CN108117518B - N-2, 4-substituted phenyl bisamide compound and preparation method and application thereof - Google Patents
N-2, 4-substituted phenyl bisamide compound and preparation method and application thereof Download PDFInfo
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- CN108117518B CN108117518B CN201611084347.4A CN201611084347A CN108117518B CN 108117518 B CN108117518 B CN 108117518B CN 201611084347 A CN201611084347 A CN 201611084347A CN 108117518 B CN108117518 B CN 108117518B
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- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention discloses an N-2, 4-substituted phenyl bisamide compound shown as a formula (I) and a preparation method and application thereof.
In the formula, R, Ar and R1、R2、R3And n has the definitions given in the description. The compound of formula (I) has insecticidal and/or bactericidal biological activity, especially activity on homoptera pests such as aphids and the like.
Description
Technical Field
The invention belongs to the field of pesticides and bactericides, and particularly relates to an N-2, 4-substituted phenyl bisamide compound with pesticidal and bactericidal biological activity, a preparation method thereof, a pesticide and bactericide composition containing the compound, and application and a method for controlling pests and harmful bacteria by using the compound.
Background
The prevention and control of pests and harmful germs are very important in the process of realizing high-efficiency agriculture. Meanwhile, the prevention and control of pests and harmful bacteria are also important in the fields of forests, herds, subsidiary crops, fisheries, public health and the like. Although many pest and harmful bacteria preventing and controlling agents are available in the market, due to the continuous expansion of the market, the problems of drug resistance, drug service life, drug economy and the like of external pests and harmful bacteria, and the increasing attention of people to the environment, scientists are required to continuously research so as to develop new high-efficiency, safe, economic and environment-compatible new varieties of pesticides and bactericides with different action modes.
Bisamide compounds are an important class of compounds in medicinal chemistry, and have broad-spectrum biological activity. As prior art for the present invention, WO2007020986 reports the general formula pyridineThe pyrazamide compound has acaricidal activity, and the example compound with the following structure is commercialized as acaricide, and the general name is Pyfluumide, which is also the only commercialized pyrazole bisamide acaricide, and Pyfluumide has excellent activity to pest mites, LC50The value is 1-3mg/L, but Pyfluzumab has no obvious activity on insect pests such as aphids and diseases such as powdery mildew.
In order to obtain novel amide compounds with more economical efficiency, higher efficiency, broader-spectrum bioactivity and/or novel action mechanism, based on relevant literatures and previous work, N-2, 4-substituted phenyl bisamide compounds with insecticidal and bactericidal activities shown in formula (I) which are not reported are designed and synthesized. The compound of the invention has higher insecticidal activity and bactericidal activity compared with the compound of WO2007020986 such as Pyfluzumab.
Disclosure of Invention
The invention provides an N-2, 4-substituted phenyl bisamide compound with biological activity of preventing and treating pests, harmful bacteria and the like and an isomer thereof, which are shown in a formula (I):
wherein:
I.R represents C1-C12Alkyl radical, C1-C12Alkoxy radical, C2-C12Alkenyl radical, C2-C12Alkenyloxy radical, C2-C12Alkynyl, C2-C12Alkynyloxy, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl oxy, C3-C8Heterocycloalkyl radical, C3-C8Heterocycloalkyloxy, phenyl, phenoxy, biphenyl, pyrazolyl, thiadiazolyl, pyridyl, thienyl, benzothienyl, furyl, benzofuryl, pyrrolyl, benzopyrryl, indolyl, benzindolyl, imidazolyl, benzimidazolyl, quinolineA group selected from the group consisting of pyranyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzopyranyl, benzopyrazinyl, benzopyrimidinyl, benzopyrazinyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, pyrimidotriazolyl;
