2-cyano-3-disubstituted phenyl acrylate compound, preparation method therefor and use thereof in pesticide

Abstract

The present invention relates to the field of pesticides, and relates to a 2-cyano-3-disubstituted phenyl acrylate compound, a preparation method therefor, and a use thereof in pesticides. Benzonitrile compound a and a hydrogen chloride anhydrous ethanol solution undergo an alcoholysis reaction to obtain intermediate b; the intermediate b and ethyl cyanoacetate undergo a condensation reaction under the action of an alkali to obtain intermediate c; and the intermediate c and a substitution compound undergo a substitution reaction under the action of an alkali and a catalyst to obtain 2-cyano-3-disubstituted phenyl acrylate compound I. The provided 2-cyano-3-disubstituted phenyl acrylate compound has good bactericidal activity, and has high bactericidal activity against pathogenic bacteria of Ustilaginoidea, Fusarium, Gaeumannomyces, Colletotrichum, Cercospora, Verticillium, Valsa, and Puccinia. The compound can be used for preparing bactericides in the fields of agriculture, horticulture, and industry, and has the advantages of broad spectrum, high efficiency, low toxicity and environmental friendliness.

Description

A 2-cyano-3-disubstituted phenyl acrylate compound, its preparation method and application in pesticides Technical Field

[0001] The invention belongs to the field of pesticides and relates to a 2-cyano-3-disubstituted phenyl acrylate compound, a preparation method thereof and application of the compound in pesticides. Background Art

[0002] Acrylate derivatives have certain biological activities, and their structures have the potential for scalability and structural modification, so they are one of the current directions of new pesticide development.

[0003] Patent document CN1160318C discloses a class of 2-cyano-3-substituted phenyl acrylate compounds represented by the following general formula (A). These compounds have preventive effects on various diseases caused by Fusarium spp., such as wheat fusarium head blight. The highest inhibition rate against wheat fusarium head blight at 0.5 mg / mL is 91.3%.

[0004] Patent document CN101381326A discloses a class of 2-cyano 3-(substituted)amino-3-phenylacrylate compounds as shown in the following general formula (B), which have a preventive and control effect on Fusarium spp., among which the highest inhibition rate against wheat fusarium head blight is 100% under 2 μg / mL conditions.

[0005] Patent document CN109879841B discloses a class of (Z)-3-imino-1-propenol compounds represented by the following general formula (C). These compounds have a preventive and therapeutic effect on wheat fusarium head blight, which causes plant diseases, and can reduce the production of wheat fusarium head blight toxin (DON). The highest inhibition rate against wheat fusarium head blight at 1 mg / mL is 91.8%.

[0006] Patent document CN109867623B discloses a class of 3-pyridyl-3-amino-2-cyanoacrylate compounds represented by the following general formula (D), which have a preventive and therapeutic effect on wheat fusarium head blight. The highest inhibition rate against wheat fusarium head blight at 20 mg / L is 90.90%.

[0007] Patent document CN114790152A discloses a class of 2-cyanoacrylate compounds represented by the following general formula (E), which have a control effect on Fusarium fungi, with the highest inhibition rate against wheat fusarium head blight being 94.8% at 0.125 mg / L.

[0008] Patent document CN115005214A discloses a fungicide composition, wherein the active ingredient thereof is a compound (ZJS178) having a structural formula (F) and has a control effect on Fusarium fungi, wherein the inhibitory concentration EC 50 The value is 0.0379μg / mL.

[0009] Cyanostrobin, also known as (Z)-2-cyano-3-amino-3-phenyl ethyl acrylate, is a successfully developed fungicide from the acrylate derivative class. It has excellent control effects against some Fusarium-type crop diseases and can significantly reduce the mycotoxins produced by these diseases, which are extremely harmful to humans and animals. Cyanostrobin has a novel mechanism of action, targeting myosin-5. However, cyanostrobin has a very narrow spectrum of activity, exhibiting excellent inhibitory effects only against wheat fusarium and rice bakanae pathogens, with little or no inhibitory effects against other pathogens. Furthermore, cyanostrobin is used at high field rates, and its biological activity does not reach highly effective levels. Therefore, the development of a broad-spectrum, ultra-effective acrylate agricultural fungicide has important applications and economic value.

[0010] Summary of the Invention

[0011] The technical problem to be solved by the present invention is to provide a 2-cyano-3-disubstituted phenyl acrylate compound for preventing and treating crop diseases with broad spectrum and high efficiency, in view of the deficiencies in the prior art.

[0012] The technical problem that the present invention also aims to solve is to provide a method for preparing the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compounds.

[0013] The final technical problem to be solved by the present invention is to provide the application of the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compounds in pesticides.

[0014] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0015] The present invention discloses a 2-cyano-3-disubstituted phenyl acrylate compound, the structural formula of the 2-cyano-3-disubstituted phenyl acrylate compound is shown in Formula I:

[0016] wherein R1, R2, and R3 are independently selected from H, halogen, CN, NO2, or unsubstituted or substituted amino, hydroxyl, sulfhydryl, thiocyanate, C1-C 10Alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C6 cycloalkyl, C1-C6 alkylthio, C1-C6 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino;

[0017] Wherein, R1, R2, and R3 are not H at the same time;

[0018] Wherein, when R1 and R3 are H, R2 is not a hydroxyl group;

[0019] wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C3-C6 trialkylsilyl, phenyl, halophenyl, benzyl, phenoxy or C2-C 10 Heterocyclic substitution.

[0020] In some embodiments, preferably, R1, R2, and R3 are independently selected from H, halogen, CN, NO2, or unsubstituted or substituted amino, hydroxyl, thiol, thiocyanate, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkylthio, C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino.

[0021] In some embodiments, the groups of R1, R2, and R3 include one of the following three situations:

[0022] In some embodiments, further preferably, case ①: R1 is F or Cl; R3 is H;

[0023] The R2 is selected from unsubstituted or substituted C1-C4 alkylthio, C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino.

[0024] In some embodiments, more preferably, case ①: R1 is F or Cl; R3 is H;

[0025] The R2 is selected from unsubstituted or substituted C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl) cycloalkylamino, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino;

[0026] wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C6 dialkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl or C2-C 10 Heterocyclic substitution.

[0027] In some embodiments, when R1 is F or Cl and R3 is H, the structural formula of the 2-cyano-3-disubstituted phenyl acrylate compound is as follows:

[0028] Table 1 lists further preferred compounds of the compound represented by formula I-1, but the compounds in Table 1 do not limit the scope of the present invention.

[0029] Table 1 Some preferred compounds of the compound represented by the structure of formula I-1

[0030] In some embodiments, further preferably, situation ②: R2 is F or Cl; R3 is H;

[0031] The R1 is selected from unsubstituted or substituted C1-C4 alkylthio, C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino.

[0032] In some embodiments, more preferably, situation ②: R2 is F or Cl; R3 is H;

[0033] The R1 is selected from unsubstituted or substituted C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino;

[0034] wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C6 dialkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl or C2-C 10 Heterocyclic substitution.

[0035] In some embodiments, when R2 is F or Cl and R3 is H, the structural formula of the 2-cyano-3-disubstituted phenyl acrylate compound is as follows:

[0036] Table 2 lists further preferred compounds of the compound represented by formula I-2, but the compounds in Table 2 do not limit the scope of the present invention.

[0037] Table 2 Some preferred compounds of the compound represented by the structure of formula I-2

[0038] In some embodiments, further preferably, situation ③: R3 is F or Cl; R2 is H;

[0039] The R1 is selected from unsubstituted or substituted C1-C4 alkylthio, C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino.

[0040] In some embodiments, further preferably, situation ③: R3 is F or Cl; R2 is H;

[0041] The R1 is selected from unsubstituted or substituted C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino;

[0042] wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C6 dialkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl or C2-C 10 Heterocyclic substitution.

[0043] In some embodiments, when R3 is F or Cl and R2 is H, the structural formula of the 2-cyano-3-disubstituted phenyl acrylate compound is as follows:

[0044] Table 3 lists further preferred compounds of the compound represented by formula I-3, but the compounds in Table 3 do not limit the scope of the present invention.

