CN117567417A - Preparation and application of benzamide compounds - Google Patents

Preparation and application of benzamide compounds Download PDF

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Publication number
CN117567417A
CN117567417A CN202311536659.4A CN202311536659A CN117567417A CN 117567417 A CN117567417 A CN 117567417A CN 202311536659 A CN202311536659 A CN 202311536659A CN 117567417 A CN117567417 A CN 117567417A
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formula
preparation
acid
compound
reacting
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张炜
翟晓露
刘柯
孙家隆
顾松东
魏泽慧
赵焱
李军
李宁
曲波
胡俊峰
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Shandong Luba Chemical Co ltd
Qingdao Agricultural University
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Shandong Luba Chemical Co ltd
Qingdao Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/58—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring 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 atoms of the carbocyclic ring
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

The invention discloses a group of benzamide compounds, a preparation method of the benzamide compounds and application of the benzamide compounds in preparing pesticides for preventing and controlling agricultural pests. When the benzamide compound with the structure is used as an insecticide, the benzamide compound has the advantages of being green and good in environmental compatibility; can be used for preventing and controlling pests such as agriculture, forestry and the like, has the advantages of broad spectrum, high efficiency, low toxicity and the like, can also be applied to pests generating drug resistance, has good effect on preventing and controlling lepidoptera pests such as cotton bollworms, corn borers, plutella xylostella, asparagus caterpillar and the like and pest mites such as tetranychus cinnabarinus and tetranychus urticae, is far higher than the related chemicals of piperine in the prior art, and has good application prospect.