ar represents phenyl, biphenyl, pyrazolyl, thiadiazolyl, pyridyl, thienyl, benzothienyl, furyl, benzofuryl, pyrrolyl, benzopyrolyl, indolyl, benzindolyl, imidazolyl, benzimidazolyl, quinolyl, pyranyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzopyranyl, benzopyrazinyl, benzopyrimidinyl, benzopyrazinyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, pyrimidotriazolyl;
III.R1and R2Are identical or different and represent halogen, cyano, nitro, C1-C12Alkyl radical, C1-C12Alkoxy radical, C1-C12Alkylcarbonyl or C1-C12An alkylsulfonyl group;
IV.R3represents hydrogen, halogen, cyano, nitro, C1-C12Alkyl or C1-C12An alkoxy group;
v.n represents an integer of 0, 1,2 or 3; and is
1) As defined in I, II, III or IV, R, Ar, R1、R2And/or R3Wherein the hydrogen atom is unsubstituted; or 2) the meanings as defined in I, II, III or IV, R, Ar, R1、R2And/or R3Wherein the hydrogen atoms may be partially or wholly substituted by the same or different substituents selected from the group consisting of: halogen, nitro, cyano, C1-C12Alkyl radical, C1-C12Haloalkyl, C1-C12Alkoxy radical, C1-C12Haloalkoxy, C1-C12Alkylthio radical, C1-C12Alkylsulfonyl radical, C1-C12Alkylsulfinyl radical, C1-C12Alkoxycarbonyl, C1-C12Alkylcarbonyloxy, C1-C12Alkylamino radical, C2-C12Alkenyl radical, C2-C12Alkenyloxy radical, C2-C12Alkenylthio radical, C2-C12Alkenyloxycarbonyl radical, C2-C12Alkenylamino radical, C2-C12Alkynyl, C2-C12Alkynyl oxy, C2-C12Alkynyl thio group, C2-C12Alkynyl oxycarbonyl, C2-C12Alkynyl amino group, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylthio radical, C3-C8Cycloalkyloxycarbonyl radical, C3-C8Cycloalkylamino group, C3-C8Heterocycloalkyl radical, C3-C8Heterocycloalkyloxy, C3-C8Heterocycloalkylthio, C3-C8Heterocycloalkyloxycarbonyl radical, C3-C8Heterocycloalkylamino, phenyl, halogen, C1-C6Alkyl and/or C1-C6Phenyl substituted by alkoxy, phenoxy, by halogen, C1-C6Alkyl and/or C1-C6Alkoxy-substituted phenoxy;
in the definitions of the compounds (I) given above, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: fluorine, chlorine, bromine or iodine;
alkyl groups: refers to straight or branched chain alkyl;
cycloalkyl groups: refers to saturated or unsaturated cycloalkyl;
an alkenyl group; refers to a straight or branched chain alkenyl group, and a double bond may be present at any position;
an alkynyl group; refers to straight or branched chain alkynyl groups, and may have a triple bond at any position;
halogenation: means that hydrogen atoms therein are partially or totally substituted by halogen atoms.
Preferred compounds of the invention are: in formula (I):
I.R represents C1-C12Alkyl radical, C2-C12Alkenyl radical, C2-C12Alkynyl, C3-C8Cycloalkyl radical, C3-C8Heterocycloalkyl radical, C1-C12Alkoxy radical, C2-C12Alkenyloxy radical, C2-C12Alkynyloxy, C3-C8Cycloalkyl oxy, C3-C8Heterocycloalkyloxy, phenyl, pyrazolyl or pyridyl;
ar represents phenyl, pyrazolyl, thiadiazolyl, pyridyl, thienyl, benzothienyl, furyl, benzofuryl, pyrrolyl, benzopyrolyl, indolyl, benzindolyl, imidazolyl, benzimidazolyl, quinolyl, pyranyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzopyranyl, benzopyrazinyl, benzopyrimidinyl, benzopyrazinyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, pyrimidotriazolyl;
III.R1and R2Are identical or different and represent halogen, cyano, nitro, C1-C12Alkyl radical, C1-C12Alkoxy radical, C1-C12Alkylcarbonyl or C1-C12An alkylsulfonyl group;
IV.R3represents hydrogen, halogen, cyano, nitro, C1-C12Alkyl or C1-C12An alkoxy group;
v.n represents an integer of 0, 1,2 or 3; and is
1) As defined in I, II, III or IV, R, Ar, R1、R2And/or R3Wherein the hydrogen atom is unsubstituted; or 2) the meanings as defined in I, II, III or IV, R, Ar, R1、R2And/or R3Wherein the hydrogen atoms may be partially or wholly substituted by the same or different substituents selected from the group consisting of: halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Halogenated alkoxy、C1-C6Alkylthio radical, C1-C6Alkylsulfonyl radical, C1-C6Alkylsulfinyl radical, C1-C6Alkylamino radical, C2-C6Alkenyl radical, C2-C6Alkenyloxy radical, C2-C6Alkenylthio radical, C2-C6Alkenylamino radical, C2-C6Alkynyl, C2-C6Alkynyl oxy, C2-C6Alkynyl thio group, C2-C6Alkynyl amino group, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylthio radical, C3-C8Cycloalkylamino, phenyl, halogen, C1-C6Alkyl and/or C1-C6Phenyl substituted by alkoxy, phenoxy, by halogen, C1-C6Alkyl and/or C1-C6Alkoxy-substituted phenoxy.
