CN112442026B - Mesoionic derivative and preparation method and application thereof - Google Patents
Mesoionic derivative and preparation method and application thereof Download PDFInfo
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- CN112442026B CN112442026B CN201910795631.XA CN201910795631A CN112442026B CN 112442026 B CN112442026 B CN 112442026B CN 201910795631 A CN201910795631 A CN 201910795631A CN 112442026 B CN112442026 B CN 112442026B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
Abstract
The invention relates to a mesoionic derivative, a preparation method and application thereof; in particular, the present invention relates to a mesoionic derivative represented by formula (I) or a stereoisomer of a mesoionic derivative represented by formula (I), a nitrogen oxide or a salt thereof, a process for producing the mesoionic derivative, and their use as pesticides in agriculture, and forms of pesticide compositions thereof, and methods of killing pests with these compounds or compositions; wherein R is 1 、R 2 And R is 3 Having the meaning described in the present invention.
Description
Technical Field
The invention relates to the field of pesticides, in particular to a mesoionic derivative, a preparation method of the mesoionic derivative and application of the mesoionic derivative serving as a pesticide in agriculture.
Background
Heterocyclic mesogenic compounds are known as pesticides and are described in the prior art WO09099929, WO11017334, WO11017347, WO11017342, WO12092115, WO12106495, WO12136724, WO14033244, WO14202582, WO14167084, WO16055431, WO16171053 and WO17093214, whereas the mesogenic derivatives according to the invention are not reported in the prior art.
Disclosure of Invention
The invention relates to a novel mesoionic derivative which has excellent control effects on pests in agriculture, in particular to plutella xylostella, armyworms, green peach aphids, brown planthoppers and the like.
Specific:
in one aspect, the present invention provides a novel mesoionic compound which is a compound represented by formula (I) or a stereoisomer, nitrogen oxide or salt thereof having a compound represented by formula (I):
wherein:
R 1 is hydrogen or C 1-6 An alkyl group;
R 2 is a 5-6 membered heteroaryl; the 5-6 membered heteroaryl is optionally substituted with one or more groups selected from halogen, cyano, hydroxy, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy or halo C 1-6 Substituents of alkylthio groups;
R 3 is C 6-10 Aryl or 5-6 membered heteroaryl; the C is 6-10 Aryl and 5-6 membered heteroaryl optionally substituted with one or more groups selected from halogen, cyano, hydroxy, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl or halo C 1-6 The substituent of the alkoxy group is substituted.
In some embodiments, R 1 Is hydrogen or C 1-4 An alkyl group.
In some embodiments, R 1 Is hydrogen, CH 3 -or CH 3 CH 2 -。
In some embodiments, R 2 Is thiazolyl, pyridinyl or pyrimidinyl; the thiazolyl, pyridyl and pyrimidinyl groups are optionally substituted with one or more groups selected from halogen, cyano, hydroxy, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo C 1-4 Alkyl, halogenated C 1-4 Alkoxy or halo C 1-4 Substituents of alkylthio groups.
In some embodiments, R 2 Thiazol-5-yl, pyridin-3-yl or pyrimidin-5-yl; the thiazol-5-yl, pyridin-3-yl and pyrimidin-5-yl groups are optionally substituted with one or more groups selected from halogen, cyano, hydroxy, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo C 1-4 Alkyl group,Halogenated C 1-4 Alkoxy or halo C 1-4 Substituents of alkylthio groups.
In some embodiments, R 2 Thiazol-5-yl, pyridin-3-yl or pyrimidin-5-yl; the thiazol-5-yl, pyridin-3-yl and pyrimidin-5-yl groups are optionally substituted with one or more groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, CH 3 -、CH 3 O-、CH 3 S-、CF 3 -or CF 3 The substituents of O-are substituted.
Still further in some embodiments, R 2 Is that
In some embodiments, R 3 Phenyl or thienyl; the phenyl and thienyl groups are optionally substituted with one or more groups selected from halogen, cyano, hydroxy, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, halo C 1-4 Alkyl or halo C 1-4 The substituent of the alkoxy group is substituted.
In some embodiments, R 3 Phenyl or thienyl; wherein said phenyl and thienyl are optionally substituted with one or more groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, CH 3 -、CH 3 O-、CF 3 -or CF 3 The substituents of O-are substituted.