Description

Preparation and application of benzamide compounds
Technical Field
The invention belongs to the field of pesticides, and particularly relates to preparation and application of a group of benzamide compounds.
Background
Piperine (Piperine), also known as piperamide, is a broad spectrum anticonvulsant. Can be used for agricultural production and can be used as pesticide.
Piperine is present in peppers (Piper nigrum l.) and requires a large amount of peppers for extraction, which is costly. If the preparation and production process by industrial production are complex. When piperine is used as an insecticide for agricultural production, the following three problems mainly exist: firstly, the cost is high in general no matter through pepper extraction or chemical production; moreover, the pest control effect is poor, and the expected ideal result is not achieved; thirdly, when piperine is applied to field pest control, the chemical stability is poor.
Conjugated double bonds exist in the alkaline chemical structure of pepper, and the following chemical changes easily occur due to the effect of light when applied in a field in agricultural production.
Piperine belongs to an excellent medical and pesticide lead compound, and is widely reported in the research and development of medical application at present, but the variety of pesticides created by taking piperine as a lead is not reported. Therefore, piperine is used as a lead compound, and the novel environment-friendly amide pesticide variety with novel structure and good environment compatibility is created, so that the novel environment-friendly amide pesticide variety has strong academic value and social value.
Disclosure of Invention
The invention aims to adapt to the current green pesticide development strategy, and provides a group of benzamide compounds, and a preparation method and application thereof. The invention takes the structure of pepper and the like as the guide, breaks through the traditional limitation according to the design and optimization principle of pesticide molecules, carries out skeleton innovation, preferably provides a group of benzamide compounds with stable structural performance, lays a foundation for preparing novel, broad-spectrum and efficient agricultural pest control agents, especially for cotton bollworms (H.armigera), corn borers (P.nubillia), plutella xylostella (Plutella xylostella), asparagus caterpillar (Spodoptera exigua), tetranychus cinnabarinus (Tetranychus viennensis Zacher), tetranychus urticae (Tetranychus urticaeKoch) and the like.
According to the pesticide molecular design and optimization principle, the inventor designs and synthesizes a group of benzamide compounds, and the design thinking is as follows:
a group of benzamide compounds as described above, which may be ortho-substituted benzamide compounds, meta-or para-substituted benzamide compounds, and R 1 Selected from the group consisting ofOr alternativelyThe R is 2 Selected from->Or->The R is 3 Selected from->Or->The R is 4 Selected from->Or->
The unique innovation of the design of the invention is that: introduction of coumarin derivatives with piperine lead compounds
Sulfonylamine->And cyanoamine->Pyrimidine derivatives (/ -as pesticide molecular structural fragments)>Or->) Is linked with benzene ring and cyclopropyl +.>And isopropyl->The novel benzamide compound is applied to the innovative design of the pesticide molecular structure, and the novel benzamide compound with novel chemical structure and stable optics is obtained as shown in the formulas (1), (2), (3) and (4). According to national pesticide activity bioassay specifications, the insecticidal activity of the benzamide compound prepared by the invention is preliminarily measured, and test data show that: the novel benzamide compound with the unique structure, which is designed by the invention, shows the unexpected insecticidal effect of the person skilled in the art and has commercial value. The original compound of the preliminary test has stable photochemical property, and the insecticidal activity is superior to that of the lead compound piperine in the aspect of preventing and controlling agricultural insect pests, and the result is far beyond the expectation of the person skilled in the art.
The group of benzamide compounds of the present invention is further preferably selected from any one of the following tables.
TABLE 1 preferred benzamide compounds
Based on the same inventive concept, the invention also provides a group of preparation methods of benzamide compounds, wherein the formula (1) comprises the following steps:
wherein the R is 2 Selected from the group consisting ofOr->The R is 3 Selected from->Or->The R is 4 Selected from->Or->
(1) Taking a certain amount ofIn a selected solvent with an appropriate amount of SOCl 2 Reacting to obtain the corresponding benzoyl chloride derivative, and then reacting with the corresponding +.>Reacting to obtain->
In saturated NaHCO 3 Hydrolyzing in water to obtain->
(2) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,and->Reacting to obtain->
(3) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,and->Reacting to obtain the formula (1).
Based on the same inventive concept, the invention also provides a group of preparation methods of benzamide compounds, wherein the formula (2) comprises the following steps:
wherein the R is 2 Selected from the group consisting ofOr->The R is 4 Selected from->Or alternatively
(1) Taking a certain amount of methylbenzoic acid, and reacting with N-bromosuccinimide in a selected solvent under the protection of nitrogen to prepare bromomethylbenzoic acid; the obtained bromomethylbenzoic acid and a proper amount of SOCl 2 Reacting to obtain corresponding bromomethyl benzoyl chloride derivative, and then reacting with corresponding bromomethyl benzoyl chloride derivativeReacting to obtain->
(2) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,and->Reacting to obtain the formula (2).
Based on the same inventive concept, the invention also provides a group of preparation methods of benzamide compounds, wherein the formula (3) comprises the following steps:
wherein the R is 1 Selected from the group consisting ofOr->The R is 2 Selected from->Or->The R is 4 Selected from->Or->
(1) In a selected solvent, with Na 2 CO 3 As acid binding agent, hydroxylamine hydrochloride andcondensation reaction to obtain