Further preferred compounds of the invention are: in formula (I):
I.R represents C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C3-C8Heterocycloalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenyloxy radical, C3-C6Alkynyloxy, C3-C8Cycloalkyl oxy, C3-C8Heterocycloalkyloxy, phenyl, pyrazolyl or pyridyl;
ar represents phenyl, pyrazolyl or pyridyl;
III.R1and R2Are identical or different and represent halogen, cyano, nitro, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Alkylcarbonyl or C1-C6An alkylsulfonyl group;
IV.R3represents hydrogen, halogen, cyano, nitro, C1-C6Alkyl or C1-C6An alkoxy group;
v.n represents an integer of 0, 1,2 or 3; and is
1) As defined in I, II, III or IV, R, Ar, R1、R2And/or R3Wherein the hydrogen atom is unsubstituted; or 2) the meanings as defined in I, II, III or IV, R, Ar, R1、R2And/or R3Wherein the hydrogen atoms may be partially or wholly substituted by the same or different substituents selected from the group consisting of: halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkylthio radical, C1-C6Alkylamino radical, C2-C6Alkenyl radical, C2-C6Alkenyloxy radical, C2-C6Alkenylthio radical, C2-C6Alkenylamino radical, C2-C6Alkynyl, C2-C6Alkynyl oxy, C2-C6Alkynyl thio group, C2-C6Alkynyl amino group, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylthio radical, C3-C8Cycloalkylamino, phenyl, substituted by halogen and/or C1-C6Alkyl-substituted phenyl.
Particularly preferred compounds of the invention are: in formula (I):
I.R represents C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C3-C8Heterocycloalkyl radical, C1-C6Alkoxy radical, C2-C6Alkenyloxy radical, C3-C6Alkynyloxy, C3-C8Cycloalkyl oxy, C3-C8Heterocycloalkyloxy, phenyl, pyrazolyl or pyridyl;
ar represents phenyl, pyrazolyl or pyridyl;
III.R1and R2Are the same or different and are substitutedEpihalogen, cyano, nitro, C1-C6Alkyl radical, C1-C6An alkoxy group;
IV.R3represents hydrogen, halogen, cyano, nitro, C1-C6Alkyl or C1-C6An alkoxy group;
v.n represents an integer of 0, 1,2 or 3; and is
1) As defined in I, II, III or IV, R, Ar, R1、R2And/or R3Wherein the hydrogen atom is unsubstituted; or 2) the meanings as defined in I, II, III or IV, R, Ar, R1、R2And/or R3Wherein the hydrogen atoms may be partially or wholly substituted by the same or different substituents selected from the group consisting of: halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, phenyl, substituted halogen and/or C1-C6Alkyl-substituted phenyl.
Particularly preferred compounds of formula (I) according to the invention are the following compounds:
N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -1, 3-dimethylpyrazole-5-carboxamide (01);
N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -1, 3-dimethylpyrazole-5-carboxamide (02);
N-isobutyryl-N- (2, 6-dichloro-4-cyanophenyl) -1, 3-dimethylpyrazole-5-carboxamide (04);
N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -1-methyl-3-ethylpyrazole-5-carboxamide (07);
N-propionyl-N- (2, 6-dichloro-4-trifluoromethylphenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide (09);
N-butyryl-N- (2, 6-dimethyl-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide (10);
N-butyryl-N- (2-chloro-6-bromo-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide (11);
N-butyryl-N- (2, 6-dichloro-4-cyanophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide (12).
N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide (16);
N-isobutyryl-N- (2, 6-dimethyl-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide (17);
N-isobutyryl-N- (2, 6-dichloro-4-trifluoromethylphenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide (19);
N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -1- (3-chloropyridin-2-yl) -3-bromopyrazole-5-carboxamide (20);
N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -1,4, 5-trimethylpyrazole-3-carboxamide (23);
N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -1,4, 5-trimethylpyrazole-3-carboxamide (24);
N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -1, 3-dimethylpyrazole-4-carboxamide (25);
N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -1, 3-dimethylpyrazole-4-carboxamide (26);
N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -3-pyridinecarboxamide (29);
N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -2-chloropyridine-3-carboxamide (31);
N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -2-chloropyridine-3-carboxamide (32);
N-butyryl-N- (2, 6-dibromo-4-cyanophenyl) -2-chloropyridine-3-carboxamide (33);
N-butyryl-N- (2, 6-dichloro-4-cyanophenyl) -2-chloropyridine-3-carboxamide (34);
N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -2, 6-dichloropyridine-3-carboxamide (35);
N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -2, 6-dichloropyridine-3-carboxamide (36);
N-butyryl-N- (2, 6-dibromo-4-cyanophenyl) -2, 6-dichloropyridine-3-carboxamide (37);
N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -2-trifluoromethylbenzamide (39);
N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -2-trifluoromethylbenzamide (40).