Still further in some embodiments, R 3 Is that
In some embodiments, the invention also relates to a compound that is a stereoisomer, nitroxide, or salt thereof, of a compound having one of the following structures:
in yet another aspect, the present invention provides a composition comprising at least one compound of the present invention.
Further, the composition of the invention comprises pharmaceutically acceptable auxiliary materials.
In another aspect, the invention provides the use of a compound of the invention or a composition of the invention as an insecticide in agriculture.
In yet another aspect, the present invention provides a method of killing pests in agriculture with a compound of the invention or a composition of the invention.
Further, the pests of the present invention include plutella xylostella, mythimna separata, aphis medicago and brown planthopper.
Detailed description of the invention
Definitions and general terms
Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated in the accompanying structural and chemical formulas. The invention is intended to cover all alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. Those skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event of one or more of the incorporated references, patents and similar materials differing from or contradictory to the present application (including but not limited to defined terms, term application, described techniques, etc.), the present application controls.
It should further be appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination.
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. All patents and publications referred to herein are incorporated by reference in their entirety.
The following definitions as used herein should be applied unless otherwise indicated. For the purposes of the present invention, chemical elements are in accordance with CAS version of the periodic Table of the elements, and handbook of chemistry and physics, 75 th edition, 1994. In addition, general principles of organic chemistry may be referenced to the descriptions in "Organic Chemistry", thomas Sorrell, university Science Books, sausalato:1999, and "March's Advanced Organic Chemistry" by Michael b.smith and Jerry March, john Wiley & Sons, new york:2007, the entire contents of which are incorporated herein by reference.
The articles "a," "an," and "the" are intended to include "at least one" or "one or more" unless the context clearly dictates otherwise or otherwise. Thus, as used herein, the articles refer to articles of manufacture that include one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., more than one component is contemplated as being employed or used in embodiments of the described embodiments.
The term "comprising" is an open-ended expression, i.e., including what is indicated by the invention, but not excluding other aspects.
"stereoisomers" refer to compounds having the same chemical structure but different arrangements of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that do not overlap but are in mirror image relationship to each other.
"diastereoisomers" refers to stereoisomers which have two or more chiralities and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting point, boiling point, spectral properties, and reactivity. The diastereomeric mixture may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.
The stereochemical definitions and rules used in the present invention generally follow S.P. Parker, ed., mcGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, new York; and Eliel, e.and Wilen, s., "Stereochemistry of Organic Compounds", john Wiley & Sons, inc., new York, 1994.
Many organic compounds exist in optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to represent the absolute configuration of the molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are symbols for specifying the rotation of plane polarized light by a compound, where (-) or l indicates that the compound is left-handed. The compound prefixed with (+) or d is dextrorotatory. One particular stereoisomer is an enantiomer, and a mixture of such isomers is referred to as an enantiomeric mixture. A50:50 mixture of enantiomers is referred to as a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.
Any asymmetric atom (e.g., carbon, etc.) of the disclosed compounds may exist in racemic or enantiomerically enriched form, such as in the (R) -, (S) -or (R, S) -configuration. In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R) -or (S) -configuration.
Depending on the choice of starting materials and methods, the compounds of the invention may be present in the form of one of the possible isomers or mixtures thereof, for example racemates and non-corresponding isomer mixtures, depending on the number of asymmetric carbon atoms. Optically active (R) -or (S) -isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituent may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the substituents of the cycloalkyl group may have cis or trans configuration.
The resulting mixture of any stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, e.g., by chromatography and/or fractional crystallization, depending on the differences in the physicochemical properties of the components.
Any of the resulting racemates of the end products or intermediates can be resolved into the optical enantiomers by methods familiar to those skilled in the art, e.g., by separation of the diastereoisomeric salts thereof obtained, using known methods. The racemic product can also be separated by chiral chromatography, e.g., high Performance Liquid Chromatography (HPLC) using chiral adsorbents. In particular, enantiomers may be prepared by asymmetric synthesis.