(2) In a selected solvent, naH is used as an acid binding agent,intermediate in the preparation process of the formula (2)Reacting to obtain the formula (3).
Based on the same inventive concept, the invention also provides a group of preparation methods of benzamide compounds, wherein the formula (4) comprises the following steps:
the R is 1 Selected from the group consisting ofOr->The R is 2 Selected from->Or->The R is 3 Selected from->Or->The R is 4 Selected from->Or->
(1) In a selected solvent, K 2 CO 3 As acid binding agent, intermediate in the preparation process of formula (1)And->Reaction to obtain->
(2) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,intermediate in the preparation of formula (3)>Reacting to obtain the formula (4).
Based on the same inventive concept, the present invention also provides a group of pesticides comprising a group of benzamide compounds represented by the structures of formula (1), formula (2), formula (3) and formula (4):
wherein the R is 1 Selected from the group consisting ofOr->The R is 2 Selected from->Or->The R is 3 Selected from->Or->The R is 4 Selected from->Or->
The pesticide is prepared from suspending agent, emulsifiable concentrate, wettable powder, water dispersible granule, microemulsion or emulsion in water.
The group of pesticides as described above, the group of pesticides and bactericides further comprises auxiliary materials acceptable in pesticide preparation.
The group of pesticides as described above, wherein the weight of the benzamide compound represented by the structures of the formula (1), the formula (2), the formula (3) and the formula (4) is 0.1% -99.9% of the total weight of the pesticide.
Based on the same inventive concept, the invention also provides application of the group of pesticides in preparing pesticides for controlling agricultural pests. Preferably, the controlling agricultural pests is controlling lepidopteran pests. More preferably, the agricultural pest control is control of lepidoptera pests such as cotton bollworms, corn borers, plutella xylostellas, asparagus caterpillars and the like, and spider mites such as tetranychus cinnabarinus and tetranychus urticae.
Compared with the prior art, the invention has the beneficial effects that:
1. the benzamide compounds with the structures of the formula (1), the formula (2), the formula (3) and the formula (4) have less three wastes generated in the preparation process, are easy to process, and have the advantages of being green and environment-friendly when used as pesticides in pesticide production.
2. The benzamide compounds with the structures of the formula (1), the formula (2), the formula (3) and the formula (4) and the insecticide prepared by the benzamide compounds can be used for controlling pests such as agriculture or forestry, have the advantages of broad spectrum, high efficiency, low toxicity and the like, can also be applied to pests with drug resistance, have good effects in controlling lepidoptera pests such as cotton bollworms, corn borers, plutella xylostella, asparagus caterpillar and the like and pest mites such as tetranychus cinnabarinus and tetranychus urticae, are far higher than piperine and related active agricultural insecticidal compounds thereof in the prior art, and have good application prospects, so the benzamide compounds can be used alone as active ingredients in the pest control process without being compounded with other insecticides.
3. The experiment results prove that the insecticidal activity of the compound prepared by the invention on cotton bollworms, corn borers, plutella xylostella, beet armyworms, tetranychus cinnabarinus and tetranychus urticae is higher than that of the control medicament piperine, and the compound has good commercial development value.
4. The benzamide compounds with the structures of the formula (1), the formula (2), the formula (3) and the formula (4) provided by the invention have the advantages of few preparation steps, simplicity in operation, high yield, capability of saving a large amount of time and cost in actual production and good economic benefit.
Drawings
FIG. 1 is a nuclear magnetic resonance 1H-NMR spectrum of compound 2 provided by the invention;
FIG. 2 is a nuclear magnetic resonance 1H-NMR spectrum of compound 29 provided by the invention;
FIG. 3 is a nuclear magnetic resonance 1H-NMR spectrum of compound 32 provided by the invention;
FIG. 4 is a nuclear magnetic resonance 1H-NMR spectrum of compound 39 according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials, instruments and the like used in the examples described below are commercially available unless otherwise specified.
A group of benzamide compounds having structures represented by formula (1), formula (2), formula (3) and formula (4):
wherein R is 1 、R 2 、R 3 、R 4 And each independently. PreferablyIn the presence of R 1 Selected from the group consisting ofOr->The R is 2 Selected from->Or->The R is 3 Selected from->Or->Said R4 is selected fromOr->
Based on the same inventive concept, the invention also provides a group of preparation methods of the benzamide compound formula (1), which specifically comprise the following steps:
wherein R is 2 、R 3 、R 4 Is within the range of R as described above 2 、R 3 、R 4 The ranges of (a) are the same and are not described in detail herein.
(1) Taking a certain amount ofIn a selected solvent with an appropriate amount of SOCl 2 Reacting to obtain the corresponding benzoyl chloride derivativeThen in the presence of an acid binding agent with the corresponding +.>Reacting to obtain->/>In saturated NaHCO 3 Hydrolyzing in water to obtain->
In the step (1) of the invention, the preparationThe preferred solvent is 1, 2-dichloroethane, the preferred acid-binding agent is triethylamine, < >>And SOCl 2 Preferably 1:3, in the second reaction step
The molar ratio to triethylamine is preferably 1:1.
(2) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,and->Reacting to obtain->In step (2) of the present invention, preparing +.>The preferred solvent is acetonitrile,/->K 2 CO 3 Preferably 1:1:1.
(3) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,and->Reacting to obtain the formula (1). In step (3) of the present invention, the preferred solvent for the preparation of formula (1) is acetonitrile,/-> K 2 CO 3 Preferably 1:1:1.5.
based on the same inventive concept, the invention also provides a group of preparation methods of the benzamide compound formula (2), which specifically comprise the following steps:
wherein R is 2 、R 3 、R 4 Is within the range of R as described above 2 、R 3 、R 4 The ranges of (a) are the same and are not described in detail herein.
(1) Taking a certain amount of methylbenzoic acid, and reacting the methylbenzoic acid with N-bromosuccinimide (NBS) in a selected solvent under the protection of nitrogen and in the presence of an initiator Azodiisobutyronitrile (AIBN) to prepare bromomethylbenzoic acid; the obtained bromomethylbenzoic acid and a proper amount of SOCl 2 Reacting to obtain corresponding bromomethyl benzoyl chloride derivative, and then reacting with corresponding bromomethyl benzoyl chloride derivativeReacting to obtain->In step (1) of the present invention, the preferred solvent for preparing bromomethylbenzoic acid is CCl 4 The molar ratio of methylbenzoic acid, AIBN, NBS is preferably 1:5:1.1; preferred solvents for the preparation of bromomethylbenzoyl chloride are 1, 2-dichloroethane, bromomethylbenzoic acid and SOCl 2 Preferably 1:3, a step of; preparation of->When the preferred acid-binding agent is triethylamine, the molar ratio of bromomethylbenzoyl chloride to triethylamine is preferably 1:1.
(2) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,and->Reacting to obtain the formula (2). In step (2) of the present invention, the preferred solvent for preparing the compound of formula (2) is acetonitrile,/->K 2 CO 3 Preferably 1.2:1:1.1.
based on the same inventive concept, the invention also provides a group of preparation methods of the benzamide compound formula (3), which specifically comprise the following steps:
wherein R is 1 、R 2 、R 4 Is within the range of R as described above 1 、R 2 、R 4 The ranges of (a) are the same and are not described in detail herein.
(1) In a selected solvent, with Na 2 CO 3 As acid binding agent, hydroxylamine hydrochloride andcondensation reaction to obtainIn step (1) of the present invention, preparing +.>The preferred solvent is methanol.
(2) In a selected solvent, naH is used as an acid binding agent,intermediate in the preparation process of the formula (2)Reacting to obtain the formula (3). In step (2) of the present invention, acetonitrile is the preferred solvent for the preparation of formula (3),the molar ratio of NaH is preferably 1.2:1.5:1.4./>
Based on the same inventive concept, the invention also provides a group of preparation methods of the benzamide compound formula (4), which specifically comprise the following steps:
wherein R is 1 、R 2 、R 3 、R 4 Is within the range of R as described above 1 、R 2 、R 3 、R 4 The ranges of (a) are the same and are not described in detail herein.
(1) In a selected solvent, K 2 CO 3 As acid binding agent, intermediate in the preparation process of formula (1)And->Reaction to obtain->In the step (1) of the invention, the preparationThe preferred solvent is acetonitrile,/->K 2 CO 3 Preferably 1:1:1.2.
(2) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,intermediate in the preparation of formula (3)>Reacting to obtain the formula (4). In step (2) of the present invention, acetonitrile is the preferred solvent for the preparation of formula (4),K 2 CO 3 preferably 1.5:1.2:1.5.
based on the same inventive concept, the invention also provides a pesticide, which comprises benzamide compounds shown in the structures of formula (1), formula (2), formula (3) and formula (4):
/>
wherein R is 1 、R 2 、R 3 、R 4 Is within the range of R as described above 1 、R 2 、R 3 、R 4 The ranges of (a) are the same and are not described in detail herein.
The benzamide compounds shown in the structures of the formula (1), the formula (2), the formula (3) and the formula (4) can be used alone or in combination with other pesticide active ingredients as active ingredients in the process of controlling agricultural pests so as to further improve the comprehensive control effect, and the invention is not particularly limited in this respect.
The pesticide is not limited in dosage form, can be prepared into various dosage forms acceptable in agriculture or forestry, and is preferably suspension, emulsifiable concentrate, wettable powder, water dispersible granule, microemulsion or emulsion in water. The weight of the benzamide compound shown in the structures of the formula (1), the formula (2), the formula (3) and the formula (4) accounts for 0.1% -99.9%, preferably 1% -99.9%, more preferably 10% -99.9%, and even more preferably 50% -99.9% of the total weight of the pesticide.
In a specific embodiment of the present invention, when the concentration of the benzamide compounds represented by the structures of the formula (1), the formula (2), the formula (3) and the formula (4) is 100mg/kg, especially, the insecticidal rates of the compound 3, the compound 8 and the compound 26 of the present invention on cotton bollworms, corn borers, plutella xylostella and asparagus caterpillar respectively reach more than 70%, and the insecticidal rates of the compound 12, the compound 18 and the compound 25 of the present invention on cotton bollworms, corn borers, plutella xylostella and asparagus caterpillar respectively reach more than 80%. The compounds 10, 13, 16, 19, 25, 28 and 38 of the invention show unexpected acaricidal activity, and the acaricidal activity on tetranychus cinnabarinus and tetranychus urticae has the acaricidal death rate of more than 90% at the concentration of 100mg/kg. The specific embodiment also shows that the insecticidal activity of the compound prepared by the invention on cotton bollworms, corn borers, plutella xylostellas and asparagus caterpillars and the insecticidal activity on tetranychus cinnabarinus and tetranychus urticae are higher than those of the control medicament at the same application concentration, and the compound has good commercial development value.
An insecticide as described above, further comprising an adjuvant acceptable in pesticide formulation. The person skilled in the art can choose the type of auxiliary materials corresponding to the dosage form according to the dosage form and the conventional auxiliary materials in the art. Adjuvants of the present invention include, but are not limited to, emulsifiers, mineral spirits, dispersants, suspending agents, wetting agents, binders, defoamers, fillers or co-solvents, and the like.
