 CO 3 、Na 2 CO 3 , Cs 2 CO 3 、NaHCO 3 , KF, CsF, K 3 PO 4 , NaOH, KOH, etc.) or at least one of an organic base (such as DMAP, pyrazole, triethylamine, DIEA, MeONa, AcOK, AcONa, t-BuONa, EtONa, etc.).

[0078] In a specific embodiment, the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU or HATU.

[0079] The present application also discloses a fungicidal and / or bacterial composition, which comprises the aforementioned nicotinic acid ester compound (active ingredient A); preferably, it also comprises other active ingredients.

[0080] 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.: 141 517-21-7), flupyraclonil (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), oxamexyl (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).

[0081] 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.

[0082] 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, the use comprising applying a compound of formula I or a composition containing the compound to soil, plants, parts of plants, leaves, and / or roots.

[0083] 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.

[0084] The invention further relates to a crop protection composition 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.

[0085] 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 the infestation of harmful microorganisms (70-100%). The control may be curative, i.e. for treating already infected plants, or protective, for protecting those plants which have not yet been infected.

[0086] "Effective but non-phytotoxic amount" means an amount of the composition of the invention which is sufficient to control fungal diseases of plants in a satisfactory manner or to completely eliminate fungal diseases, and at the same time does not cause any significant phytotoxic symptoms. 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 plants, the climatic conditions and the ingredients of the composition of the invention.

[0087] 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, and cyclic solvents, such as N-methyl-pyrrolidone, N-octyl-pyrrolidone, N-dodecyl-pyrrolidone, N-octyl-caprolactam, N-dodecyl-caprolactam and butyrolactone, and strongly polar solvents, such as dimethyl sulfoxide, and aromatic hydrocarbons, such as xylene, mineral oils, such as white spirit, petroleum oil, alkylbenzenes and spindle oil, and 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.

[0088] According to the invention, the carrier is a natural or synthetic, organic or inorganic substance, which is mixed or combined with the active ingredient to obtain better applicability, especially 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.

[0089] 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 carriers mentioned can likewise be used.

[0090] Suitable solid fillers and carriers include inorganic particles having an average particle size of 0.005-20 μm, preferably 0.02-10 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.

[0091] Useful solid carriers for the 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, for example sawdust, coconut shells, corn cobs and tobacco stems.

[0092] 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.

[0093] 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.

[0094] 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, such as mineral oil fractions, mineral oils and vegetable oils, alcohols such as butanol or diols and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and also water.

[0095] 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, and also fatty acid esters, alkylsulfonates, alkyl sulfates, alkyl ether sulfates, alkyl ether phosphates, aryl sulfates, ethoxylated arylalkylphenols, for example tristyrylphenol ethoxylates, 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 necessary. The proportion of the surfactant is 5 to 40% by weight, based on the weight of the composition according to the invention.

[0096] 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 may also be used.

[0097] 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.

[0098] Examples of thickeners are polysaccharides, such as xanthan gum or veegum, silicates, such as attapulgite, bentonite, and finely divided silica.

[0099] If appropriate, other auxiliary ingredients may also be present, for example 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.

[0100] 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, macrogranules, 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 preparations.

[0101] The compositions according to the invention include not only formulations which are ready for use and can be applied to plants or seeds with suitable equipment, but also 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.

[0102] The compositions and preparations 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 active ingredients. For special applications, such as protecting wood and derived timber products, the compositions and preparations of the present invention generally contain 0.0001-95% by weight, preferably 0.001-60% by weight of active ingredients.

[0103] 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.

[0104] The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredient with at least one conventional extender, solvent or diluent, adjuvant, emulsifier, dispersant, and / or binder or fixative, wetting agent, waterproofing agent, if appropriate desiccant and UV stabilizer, and if appropriate dyes and pigments, defoamers, preservatives, inorganic and organic thickeners, adhesives, gibberellins and also further processing aids and also water. Depending on the type of formulation to be prepared, further processing steps are necessary, such as wet grinding, dry grinding and granulation.

[0105] 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, miticides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners and / or semiochemicals in their (commercial) formulations and in the use forms prepared from these formulations. Examples of known fungicides, insecticides, miticides, nematicides and bactericides are disclosed in Pesticide Manual 17th edition.