The compounds of the invention may be optionally substituted with one or more substituents, as described in the present invention, such as the compounds of the general formula above, or as specific examples within the examples, subclasses, and classes of compounds encompassed by the invention. It is to be understood that the term "optionally substituted" may be used interchangeably with the term "substituted or unsubstituted". In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a specific substituent. An optional substituent group may be substituted at each substitutable position of the group unless otherwise indicated. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, then the substituents may be the same or different at each position. Specifically, examples of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Wherein the substituents may be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino alkyl, alkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxyl-substituted alkyl, hydroxyl-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkanoyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.
In addition, unless explicitly indicated otherwise, the descriptions used in this disclosure of the manner in which each … is independently "and" … is independently "and" … is independently "are to be construed broadly as meaning that particular items expressed between the same symbols in different groups do not affect each other, or that particular items expressed between the same symbols in the same groups do not affect each other.
In the various parts of the present specification, substituents of the presently disclosed compounds are disclosed in terms of the type or scope of groups. It is specifically noted that the present invention includes each individual subcombination of the individual members of these group classes and ranges. For example, the term "C 1 -C 6 Alkyl "or" C 1-6 Alkyl "means in particular methyl, ethyl, C independently disclosed 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 An alkyl group.
The term "alkyl" or "alkyl group" as used herein, means a saturated straight or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, alkyl groups contain 1 to 20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in one embodiment, the alkyl group contains 1 to 8 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.
Alkyl groupExamples of (C) include, but are not limited to, methyl (Me, -CH 3 ) Ethyl (Et, -CH) 2 CH 3 ) N-propyl (n-Pr, -CH) 2 CH 2 CH 3 ) Isopropyl (i-Pr, -CH (CH) 3 ) 2 ) N-butyl (n-Bu, -CH) 2 CH 2 CH 2 CH 3 ) Isobutyl (i-Bu, -CH) 2 CH(CH 3 ) 2 ) Sec-butyl (s-Bu, -CH (CH) 3 )CH 2 CH 3 ) Tert-butyl (t-Bu, -C (CH) 3 ) 3 ) N-pentyl (-CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH) 3 )CH 2 CH 2 CH 3 ) 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) And so on.
The term "alkoxy" means that the alkyl group is attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH) 3 ) Ethoxy (EtO, -OCH) 2 CH 3 ) 1-propoxy (n-PrO, n-propoxy, -OCH) 2 CH 2 CH 3 ) 2-propoxy (i-PrO, i-propoxy, -OCH (CH) 3 ) 2 ) Etc.
The term "alkylthio" means that the alkyl group is attached to the remainder of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, -SCH 3 、-SCH 2 CH 3 、-SCH 2 CH 2 CH 3 、-SCH(CH 3 ) 2 Etc.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "heteroaryl" means monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5 to 7 atoms and has one or more attachment points attached to the remainder of the molecule. The term "heteroaryl" may be used interchangeably with the term "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, the heteroaryl group of 5 to 10 atoms comprises 1,2,3 or 4 heteroatoms independently selected from O, S and N.
Examples of heteroaryl groups include, but are not limited to, furan-2-yl, furan-3-yl, N-imidazolyl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, N-pyrrolyl, pyrrol-2-yl, pyrrol-3-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazinyl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, tetrazolyl, triazolyl, thiophen-2-yl, thiophen-3-yl, pyrazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 3-triazolyl, 1, 3-triazolyl, 3-thiozinyl, 1, 3-thiotriazinyl, 1, 2-thiotriazinyl; the following bicyclic rings are also included, but are in no way limited to: benzimidazolyl, benzofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), benzopiperidinyl, and the like.
The term "haloalkyl" means an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to, -CF 3 ，-CHF 2 ，-CH 2 Cl，-CH 2 CF 3 ，-CH 2 CHF 2 ，-CH 2 CH 2 CF 3 Etc.
The term "haloalkoxy" means that the alkoxy group is substituted with one or more halogen atoms, examples of which include, but are not limited to, -OCF 3 ，-OCHF 2 ，-OCHCl 2 ，-OCH 2 CHF 2 ，-OCH 2 CHCl 2 ，-OCH(CH 3 )CHF 2 Etc.
The term "haloalkylthio" means that the alkylthio group is substituted with one or more halogen atoms.
Salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and have the formula N + (R AA R BB R CC R DD ) Wherein R is an ammonium cation of AA 、R BB 、R CC And R is DD Independently selected from hydrogen, C 1 -C 6 Alkyl and C 1 -C 6 A hydroxyalkyl group. Salts of the compounds of formula (I) may be prepared by treating a compound of formula (I) with a metal hydroxide (e.g. sodium hydroxide) or an amine (e.g. ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecamine or benzylamine).
When the compounds of the present invention contain a base moiety, acceptable salts may be formed with organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.
Compositions and formulations of the compounds of the invention
The compound of the invention can be generally used as an active ingredient of a pesticide in a composition or a preparation, and generally comprises an auxiliary material acceptable in agriculture and pharmacy, wherein the auxiliary material is a surfactant and/or a carrier and the like, and the components meeting the use requirements of the pesticide belong to the scope of the invention.
The surfactant may be various surfactants known in the art of pesticide formulation, and the present invention is preferably one or more of an emulsifier, a dispersant and a wetting agent.
Other carriers besides the above surfactants may be various carriers well known in the art of pesticide formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, an amine fertilizer, a mixture of urea and an amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.
The emulsifier can be various emulsifiers known in the field of pesticide preparations, and specifically, the emulsifier is one or more of calcium dodecyl benzene sulfonate, triphenyl ethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, ethylene oxide adduct of abietic acid, polyol fatty acid ester and ethylene oxide adduct thereof, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.
The dispersing agent can be various dispersing agents known in the pesticide preparation field, and specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl ethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignin sulfonic acid sodium salt.
The wetting agent is various wetting agents well known in the pesticide preparation field, and concretely, the wetting agent is one or more of sodium dodecyl sulfate, secondary sodium alkyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl naphthalene sulfonate and alkylphenol resin polyoxyethylene ether sulfate.
The pesticide composition according to the present invention may further contain various adjuvants for formulation commonly used in the field of pesticide preparations, specifically, one or more of solvents, co-solvents, thickeners, antifreezes, capsules, protectants, antifoaming agents, disintegrants, stabilizers, preservatives and binders.
The solvent is various solvents well known in the pesticide preparation field, and concretely, the solvent is one or more of organic solvents, vegetable oils, mineral oils, solvent oils and water.
Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyl capramide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, N-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.
The vegetable oil comprises one or more of methylated vegetable oil, turpentine-based vegetable oil, turpentine, epoxidized soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine seed oil.
The mineral oil includes one or more of liquid wax, engine oil, kerosene, and lubricating oil.
Meanwhile, the solvent can also be used as a cosolvent.
The antifreezing agent is various antifreezing agents known in the pesticide preparation field, and the antifreezing agent is preferably one or more of ethylene glycol, propylene glycol, glycerol and urea.
The thickener is various thickeners known in the pesticide preparation field, and specifically, the thickener is one or more of xanthan gum, polyvinyl alcohol, polyacrylate alcohol, polyethylene glycol, white carbon black, diatomite, kaolin, clay, sodium alginate, aluminum magnesium silicate, aluminum sodium silicate, carboxymethyl cellulose, hydroxypropyl cellulose sodium and organic bentonite.
The capsule wall material is various capsule wall materials known in the pesticide preparation field, and the invention is preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.
The protective agent is various protective agents known in the pesticide preparation field, and the invention is preferably polyvinyl alcohol and/or polyethylene glycol.
The defoamer is various defoamers known in the pesticide preparation field, and the defoamer is preferably one or more of organic siloxane, tributyl phosphate and silicone.
The stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.
The preservative is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (BIT for short), pinocembrane and potassium sorbate.
The invention also provides a preparation prepared from the pesticide composition, and the preparation formulation of the preparation is emulsifiable concentrate, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspension emulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water spreading oil, wettable powder, water dispersible granules, dry suspension, soluble powder, soluble granules, emulsifiable powder, emulsifiable granules, solid microcapsule preparation, effervescent tablets, effervescent granules, water floating dispersible granules or seed coating. The dosage forms may all be prepared by methods conventional in the art.
The preparation method of the emulsifiable concentrate preparation can comprise, for example, mixing and stirring the active components, the solvent, the cosolvent and the emulsifier to form a uniform transparent oil phase, thus obtaining the emulsifiable concentrate preparation.