Based on the same inventive concept, the invention also provides application of the pesticide in preparing pesticide for controlling agricultural pests. Preferably, the controlling agricultural pests is controlling lepidopteran pests. Preferably, the agricultural pest control is to control lepidoptera pests such as cotton bollworms, corn borers, plutella xylostellas, asparagus caterpillars and the like, and pest mites such as tetranychus cinnabarinus and tetranychus urticae.
Example 1: preparation of compound 19:
the compound numbered 19 belongs to the type of formula (1) and has the following chemical structure:
1. intermediate productsThe preparation route is as follows:
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(1) Into a 100mL three-necked flask equipped with a stirrer, a reflux condenser, a drying tube and a thermometer, 0.01mol of m-acetylbenzoic acid was added50mL of 1, 2-dichloroethane, 0.03mol of thionyl chloride was added under stirring, the mixture was refluxed, and after the completion of the reaction, the thionyl chloride and the solvent 1, 2-dichloroethane were distilled off under reduced pressure to obtain m-acetyl benzoyl chlorideDirectly used in the next reaction.
(2) 50mL of 1, 2-dichloroethane (m-acetyl benzoyl chloride) obtained in the step (1) was stirred in an ice bath at a temperature of 0.+ -. 2 ℃ and a mixture of 0.012mol of 1, 1-dimethylaminoacetonitrile and 0.012mol of triethylamine was added dropwise to the mixture via a constant pressure funnel. After the dripping, slowly heating to room temperature to continue the reaction. After completion of the reaction, the mixture was suction-filtered, and the liquid was washed with 50mL of distilled water and then with 2g of MgSO 4 And (5) drying. Drawing machineFiltering and desolventizing to obtain 2.1g brown solidThe yield was 85.5% and was used directly in the next reaction.
(3) The product prepared in (2) is added into a 100mL single-mouth bottle10mL of methanol, 40mL of saturated sodium bicarbonate solution, stirring at room temperature until the reaction is completed, adjusting the pH to 5, extracting with 50mL of dichloromethane, and extracting the extract with 2g of MgSO 4 Drying, suction filtration and desolventizing to obtain 1.5g of white solid +.>Yield 86.2%;
2. intermediate productsThe preparation route is as follows:
into a 100mL three-necked flask equipped with a thermometer, a stirrer and a condensate return tube, 0.01mol of 2, 4-dichloro-5-trifluoromethylpyrimidine was addedAdding 50mL of acetonitrile as a solvent, adding 0.01mol of potassium carbonate, stirring, heating to 50 ℃, and dropwise adding 10mL of sesamol containing 0.01mol of sesamol into the mixture through a constant pressure dropping funnel>After the dripping is finished, the reaction is continued to be carried out with heat preservation. After the reaction is finished, standing and cooling to room temperature, suction filtering, liquid phase desolventizing and drying to obtain 2.9g of white solid +.>The yield was 93.1%; />
3. The preparation of compound 19 is as follows:
adding into 100ml three-mouth bottle equipped with stirrer, reflux condenser and thermometer,
0.01mol0.015mol of potassium carbonate, 50mL of acetonitrile as a solvent, and stirring at 60℃for 1 hour, 10mL of a solution containing 0.01mol of->Slowly heating to reflux, standing and cooling to room temperature after the reaction is finished, filtering, desolventizing in liquid phase, drying, recrystallizing with acetonitrile to obtain 3.67g of white solid which is 19 # target compound->The yield thereof was found to be 75.6%.
In the same or similar manner, the compounds of the present invention having the structure of the type of formula (1) such as compounds nos. 3, 5, 7, 8, 10, 11, 12, 13, 18, 29, 30, 31, 37, 38, etc. in table 1 can be produced.
Example 2: preparation of compound 34:
the compound numbered 34 belongs to the type of formula (2) and has the following chemical structure:
1. intermediate productsThe preparation route is as follows:
(1) Into a 100mL reaction flask equipped with a stirrer, a reflux condenser, a drying tube and a thermometer, 0.01mol of p-methylbenzoic acid, 0.05 mmole of AIBN and 50mL of LCCl were charged 4 Introducing N 2 Then, 0.011mol of NBS was added thereto, followed by stirring, and the reaction was carried out at 65.+ -. 2 ℃. After the reaction is finished, 10mL of water is added for quenching reaction, and 1.9g of solid p-bromomethylbenzoic acid is obtained by suction filtrationThe yield thereof was found to be 88.4%.
(2) Into a 100mL reaction flask equipped with a stirrer, a reflux condenser, a drying tube and a thermometer, 0.01mol of p-bromomethylbenzoic acid, 50mL of 1, 2-dichloroethane were added, and 0.03mol of SOCl was added dropwise under stirring 2 Reflux reaction, TLC detection of reaction progress; after the reaction, the SOCl is distilled off under reduced pressure 2 To obtainDirectly used in the next reaction.
(3) To evaporate SOCl 2 And solvent 1, 2-dichloroethane in the presence ofIn the reaction flask of (2), the temperature was controlled at 0.+ -. 2 ℃ by adding 10mL of 0.012mol of 1, 1-dimethylaminoacetonitrile to the constant pressure funnel>And 0.012mol of triethylamine in 1, 2-dichloroethane, and slowly raising the temperature to room temperature after the dripping. After completion of the reaction, the liquid phase was suction-filtered, washed with 50mL of distilled water, and then with 3g of MgSO 4 Drying and desolventizing to obtain 2.6g yellow solid +.>The yield thereof was found to be 92.4%.
2. The preparation of compound number 34 is as follows:
adding 0.012mol of sesamol and 0.011mol of potassium carbonate, 50mL of acetonitrile into a 100mL reaction bottle provided with a stirrer, a reflux condenser and a thermometer, stirring and heating to 60 ℃, and preserving heat for 1h; then, 10mL containing 0.01mol was added dropwise via an isopipeAfter dripping, slowly heating to reflux reaction. Standing and cooling to room temperature after the reaction is finished, and carrying out suction filtration; desolventizing the filtrate, recrystallizing the obtained solid with 1, 2-dichloroethane to obtain 2.4g of white solid compound which is 34 # target +.>The yield thereof was found to be 71%.
In the same or similar manner, the compounds of the present invention of the type of formula (2) can be prepared, such as compounds 1,2, 6, 9, etc. in Table 1.
Example 3: preparation of compound 22:
the compound numbered 22 belongs to the type of formula (3) and has the following chemical structure:
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1. intermediate productsThe preparation route is as follows:
the preparation is analogous to that in example 2Is prepared from the raw materials of the preparation,the difference is thatReplaced by->Other operations are as in example 2 +.>Is prepared by the following steps.
2. Intermediate productsThe preparation route is as follows:
into a 100mL three-necked flask was charged 0.02mol of 3, 4-methylenedioxyphenyl isopropyl ketoneThe mixture was dissolved in 15mL of methanol under heating, and 0.02mol of sodium carbonate was added. Dropwise adding a solution of 0.024mol hydroxylamine hydrochloride (NH 2 OH. HCl) and 3mL of water under stirring to generate a large amount of solid, stirring and refluxing for continuous reaction, detecting by TLC, after the point of the raw material disappears, filtering, washing the solid with 10mL of distilled water to obtain 3.15g of light yellow solid 3, 4-methylenedioxyphenyl cyclopropyl methyl oxime>The yield thereof was found to be 95.5%.
3. The preparation of compound No. 22 is as follows:
into a 100mL reaction flask equipped with a stirrer, a reflux condenser and a thermometer was charged 0.012mol of 3, 4-methylenedioxyphenyl cyclopropylmethoxime50mL of anhydrous acetonitrile, 0.0144mol NaH; 10mL of a mixture containing 0.015mol of 3-bromomethyl-N- (2, 2-dimethyl-1-methylsulfonyl) propylbenzamide>After dripping, the temperature is slowly increased to reflux reaction. Standing and cooling to room temperature after the reaction is finished, and carrying out suction filtration; desolventizing the filtrate and recrystallizing the obtained solid 1, 2-dichloroethane to obtain compound No. 22The yield thereof was found to be 75.8%.
In the same or similar manner, the compounds of the present invention of the type of formula (3) can be prepared, such as compounds 4, 20, 23, 27, 39 in Table 1, and the like.
Example 4 preparation of compound 33:
the compound numbered 33 belongs to the type of formula (4) and has the following chemical structure:
1. intermediate productsThe preparation route is as follows:
(1) Intermediate productsPreparation, specific preparation method is similar to that in example 1Is different from the preparation of (a)Where is will->Replaced by->Other operations are as in example 1 +.>Is prepared by the following steps. />
(2) Into a 100mL reaction flask equipped with a thermometer, a magnetic stirrer and a condensing reflux tube with a drying tube was added 0.01mol of 4, 6-dichloropyrimidineAdding 50mL of acetonitrile as a solvent, adding 0.012moL of potassium carbonate, stirring and heating to 50 ℃; 10mL of a solution containing 0.01mol of N- (2-cyanoisopropyl) -2-hydroxybenzoamide was added dropwise via an isobaric funnelAfter the completion of the dropwise addition, the reaction was carried out at a constant temperature, after the completion of the TLC detection, the reaction was allowed to stand still and cooled to room temperature, and then suction filtration was carried out to obtain a solid by liquid phase desolventizing and recrystallization with 1, 2-dichloroethane to obtain 2.7g of brown solidYield 85.2%;
2. the preparation of compound number 33 of interest is routed as follows:
(1) Intermediate productsPreparation, in particular preparation method, is analogous to example 3Is prepared by (a) and (b)Except that->Replaced by->Other operations are as in example 3->Is prepared by the following steps.
(2) Into a 100mL reaction flask equipped with a stirrer, a reflux condenser and a thermometer, 50mL of acetonitrile and 0.012mol of 3, 4-methylenedioxyphenyl cyclopropylmethoxime were added0.015mol of potassium carbonate, stirring at room temperature, and adding 10mL of a solution containing 0.015mol of +.>The acetonitrile solution of (2) is subjected to heat preservation reaction, TLC (thin layer chromatography) detects the reaction progress, and after the reaction is finished, the mixture is stood and cooled to room temperature, and suction filtration is carried out; liquid phase desolventizing and recrystallising the solid acetonitrile obtained gives 3.2g of the compound 33 as a white solid>The yield thereof was found to be 65%.
In the same or similar manner, the compounds of the present invention of the type of formula (4) can be prepared as shown in Table 1 as 15, 16, 17, 21, 25, 26, 28, 32, number compounds and the like.
Example 5 physicochemical parameter determination and chemical structure identification of a partially preferred compound of the invention:
the chemical formula, molecular weight, melting point and physical and chemical properties of the partially preferred compounds of the present invention are shown in Table 2.
Oxime ester thiophosphamides of partially preferred compounds of the invention 1 The H-NMR data are shown in Table 3. Nuclear magnetic resonance of partially related compounds 1 The H-NMR spectra are shown in FIGS. 1 to 4.
TABLE 2 physicochemical Properties of some preferred Compounds of the invention (numbering corresponds to the structure of the compounds in accordance with TABLE 1)
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TABLE 3 partial preference Compounds of the invention 1 H-NMR data (number corresponds to the structure of the compound in accordance with Table 1)
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/>
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Example 6 test of insecticidal Activity of a partially preferred compound of the invention against Heliothis armyworm, corn borer, plutella xylostella, and asparagus caterpillar:
(1) Insect source testing: insect fed by artificial feed in the insect-raising room of the teaching and research room of the Qingdao university student in the measuring room. Feeding conditions: t, 27+ -1deg.C; RH,60% -80%; L/D,14h/10h.
(2) Preferred compounds of the present invention have the structures shown in Table 4:
TABLE 4 preferred partial benzamide compounds of the invention
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Control drug: CK1 is piperine, and has the following structure:
CK2 is distilled water.
Test compound and control drug concentration: 100mg/kg.
Activity test on bollworm: a feed mixing method. About 5mg of the test compound was weighed into a penicillin bottle, 5g of acetone (or a suitable solvent) was added thereto, and the mixture was dissolved by shaking to prepare 1000mg/kg of a mother liquor. 3g of the prepared solution was removed and added to about 27g of freshly prepared feed, thereby obtaining a 10-fold dilution of the desired concentration. The medicines are evenly mixed and poured into a clean 24-hole plate, and after cooling, 24 cotton bollworms with the age of 3 are inoculated, and after 48 hours observation, the result is checked. Each compound was repeated 3 times. An aqueous solution containing 0.5mL of the test solvent was used as a blank.