[0106] 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. strain 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,

[0107] 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, fentin hydroxide hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fol), fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furaxyl, furametpyr, guazatine, guazatineacetates, sodium tetrathionate (GY-81), hexachlorobenzene, hexaconazole, hymexazol, imazalil,imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprothiolane, 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, methyliodide, methyl isothiocyanate isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fattyacid), 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, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyraclostrobin, zophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutriasachalinensisextract, sedaxane, silthiofam, simeconazole, sodium 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, tridemorph, 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,

[0108] 1,3-dichloro-1,1,3,3-tetrafluoroacetone 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-methoxyethylmercuryacetate,2-methoxyethylmercurychloride chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenylthiocyanate, ampropylfos, anilazine, azithiram, barium polysulfide 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, copperbis(3-phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapyr anil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA 0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-dichlorophenylsuccinimide,N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickelbis(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.

[0109] The treatment according to the invention of plants and plant parts with the active ingredients or compositions is carried out directly by customary treatment methods or by acting on their surroundings, habitat or storage space, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, spraying, sowing, foaming, spraying, spreading, watering (dip), drip irrigation, and in the case of propagation materials, especially in the case of seeds, also by dry seed treatment, wet seed treatment, slurry treatment, encrustation, coating with one or more coatings, etc. It is also 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.

[0110] 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.

[0111] 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 habitat.

[0112] 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, in particular members of the following classes: Plasmodiophoromycetes, Peronosporomycetes (Syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (Syn. Fungiimperfecti). Some fungicides are systemically active and can be used in plant protection as foliar, seed dressing or soil fungicides. In addition, they are suitable for controlling fungi which infect, in particular, wood or the roots of plants.

[0113] Fungicides can be used in crop protection for the control of Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

[0114] Non-limiting examples of pathogens of fungal diseases that can be treated according to the present invention include:

[0115] 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 Uncinulanecator;

[0116] Diseases caused by rust pathogens, for example Gymnosporangium species, such as Gymnosporangium sabinae; Hemileia species, such as Hemileiavastatrix; 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;

[0117] Diseases caused by Oomycete pathogens, such as Albugo species, e.g., Algubo candida; Bremia species, e.g., Bremia lactucae; Peronospora species, e.g., Peronospora spp.

[0118] Peronospora pisi or P. brassicae; Phytophthora species, such as Phytophthora infestans

[0119] (Phytophthora infestans); Plasmopara species, such as Plasmopara viticola; Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, such as Pythium ultimum;

[0120] 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 Pyrenophorateres, 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 inaequalis;.

[0121] 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 spp.

[0122] Rhizoctonia species, such as, for example, Rhizoctonia solani;

[0123] Rice leaf sheath rot caused by Sarocladium oryzae; for example, Sclerotium disease caused by Sclerotium oryzae; Tapesia species, for example, Tapesia acuformis; Thielaviopsis species, for example, Thielaviopsis basicola;

[0124] Ear and inflorescence diseases (including corn cobs) caused by pathogens such as Alternaria species, such as Alternaria spp.; Aspergillus species, such as Aspergillus flavus; Cladosporium species, such as Cladosporium cladosporioides; Claviceps species, such as Claviceps purpurea; Fusarium species, such as Fusarium culmorum; Gibberella species, such as Gibberella zeae; Monographella species, such as Monographella nivalis; Septoria species, such as Septorianodorum;

[0125] Diseases caused by smut, 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.nudatritici;

[0126] Fruit rot caused by pathogens such as Aspergillus species, such as Aspergillus flavus; Botrytis species, such as Botrytis cinerea; Penicillium species, such as Penicillium expansum and P. purpurogenum; Sclerotinia species, such as Sclerotinia sclerotiorum; Verticilium species, such as Verticilium alboatrum;

[0127] Seed and soil-borne rots, mildews, wilts, decays 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 nigromaculata; lingam); Phomopsis species, such as Phomopsis sojae; Phytophthora species, such as Phytophthora caerulea

[0128] (Phytophthora cactorum); Pyrenophora species, such as Pyrenophora cactorum

[0129] species, such as that caused by Sclerotium rolfsii; species of the genus Septoria, such as that caused by Septoria nodorum; species of the genus Typhula, such as that caused by Typhula spores. incarnata; Verticillium species, such as Verticillium dahliae;