[0045] Table 3 Some preferred compounds of the compound represented by the structure of formula I-3

[0046] In some embodiments, preferably, the groups of R1, R2, and R3 include one of the following three situations:

[0047] Case ①: R1 is F; R3 is H;

[0048] The R2 is selected from unsubstituted or substituted C1-C5 alkylamino, C1 dialkylamino, C3 cycloalkylamino, C6-C7 arylamino, C6 arylsulfonylamino;

[0049] wherein the substitution is selected from substitution by hydroxyl, halogen, C1 alkoxy or C4-C6 heterocyclic group;

[0050] More preferably, the R1 is F; the R3 is H;

[0051] The R2 is selected from unsubstituted methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, cyclopropylamino, isopentylamino or isobutylamino, or substituted benzylamino, n-propylamino, phenylamino, methylamino, ethylamino, 1,2-dimethyl-n-propylamino or benzenesulfonylamino;

[0052] Wherein, the substitution is selected from substitution by any number of the same or different groups; more preferably, the substitution is selected from substitution by any number of the same or different hydroxyl, fluorine, chlorine, methoxy or furyl groups;

[0053] Case ②: R2 is F; R3 is H;

[0054] The R1 is selected from unsubstituted or substituted C1-C5 alkylamino, C1 dialkylamino, C3 cycloalkylamino, C6-C7 arylamino, C6 arylsulfonylamino;

[0055] wherein the substitution is selected from substitution by hydroxyl, halogen, C1 alkoxy or C4-C6 heterocyclic group;

[0056] More preferably, said R2 is F; said R3 is H;

[0057] The R1 is selected from unsubstituted methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, cyclopropylamino, isopentylamino or isobutylamino, or substituted benzylamino, n-propylamino, phenylamino, methylamino, ethylamino, 1,2-dimethyl-n-propylamino or benzenesulfonylamino;

[0058] Wherein, the substitution is selected from substitution by any number of the same or different groups; more preferably, the substitution is selected from substitution by any number of the same or different hydroxyl, fluorine, chlorine, methoxy or furyl groups;

[0059] Case ③: R3 is F; R2 is H;

[0060] The R1 is selected from unsubstituted or substituted C1-C5 alkylamino, C1 dialkylamino, C3 cycloalkylamino, C6-C7 arylamino, C6 arylsulfonylamino;

[0061] wherein the substitution is selected from substitution by hydroxyl, halogen, C1 alkoxy or C4-C6 heterocyclic group;

[0062] More preferably, said R3 is F; said R2 is H;

[0063] The R1 is selected from unsubstituted methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, cyclopropylamino, isopentylamino or isobutylamino, or substituted benzylamino, n-propylamino, phenylamino, methylamino, ethylamino, 1,2-dimethyl-n-propylamino or benzenesulfonylamino;

[0064] Wherein, the substitution is selected from substitution by any number of the same or different groups; more preferably, the substitution is selected from substitution by any number of the same or different hydroxyl, fluorine, chlorine, methoxy or furyl groups.

[0065] In some embodiments, most preferably, the 2-cyano-3-disubstituted phenyl acrylate compound is any one of the following structures:

[0066] The following Table 4 is the NMR data of some compounds in Tables 1, 2 and 3. The compound numbers in Table 4 correspond to the compound numbers in Tables 1, 2 and 3, that is, the compound No. 1 in Table 4 is consistent with the compound No. 1 in Table 1; in Table 4, s is a singlet, d is a doublet, dd is a doublet of doublets, t is a triplet of doublets, q is a quartet, and m is a multiplet.

[0067] Table 4 NMR data of some compounds

[0068] The present invention further discloses pharmaceutically acceptable salts of the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compounds.

[0069] Specifically, the pharmaceutically acceptable salt of the 2-cyano-3-disubstituted phenylacrylate compound is hydrochloride.

[0070] The present invention further discloses a method for preparing the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compounds, which includes one of the following three methods:

[0071] Method 1 is as follows:

[0072] In some embodiments, when R1 is F or Cl and R3 is H, the preparation method of the 2-cyano-3-disubstituted phenyl acrylate compound comprises the following steps: a benzonitrile compound a-1 undergoes a first alcoholysis reaction with an anhydrous ethanol solution of hydrogen chloride to obtain an intermediate b-1; the intermediate b-1 undergoes a first condensation reaction with ethyl cyanoacetate in the presence of a first base to obtain an intermediate c-1; the intermediate c-1 undergoes a first substitution reaction with a substituted compound in the presence of a second base and a first catalyst to obtain a 2-cyano-3-disubstituted phenyl acrylate compound I-1;

[0073] Wherein, X=-Br,-I

[0074] The substituted compound is an amine compound, an amide compound or an alcohol compound;

[0075] R2 is selected from unsubstituted or substituted amino, hydroxyl, mercapto, thiocyano, C1-C6 alkylthio, C1-C6 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino;

[0076] wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C3-C6 trialkylsilyl, phenyl, halophenyl, benzyl, phenoxy or C2-C 10 Heterocyclic substitution.

[0077] In some embodiments, in the method one, the molar ratio of the benzonitrile compound a-1 to the anhydrous ethanol solution of hydrogen chloride is 1:5 to 20, preferably 1:8 to 15, and more preferably 1:10; the first alcoholysis reaction, the reaction temperature is -10 to 25 ° C, and the reaction time is 24 to 96 hours; the first base is an organic base or an inorganic base; the organic base is triethylamine, pyridine, 1,8-diazabicyclo-bicyclo (5,4,0)-7-undecene, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is sodium carbonate, potassium carbonate or sodium hydroxide; the molar ratio of the intermediate b-1 to ethyl cyanoacetate and the first base is 1:1 to 5:1 to 10, preferably 1:1 to 2:1 to 5, and more preferably 1:1.1:1.2; the first condensation reaction, the reaction temperature is 70 to 150 ℃, and the reaction time is 5 to 24 hours; the second base is an organic base or an inorganic base; the organic base is triethylamine, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is cesium carbonate, potassium carbonate, potassium phosphate or sodium hydroxide; the first catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the first catalyst is 1:1 to 10, preferably 1:1 to 5, and more preferably 1:2; the molar ratio of the intermediate c-1 to the substituted compound, the second base, and the first catalyst is 1:1 to 10:1 to 10:1 to 20, preferably 1:1 to 5:1 to 5:1 to 10, more preferably 1:1 to 2:1 to 2:1 to 5, and even more preferably 1:2:2:3; the first substitution reaction, the reaction temperature is 100 to 180℃, and the reaction time is 6 to 24 hours.

[0078] In some embodiments, preferably, the molar ratio of the benzonitrile compound a-1 to the anhydrous ethanol solution of hydrogen chloride is 1:10; the first alcoholysis reaction has a reaction temperature of -5 to 5°C and a reaction time of 24 to 36 hours; the first base is an organic base; the organic base is triethylamine; the molar ratio of the intermediate b-1 to ethyl cyanoacetate and the first base is 1:1.1:1.2; the first condensation reaction has a reaction temperature of 70 to 100°C and a reaction time of 6 to 12 hours; the second base is an inorganic base; the inorganic base is cesium carbonate; the first catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the first catalyst is 1:2; the molar ratio of the intermediate c-1 to the substituted compound, the second base, and the first catalyst is 1:2:2:3; the first substitution reaction has a reaction temperature of 100 to 140°C and a reaction time of 24 hours.

[0079] The solvent used in the first alcoholysis reaction is any one or a combination of anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide and anhydrous dimethyl sulfoxide, preferably anhydrous 1,2-dichloroethane. The amount of the solvent used is such that the materials in the reaction system are dissolved and the viscosity is moderate.

[0080] The solvent used in the first condensation reaction is any one or a combination of anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide and anhydrous dimethyl sulfoxide, preferably anhydrous ethanol. The amount of the solvent used is such that the materials in the reaction system are dissolved and the viscosity is moderate.

[0081] The solvent used in the first substitution reaction is any one or a combination of anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide and anhydrous dimethyl sulfoxide, preferably anhydrous dimethyl sulfoxide. The amount of the solvent used is such that the materials in the reaction system are dissolved and the viscosity is moderate.

[0082] Wherein, the first substitution reaction is carried out under the protection of an inert gas, preferably argon.

[0083] or,

[0084] Method 2 is as follows:

[0085] In some embodiments, when R2 is F or Cl and R3 is H, the preparation method of the 2-cyano-3-disubstituted phenyl acrylate compound comprises the following steps: a benzonitrile compound a-2 undergoes a second alcoholysis reaction with an anhydrous ethanol solution of hydrogen chloride to obtain an intermediate b-2; the intermediate b-2 undergoes a second condensation reaction with ethyl cyanoacetate in the presence of a third base to obtain an intermediate c-2; the intermediate c-2 undergoes a second substitution reaction with a substituted compound in the presence of a fourth base and a second catalyst to obtain a 2-cyano-3-disubstituted phenyl acrylate compound I-2;

[0086] Wherein, X=-Br,-I

[0087] The substituted compound is an amine compound, an amide compound or an alcohol compound;

[0088] R1 is selected from unsubstituted or substituted amino, hydroxyl, mercapto, thiocyano, C1-C6 alkylthio, C1-C6 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino;

[0089] wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C3-C6 trialkylsilyl, phenyl, halophenyl, benzyl, phenoxy or C2-C 10 Heterocyclic substitution.