Activity test for corn borers: leaf soaking method. About 5mg of the test compound was weighed into a penicillin bottle, 5g of acetone (or a suitable solvent) was added thereto, and the mixture was dissolved by shaking to prepare 1000mg/kg of a mother liquor. After the required concentration is prepared, the leaves with the diameter of 5-6 cm are immersed in the liquid medicine for 5-6 seconds, taken out, put on absorbent paper for airing, put in a designated culture dish, inoculated with 10-head 3-year larvae, put in an insect-breeding room with the temperature of 27+/-1 ℃ for observation for 48 hours, and then the result is checked. Each compound was repeated 3 times. An aqueous solution containing 0.5mL of the test solvent was used as a blank.
Activity test for plutella xylostella and asparagus caterpillar: leaf soaking method. 2mg of the drug sample was weighed on an analytical balance in a 10mL small beaker, 50. Mu.L of dimethylformamide (analytically pure) was added for dissolution, and 10g of water was added to prepare 200mg/kg of a drug solution. The cabbage leaves are immersed in the straight ophthalmic forceps for 2-3 seconds, and the residual liquid is thrown away. 1 tablet at a time, 3 tablets per sample. Sequentially placed on the treated paper in the order of sample marking. After the liquid medicine is dried, the liquid medicine is put into a straight pipe with a length of 10cm and a mark, 3-year-old plutella xylostella or asparagus caterpillar larva is inoculated, and the pipe orifice is covered by gauze. The test treatment was placed in a standard treatment chamber and the results were checked after 48 hours. Each compound was repeated 3 times. The control was prepared by adding only the solvent to distilled water and stirring well.
TABLE 5 Activity measurement of preferred Compounds of the invention on Heliothis armyworm, corn borer, plutella xylostella and beet armyworm (mortality (%)) (Structure of compounds corresponding to numbering is the same as that of TABLE 1, TABLE 4)
Numbering device Bollworm (Bowls) Corn borer Plutella xylostella Beet armyworm Numbering device Bollworm (Bowls) Corn borer Plutella xylostella Beet armyworm
1 54 49 38 35 22 54 31 18 47
2 45 37 31 39 23 24 39 41 20
3 81 78 73 79 24 34 45 0 0
4 0 45 0 43 25 81 86 83 82
5 68 57 51 49 26 79 89 72 87
6 60 55 63 53 27 34 56 29 49
7 88 71 57 80 28 47 69 85 83
8 81 77 80 81 29 65 37 48 81
9 37 0 32 41 30 78 27 35 82
10 76 54 49 37 31 79 82 54 71
11 47 82 83 62 32 46 89 56 69
12 84 87 89 86 33 81 82 45 84
13 43 26 38 53 34 24 19 0 34
14 56 43 61 37 35 36 14 21 18
15 41 39 35 29 36 45 37 31 0
16 81 47 81 84 37 84 51 89 86
17 59 84 82 47 38 0 37 84 85
18 88 84 83 82 39 56 28 41 39
19 79 65 39 48 CK1 44 57 29 41
20 0 48 21 24 CK2 0 0 0 0
21 0 19 39 0
As can be seen from the data in table 5, the insecticidal activity of the preferred compounds of the present invention against cotton bollworms, corn borers, plutella xylostellas and beet armyworms is all higher than that of the control agent piperine, wherein the compounds 3, 8 and 26 of the present invention exhibit unexpected insecticidal activity, the insecticidal activity against cotton bollworms, corn borers, plutella xylostellas and beet armyworms reaches more than 70% at a concentration of 100mg/kg, and the insecticidal activity against cotton bollworms, corn borers, plutella xylostellas and beet armyworms reaches more than 80% at a concentration of 100 mg/kg; specifically, the insecticidal activity of 3, 7, 8, 12, 16, 18, 25, 33 and 27 on cotton bollworms reaches more than 80% at a concentration of 100mg/kg, the insecticidal activity of 11, 12, 17, 18, 25, 26, 31, 32 and 33 on corn borers reaches more than 80% at a concentration of 100mg/kg, the insecticidal activity of 8, 11, 12, 16, 17, 18, 25, 28, 37 and 38 on plutella xylostella reaches more than 80% at a concentration of 100mg/kg, and the insecticidal activity of 7, 8, 12, 16, 18, 25, 26, 28, 29, 30, 33, 37 and 38 on asparagus caterpillar reaches more than 80% at a concentration of 100mg/kg. The novel compounds exhibit high insecticidal activity and have good commercial development value.
Example 7 in-house bioactivity test of a partially preferred compound of the invention against Tetranychus cinnabarinus, tetranychus urticae:
(1) The test compound is dissolved in acetone and diluted to the desired concentration with a 0.1% tween 80 solution, with an acetone content of no more than 5%.
(2) And (3) removing one true leaf of the kidney bean seedlings growing to two true leaves, inoculating tetranychus cinnabarinus, investigating the cardinality, carrying out the whole plant spraying treatment by using a handheld sprayer, repeating the treatment for 3 times, observing in a constant-temperature observation room after the treatment, investigating the number of live mites after 72 hours, and calculating the death rate. The number of the tetranychus cinnabarinus inoculated each time is 100-200.
(3) Mortality = (number of vaccinations-number of live insects after drug)/(number of vaccinations x 100%).
(4) Insect source testing: tetranychus cinnabarinus and Tetranychus urticae fed by artificial feed in a laboratory of test, teaching and research room of Qingdao university students. Feeding conditions: t, 28+ -2deg.C; RH,40% -60%; L/D,14h/10h.
(5) Control drug: CK1 is piperine, and has the following structure:
CK2 is distilled water.
TABLE 6 determination of the Activity of preferred Compounds of the invention against Tetranychus cinnabarinus (mortality (%)) (Structure of compounds corresponding to numbering is the same as that of TABLE 1, TABLE 4)
As can be seen from the data in table 6, the preferred compounds of the present invention all showed higher acaricidal activity against tetranychus cinnabarinus and tetranychus urticae than the control agent piperine, wherein the compounds 10, 13, 16, 19, 25, 28, 38 of the present invention showed unexpected insecticidal activity, and the acaricidal activity against tetranychus cinnabarinus and tetranychus urticae reached a mite killing mortality of 90% or more at a concentration of 100mg/kg. The novel compounds exhibit high acaricidal activity and have good commercial development value.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. A benzamide compound having a structure of formula (1), formula (2), formula (3), or formula (4):