The compounds of the present invention may exist in the form of one or more isomers. Isomers include enantiomers, diastereomers, geometric isomers and cis-trans isomers. The compounds of formula (I) according to the invention, in which the carbon-carbon double bonds are linked to different substituents, may form geometrical isomers (different configurations in Z and E, respectively), and the invention includes both the Z and E isomers and mixtures thereof in any proportion. The compound shown in the formula (I) forms stereoisomers (R and S respectively represent different configurations) due to the fact that four different substituents are connected to one carbon atom of the compound, and the compound comprises an R-type isomer, an S-type isomer and a mixture of the R-type isomer and the S-type isomer in any proportion. The invention relates to a compound shown in formula (I), wherein a cycloalkyl or a heterocycloalkyl is connected with more than 2 substituents to form cis-trans isomers (cis and trans represent different configurations respectively), and the invention comprises cis isomers and trans isomers and mixtures thereof in any proportion.
The invention also relates to a composition for controlling pests and harmful bacteria, comprising a biologically effective amount of a compound of formula (I) and at least one further diluent selected from the group consisting of surfactants, solid diluents and liquid diluents.
The invention also relates to a composition for controlling pests and harmful bacteria, comprising a biologically effective amount of a compound of formula (I) and an effective amount of at least one further biologically active compound or agent.
The invention also relates to a method for controlling pests, harmful bacteria, which comprises contacting the pests, harmful bacteria or their environment with a biologically effective amount of a compound of formula (I). Also disclosed is a method for controlling pests or harmful bacteria by contacting the pests or harmful bacteria or their environment with a biologically effective amount of a compound of formula (I) or a mixture containing a compound of formula (I) and a biologically effective amount of at least one additional compound or agent.
The compounds of formula (I) of the present invention have a broad spectrum of activity: some compounds can be used for preventing and controlling harmful germs and pests; and some compounds have high biological activity to some target harmful germs, so that good effect can be obtained under low dosage.
Preferred compositions of the invention are those containing the preferred compounds described above. Preferred methods are those using the preferred compounds described above.
The invention is further illustrated, but not limited, by the following list of some compounds of formula (I) in Table 1. The melting points given in the present invention are not corrected, some of the viscous solids solidify into non-viscous solids after being placed in the compound of formula (I) synthesized by the present invention, and some of the viscous liquids solidify after being placed in the compound of formula (I) synthesized by the present invention, and all the compounds in Table 1 have their molecular ion peaks observed in LC-MS (APCI, Pos) (Agilent 1100Series LC/MSD). Of the compounds in Table 11H NMR (Varian INOVA-300spectrometer) with Tetramethylsilane (TMS) as internal standard, deuterated chloroform (CDCl)3) Or deuterated dimethyl sulfoxide (DMSO) as a solvent.
Table 1:
TABLE 2
The compound represented by formula (I) of the present invention can be obtained by reaction formula 1 or reaction formula 2 shown below; the (II), (III) or (V) in the reaction formula 1 or the reaction formula 2 can be synthesized by purchasing or referring to relevant documents; in the reaction scheme, L represents chlorine, bromine, iodine, sulfonate, hydroxyl, etc., and other substituents are as defined above unless otherwise specified.
Reaction formula 1:
reaction formula 2:
the compound of formula (I) may be prepared by (reaction formula 1): reacting the compound of formula (II) with the compound of formula (III) in a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N-Dimethylformamide (DMF), tetrahydrofuran, acetonitrile or dioxane, etc., at a temperature of 0 ℃ to the reflux temperature of the system in the presence of a suitable base such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate, etc., to obtain a compound of formula (IV); reacting the compound of formula (IV) with the compound of formula (V) in a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N-Dimethylformamide (DMF), tetrahydrofuran, acetonitrile or dioxane, etc., at a temperature of 0 ℃ to the reflux temperature of the system in the presence of a suitable base such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate, etc., to obtain the compound of formula (I).
The compounds of formula (I) may also be prepared by (equation 2): reacting a compound of formula (II) with a compound of formula (V) in a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N-Dimethylformamide (DMF), tetrahydrofuran, acetonitrile or dioxane, etc., at a temperature of 0 ℃ to the reflux temperature of the system, in the presence of a suitable base such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate, etc., to obtain a compound of formula (VI); reacting the compound of formula (VI) with the compound of formula (III) in a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N-Dimethylformamide (DMF), tetrahydrofuran, acetonitrile or dioxane, etc., at a temperature of 0 ℃ to the reflux temperature of the system, in the presence of a suitable base such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate, etc., to obtain the compound of formula (I).
The compounds of formula (II), formula (III) and formula (V) may be prepared by purchase or by reference to conventional synthetic methods or related references.