[0130] Cancer, gall and witches'-broom diseases caused by pathogens such as Nectria species, for example Nectria galligena;

[0131] blight caused by Monilinia species, such as Monilinia laxa;

[0132] Leaf blisters or leaf curls caused by, for example, Exobasidium species, such as Exobasidium vexans; Taphrina species, such as Taphrina deformans;

[0133] Decline diseases of woody plants caused by pathogens such as Phaemoniella clamydospora, Phaeoacremonium aleophilum and

[0134] Esca caused by Fomitiporia mediterranea; Eutypa dyeback caused by Eutypalata; Ganoderma diseases caused by Ganoderma boninense; Rigidoporus diseases caused by Rigidoporus lignosus;

[0135] Flower and seed diseases, such as those caused by Botrytis diseases, such as Botrytis cinerea;

[0136] Root and stem diseases caused by pathogens such as Rhizoctonia species, for example Rhizoctonia solani; Helminthosporium species, for example Helminthosporium solani.

[0137] For example, clubroot caused by Plasmodiophora species, such as Plamodiophorabrassicae;

[0138] Diseases caused by bacterial pathogens such as Xanthomonas species, for example Xanthomonas campestris pv. oryzae; Pseudomonas species, for example Pseudomonas syringae pv. lachrymans; Erwinia species, for example Erwinia amylovora.

[0139] The following soybean diseases can be preferentially controlled:

[0140] 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 kikuchiensis),

[0141] (Cercospora kikuchii)), Cercospora leaf blight (Cercospora kikuchii

[0142] (Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot

[0143] (Dactuliophora glycines), soybean downy mildew (downy mildew) (Northeast downy mildew

[0144] (Peronospora manshurica), Drechslera glycini, frog eye disease (Cercospora sojina), bean leaf spot (Leptosphaerulina trifolii), phyllosporin leaf spot (Phyllosticta sojaecola), pod and stem blight (Phomopsis sojae); powdery mildew (Microsphaera diffusa), Pyrenochaeta glycines, Rhizoctonia aerial parts, leaf blight and damping-off (Rhizoctonia solani), rust (Psora pachyrhizi

[0145] (Phakopsora pachyrhizi), Phakopsora meibomiae), scab (Sphaceloma glycines), Stemphylium botryosum, and target spot (Corynespora cassiicola).

[0146] Fungal diseases on the roots and stem base, such as black root rot, caused by e.g.

[0147] 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 spp. 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).

[0148] The fungicidal compositions of the invention can be used for the treatment or protective / preventive control of phytopathogenic fungi. The invention therefore also relates to a method for the treatment and protection of phytopathogenic fungi by using the active ingredients or compositions of the invention, which are applied to seeds, plants or plant parts, fruits or the soil in which the plants grow.

[0149] 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.

[0150] According to the present invention, all plants and plant parts can be processed.Plant refers to all plants and plant populations, such as desired (desirable) and undesirable (undesirable) wild plants, cultivated plants and plant varieties (whether protected by the rights of plant varieties or plant breeders).Cultivated plants and plant varieties can be plants obtained by conventional breeding and breeding methods, and the method can be assisted or supplemented by one or more following biotechnology methods, such as: by using double haploid, protoplast fusion, random and directed mutagenesis, molecule or genetic markers or utilizing bioengineering and genetic engineering methods.Plant parts refer to the organs of all above-ground and underground parts and plants, such as buds, leaves, flowers and roots, wherein list such as leaves, needle leaves, stems, trunks, flowers, fruit bodies, fruits and seeds and roots, bulbs and rhizomes.Crops and asexual and sexual propagation materials, such as cuttings, bulbs, rhizomes, runners and seeds also belong to plant parts.

[0151] The active ingredients of the invention, when they are well tolerated by plants, have favorable toxicity to warm-blooded animals and good environmental tolerance, are suitable for protecting plants and plant organs, for increasing harvest yields, 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 certain developmental stages.