[0090] In some embodiments, in the method 2, the molar ratio of the benzonitrile compound a-2 to the anhydrous ethanol solution of hydrogen chloride is 1:5 to 20, preferably 1:8 to 15, and more preferably 1:10; the second alcoholysis reaction, the reaction temperature is -10 to 25 ° C, and the reaction time is 24 to 96 hours; the third base is an organic base or an inorganic base; the organic base is triethylamine, pyridine, 1,8-diazabicyclo-bicyclo (5,4,0)-7-undecene, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is sodium carbonate, potassium carbonate or sodium hydroxide; the molar ratio of the intermediate b-2 to ethyl cyanoacetate and the third base is 1:1 to 5:1 to 10, preferably 1:1 to 2:1 to 5, and more preferably 1:1.1:1.2; the second condensation reaction, the reaction temperature is 70 to 150 ℃, the reaction time is 5 to 24 hours; the fourth base is an organic base or an inorganic base; the organic base is triethylamine, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is cesium carbonate, potassium carbonate, potassium phosphate or sodium hydroxide; the second catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the second catalyst is 1:1 to 10, preferably 1:1 to 5, and more preferably 1:2; the molar ratio of the intermediate c-2 to the substituted compound, the fourth base, and the second catalyst is 1:1 to 10:1 to 10:1 to 20, preferably 1:1 to 5:1 to 5:1 to 10, more preferably 1:1 to 2:1 to 2:1 to 5, and even more preferably 1:2:2:3; the second substitution reaction, the reaction temperature is 100 to 180℃, and the reaction time is 6 to 24 hours.

[0091] In some embodiments, preferably, the molar ratio of the benzonitrile compound a-2 to the anhydrous ethanol solution of hydrogen chloride is 1:10; the second alcoholysis reaction has a reaction temperature of -5 to 5°C and a reaction time of 24 to 36 hours; the third base is an organic base; the organic base is triethylamine; the molar ratio of the intermediate b-2 to ethyl cyanoacetate and the third base is 1:1.1:1.2; the second condensation reaction has a reaction temperature of 70 to 100°C and a reaction time of 6 to 12 hours; the fourth base is an inorganic base; the inorganic base is cesium carbonate; the second catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the second catalyst is 1:2; the molar ratio of the intermediate c-2 to the substituted compound, the fourth base, and the second catalyst is 1:2:2:3; the second substitution reaction has a reaction temperature of 100 to 140°C and a reaction time of 24 hours.

[0092] The solvent used in the second alcoholysis reaction is any one or a combination of anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide and anhydrous dimethyl sulfoxide, preferably anhydrous 1,2-dichloroethane. The amount of the solvent used is such that the materials in the reaction system are dissolved and the viscosity is moderate.

[0093] The solvent used in the second condensation reaction is any one or a combination of anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide and anhydrous dimethyl sulfoxide, preferably anhydrous ethanol. The amount of the solvent used is such that the materials in the reaction system are dissolved and the viscosity is moderate.

[0094] The solvent used in the second substitution reaction is any one or a combination of anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide and anhydrous dimethyl sulfoxide, preferably anhydrous dimethyl sulfoxide. The amount of the solvent used is such that the materials in the reaction system are dissolved and the viscosity is moderate.

[0095] The second substitution reaction is carried out under the protection of an inert gas, preferably argon.

[0096] or,

[0097] Method three is as follows:

[0098] In some embodiments, when R3 is F or Cl and R2 is H, the preparation method of the 2-cyano-3-disubstituted phenyl acrylate compound comprises the following steps: a benzonitrile compound a-3 undergoes a third alcoholysis reaction with an anhydrous ethanol solution of hydrogen chloride to obtain an intermediate b-3; the intermediate b-3 undergoes a third condensation reaction with ethyl cyanoacetate in the presence of a fifth base to obtain an intermediate c-3; the intermediate c-3 undergoes a third substitution reaction with a substituted compound in the presence of a sixth base and a third catalyst to obtain a 2-cyano-3-disubstituted phenyl acrylate compound I-3;

[0099] Wherein, Y=-Br,-I

[0100] The substituted compound is an amine compound, an amide compound or an alcohol compound;

[0101] R1 is selected from unsubstituted or substituted amino, hydroxyl, mercapto, thiocyano, C1-C6 alkylthio, C1-C6 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino;

[0102] wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C3-C6 trialkylsilyl, phenyl, halophenyl, benzyl, phenoxy or C2-C 10 Heterocyclic substitution.

[0103] In some embodiments, in the method three described above, the molar ratio of the benzonitrile compound a-3 to the anhydrous ethanol solution of hydrogen chloride is 1:5 to 20, preferably 1:8 to 15, and more preferably 1:10; the third alcoholysis reaction has a reaction temperature of -10 to 25°C and a reaction time of 24 to 96 hours; the fifth base is an organic base or an inorganic base; the organic base is triethylamine, pyridine, 1,8-diazabicyclo-bicyclo (5,4,0)-7-undecene, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is sodium carbonate, potassium carbonate or sodium hydroxide; the molar ratio of the intermediate b-3 to ethyl cyanoacetate and the fifth base is 1:1 to 5:1 to 10, preferably 1:1 to 2:1 to 5, and more preferably 1:1.1:1.2; the third condensation reaction has a reaction temperature of 70 to 150 ℃, the reaction time is 5 to 24 hours; the sixth base is an organic base or an inorganic base; the organic base is triethylamine, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is cesium carbonate, potassium carbonate, potassium phosphate or sodium hydroxide; the third catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the third catalyst is 1:1 to 10, preferably 1:1 to 5, and more preferably 1:2; the molar ratio of the intermediate c-3 to the substituted compound, the sixth base, and the third catalyst is 1:1 to 10:1 to 10:1 to 20, preferably 1:1 to 5:1 to 5:1 to 10, more preferably 1:1 to 2:1 to 2:1 to 5, and even more preferably 1:2:2:3; the reaction temperature of the third substitution reaction is 100 to 180℃, and the reaction time is 6 to 24 hours.

[0104] In some embodiments, preferably, the molar ratio of the benzonitrile compound a-3 to the anhydrous ethanol solution of hydrogen chloride is 1:10; the third alcoholysis reaction has a reaction temperature of -5 to 5°C and a reaction time of 24 to 36 hours; the fifth base is an organic base; the organic base is triethylamine; the molar ratio of the intermediate b-3 to ethyl cyanoacetate and the fifth base is 1:1.1:1.2; the third condensation reaction has a reaction temperature of 70 to 100°C and a reaction time of 6 to 12 hours; the sixth base is an inorganic base; the inorganic base is cesium carbonate; the third catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the third catalyst is 1:2; the molar ratio of the intermediate c-3 to the substituted compound, the sixth base, and the third catalyst is 1:2:2:3; the third substitution reaction has a reaction temperature of 100 to 140°C and a reaction time of 24 hours.

[0105] The solvent used in the third alcoholysis reaction is any one or a combination of anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide and anhydrous dimethyl sulfoxide, preferably anhydrous 1,2-dichloroethane. The amount of the solvent used is such that the materials in the reaction system are dissolved and the viscosity is moderate.

[0106] Among them, the solvent used in the third condensation reaction is any one or a combination of anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide and anhydrous dimethyl sulfoxide, preferably anhydrous ethanol. The amount of the solvent used is such that the materials in the reaction system are dissolved and the viscosity is moderate.

[0107] The solvent used in the third substitution reaction is any one or a combination of anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide and anhydrous dimethyl sulfoxide, preferably anhydrous dimethyl sulfoxide. The amount of the solvent used is such that the materials in the reaction system are dissolved and the viscosity is moderate.

[0108] Wherein, the third substitution reaction is carried out under the protection of an inert gas, preferably argon.

[0109] Furthermore, the present invention discloses a pesticide preparation containing 0.1% to 45% by weight of the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compound or a pharmaceutically acceptable salt of the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compound.

[0110] Specifically, the dosage form of the pesticide preparation is a suspension, a dispersible oil suspension, a dispersible liquid, a suspension seed coating, a tablet, a microemulsion, an aqueous solution, an emulsion, an emulsifiable concentrate, an aqueous suspension, a powder, a wettable powder, a soluble powder, a soluble liquid, a granule, a soluble granule, a water-dispersible granule, a capsule, a microcapsule, a microcapsule suspension or a nano preparation.

[0111] Specifically, the pesticide formulation contains agriculturally acceptable carriers and / or adjuvants.

[0112] The use of the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compounds or the above-mentioned pharmaceutically acceptable salts of the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compounds or the above-mentioned pesticide preparations in preventing and controlling fungal diseases of crops is also within the scope of protection of the present invention.

[0113] Specifically, the fungal diseases are diseases caused by any one or more of the genera Chlorophytum, Fusarium, Acrocystis, Colletotrichum, Cercospora, Verticillium and Sclerotium; the diseases are any one or more of rice false smut, wheat fusarium, rice seedling blight, banana wilt, wheat stem rot, wheat take-all, strawberry anthracnose, apple anthracnose, grape anthracnose, osmanthus anthracnose, citrus anthracnose, rubber tree anthracnose, corn anthracnose, soybean anthracnose, onion anthracnose, pepper anthracnose, wolfberry anthracnose, mango anthracnose, camellia anthracnose, yam anthracnose, peanut brown spot, cotton wilt and apple tree rot.