Specific synthetic methods are set forth in more detail in the examples below.
The compound of formula (I) provided by the invention has broad-spectrum bioactivity at the dosage of 15-2250 g of active ingredient per hectare, and can be used for preventing and treating harmful bacteria and harmful insects. Some compounds have good prevention and treatment effects on harmful insects or germs, and can obtain good effects at very low dosage.
The compound of formula (I) provided by the invention has bioactivity, and the compound has good bioactivity, and particularly shows activity in the aspects of preventing and controlling agricultural, horticultural, flower and sanitary pests and harmful bacteria. Pests as used herein include, but are not limited to:
harmful pathogenic bacteria: phytophthora species, erysiphe species, gibberella species, venturia species, sclerotinia species, rhizoctonia species, botrytis species, pyricularia species, fusarium species. Such as rice blast (pyricularia oryzae); wheat stripe rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust diseases; barley stripe rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust; barley and wheat powdery mildew (Erysiphe graminis), cucumber powdery mildew (Sphaerotheca fuligena), apple powdery mildew (podosphaea leucotricha) and grape powdery mildew (podosphaea leucotricha); sheath and glume blight of wheat (Septoria nodorum). Helminthosporium, Mortierella, Sclerotiella, Pseudocercospora herpotrichoides, and wheat take-all (Gaeumannomyces graminis) on cereals. Cercospora arachidicola (Cercospora arachidicola) and Cercospora black spot (Cercospora personata); apple ring rot pathogen (Botryosphaeria berenggiana f.sp. piricola), apple rot pathogen (cytopora sp.); urospora disease on beet, soybean and rice. Tomato, cucumber, grape gray mold (Botrytis cinerea). Geobacillus disease in vegetables (e.g., cucumber). Anthracnose in cucumber, apple scab, cucumber downy mildew, grape downy mildew, blight in potato and tomato, the monad Thanatephorus cupmeris on rice and other rhizoctonia species on other hosts such as wheat and barley, vegetables; sclerotinia sclerotiorum (sclerotiorum); wheat scab (gibberella zeae); phytophthora capsici (Phytophythora capsicii).
Harmful insects: lepidopteran pests such as oriental armyworm, prodenia litura, diamond back moth, beet armyworm, cabbage looper, orthopteran such as blattaria, thysanoptera such as cotton thrips, rice thrips, melon thrips, homopteran such as leafhopper, plant hopper, aphid, hymenopteran such as leaf bee larva, dipteran such as aedes, culex, fly; acarina pest mites such as Panonychus citri, Tetranychus gossypii, Tetranychus urticae, etc.
The compounds of formula (I) of the present invention are effective against pests, harmful bacteria, alone, and they may also be used together with other biochemical substances including other insecticides, nematocides, acaricides and bactericides.
The agricultural preparation using the compound of formula (I) provided by the invention as an effective ingredient can be made into any desired dosage forms such as dry compressed particles, flowable compositions, granules, wettable powders, water dispersible granules, emulsifiable concentrates, powders, powdery concentrates, microemulsions, suspensions, emulsifiable concentrates, aqueous emulsions, soluble liquid agents, aqueous solutions, dispersible liquid agents, and suitable auxiliaries including carriers (diluents) and other adjuvants such as spreaders, emulsifiers, wetting agents, dispersants, stickers and decomposers. These formulations comprise the compounds of the present invention in admixture with an inert, pharmacologically acceptable solid or liquid diluent.
Examples of the compositions of the present invention may also be formulated into any desired dosage form such as dry compressed granules, flowable compositions, granules, wettable powders, water dispersible granules, emulsifiable concentrates, dusts, powdered concentrates, microemulsions, suspensions, emulsifiable concentrates, emulsions in water, soluble liquids, mists, dispersible liquids, suitable adjuvants including carriers (diluents) and other adjuvants such as spreaders, emulsifiers, wetting agents, dispersants, stickers and disintegrants. These formulations comprise the compounds of the present invention in admixture with an inert, pharmacologically acceptable solid or liquid diluent.
The present invention is further illustrated by the following examples, wherein the yields are not optimized, and other compounds of the present invention can be prepared by reference to the following examples and related references.
Detailed Description
Example 1 this example illustrates the preparation of compound 10 of table 1 (method one)
1-methyl-3-ethyl-4-chloropyrazole-5-formyl chloride 1-methyl-3-ethyl-4-chloropyrazole-5-formic acid (100mmol), thionyl chloride (150mmol) and 1, 2-dichloroethane (100mL) are reacted at 35 ℃ to the system reflux temperature for 3-5hr, and the solvent is removed to obtain 15.8g of the title compound.