The aqueous emulsion preparation method may include, for example, mixing the active ingredient, the emulsifier, the co-solvent and the solvent to make it a homogeneous oil phase; water, thickener, antifreeze, etc. are mixed to make it into a uniform aqueous phase. Under high-speed shearing, adding the water phase into the oil phase or adding the oil phase into the water phase to form the aqueous emulsion with good dispersibility.
The microemulsion may be prepared, for example, by mixing and stirring the active ingredient, the emulsifier and the solvent into a uniform and transparent oil phase. Under stirring, water was gradually added to form a uniform transparent microemulsion.
The preparation method of the water/oil suspending agent comprises the following steps: for example, water or oil is used as a medium, and additives such as active components, surfactants and the like are added into a sanding kettle, ground to a certain particle size, and filtered. And adding the metered thickener into the ground mother solution, and shearing and dispersing uniformly. Making into oil suspension or water suspension.
The preparation method of the water-dispersible granule and the soluble granule comprises the following steps: for example, the water-dispersible granule or soluble granule can be obtained by uniformly mixing the active components, the dispersing agent, the wetting agent, the carrier and the like, then crushing the mixture to a certain particle size by air flow, adding water for kneading, finally adding the mixture into a granulator for granulating, and drying the mixture.
The preparation method of the soluble powder and the wettable powder comprises the following steps: for example, the active ingredients, various auxiliary agents, and other fillers such as carriers may be thoroughly mixed and pulverized by a pulverizer.
The pesticide composition of the present invention may be provided in the form of a finished formulation, i.e. the materials of the composition have been mixed; or in the form of separate preparations which are self-mixed in a tank or can before use and optionally diluted with water depending on the desired concentration of active substance.
For additional information regarding The field of formulation, see "The Formulator's Toolbox-Product Forms for Modern Agriculture", pesticide Chemistry and Bioscience, the Food-Environment Challenge, edited by t.s. Brooks and t.r. roberts, proceedings of The 9th International Congress on Pesticide Chemistry,The Royal Society of Chemistry,Cambridge,1999, pages 120-133, of t.s. woods. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S.3,309,192, column 5, line 43 to column 7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S.2,891,855, column 3, line 66 to column 5, line 17 and examples 1-4; klingman Weed Control as a Science, john Wiley and Sons, inc., new York,1961, pages 81-96; hance et al Weed Control Handbook, 8 th edition, blackwell Scientific Publications, oxford,1989; and Developments in formulation technology, PJB Publications, richmond, UK,2000.
Use of the compounds and compositions of the invention
The compounds of the invention are particularly suitable for controlling animal pests such as arthropods, gastropods and nematodes in useful plants, including but not limited to:
hemiptera (Hemiptera): plant hoppers (Delphacidae) such as brown plant hoppers (Nilaparvata lugens), small brown plant hoppers (Laodelphax striatellus); leafhoppers (deltecellidae) such as leafhoppers of green rice (black tail leafhoppers (Nephotettix cincticeps)); aphids (aphidae) such as Aphis gossypii (Aphis gossypii), aphis medica (Aphis craccivora Koch); stinkbugs (Pentatomidae) such as lygus lucorum (Nezara antennata); aleyrodidae (Aleyrodidae) such as aleyrodide greenhouse (Trialeurodes vaporariorum); scale (Coccidae) such as california red mussel scale (Calformia red scale) (Aonidiella aurantii); net bugs (Tingidae); psyllids (Homoptera, psyllidea);