[0114] Specifically, the fungal disease is a disease caused by Puccinia spp.; the disease is any one or both of wheat stripe rust and wheat leaf rust.

[0115] Specifically, the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compounds are applied to the pathogens to be controlled or the medium in which they grow, with a dosage of 0.001 to 1000 g / hectare, preferably 1 to 1000 g / hectare, more preferably 5 to 750 g / hectare, further preferably 50 to 500 g / hectare, and most preferably 75 to 300 g / hectare.

[0116] Specifically, the pharmaceutically acceptable salt of the above-mentioned 2-cyano-3-disubstituted phenyl acrylate compound is applied to the pathogen to be controlled or the medium in which it grows, with a dosage of 0.001 to 1000 g / hectare, preferably 1 to 1000 g / hectare, more preferably 5 to 750 g / hectare, further preferably 50 to 500 g / hectare, and most preferably 75 to 300 g / hectare.

[0117] Specifically, the above-mentioned pesticide formulation is applied to the pathogens to be controlled or the medium in which they grow, and the dosage, calculated as the 2-cyano-3-disubstituted phenyl acrylate compound or the pharmaceutically acceptable salt of the 2-cyano-3-disubstituted phenyl acrylate compound in the pesticide formulation, is 0.001 to 1000 g / hectare, preferably 1 to 1000 g / hectare, more preferably 5 to 750 g / hectare, further preferably 50 to 500 g / hectare, and most preferably 75 to 300 g / hectare.

[0118] Among the 2-cyano-3-disubstituted phenyl acrylate compounds prepared by the present invention, compound No. 1 and compound No. 2 have relatively high activity. The inhibitory concentration EC of compound No. 1 and compound No. 2 inhibits the growth of wheat scab fungus mycelium by 50%. 50 The values ​​were 0.0153μg / mL and 0.0077μg / mL respectively, while the control agent cyanothiocarb was EC 50 The value is 0.1419 μg / mL. Therefore, compounds such as Compound No. 1 and Compound No. 2 prepared by the present invention have the potential to be developed into ultra-high-efficiency pesticides. Beneficial effects:

[0119] (1) The present invention provides a novel 2-cyano-3-disubstituted phenyl acrylate compound, which has a broad-spectrum and highly effective fungicidal activity, and has high fungicidal activity against pathogens of the genera Chlorophytum, Fusarium, Acrocystis, Colletotrichum, Cercospora, Verticillium, Puccinia and Puccinia.

[0120] (2) The 2-cyano-3-disubstituted phenyl acrylate compounds provided by the present invention can be used to prepare fungicides in the fields of agriculture, horticulture and industry, and have the advantages of broad spectrum, high efficiency, low toxicity and environmental friendliness. BRIEF DESCRIPTION OF THE DRAWINGS

[0121] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more apparent.

[0122] FIG1 is a hydrogen NMR spectrum of compound No. 1 prepared in Example 1;

[0123] FIG2 is a C NMR spectrum of compound No. 1 prepared in Example 1;

[0124] FIG3 is a hydrogen NMR spectrum of compound No. 87 prepared in Example 2;

[0125] FIG4 is a C NMR spectrum of compound No. 87 prepared in Example 2;

[0126] FIG5 is a hydrogen NMR spectrum of compound No. 173 prepared in Example 3;

[0127] FIG6 is a C NMR spectrum of compound No. 173 prepared in Example 3;

[0128] FIG7 shows the inhibitory effects of the compounds prepared in the present invention on pathogens of the genera Chlorisothia, Fusarium, Acrocystis, and Colletotrichum;

[0129] FIG8 shows the inhibitory effect of the compounds prepared in the present invention on Anthrax and Cercospora pathogens;

[0130] FIG9 shows the inhibitory effect of the compounds prepared in the present invention on Verticillium and Melanocortisone pathogens;

[0131] Figure 10 is a graph showing the inhibitory effects of the compounds prepared in the present invention on pathogens of the genera Chlorinia, Fusarium, Acrocystis, Colletotrichum, Colletotrichum, Cercospora, Verticillium, Black Cortex, and Puccinia; wherein, Figure 10A is a graph showing the inhibitory effects of compound No. 182, compound No. 183, compound No. 185, and compound No. 204 on pathogens of the genera Chlorinia, Fusarium, Acrocystis, and Colletotrichum; Figure 10B is a graph showing the inhibitory effects of compound No. 182, compound No. 183, compound No. 185, and compound No. 204 on pathogens of the genera Anthracnose, Cercospora, Verticillium, and Black Cortex; 10C is a graph showing the inhibitory effects of Compound No. 1, Compound No. 2, Compound No. 3, Compound No. 4, Compound No. 6, Compound No. 7, Compound No. 87, Compound No. 88, Compound No. 89, and Compound No. 92 on Puccinia pathogens; FIG10D is a graph showing the inhibitory effects of Compound No. 173, Compound No. 174, Compound No. 175, Compound No. 176, Compound No. 179, Compound No. 180, Compound No. 182, Compound No. 183, Compound No. 185, and Compound No. 204 on Puccinia pathogens. DETAILED DESCRIPTION

[0132] The present invention is further described in detail below in conjunction with examples and data, but the present invention is not limited to these specific embodiments. Those skilled in the art will recognize that the present invention encompasses all alternatives, improvements and equivalents that may be included within the scope of the claims. In the present invention, unless otherwise specified, all parts and percentages are weight units, and the equipment and raw materials used, etc., all can be purchased from the market or are commonly used in this area. The methods in the following examples, unless otherwise specified, are conventional methods in this area.

[0133] (1) Preparation of compounds

[0134] Example 1

[0135] 1. Synthesis of No.1

[0136] Weigh compound a-1-1 (10.00mmol, 2.00g) and place it in a 50mL eggplant-shaped flask, add anhydrous ethanol hydrogen chloride solution (100.0mmol, 8.50g, 8.00mol / L) and 10mL anhydrous 1,2-dichloroethane at 2°C, continue stirring at 2°C for alcoholysis reaction for 30h, and after the reaction, concentrate the reaction solution and vacuum dry to obtain intermediate b-1-1, which is directly used in the next reaction without purification; weigh intermediate b-1-1 (10.00mmol, 2.40g) and place it in a three-necked flask, add 20mL anhydrous ethanol to dissolve it, place it at 0°C, slowly add triethylamine (Et3N, 12.00mmol, 1.20g) to the system, control the reaction temperature not higher than 5°C, and continue stirring for 30min; then slowly heat it to 80°C and reflux, slowly add ethyl cyanoacetate (11.00mmol, 1.24g), and add After completion, the condensation reaction was refluxed and the degree of reaction was observed every 2 hours until the reaction was complete. The reaction time was 8 hours. After the reaction, the reaction solution was concentrated and separated by column chromatography to obtain intermediate c-1-1; intermediate c-1-1 (1.00 mmol, 0.31 g), L-proline (1.00 mmol, 0.12 g), CuI (2.00 mmol, 0.38 g), Cs2CO3 (2.00 mmol, 0.65 g) and methylamine hydrochloride (2.00 mmol, 0.16 g) were weighed and placed in a 25 mL pressure bottle, replaced with argon, and then 5 mL of anhydrous DMSO was added. The substitution reaction was carried out at 120°C for 24 hours and the reaction was monitored by TLC; after the reaction, the reaction solution was concentrated and separated by column chromatography (PE:DCM=1:1) to obtain product I-1-1, which was recorded as No.1; the H NMR spectrum of compound No.1 is shown in Figure 1, and the C NMR spectrum is shown in Figure 2.

[0137] 2. The preparation methods of compounds No. 2 to No. 86 (i.e., the compounds described in Index Table 1) were the same as those described in "1. Synthesis of No. 1" in Example 1. The preparation methods of compounds No. 2, No. 3, No. 4, No. 6, and No. 7 were as follows:

[0138] Synthesis of Compound No. 2: The preparation method is the same as that of "1. Synthesis of No. 1" in Example 1, except that methylamine hydrochloride is replaced by ethylamine hydrochloride, thereby preparing product I-1-2, which is recorded as No. 2.

[0139] Synthesis of Compound No. 3: The preparation method is the same as that of "1. Synthesis of No. 1" in Example 1, except that methylamine hydrochloride is replaced by n-propylamine, thereby preparing product I-1-3, which is recorded as No. 3.

[0140] Synthesis of Compound No. 4: The preparation method is the same as that of "1. Synthesis of No. 1" in Example 1, except that methylamine hydrochloride is replaced by isopropylamine, thereby obtaining product I-1-4, which is designated as No. 4.

[0141] Synthesis of Compound No. 6: The preparation method is the same as that of "1. Synthesis of No. 1" in Example 1, except that methylamine hydrochloride is replaced by dimethylamine, thereby preparing product I-1-6, which is recorded as No. 6.

[0142] Synthesis of Compound No. 7: The preparation method is the same as that of "1. Synthesis of No. 1" in Example 1, except that methylamine hydrochloride is replaced by cyclopropylamine, thereby preparing product I-1-7, which is recorded as No. 7.