The mixture of N- (2, 6-dimethyl-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-formamide 2, 6-dimethyl-4-nitroaniline (50mmol), 1-methyl-3-ethyl-4-chloropyrazole-5-formyl chloride (50mmol) and triethylamine (65mmol) in tetrahydrofuran (40mL) is reacted for 2-6h at 10-60 ℃ until the reaction is completed, the reaction mixture is poured into ice water, extracted by ethyl acetate, washed by an organic layer, dried by anhydrous sodium sulfate, subjected to solvent removal, and purified by column chromatography or recrystallization to obtain the title product, namely 12.1g of light yellow solid with the purity of 96.5%. .
A mixture of N-butyryl-N- (2, 6-dimethyl-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide (25mmol), butyryl chloride (25mmol) and sodium hydride (60%, 25mmol) in tetrahydrofuran (40mL) was stirred at 25-60 ℃ for 2-6h to completion. The reaction mixture was poured into ice water, extracted with ethyl acetate, the organic layer washed with water, dried over anhydrous sodium sulfate, the solvent removed, and the crude product was purified by column chromatography or recrystallization to give the title compound as a pale yellow solid 6.6g, 98.1% pure.
Example 2 this example illustrates the preparation of compound 10 in Table 1 (method two)
The method comprises the following steps of reacting N- (2, 6-dimethyl-4-nitrophenyl) butanamide 2, 6-dimethyl-4-nitroaniline (100mmol), butyric acid (50mmol), phosphorus oxychloride (100mmol) and acetonitrile (100mL) at the temperature of 35 ℃ to the system reflux temperature for 2-6h until the reaction is complete, pouring a reaction mixture into ice water, separating out a solid, filtering the obtained solid, washing with water, and drying to obtain 7.2g of a title compound white solid.
A mixture of N-butyryl-N- (2, 6-dimethyl-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide N- (2, 6-dimethyl-4-nitrophenyl) butanamide (25mmol), 1-methyl-3-ethyl-4-chloropyrazole-5-carbonyl chloride (25mmol) and sodium hydride (60%, 25mmol) in tetrahydrofuran (40mL) was stirred at 20-60 ℃ until the reaction was complete. The reaction mixture was poured into ice water, extracted with ethyl acetate, the organic layer washed with water, dried over anhydrous sodium sulfate, freed of solvent, and purified by column chromatography or recrystallization to give the title compound as a pale yellow solid 5.8g, 98.0% pure.
Other compounds of the present invention can be synthesized by referring to example 1 or example 2, and if necessary, referred to the relevant literature.
EXAMPLE 3 preparation of N-butyryl-N- (2, 6-dimethyl-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide (10) 10% tall oil
Weighing a proper amount (10% by weight) of the compound of formula (I) provided by the invention, such as the compound 10 in Table 1, a proper amount of cosolvent (such as ethyl acetate or acetone), a proper amount of pesticide auxiliary agent, a solvent (such as toluene and dimethyl) and the like, putting into a reaction kettle, firstly adding a certain amount of solvent (such as toluene) and defoamer, stirring for 10-30 min, then adding a proper amount of stabilizer, synergist, penetrating agent and the like, continuously stirring for 10-30 min, adjusting the pH value, then putting an effective amount of solvent into the kettle, uniformly stirring, and then discharging to obtain the N-butyryl-N- (2, 6-dimethyl-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-formamide (10) 10% emulsifiable solution.
Bioassay examples
The compounds of the present invention were tested for bactericidal and insecticidal activity, and some of the results are shown below.
Example 4 evaluation of insecticidal Activity against aphid (Aphis fabae)
In order to evaluate the activity of the compound on homoptera pests, aphids are selected as targets, and the activity of the compound on the aphids is measured by an immersion method.
The dipping method comprises the following steps: the test compound is dissolved in a suitable solvent such as N, N-Dimethylformamide (DMF), diluted to the desired concentration with clear water containing 0.2% Tween80 emulsifier, and treated 3 times with a blank containing no test compound as a control. The broad bean aphids are inoculated on the just-emerged bean seedlings, each plant is inoculated with more than 20 heads, then the bean seedlings and the test insects are immersed in the liquid medicine of the formula (I) provided by the invention, the bean seedlings and the test insects are taken out after 5 seconds, the redundant liquid medicine is absorbed, the bean seedlings are inserted into absorbent sponge and covered by a glass tube, the number of the living and dead insects is checked after 24 hours, and the result is averaged. The activity (mortality) is divided into A, B, C, D grades by percentage relative to a blank control, wherein the mortality (%) of more than or equal to 100 is A grade, the mortality (%) of more than 90 is B grade, the mortality (%) of more than 70 is C grade, and the mortality (%) of more than 50 is D grade. The results show that the compounds of the invention are active against aphids, and that some compounds are still active at lower concentrations, some of which are listed below:
at the concentration of 500mg/L, the compounds 10, 29 and the like of the invention have A-level activity on aphids; 16. 19, 31 and the like have B-level activity on aphids; 04. 09, 11, 25, 26, 34, 37, etc. have class C activity on aphids;
at the concentration of 50mg/L, the compound 10 (78.39%) and the like have B-level activity on aphids;
at a concentration of 12.5mg/L, compound 10 (65.94%) and the like of the invention have class C activity on aphids.