[0152] Plants that can be treated according to the invention include the following major crop plants: corn, soybeans, alfalfa, cotton, sunflower, Brassica oil seeds, such as Brassica napus (e.g. Corona, rapeseed), 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), Sterculiceae sp., Rutaceae sp. (e.g., lemons, oranges, tangerines, and grapefruits); Solanaceae sp. (e.g., tomatoes, potatoes, peppers, chili peppers, eggplants, tobacco), Liliaceae sp., Compositae sp. sp.) (e.g., lettuce, artichokes, and endive - including root chicory, endive, or common chicory), Umbelliferae sp. (e.g., carrots, parsley, celery, and celeriac), Cucurbitaceae sp. (e.g., cucumbers - including cucumbers, squash, watermelon, gourds, and honeydew melons), Alliaceae sp. (e.g., onions and leeks), Cruciferae sp. (e.g., white and red cabbage, broccoli, cauliflower, Brussels sprouts, cabbage, kohlrabi, radish, horseradish, watercress, and Chinese cabbage), Leguminos ...) (e.g. peanuts, peas, lentils and pulses - such as common beans and broad beans), Chenopodiaceae sp. (e.g. Swiss chard, fodder beets, spinach, beetroot); Malvaceae sp. (e.g. okra, cocoa), Asparagaceae (e.g. asparagus); useful plants for gardens and woods and ornamental plants including turf, lawn, grass and Stevia rebaudiana and in each case genetically modified types of these plants.

[0153] When using the active ingredient of the present 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 of the present invention is:

[0154] in the case of the treatment of plant parts, for example 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, especially when using inert substrates such as rock wool or perlite);

[0155] 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;

[0156] In the case of soil treatment: 0.1-10000 g / hectare, preferably 1-5000 g / hectare.

[0157] The active ingredient or composition of the present invention can therefore be used to protect plants from the above-mentioned pathogens within 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 treating the plants with the active ingredient, or up to 200 days after seed treatment.

[0158] It will be apparent to the skilled artisan understanding the teachings herein that any range or desired value given herein may be expanded or altered without losing the effect sought. DETAILED DESCRIPTION

[0159] The following examples are used to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights required to be protected by the present invention is described by the claims.

[0160] In view of the economic efficiency and diversity of the compounds, we preferably synthesized some compounds, and among the many synthesized compounds, some are selected and listed in the following Table 1. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustrating the present invention, but not for limiting the present invention. For those skilled in the art, this should not be understood as the scope of the above subject matter of the present invention is limited to the following compounds.

[0161] Table 1 Compound structures and 1 H NMR

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The raw materials can be purchased from the market or can be prepared by methods known in the literature or as shown in the detailed description. It will be appreciated 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 raw materials and conditions in the synthetic route have been described below, it can be easily replaced with other similar raw materials and conditions, and these modifications or variations of the preparation method of the present invention such as various isomers of the compound are included within the scope of the present invention. In addition, the preparation method described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, appropriate groups are protected during the reaction, etc.

[0172] The method examples provided below are used to promote further understanding of the preparation method of the present invention. The specific substances, types and conditions used are determined to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds shown in the following table can be purchased commercially or can be easily prepared by a person of ordinary skill in the art.

[0173] Examples of representative compounds are as follows. The synthesis methods of other compounds are similar and will not be described in detail here.

[0174] 1. Synthesis of Compound 5

[0175] Add substrate 5-1 (1 eq) to a single-mouth bottle, dissolve in methanol, add sodium borohydride in batches at 0 degrees Celsius, stir for one hour and send to sample, liquid quality detection reaction is complete. Add water to quench, spin off methanol and extract with EA, dry and spin dry to obtain product 5-2 which is directly used in the next step.

[0176]

[0177] Substrate 5-2 (1 eq) and DCM were added to a single-necked bottle, thionyl chloride (1.5 eq) was added dropwise at 0°C, and the mixture was reacted at room temperature for 5 hours. The reaction was completed by liquid mass spectrometry. After being spin-dried, 5-3 was obtained and used directly in the next step.

[0178]

[0179] Add substrate 5-3 (1 eq) to acetonitrile in a single-mouth bottle and stir evenly, add potassium carbonate (2 eq) and 5-4 (1.2 eq), react at room temperature for 5 hours, and the liquid mass spectrometry reaction is basically completed. Directly mix the sample and pass it through the column to obtain solid product 5 (40 mg, purity 91%).