[0143] Example 2

[0144] 1. Synthesis of No.87

[0145] Weigh compound a-2-87 (10.00mmol, 2.00g) and place it in a 50mL eggplant-shaped flask, add anhydrous ethanol hydrogen chloride solution (100.0mmol, 8.50g, 8.00mol / L) and 10mL anhydrous 1,2-dichloroethane at 2°C, continue stirring at 2°C for alcoholysis reaction for 30h, and after the reaction is completed, concentrate the reaction solution and vacuum dry to obtain intermediate b-2-87, which is directly used in the next reaction without purification; weigh intermediate b-2-87 (10.00mmol, 2.40g) and place it in a three-necked flask, add 20mL anhydrous ethanol to dissolve it, place it at 0°C, slowly add triethylamine (Et3N, 12.00mmol, 1.20g) to the system, control the reaction temperature not higher than 5°C, and continue stirring for 30min; then slowly heat it to 80°C and reflux, slowly add ethyl cyanoacetate (11.00mmol, 1.24g), and add it dropwise. The reaction mixture was refluxed for condensation reaction, and the degree of reaction was observed every 2 hours until the reaction was complete. The reaction time was 8 hours. After the reaction, the reaction solution was concentrated and separated by column chromatography to obtain intermediate c-2-87. Intermediate c-2-87 (1.00 mmol, 0.31 g), L-proline (1.00 mmol, 0.12 g), CuI (2.00 mmol, 0.38 g), Cs2CO3 (2.00 mmol, 0.65 g) and methylamine hydrochloride (2.00 mmol, 0.16 g) were weighed and placed in a 25 mL pressure bottle, replaced with argon, and then 5 mL of anhydrous DMSO was added. The substitution reaction was carried out at 120°C for 24 hours and the reaction was monitored by TLC. After the reaction, the reaction solution was concentrated and separated by column chromatography (PE:DCM=1:1) to obtain product I-2-87, which was recorded as No. 87. The H NMR spectrum of compound No. 87 is shown in Figure 3, and the C NMR spectrum is shown in Figure 4.

[0146] 2. The preparation methods of compounds No. 88 to No. 172 (i.e., the compounds described in Index Table 2) were the same as those described in "1. Synthesis of No. 87" in Example 2. The preparation methods of compounds No. 88, No. 89, and No. 92 were as follows:

[0147] Synthesis of Compound No. 88: The preparation method was the same as that of "1. Synthesis of No. 87" in Example 2, except that methylamine hydrochloride was replaced with ethylamine hydrochloride, thereby obtaining product I-2-88, designated as No. 88.

[0148] Synthesis of Compound No. 89: The preparation method is the same as that of "1. Synthesis of No. 87" in Example 2, except that methylamine hydrochloride is replaced with n-propylamine, thereby preparing product I-2-89, which is recorded as No. 89.

[0149] Synthesis of Compound No. 92: The preparation method is the same as that of "1. Synthesis of No. 87" in Example 2, except that methylamine hydrochloride is replaced with dimethylamine, thereby obtaining product I-2-92, designated as No. 92.

[0150] Example 3

[0151] 1. Synthesis of No.173

[0152] Weigh compound a-3-173 (10.00 mmol, 2.00 g) and place it in a 50 mL eggplant-shaped flask. Add anhydrous ethanol hydrogen chloride solution (100.0 mmol, 8.50 g, 8.00 mol / L) and 10 mL of anhydrous 1,2-dichloroethane at 2 ° C. Continue stirring at 2 ° C for alcoholysis reaction for 30 h. After the reaction is completed, the reaction solution is concentrated and vacuum-dried to obtain intermediate b-3-173, which is directly used in the next reaction without purification. The intermediate b-3-173 (10.00 mmol, 2.40 g) was weighed and placed in a three-necked flask, 20 mL of anhydrous ethanol was added to dissolve it, and the mixture was placed at 0 ° C. Triethylamine (Et3N, 12.00 mmol, 1.20 g) was slowly added dropwise to the system, and the reaction temperature was controlled not to exceed 5 ° C. Stirring was continued for 30 min; then the temperature was slowly raised to 80 ° C and refluxed, and ethyl cyanoacetate (11.00 mmol, 1.24 g) was slowly added dropwise until the addition was complete. The condensation reaction was carried out under reflux, and the degree of reaction was observed every 2 hours until the reaction was complete. The reaction time was 8 hours. After the reaction, the reaction solution was concentrated and separated by column chromatography to obtain intermediate c-3-173; intermediate c-3-173 (1.00 mmol, 0.31 g), L-proline (1.00 mmol, 0.12 g), CuI (2.00 mmol, 0.38 g), Cs2CO3 (2.00 mmol, 0.65 g) and methylamine hydrochloride (2.00 mmol, 0.16 g) were weighed and placed in a 25 mL pressure bottle, replaced with argon, and then 5 mL of anhydrous DMSO was added. The substitution reaction was carried out at 120°C for 24 hours and the reaction was monitored by TLC; after the reaction, the reaction solution was concentrated and separated by column chromatography (PE:DCM=1:1) to obtain product I-3-173, recorded as No. 173; the H NMR spectrum of compound No. 173 is shown in Figure 5, and the C NMR spectrum is shown in Figure 6.

[0153] 2. The preparation methods of compounds No. 174 to No. 258 (i.e., the compounds described in Index Table 3) were the same as those described in "1. Synthesis of No. 173" in Example 3. The preparation methods of compounds No. 174, No. 175, No. 176, No. 179, and No. 180 were as follows:

[0154] Synthesis of Compound No. 174: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced by ethylamine hydrochloride, thereby preparing product I-3-174, which is recorded as No. 174.

[0155] Synthesis of compound No. 175: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced with n-propylamine, thereby preparing product I-3-175, which is recorded as No. 175.

[0156] Synthesis of Compound No. 176: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced with isopropylamine, thereby preparing product I-3-176, which is recorded as No. 176.

[0157] Synthesis of Compound No. 179: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced with cyclopropylamine, thereby preparing product I-3-179, which is recorded as No. 179.

[0158] Synthesis of Compound No. 180: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced with isopentylamine, thereby obtaining product I-3-180, designated as No. 180.

[0159] Synthesis of Compound No. 181: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced with 3-chloro-4-fluorobenzylamine, thereby preparing product I-3-181, which is recorded as No. 181.

[0160] Synthesis of Compound No. 182: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced with isobutylamine, thereby preparing product I-3-182, which is recorded as No. 182.

[0161] Synthesis of Compound No. 183: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced with 3-methoxypropylamine, thereby preparing product I-3-183, which is recorded as No. 183.

[0162] Synthesis of Compound No. 185: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced with 2-furylmethylamine, thereby preparing product I-3-185, which is recorded as No. 185.

[0163] Synthesis of Compound No. 203: The preparation method was the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride was replaced with 2-aminoethanol, thereby obtaining product I-3-203, designated as No. 203.

[0164] Synthesis of Compound No. 204: The preparation method was the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride was replaced with 2-amino-3-methyl-1-butanol, thereby obtaining product I-3-204, designated as No. 204.

[0165] Synthesis of Compound No. 205: The preparation method is the same as that of "1. Synthesis of No. 173" in Example 3, except that methylamine hydrochloride is replaced with 4-chlorobenzenesulfonamide, thereby obtaining product I-3-205, designated as No. 205.

[0166] (2) Preparation of preparations

[0167] The following Examples 4 to 9 provide examples of the preparation of several fungicide formulations using Compound No. 2 of the present invention as the active ingredient. It should be noted that the present invention is not limited to the following examples. In these formulation examples, all "%" refers to weight percentage.

[0168] Example 4: Suspension Concentrate Formulation

[0169] 25% of compound No. 2, 35% of light calcium carbonate, 34% of diatomaceous earth, 1% of lauryl alcohol polyoxyethylene ether (JFC) and 5% of lignin sulfonate are uniformly mixed and crushed to obtain a suspension.

[0170] Example 5: Wettable powder formulation

[0171] 20% of compound No. 2, 38% of light calcium carbonate, 36% of diatomaceous earth, 1% of lauryl alcohol polyoxyethylene ether (JFC) and 5% of lignin sulfonate are uniformly mixed and pulverized to obtain a wettable powder.

[0172] Example 6: Emulsifiable Concentrate Formulation

[0173] Heat and stir 15% of compound No. 2, 5% of N-methyl-2-pyrrolidone, 5% of Nongru No. 500 (calcium salt), 5% of Nongru No. 602 and 70% of xylene to obtain an emulsifiable concentrate.

[0174] Example 7: Water-dispersible granule formulation

[0175] 30% of Compound No. 2, 2% of white carbon black, 1% of naphthalenesulfonate, 4% of naphthalenesulfonate formaldehyde condensate, and 63% of kaolin were mixed and ground, then kneaded with water. The mixture was then added to a granulator equipped with a screen of a specified size for granulation. The mixture was then dried and sieved (according to the screen size range) to obtain a granular product.