Example 5 evaluation of biological Activity of armyworm (Mythimna separata)
Potter spray method: weighing a proper amount of the compound of the invention, dissolving the compound in N, N-dimethylformamide, adding a small amount of Tween80 emulsifier, uniformly stirring, adding a certain amount of clear water to prepare the required concentration, and taking the clear water as a reference. Fresh and tender corn leaves are cut into segments with basically consistent sizes and placed into a culture dish (phi 90mm) in which filter paper is placed in advance. Then 10 heads of mythimna separata larvae of 3 years old are inoculated into the dish, the dish is put under a Potter spray tower for quantitative spraying, the amount of the sprayed liquid medicine is 1ml, and the spraying is repeated for 3 times per concentration. After the treatment, the dish cover is covered, the dish cover is placed in a recovery room for culture, the culture is regularly observed, the death condition of the test insects is checked and recorded after 72 hours, the death rate (%) is calculated, and the results are averaged. The activity is divided into A, B, C, D grades in percentage relative to a blank control, wherein the mortality rate ((%) is more than 100 and more than 90) is A grade, and 90>The mortality rate (%) is more than or equal to 70 and is B grade, 70>The death rate (%) is more than or equal to 50 and is grade C, 50>The mortality rate (%) is more than or equal to 0 and is D grade. The results show that the compounds 16 and 20 and the like of the invention have more than 80 percent of B-grade activity on armyworms.
Example 6 controlling Effect on Rice sheath blight disease (Rhizoctonia solani)
Dissolving the compound to be tested in a suitable solvent such as N, N-Dimethylformamide (DMF), diluting with sterile water containing 0.2% Tween80 emulsifier to desired concentration, setting blank containing no compound to be tested as control, and repeating the treatment for 4 times; transferring the rhizoctonia solani pathogenic bacteria to a PDA flat plate for activation culture, transferring the rhizoctonia solani pathogenic bacteria to a PD culture medium, and performing constant-temperature water bath culture for 4 days; crushing the cultured mycelium pellets by using a homogenizer and blending the crushed mycelium pellets into bacterial suspension with a certain concentration by using clear water; spraying the liquid medicine of the compound to be detected when the cucumber grows to flatten two true leaves, spraying bacterial suspension to the surfaces of the seedlings after 1 day, carrying out moisturizing culture and observing the disease occurrence condition of the seedlings, starting recording the disease occurrence condition of each treatment when the disease occurrence condition of the control treatment is obvious, and calculating the disease index and the medicament control effect. The results show that the compound has good control effect on rice sheath blight disease. At a concentration of 500mg/L, the compounds 09, 39 and the like have a control effect on rice sheath blight disease of more than 90%; 07. 17, 19, 31, 33 and the like have 70-90% of control effect on rice sheath blight disease.
Example 7 controlling Effect on corn Rust (Puccinia Polysora)
The method comprises the following steps: dissolving the compound to be tested in a suitable solvent such as N, N-Dimethylformamide (DMF), diluting with sterile water containing 0.2% Tween80 emulsifier to desired concentration, setting blank containing no compound to be tested as control, and repeating the treatment for 4 times; cutting corn leaf, washing spore with 0.05-0.2% Tween80 or other appropriate surfactant water solution, and filtering with 2-4 layers of gauze to obtain 1 × 105spore/mL of suspension; spraying the liquid medicine of the compound to be detected when the corn grows to 2 leaves and 1 heart stage, spraying and inoculating the spore suspension after 1 day, transferring to a moisturizing cabinet (the relative humidity is more than 95 percent, the temperature is 20-22 ℃), and culturing for 15-24 hours under the low light condition (the illumination intensity is 5000-10000 Lux); and when the blank control disease leaf rate reaches more than 50%, investigating the disease condition of each treatment, and calculating the disease index and the medicament control effect. The result shows that the compound has a control effect on the corn rust. At a concentration of 500mg/L, the compounds 24, 29, 32 and the like of the invention have a control effect on corn rust of more than 70%.