[0180]

[0181] 2. Synthesis of Compound 65

[0182] 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.

[0183]

[0184] Add substrate 65-2 (1 eq) to acetonitrile in a single-mouth bottle and stir evenly, add potassium carbonate (2 eq) and 65-3 (1.2 eq), react at room temperature for 5 hours, and the liquid mass spectrometry reaction is basically completed. Mix the sample and pass it through the column to obtain a solid product 65 (70 mg).

[0185]

[0186] 3. Synthesis of compound 39

[0187] In a 50mL round-bottom flask, compound 5-3 (0.77g, 1.1eq, 3.21mmol) was added to 10mL DMF, followed by 39-1 (1.0eq, 2.92mmol), and potassium carbonate (1.21g, 3.0eq, 8.76mmol), and the mixture was reacted at room temperature overnight. The reaction was monitored until the starting material disappeared, the reaction solution was poured into 80mL saturated brine, extracted with ethyl acetate 20mL x 2, the organic phase was collected, concentrated under reduced pressure, silica gel was added to mix the sample, and separated by normal phase column chromatography. White oily compound 39 (0.04g, yield 4%) was obtained.

[0188]

[0189] 4. Synthesis of Compound 40

[0190] In a 50mL single-mouth bottle, compound 5 (0.1g, 1.0eq, 0.28mmol) was added to 5mL toluene, TEA (0.086g, 3.0eq, 0.85mmol) and acetyl chloride (0.026g, 1.2eq, 0.34mmol) were added, and the mixture was reacted at 70°C overnight. After the reaction was completed, the reaction solution was poured into 50mL water, and 30mL x 2 of ethyl acetate was added for extraction. The organic phase was collected, concentrated under reduced pressure, and silica gel was added for sample mixing. The product 40 (0.047g, purity 95%, yield 42%) was obtained.

[0191]

[0192] 5. Synthesis of Compound 43

[0193] In a 50mL single-mouth bottle, compound 5 (0.3g, 1.0eq, 0.85mmol) and methoxyacetic anhydride (0.273g, 2.0eq, 1.69mmol) were added to 5mL THF, and DMAP (0.021g, 0.2eq, 0.17mmol) was added, and the mixture was reacted at 70°C overnight. After the reaction was completed, the reaction solution was poured into 50mL water, and 30mL of ethyl acetate was added for extraction. The organic phase was collected, concentrated under reduced pressure, and silica gel was added for sample mixing. The product 43 (0.093g, purity 98%, yield 24%) was obtained.

[0194]

[0195] 6. Synthesis of Compound 45

[0196] In a 50mL single-mouth bottle, compound 5 (0.2g, 1.0eq, 0.56mmol) was dissolved in 3mL of dichloromethane, triethylamine (0.17g, 3.0eq, 1.68mmol) was added, the temperature was lowered to 0°C and stirred, triphosgene (0.18g, 1.1eq, 0.61mmol) was added, the temperature was raised to 30°C, the reaction was carried out for 5min, and methanol was used to monitor the disappearance of the starting material of the reaction. The solution of compound 45-1 was obtained and used directly in the next step without post-treatment, and the yield was calculated as 100%.

[0197]

[0198] In a 50mL flask, add dichloromethane (10mL), dimethylamine hydrochloride (0.45g, 10.0eq, 5.6mmol), triethylamine (0.23g, 20.0eq, 11.2mmol), cool to 0℃ and stir. Slowly add the newly prepared solution of compound 45-1 dropwise to the dichloromethane system, and monitor the reaction until the starting material disappears. The reaction solution is concentrated, and the sample is passed through a silica gel column to obtain a white solid compound 45 (0.15g, yield 60%).

[0199]

[0200] 7. Synthesis of Compound 70

[0201] In a 50mL flask, add 10mL of ethanol and stir at room temperature. Slowly drop the solution of 45-1 prepared as above into the ethanol system and monitor the reaction until the starting material disappears. The reaction solution is concentrated and the sample is passed through a silica gel column to obtain 70 (0.05g, two-step yield 20%) as a light yellow oil.