[0176] Example 8: Granule Formulation

[0177] 10% of compound No. 2, 4% of sodium naphthalenesulfonate formaldehyde condensate (NMO), 1% of polyvinyl alcohol (PVA) and 85% of clay were uniformly mixed and pulverized. Then, 20 parts of water were added to 100 parts of the mixture, kneaded, and formed into 14-32 mesh granules using an extruder. The granules were dried to obtain granules.

[0178] Example 9: Aqueous Suspension Concentrate Formulation

[0179] 30% of compound No. 2, 0.4% of silicone defoamer, 1% of magnesium aluminum silicate, 3% of rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, 1% of fatty alcohol polyoxyethylene ether, 5% of propylene glycol and deionized water (59.5%) are pre-mixed and then added to a sand mill for sand grinding. After filtering, a suspension mother liquor is obtained, and the prepared xanthan gum (0.1%) aqueous solution is added and sheared and mixed evenly.

[0180] (III) Determination of biological activity of compounds and field efficacy tests

[0181] Example 10: In vitro biological activity assay of compounds

[0182] The mycelial growth rate method was used to determine the antifungal activity of the target compound. The specific procedure is as follows:

[0183] (1) The above-synthesized 2-cyano-3-disubstituted phenyl acrylate compound (prepared in Examples 1 to 3) was dissolved in dimethyl sulfoxide (DMSO) to prepare a concentration of 10 4 The stock solution was then diluted to 10 μg / mL. 3 μg / mL dilution; pipette the dilution into PDA culture medium and shake quickly to prepare a drug treatment group with a final concentration of 1 μg / mL; use a PDA plate containing an equal volume of DMSO as the solvent control group; use an equal concentration of cyanobacterium as the control drug group; "μg / mL" refers to micrograms of active ingredient / ml.

[0184] (2) The test pathogens were inoculated on PDA plates and cultured in a biochemical incubator at 25°C until the logarithmic growth phase. A 5 mm diameter bacterial disc was punched out from the edge of the fresh colony using a hole punch and inoculated on a PDA plate containing a certain concentration of the drug to be tested. At the same time, the bacterial blocks were inoculated into PDA culture medium containing no drug to be tested and cyanocobalamin as a control group. The plates were cultured in the dark in a biochemical incubator at 25°C until the control group without the drug to be tested was almost full of the plate. The colony diameter was measured by the cross-cross method (excluding the 5 mm bacterial disc diameter); the mycelial growth inhibition rate (MGIR) was calculated using the following formula:

[0185] MGIR%=[(CN) / C]×100%;

[0186] Where C is the colony diameter of the control group, and N is the colony diameter of the treatment group. In this experiment, three replicates were set for each treatment, and the experiment was repeated three times.

[0187] (3) The pathogens tested were rice false smut (Chlorophytum spp.), wheat fusarium (Fusarium graminearum, Fusarium spp.), rice seedling rot (Fusarium moniliforme, Fusarium spp.), banana wilt (Fusarium oxysporum, Fusarium spp.), wheat stem rot (Pseudofusarium graminearum, Fusarium spp.), wheat take-all pathogen (Acrocystis spp.), strawberry anthracnose (Colletotrichum spp.), apple anthracnose (Colletotrichum spp.), grape anthracnose (Colletotrichum spp.), osmanthus anthracnose (Colletotrichum spp.), citrus anthracnose (Colletotrichum spp.), rubber tree anthracnose Anthracnose (Colletotrichum spp.), corn anthracnose (Colletotrichum spp.), soybean anthracnose (Colletotrichum spp.), onion anthracnose (Colletotrichum spp.), pepper anthracnose (Colletotrichum spp.), wolfberry anthracnose (Colletotrichum spp.), mango anthracnose (Colletotrichum spp.), camellia anthracnose (Colletotrichum spp.), yam anthracnose (Colletotrichum spp.), peanut brown spot fungus (Cercospora spp.), cotton wilt fungus (Verticillium spp.), apple tree rot fungus (Puccinia spp.), wheat stripe rust (Puccinia spp.), wheat leaf rust (Puccinia spp.).

[0188] (4) The present invention evaluated the in vitro fungicidal activity of the numbered compounds described in Index Tables 1 to 3 (prepared in Examples 1 to 3), as shown in Figures 7, 8, 9, and 10. The experimental results show that compared with the control agent cyanoacrylate, the compounds prepared by the present invention not only have ultra-high inhibitory activity against the mycelial growth of pathogens of the genus Fusarium, but also significantly expand the control spectrum.

[0189] (5) In addition, as shown in Table 5, under low concentration conditions, some compounds of the present invention (prepared in Examples 1 to 3) have ultra-high inhibitory activity against the mycelial growth of wheat fusarium, and the inhibition rate is significantly higher than that of the control agent cyanocobalamin.

[0190] Table 5 Inhibitory activity of some compounds on the mycelial growth of wheat scab at lower concentrations

[0191] (6) As shown in Table 6, the inhibitory concentration EC of some compounds (prepared in Examples 1 to 3) that inhibited the growth of mycelium of wheat fusarium by 50% was 50 , where the EC of compound No.1 is 50 The value is 0.0153 μg / mL, which is the EC of the control agent cyanothiocarb 50 The EC value of compound No.2 is 11 times that of 50 The value is 0.0077 μg / mL, which is the EC of the control agent cyanothiocarb 50 The results showed that the inhibitory activity of compound No.1 and compound No.2 on the mycelial growth of wheat fusarium was significantly higher than that of the control agent cyanocobalamin.

[0192] Table 6 EC of some compounds on the mycelial growth of Gibberella graminearum 50 Determination of value

[0193] Example 11: Preventive Effect of Compound No. 2 on Wheat Scab under Greenhouse Conditions

[0194] Compound No. 2 (prepared in Example 1) was diluted with sterile water containing 0.2 v / v% Tween 20 to 5, 50, 250 and 500 μg / mL drug solutions. Cyanocyanobacterium was diluted to the same concentration as a positive control, and sterile water containing 0.2 v / v% Tween 20 was used as a negative control. The middle section of wheat leaves with similar growth conditions were marked and coated with drug solutions of different concentrations. Each drug concentration was repeated 6 times. 3-4 hours after application, the wheat fusarium graminearum wild-type strain PH-1 was inoculated at the application site, and the bacteria were inoculated at the unapplied sites on both sides of the mark to determine the conductivity of the drug. The inoculated site was wrapped with absorbent cotton to keep it moist. The wheat was cultured at 21°C, with a photoperiod of 12h and a relative humidity of 90%. After 3 days, the length of the lesion was measured.

[0195] The experimental data in Table 7 show that Compound No. 2 has a protective effect against wheat fusarium head blight, and its effectiveness increases with increasing concentration. At concentrations of 5 μg / mL, 50 μg / mL, 250 μg / mL, and 500 μg / mL, compound No. 2 exhibited superior protection against wheat head blight compared to the control agent, cyanothiocarb, in the upper, middle, and lower leaf zones.

[0196] Table 7 Preventive effect of compound No.2 on wheat scab

[0197] Example 12: Field efficacy test of compound No. 2 against wheat scab

[0198] The wheat used was the fusarium susceptibility variety Yannong 1212. The test was conducted on Longmiao Road, Gaoliangjian Subdistrict, Hongze District, Huai'an City. Five treatments were used: ① 25% cyanocyanamide SC 375 g ai / ha; ② 25% No. 2 SC 75 g ai / ha; ③ 25% No. 2 SC 150 g ai / ha; ④ 25% No. 2 SC 225 g ai / ha; and ⑤ clean water treatment (CK). All 25% SCs were measured at mass concentrations. The 25% No. 2 SC used was prepared in Example 4.

[0199] Each treatment was sprayed for the first time on April 25, 2023, and for the second time on May 1. The plot area was 2m×10m=20m 2 The experiment was conducted in accordance with the "Guidelines for Field Efficacy Tests of Pesticides Part 15: Control of Wheat Scab by Fungicides" (NY / T 1464.15). The disease survey was conducted in accordance with the "Technical Specifications for Monitoring and Reporting Wheat Scab" (GB / T 15796-2011). On May 19, 2023, the number of wheat scab-infected ears and the disease grade of each ear were surveyed. The disease index and control efficacy were calculated according to NY / T 1464.15. The calculation formula is as follows:

[0200] Table 8 Field efficacy of 25% No.2 suspension concentrate against wheat scab

[0201] The experimental results, shown in Table 8, show that compared to the control agent, cyanostrobin, Compound No. 2, at a lower application rate of 75 g ai / ha, demonstrated comparable efficacy to the control agent, a 25% cyanostrobin suspension concentrate at 375 g ai / ha. Compound No. 2's efficacy gradually improved with increasing application rates per hectare.