wherein R is 1 、R 2 、R 3 、R 4 Each independently selected from different groups.
2. Benzamide compound according to claim 1, characterized in that R 1 Selected from the group consisting of Or alternativelyThe R is 2 Selected from->Or->The R is 3 Selected from->Or->The R is 4 Selected from->Or->
3. The benzamide compound according to claim 2, characterized in that it is selected from any one of the following:
4. a process for the preparation of the benzamide compound of claim 2, comprising the steps of:
the preparation method of the compound with the chemical structural formula (1) comprises the following steps:
wherein the R is 2 Selected from the group consisting ofOr->The R is 3 Selected from->Or->The R is 4 Selected from->Or->
(1) Taking a certain amount ofIn a selected solvent with an appropriate amount of SOCl 2 Reacting to obtain the corresponding benzoyl chloride derivative, and then reacting with the corresponding +_ in the presence of an acid-binding agent>Reacting to obtainIn saturated NaHCO 3 Hydrolyzing in aqueous solution to obtainIn step (1), preparing +.>The preferred solvent is 1, 2-dichloroethane, the preferred acid-binding agent is triethylamine, < >>And SOCl 2 Preferably 1:3, in the second reaction step->The molar ratio to triethylamine is preferably 1:1, a step of;
(2) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,and->Reacting to obtain->In step (2), preparing +.>The preferred solvent is acetonitrile,/->K 2 CO 3 Preferably 1:1:1, a step of;
(3) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,and->Reacting to obtain the product; the preferred solvent is acetonitrile,/->d、K 2 CO 3 Preferably 1:1:1.5;
the preparation method of the compound with the chemical structural formula (2) comprises the following steps:
wherein the R is 2 Selected from the group consisting ofOr->The R is 4 Selected from->Or alternatively
(1) Taking a certain amount of methylbenzoic acid, inReacting with N-bromosuccinimide (NBS) in a selected solvent under the protection of nitrogen and in the presence of an initiator Azodiisobutyronitrile (AIBN) to prepare bromomethylbenzoic acid; the obtained bromomethylbenzoic acid and a proper amount of SOCl 2 Reacting to obtain corresponding bromomethyl benzoyl chloride derivative, and then reacting with corresponding bromomethyl benzoyl chloride derivativeReacting to obtainIn step (1), the preferred solvent for preparing bromomethylbenzoic acid is CCl 4 The molar ratio of methylbenzoic acid, AIBN, NBS is preferably 1:5:1.1; preferred solvents for the preparation of bromomethylbenzoyl chloride are 1, 2-dichloroethane, bromomethylbenzoic acid and SOCl 2 Preferably 1:3, a step of; preparation of->When the preferred acid-binding agent is triethylamine, the molar ratio of bromomethylbenzoyl chloride to triethylamine is preferably 1:1, a step of;
(2) In a selected solvent, K 2 CO 3 As the acid-binding agent, the water-soluble polymer is a water-soluble polymer,and->Reacting to obtain a formula (2); in step (2), the preferred solvent for the preparation of formula (2) is acetonitrile, < >>e、K 2 CO 3 Preferably 1.2:1:1.1;
the preparation method of the compound with the chemical structural formula (3) comprises the following steps:
wherein the R is 1 Selected from the group consisting ofOr->The R is 2 Selected from->Or->The R is 4 Selected from->Or->
The preparation method of the compound with the chemical structural formula (4) comprises the following steps:
wherein the R is 1 Selected from the group consisting ofOr->The R is 2 Selected from->Or->The R is 3 Selected from->Or->The R is 4 Selected from->Or->
5. An insecticide comprising a benzamide compound having a structure of formula (1), formula (2), formula (3), or formula (4):
wherein the R is 1 Selected from the group consisting ofOr->The R is 2 Selected from->Or->The R is 3 Selected from->Or->The R is 4 Selected from->Or->
6. An insecticide according to claim 5, wherein the insecticide further comprises adjuvants acceptable in pesticide formulations.
7. The pesticide according to claim 5, wherein the benzamide compound represented by the structures of the formula (1), the formula (2), the formula (3) and the formula (4) accounts for 0.1% -99.9% of the total weight of the pesticide.
8. Use of a benzamide compound according to any one of claims 1 to 3 or a benzamide compound prepared by the method of claim 4 or an insecticide according to any one of claims 5 to 7 for the preparation of a pesticide for controlling agricultural pests.
9. The use according to claim 8, wherein the control of agricultural pests is control of lepidopteran pests.
10. The use according to claim 8, wherein the control of agricultural pests is control of spider mites pests.
CN202311536659.4A 2023-11-17 2023-11-17 Preparation and application of benzamide compounds Pending CN117567417A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008134969A1 (en) * 2007-04-30 2008-11-13 Sinochem Corporation Benzamide compounds and applications thereof
CN109206397A (en) * 2017-06-29 2019-01-15 沈阳中化农药化工研发有限公司 A kind of pepper acid derivative and its preparation and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008134969A1 (en) * 2007-04-30 2008-11-13 Sinochem Corporation Benzamide compounds and applications thereof
CN109206397A (en) * 2017-06-29 2019-01-15 沈阳中化农药化工研发有限公司 A kind of pepper acid derivative and its preparation and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEN, YOUWEI等: "Synthesis, insecticidal activities and SAR of novel phthalamides targeting calcium channel", 《BIOORGANIC & MEDICINAL CHEMISTRY》, vol. 22, no. 22, 15 November 2014 (2014-11-15), pages 6366 - 6379, XP029091125, DOI: 10.1016/j.bmc.2014.09.052 *

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Inventor after: Zhang Wei

Inventor after: Qu Bo

Inventor after: Hu Junfeng

Inventor after: Zhai Xiaolu

Inventor after: Liu Ke

Inventor after: Sun Jialong

Inventor after: Gu Songdong

Inventor after: Wei Zehui

Inventor after: Zhao Yan

Inventor after: Li Jun

Inventor after: Li Ning

Inventor before: Zhang Wei

Inventor before: Qu Bo

Inventor before: Hu Junfeng

Inventor before: Zhai Xiaolu

Inventor before: Liu Ke

Inventor before: Sun Jialong

Inventor before: Gu Songdong

Inventor before: Wei Zehui

Inventor before: Zhao Yan

Inventor before: Li Jun

Inventor before: Li Ning