[0202]

[0203] 8. Synthesis of Compound 71

[0204] In a 50mL flask, add dichloromethane (5mL), 1-octanethiol (0.1g, 1.2eq, 0.56mmol), triethylamine (0.17g, 3.0eq, 1.68mmol), cool to 0℃ and stir. Slowly add the reaction solution of 45-1 prepared as above to the dichloromethane system, and monitor the reaction until the starting material disappears. The reaction solution is concentrated, and the sample is passed through a silica gel column to obtain 71 (0.09g, yield 30%) as a white solid.

[0205]

[0206] 1. Evaluation of biological activity of compounds:

[0207] (1) Plate method: The agent 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 flasks respectively, and shaken thoroughly. Then an equal amount is poured into 3 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 puncher with a diameter of 5 mm under aseptic conditions. The bacterial cake is inoculated with an inoculator in the center of the drug-containing plate, with the mycelium side facing up, covered, and placed in a 25°C incubator for culture. After the corresponding number of days, the growth of pathogen mycelium is investigated according to 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 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) in percentage (%).

[0208] D=D 1 -D 2 …………………………………………(1)

[0209] Where: D——colony growth diameter; D 1 ——colony diameter; D 2 ——Diameter of mushroom cake.

[0210]

[0211] Where: I——hyphae growth inhibition rate; D 0 ——Blank control colony growth diameter; D t ——The growth diameter of the colony after treatment with chemicals.

[0212] Table 2 Representative test results of fungicide inhibition of pathogenic fungal hyphae growth by plate method

[0213]

[0214] Note: N stands for no data.

[0215] Table 3 Results of control test on the inhibition of pathogenic fungal hyphae growth by fungicides by plate method

[0216]

[0217] Note: Control compound A: Control compound B: N stands for no data.

[0218] (2) Bactericidal activity test - pot method:

[0219] The agent was dissolved in dimethyl sulfoxide and diluted to different concentrations with 0.1% Tween 80 aqueous solution. The solution was evenly sprayed on the surface of the leaves until they were completely wetted, and the solution was allowed to dry naturally before use. The treatment without the agent was set as a blank control. Three controls were set for each agent.

[0220] Cucumber powdery mildew and wheat powdery mildew inoculation: The test targets are Sphaerotheca cucurbitae (Jacz.) ZYZhao cultured on live cucumber pots or detached leaves, and Blumeria graminis cultured on live wheat pots or detached leaves. Pick off the infected and spore-producing cucumber or wheat leaves, shake off the floating powder, and gently tap the leaves with a glass rod to make the powdery mildew spores evenly fall on the test leaves. The protective test is inoculated 24 hours after the treatment of the agent. After inoculation, place the temperature at about 25°C and culture alternately in light / dark for 12 hours each. Investigate the results after 10 days and calculate the control effect of each treatment.

[0221] Cucumber gray mold inoculation: Protective test was inoculated 24 hours after the treatment. In a culture dish full of cucumber gray mold spores (Botritis cinerea), culture solution 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 into an incubator or artificial climate room without light for cultivation, and the control effect was investigated after 2 days.

[0222] Inoculation of rice sheath blight, tomato gray mold, cucumber anthracnose, and wheat fusarium: Select tomato gray mold, cucumber anthracnose, and wheat fusarium that produce 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 4x10 per ml) 5 pcs~1x10 6 spores) and stored at 4°C for future use. Spray the fresh spore suspension on the leaf surface. For rice sheath blight, 5 mm bacterial cake was used to inoculate cucumber leaves. For protective tests, inoculation was performed 24 hours after the treatment with the agent. After inoculation, the leaves were placed in a dark environment with a relative humidity of more than 90% and a temperature of about 25°C to cause disease. After 24 hours, the leaves were cultured alternately in light / dark conditions for 12 hours each.

[0223] 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:

[0224] Level 0: no disease;

[0225] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0226] Level 3: The lesion area accounts for 6% to 10% of the entire leaf area;

[0227] Level 5: The lesion area accounts for 11% to 25% of the entire leaf area;

[0228] Level 7: The lesion area accounts for 26% to 50% of the entire leaf area;

[0229] Level 9: The lesion area accounts for more than 50% of the entire leaf area.

[0230] Based on the survey data, the disease index and prevention and control effect of each treatment were calculated.

[0231] The disease index is calculated according to formula (1), and the result is rounded to two decimal places:

[0232] X={(∑(Ni xi)) / (N x 9)}x 100……………………………………(1)

[0233] 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.