EXAMPLE 8 fungicidal Activity against Erisiphe grimminis (Erisiphe grimminis) (potting method)
The method comprises the following steps: dissolving the compound to be tested in a suitable solvent such as N, N-Dimethylformamide (DMF), and diluting with sterile water containing 0.2% Tween80 emulsifier to desired concentration; taking pots with straight stems of about 15cm, sowing 20 plump and robust seeds of wheat in each pot, and supplying the seeds for testing after first true leaves grow out; and (3) spraying the prepared wheat seedling plants with a medicament with a certain concentration, and inoculating germs after one day. Repeating the treatment for 3 times, and setting a blank without the compound to be detected as a blank control; after the blank control disease is carried out after the culture with moisture preservation and proper temperature, the area of the disease spot is checked, and the disease index and the medicament control effect are calculated. The results show that the compound has good control effect on wheat powdery mildew. At a concentration of 500mg/L, the compounds 12, 19, 31 and the like have a control effect on wheat powdery mildew of more than 90%; 01. 02, 09, 23, 32, 35, 36, 40 and the like have the prevention and treatment effect of more than 70 percent on wheat powdery mildew.
Claims (6)
- An N-2, 4-substituted phenyl bisamide compound, characterized in that the N-2, 4-substituted phenyl bisamide compound represented by the general formula (I) is the following compound:
N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -1, 3-dimethylpyrazole-5-carboxamide;N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -1, 3-dimethylpyrazole-5-carboxamide;N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -1-methyl-3-ethylpyrazole-5-carboxamide;N-butyryl-N- (2, 6-dimethyl-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide;N-butyryl-N- (2-chloro-6-bromo-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide;N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide;N-isobutyryl-N- (2, 6-dimethyl-4-nitrophenyl) -1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide;N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -1,4, 5-trimethylpyrazole-3-carboxamide;N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -1,4, 5-trimethylpyrazole-3-carboxamide;N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -1, 3-dimethylpyrazole-4-carboxamide;N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -1, 3-dimethylpyrazole-4-carboxamide;N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -3-pyridinecarboxamide;N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -2-chloropyridine-3-carboxamide;N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -2-chloropyridine-3-carboxamide;N-butyryl-N- (2, 6-dichloro-4-nitrophenyl) -2, 6-dichloropyridine-3-carboxamide;N-isobutyryl-N- (2, 6-dichloro-4-nitrophenyl) -2, 6-dichloropyridine-3-carboxamide. - 2. The process for producing an N-2, 4-substituted phenylbisamide compound according to claim 1, wherein the compound represented by the formula (I) is produced by the reaction shown below,reaction formula 1:
reaction formula 2:
the compounds of formula (I) may be prepared by: reacting the compound of the formula (II) with the compound of the formula (III) in a solvent such as dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, tetrahydrofuran, acetonitrile or dioxane at a temperature of 0-system reflux temperature in the presence of bases such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate to obtain the compound of the formula (IV); reacting the compound of formula (IV) with the compound of formula (V) in a solvent such as dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, tetrahydrofuran, acetonitrile or dioxane at a temperature of 0 ℃ to system reflux temperature in the presence of a base such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate to obtain the compound of formula (I);the compounds of formula (I) may also be prepared by: reacting the compound of formula (II) with the compound of formula (V) in a solvent such as dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, tetrahydrofuran, acetonitrile or dioxane at a temperature of 0 ℃ to system reflux temperature in the presence of bases such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate to obtain the compound of formula (VI); reacting the compound of formula (VI) with the compound of formula (III) in a solvent such as dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, tetrahydrofuran, acetonitrile or dioxane at a temperature of 0-system reflux temperature in the presence of a base such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate to obtain the compound of formula (I);the compounds of formula (II), formula (III) and formula (V) may be prepared by purchase or by reference to conventional synthetic methods or related references;in the formula, R, Ar and R1、R2、R3And n has the meaning given in claim 1, L is a leaving group chlorine, bromine, iodine, sulfonate, hydroxy. - 3. The use of N-2, 4-substituted phenylbisamides according to claim 1, characterized by insecticidal and/or fungicidal biological activity at a dose of 15-5000 g active ingredient/ha.
- 4. Use of N-2, 4-substituted phenylbisamides according to claim 1 for producing medicaments with insecticidal and/or fungicidal activity.
- 5. An insecticidal and/or fungicidal composition, characterized in that: contains the N-2, 4-substituted phenyl bisamide compound as the active component according to claim 1, wherein the weight percentage of the active component in the composition is 0.5-99%.
- 6. A method of controlling pests or pathogens, characterized by: applying an effective amount of the N-2, 4-substituted phenylbisamide compound of claim 1 to the pest, pathogen, or growth medium thereof.
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