[0202] In summary, the results of indoor bioassays and field efficacy tests of the compounds showed that compared with the control agent cyanoacrylate, the compounds prepared by the present invention had a stronger inhibitory effect on wheat fusarium, and the biological activity was significantly improved. At the same time, the compounds prepared by the present invention significantly expanded the control spectrum and had significant control effects on plant diseases caused by the genus Chlorophytum, Fusarium, Acrocystis, Colletotrichum, Cercospora, Verticillium, Black Coriolus, and Puccinia, while the control agent cyanoacrylate was only effective against plant diseases caused by wheat fusarium and rice seedling pathogen in the genus Fusarium, and had no control effect or very poor effect on other diseases. The compounds prepared by the present invention have significant application and economic value.

[0203] The present invention provides a 2-cyano-3-disubstituted phenyl acrylate compound, a method for preparing the compound, and a method for its application in pesticides. Numerous methods and approaches exist for implementing this technical solution. The foregoing description is merely a preferred embodiment of the present invention. It should be noted that those skilled in the art may make various improvements and modifications without departing from the principles of the present invention, and such improvements and modifications are also within the scope of protection of the present invention. Any components not specified in this embodiment may be implemented using existing technologies.

Claims

1. A 2-cyano-3-disubstituted phenyl acrylate compound, characterized in that: The structural formula of the 2-cyano-3-disubstituted phenyl acrylate compound is shown in Formula I: wherein R1, R2, and R3 are independently selected from H, halogen, CN, NO2, or unsubstituted or substituted amino, hydroxyl, thiol, thiocyanate, C1-C 10 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C6 cycloalkyl, C1-C6 alkylthio, C1-C6 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl group, C3-C6 trialkylsilyl group, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino; Wherein, R1, R2, and R3 are not H at the same time; Wherein, when R1 and R3 are H, R2 is not a hydroxyl group; wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C3-C6 trialkylsilyl, phenyl, halogenated phenyl, benzyl, phenoxy or C2-C 10 Heterocyclic substitution.

2. The 2-cyano-3-disubstituted phenyl acrylate compound according to claim 1, characterized in that: The R1, R2, and R3 are independently selected from H, halogen, CN, NO2, or unsubstituted or substituted amino, hydroxyl, mercapto, thiocyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkylthio, C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl group, C3-C6 trialkylsilyl group, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4dialkylaminosulfonylamino.

3. The 2-cyano-3-disubstituted phenyl acrylate compound according to claim 2, characterized in that: The groups of R1, R2, and R3 include one of the following three situations: Case ①: R1 is F or Cl; R3 is H; The R2 is selected from unsubstituted or substituted C1-C4 alkylthio, C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino; Case ②: R2 is F or Cl; R3 is H; The R1 is selected from unsubstituted or substituted C1-C4 alkylthio, C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino; Case ③: R3 is F or Cl; R2 is H; The R1 is selected from unsubstituted or substituted C1-C4 alkylthio, C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4dialkylaminosulfonylamino.

4. The 2-cyano-3-disubstituted phenyl acrylate compound according to claim 3, characterized in that: The groups of R1, R2 and R3 include one of the following three situations: Case ①: R1 is F or Cl; R3 is H; The R2 is selected from unsubstituted or substituted C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino; wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C6 dialkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl or C2-C 10 Heterocyclyl substitution; Case ②: R2 is F or Cl; R3 is H; The R1 is selected from unsubstituted or substituted C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino; wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C6 dialkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl or C2-C 10 Heterocyclyl substitution; Case ③: R3 is F or Cl; R2 is H; The R1 is selected from unsubstituted or substituted C1-C5 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C 10 Heterocyclic group, C3-C8 dialkylaminocarbonyl, C6-C 10 Aryl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino; wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C6 dialkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl or C2-C 10 Heterocyclic substitution.

5. The 2-cyano-3-disubstituted phenyl acrylate compound according to claim 4, characterized in that: The groups of R1, R2 and R3 include one of the following three situations: Case ①: R1 is F; R3 is H; The R2 is selected from unsubstituted or substituted C1-C5 alkylamino, C1 dialkylamino, C3 cycloalkylamino, C6-C7 arylamino, C6 arylsulfonylamino; Wherein, the substitution is selected from substitution by hydroxyl, halogen, C1 alkoxy or C4-C6 heterocyclic group; Preferably, The R1 is F; the R3 is H; The R2 is selected from unsubstituted methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, cyclopropylamino, isopentylamino or isobutylamino, or substituted benzylamino, n-propylamino, phenylamino, methylamino, ethylamino, 1,2-dimethyl-n-propylamino or benzenesulfonylamino; Wherein, the substitution is selected from substitution by any identical or different groups; further preferably, the substitution is selected from substitution by any identical or different hydroxyl, fluorine, chlorine, methoxy or furanyl groups; Case ②: R2 is F; R3 is H; The R1 is selected from unsubstituted or substituted C1-C5 alkylamino, C1 dialkylamino, C3 cycloalkylamino, C6-C7 arylamino, C6 arylsulfonylamino; Wherein, the substitution is selected from substitution by hydroxyl, halogen, C1 alkoxy or C4-C6 heterocyclic group; Preferably, said R2 is F; said R3 is H; The R1 is selected from unsubstituted methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, cyclopropylamino, isopentylamino or isobutylamino, or substituted benzylamino, n-propylamino, phenylamino, methylamino, ethylamino, 1,2-dimethyl-n-propylamino or benzenesulfonylamino; Wherein, the substitution is selected from substitution by any identical or different groups; further preferably, the substitution is selected from substitution by any identical or different hydroxyl, fluorine, chlorine, methoxy or furanyl groups; Case ③: R3 is F; R2 is H; The R1 is selected from unsubstituted or substituted C1-C5 alkylamino, C1 dialkylamino, C3 cycloalkylamino, C6-C7 arylamino, C6 arylsulfonylamino; Wherein, the substitution is selected from substitution by hydroxyl, halogen, C1 alkoxy or C4-C6 heterocyclic group; Preferably, The R3 is F; the R2 is H; The R1 is selected from unsubstituted methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino, cyclopropylamino, isopentylamino or isobutylamino, or substituted benzylamino, n-propylamino, phenylamino, methylamino, ethylamino, 1,2-dimethyl-n-propylamino or benzenesulfonylamino; Wherein, the substitution is selected from substitution by any number of the same or different groups; more preferably, the substitution is selected from substitution by any number of the same or different hydroxyl, fluorine, chlorine, methoxy or furanyl groups.

6. The 2-cyano-3-disubstituted phenyl acrylate compound according to claim 1, characterized in that: The 2-cyano-3-disubstituted phenyl acrylate compound is any one of the following structures:

7. The pharmaceutically acceptable salt of the 2-cyano-3-disubstituted phenyl acrylate compound according to claim 1, characterized in that: The pharmaceutically acceptable salt is hydrochloride.

8. The method for preparing the 2-cyano-3-disubstituted phenyl acrylate compound according to claim 1, characterized in that: This includes one of the following three methods: Method 1 is: the preparation method of the 2-cyano-3-disubstituted phenyl acrylate compound comprises the following steps: a benzonitrile compound a-1 undergoes a first alcoholysis reaction with an anhydrous ethanol solution of hydrogen chloride to obtain an intermediate b-1; the intermediate b-1 undergoes a first condensation reaction with ethyl cyanoacetate under the action of a first base to obtain an intermediate c-1; the intermediate c-1 undergoes a first substitution reaction with a substitution compound under the action of a second base and a first catalyst to obtain a 2-cyano-3-disubstituted phenyl acrylate compound I-1; Where X=-Br,-I The substituted compound is an amine compound, an amide compound or an alcohol compound; R2 is selected from unsubstituted or substituted amino, hydroxyl, mercapto, thiocyano, C1-C6 alkylthio, C1-C6 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 heterocyclic group, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino; wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C3-C6 trialkylsilyl, phenyl, halogenated phenyl, benzyl, phenoxy or C2-C 10 Heterocyclic substitution; or Method 2 is: the preparation method of the 2-cyano-3-disubstituted phenyl acrylate compound comprises the following steps: a benzonitrile compound a-2 undergoes a second alcoholysis reaction with an anhydrous ethanol solution of hydrogen chloride to obtain an intermediate b-2; the intermediate b-2 undergoes a second condensation reaction with ethyl cyanoacetate under the action of a third base to obtain an intermediate c-2; the intermediate c-2 undergoes a second substitution reaction with a substitution compound under the action of a fourth base and a second catalyst to obtain a 2-cyano-3-disubstituted phenyl acrylate compound I-2; Where X=-Br,-I The substituted compound is an amine compound, an amide compound or an alcohol compound; R1 is selected from unsubstituted or substituted amino, hydroxyl, mercapto, thiocyano, C1-C6 alkylthio, C1-C6 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 heterocyclic group, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino; wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C3-C6 trialkylsilyl, phenyl, halogenated phenyl, benzyl, phenoxy or C2-C 10 Heterocyclic substitution; or Method three is: the preparation method of the 2-cyano-3-disubstituted phenyl acrylate compound comprises the following steps: a benzonitrile compound a-3 undergoes a third alcoholysis reaction with an anhydrous ethanol solution of hydrogen chloride to obtain an intermediate b-3; the intermediate b-3 undergoes a third condensation reaction with ethyl cyanoacetate under the action of a fifth base to obtain an intermediate c-3; the intermediate c-3 undergoes a third substitution reaction with a substitution compound under the action of a sixth base and a third catalyst to obtain a 2-cyano-3-disubstituted phenyl acrylate compound I-3; Where Y=-Br,-I The substituted compound is an amine compound, an amide compound or an alcohol compound; R1 is selected from unsubstituted or substituted amino, hydroxyl, mercapto, thiocyano, C1-C6 alkylthio, C1-C6 alkylamino, C1-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C5-C 10 Bicyclic, C2-C 10 heterocyclic group, C3-C8 dialkylaminocarbonyl, C3-C6 trialkylsilyl, benzyl, phenoxy, C1-C6 alkoxy, C1-C4 haloalkoxy, C2-C6 alkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C6-C 10 Arylamino, C1-C4 alkylcarbonylamino, (C1-C4 alkyl)(C1-C4 alkylcarbonyl)amino, C1-C4 alkylsulfonylamino, (C1-C4 alkyl)(C1-C4 alkylsulfonyl)amino, C1-C4 10 Arylsulfonylamino, C3-C 10 Cycloalkylsulfonylamino or C1-C4 dialkylaminosulfonylamino; wherein the substitution is selected from hydroxy, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C3-C6 (alkyl)cycloalkylamino, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C1-C6 alkoxycarbonylamino, C3-C6 trialkylsilyl, phenyl, halogenated phenyl, benzyl, phenoxy or C2-C 10 Heterocyclic substitution.