[0234] The control effect is calculated according to the formula:

[0235]

[0236] 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.

[0237] Table 4 Representative bactericidal activity test results

[0238]

[0239] Note: N stands for no data.

[0240] (3) Bactericidal activity test - turbidity method

[0241] The compound agent is dissolved in DMSO, and 0.1% Tween 20 solution is used for dilution. Different mass concentrations are set according to the activity of the agent, and three replicates are set for each treatment group; the DMSO amount is kept equal at each concentration, and a DMSO blank control is set according to the highest dose. In addition, a blank agent control and a DMSO inoculation control are required, and three replicates are set for each control group. Under sterile conditions, the sterilized NB culture medium is quantitatively added to the sterilized shaking tube for use; the drug solution is quantitatively drawn from low concentration to high concentration, and added to the above-mentioned shaking tubes respectively, and shaken thoroughly; the control is treated in the same way.

[0242] 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 180rpm for shaking culture.

[0243] The bacterial solution in the control shaking 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 was percentage (%).

[0244] D=D 1 -D 2 …………………………………………(1)

[0245] Where:

[0246] D——OD value of the treated bacterial solution after correction;

[0247] D 1 ——OD value of bacterial solution treated with drugs;

[0248] D 2 ——Blank reagent control OD value.

[0249]

[0250] Where:

[0251] I——inhibition rate;

[0252] D 0 ——OD value of control bacterial solution after correction;

[0253] D t ——OD value of the treated bacterial solution after correction.

[0254] Table 5 Representative bactericidal activity test results

[0255] Serial number Rice bacterial blight / % Wheat bacterial leaf blight / % Dose / ppm 5 100 98 100

[0256] 2. Evaluation of biological activity of the composition:

[0257] 1) In vitro

[0258] The above-mentioned plate method was used to investigate the growth of pathogenic fungi hyphae based on the growth of bacteria in the blank control culture dish after 4 days. The colony diameter was measured with a caliper in millimeters (mm). The diameter of each colony was measured vertically once using the cross method, and the average value was taken.

[0259] Observation efficacy (%) = (control colony growth diameter - treatment colony growth diameter) / control colony growth diameter × 100

[0260] 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.

[0261] 2) Living

[0262] The agent was dissolved in dimethyl sulfoxide and then diluted to different concentrations with 0.1% Tween 80 aqueous solution. Each concentration treatment was repeated 3 times. The experiment set up a solvent control without the agent and a water treatment as a blank control. Use a walking sprayer to apply the agent, and wait for the solution to dry naturally before use.

[0263] 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 pcs~1x10 6 spores) and stored at 4°C for future use. Spray the fresh spore suspension on the leaf surface. For protective tests, inoculate 24 hours after the treatment with the agent. After inoculation, place the leaves in a dark environment with a relative humidity of more than 90% and a temperature of about 25°C to cause disease. After 24 hours, alternate light / darkness for 12 hours each.

[0264] A graded survey was conducted according to the aforementioned method, and the disease index of each treatment was calculated.

[0265] Observation efficacy (%) = (control disease index - treatment disease index) / control disease index × 100

[0266] 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.

[0267] 3) Evaluation method

[0268] The expected efficacy (Cexp) of the combination was determined using the Abbott method (see Liu Xuemin et al., Synergistic Effect of Mixed Fungicides, Pesticide Science and Management, 2002, 23(5), 12-15).

[0269] Cexp=X+Y–XY / 100

[0270] Wherein, X: the efficacy of active ingredient A at concentration a;

[0271] Y: The efficacy of active ingredient B at concentration b.

[0272] The synergistic effect of the combination is evaluated by the ratio of the observed efficacy (Cobs) and the expected efficacy (Cexp). When the ratio (synergistic ratio)>1, the combination exhibits a synergistic effect; when the ratio (synergistic ratio)=1, the combination exhibits an additive effect; when the ratio (synergistic ratio)<1, it indicates that the combination is antagonistic.

[0273] Table 6 Results of qualitative evaluation of the synergistic effect of the composition (active ingredient A is compound 5 in Table 1)

[0274]

[0275]

[0276] 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 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; 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 represents 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, 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 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 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 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; 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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