9. The preparation method according to claim 8, characterized in that: In the method 1, the molar ratio of the benzonitrile compound a-1 to the anhydrous ethanol solution of hydrogen chloride is 1:5-20, preferably 1:8-15, and more preferably 1:10; the first alcoholysis reaction, the reaction temperature is -10-25°C, and the reaction time is 24-96h; the first base is an organic base or an inorganic base; the organic base is triethylamine, pyridine, 1,8-diazabicyclo-bicyclo (5,4,0)-7-undecene, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is sodium carbonate, potassium carbonate or sodium hydroxide; the molar ratio of the intermediate b-1 to ethyl cyanoacetate and the first base is 1:1-5:1-10, preferably 1:1-2:1-5, and more preferably 1:1.1:1.2; the first condensation reaction, the reaction temperature is 70-150°C, the reaction The time is 5 to 24 hours; the second base is an organic base or an inorganic base; the organic base is triethylamine, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is cesium carbonate, potassium carbonate, potassium phosphate or sodium hydroxide; the first catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the first catalyst is 1:1 to 10, preferably 1:1 to 5, and more preferably 1:2; the molar ratio of the intermediate c-1 to the substituted compound, the second base, and the first catalyst is 1:1 to 10:1 to 10:1 to 20, preferably 1:1 to 5:1 to 5:1 to 10, more preferably 1:1 to 2:1 to 2:1 to 5, and more preferably 1:2:2:3; the first substitution reaction, the reaction temperature is 100 to 180°C, and the reaction time is 6 to 24 hours; In the method 2, the molar ratio of the benzonitrile compound a-2 to the anhydrous ethanol solution of hydrogen chloride is 1:5-20, preferably 1:8-15, and more preferably 1:10; the second alcoholysis reaction, the reaction temperature is -10-25°C, and the reaction time is 24-96h; the third base is an organic base or an inorganic base; the organic base is triethylamine, pyridine, 1,8-diazabicyclo-bicyclo (5,4,0)-7-undecene, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is sodium carbonate, potassium carbonate or sodium hydroxide; the molar ratio of the intermediate b-2 to ethyl cyanoacetate and the third base is 1:1-5:1-10, preferably 1:1-2:1-5, and more preferably 1:1.1:1.2; the second condensation reaction, the reaction temperature is 70-150°C, the reaction The time is 5 to 24 hours; the fourth base is an organic base or an inorganic base; the organic base is triethylamine, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is cesium carbonate, potassium carbonate, potassium phosphate or sodium hydroxide; the second catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the second catalyst is 1:1 to 10, preferably 1:1 to 5, and more preferably 1:2; the molar ratio of the intermediate c-2 to the substituted compound, the fourth base, and the second catalyst is 1:1 to 10:1 to 10:1 to 20, preferably 1:1 to 5:1 to 5:1 to 10, more preferably 1:1 to 2:1 to 2:1 to 5, and more preferably 1:2:2:3; the second substitution reaction, the reaction temperature is 100 to 180°C, and the reaction time is 6 to 24 hours; In the method three described above: the molar ratio of the benzonitrile compound a-3 to the anhydrous ethanol solution of hydrogen chloride is 1:5-20, preferably 1:8-15, and more preferably 1:10; the third alcoholysis reaction, the reaction temperature is -10-25°C, and the reaction time is 24-96h; the fifth base is an organic base or an inorganic base; the organic base is triethylamine, pyridine, 1,8-diazabicyclo-bicyclo (5,4,0)-7-undecene, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is sodium carbonate, potassium carbonate or sodium hydroxide; the molar ratio of the intermediate b-3 to ethyl cyanoacetate and the fifth base is 1:1-5:1-10, preferably 1:1-2:1-5, and more preferably 1:1.1:1.2; the third condensation reaction, the reaction temperature is 70-150°C, the reaction The time is 5 to 24 hours; the sixth base is an organic base or an inorganic base; the organic base is triethylamine, lithium diisopropylamide or N,N-diisopropylethylamine; the inorganic base is cesium carbonate, potassium carbonate, potassium phosphate or sodium hydroxide; the third catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the third catalyst is 1:1 to 10, preferably 1:1 to 5, and more preferably 1:2; the molar ratio of the intermediate c-3 to the substituted compound, the sixth base, and the third catalyst is 1:1 to 10:1 to 10:1 to 20, preferably 1:1 to 5:1 to 5:1 to 10, more preferably 1:1 to 2:1 to 2:1 to 5, and even more preferably 1:2:2:3; the third substitution reaction has a reaction temperature of 100 to 180°C and a reaction time of 6 to 24 hours.

10. A pesticide formulation, characterized in that: The pesticide preparation contains 0.1%-45% by weight of the 2-cyano-3-disubstituted phenyl acrylate compound according to claim 1 or a pharmaceutically acceptable salt of the 2-cyano-3-disubstituted phenyl acrylate compound according to claim 7.

11. The pesticide formulation according to claim 10, characterized in that: The dosage form of the pesticide preparation is a suspension, a dispersible oil suspension, a dispersible liquid, a suspension seed coating, a tablet, a microemulsion, an aqueous solution, an emulsion, an emulsifiable concentrate, an aqueous suspension, a powder, a wettable powder, a soluble powder, a soluble liquid, a granule, a soluble granule, a water-dispersible granule, a capsule, a microcapsule, a microcapsule suspension or a nano preparation.

12. The pesticide formulation according to claim 10, characterized in that The pesticide preparation comprises agriculturally acceptable carriers and / or adjuvants.

13. Use of the 2-cyano-3-disubstituted phenylacrylate compound according to claim 1, the pharmaceutically acceptable salt of the 2-cyano-3-disubstituted phenylacrylate compound according to claim 7, or the pesticide preparation according to claim 10 in preventing and controlling fungal diseases of crops.

14. The use according to claim 13, characterized in that The fungal diseases are diseases caused by any one or more of the genera Chlorotrichum, Fusarium, Acrocystis, Colletotrichum, Cercospora, Verticillium and Sphaerocarp; the diseases are any one or more of rice false smut, wheat fusarium wilt, rice seedling blight, banana wilt, wheat stem base rot, wheat take-all, strawberry anthracnose, apple anthracnose, grape anthracnose, osmanthus anthracnose, citrus anthracnose, rubber tree anthracnose, corn anthracnose, soybean anthracnose, onion anthracnose, pepper anthracnose, wolfberry anthracnose, mango anthracnose, camellia anthracnose, yam anthracnose, peanut brown spot, cotton wilt and apple tree rot.

15. The use according to claim 13, characterized in that: The fungal disease is caused by Puccinia spp.; the disease is any one or both of wheat stripe rust and wheat leaf rust.

16. The use according to claim 13, characterized in that: The 2-cyano-3-disubstituted phenylacrylate compound according to claim 1 or the pharmaceutically acceptable salt of the 2-cyano-3-disubstituted phenylacrylate compound according to claim 7 or the pesticide preparation according to claim 10 is applied to the pathogen to be controlled or the medium in which it grows, and the dosage is 0.001 to 1000 g / hectare, preferably 1 to 1000 g / hectare, more preferably 5 to 750 g / hectare, further preferably 50 to 500 g / hectare, and most preferably 75 to 300 g / hectare.

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