lepidoptera (Lepidoptera): stem borers (Pyralidae) such as chilo suppressalis (Chilo suppressalis); noctuid (notuisae) such as spodoptera litura (Spodoptera litura), armyworm (Pseudaletia separata), spodoptera (Heliothis spp.), and spodoptera (Helicoverpa spp.); pincerus (Pieridae) such as Pincerus rapae; a strongylodes (torricidae) such as strongylodes (adoxoplasma); lepidoptera (gracilariidae) such as lepidoptera theanine (Caloptilia theivora) and lepidoptera apple (Phyllonorycter ringoneella); carpothrix (Carposinidae) such as carpothrix (Carposina niponensis); a moth (Lyonetiidae) such as the genus of plutella (Lyonetia spp.); moth (lymantidae) such as the genera of moth (Lymantria spp.) and Huang Due (Euproctis spp.); nest moth (Yponomeutidae) such as plutella xylostella (Plutella xylostella); gelechiidae (Gelechiidae) such as red bell moth (Pectinophora gossypiella) and potato moth (Phthorimaea operculella); lamp moth (Arctidae) such as fall webworm (Hyphantrichia cunea); a moth (Tineidae) such as a clothes moth (tineranslicens) and a curtain moth (Tineola bisselliella);
Thysanoptera (Thysanoptera): frankliniella occidentalis (Frankliniella occidentalis), palmi Thrips palmi (threp palmi), yellow Thrips tabaci (Scirtothrips dorsalis), thrips tabaci (threp tabaci), thrips dahurica (Frankliniella intonsa) and Thrips solani (Frankliniella fusca);
diptera (Diptera): housefly (Musca domestica), culex pallidum (Culex popiens pallens), tabanus trigonella (Tabanus trigoneus), shallot fly (Hylemia anita), gray ground seed fly (Hylemia platura), anopheles sinensis (Anopheles sinensis), oryza japonica (Agromyza oryzae), oryza sativa (Hydrellia griseola), rice straw fly (Chromps oryzae), barbaria melo (Dacus trichocarpa), mediterranean fruit fly (Ceratitis capitata), and Leptodermia trilobata (Liriomyza trifolii);
coleoptera (Coleoptera): the plant species include, for example, a plant species such as ladybug (Epilachna vigintioctopunctata), yellow leaf flea beetle (Phyllotreta striolata), rice negative mud worm (Oulema oryzae), rice weevil (Echinocnemus squameus), rice weevil (Lissorhoptrus oryzophilus), cotton boll weevil (Anthonomus grandis), green bean weevil (Callosobruchus chinensis), parasitic rice weevil (Sphenophorus venatus), japanese arc beetle (Popillia japonica), bronze tortoise (Anomala cupra), root beetle (Diabrotica spp.), potato beetle (Leptinotarsa decemlineata), click beetle (Agriotes spp.), weeping beetle (Lasioderma serricorne), small beetle (Anthrenus verbasci), red larch (Tribolium castaneum), brown beetle (Lyctus brunneus), white spot beetle (Anoplophora malasiaca), and corktree bark beetle (Tomicus piniperda);
Orthoptera (Orthoptera): locusts (Locusta migratoria), mole cricket africana (Gryllotalpa afficana), locusts of North sea daylily (Oxya yezoensis) and locusts of Japanese rice (Oxya japonica);
hymenoptera (Hymenoptera): sinkiang Apis cerana (Athalia rosae), formica (Acromarmex spp.) and Formica (Solenopsis spp.);
nematodes (Nematodes): aphelenchus xylophilus (Aphelenchoides besseyi), strawberry bud nematode (Nothotylenchus acris), soybean cyst nematode (Heterodera glycines), meloidogyne incognita (Meloidogyne incognita), aphelenchus (Pratylenchus penetrans) and abnormal pearl nematode (Nacobbus aberrans);
blattaria (blattaria): german cockroaches (Blattella germanica), periplaneta melanogaster (Periplaneta fuliginosa), periplaneta americana (Periplaneta Americana), periplaneta brown (Periplaneta brunnea) and periplaneta orientalis (Blatta orientalis);
acarina (Acarina): tetranychidae (e.g., tetranychidae (Tetranychus cinnabarinus), tetranychus urticae), panonychus citri (pannychus citri) and Panonychus (olignichus spp.)); goiteraceae (eriophtyiidae) (e.g., citrus fruit Pi Ying mites (Aculops pelekassi)); tarsonemidae (Tarsonemidae); tenaculum (tenuiapalpidae); duckacaridae (Tuckerellidae); pink mite family (Tuckerellidae Acaridae); acaridae (Pyroglyphidae) (e.g., dermatophagoides farinae (Dermatophagoides farinae) and house dust mites (Dermatophagoides ptrenyssnus)); acaridae (Cheyletidae), marxiana acaridae (Cheyletus malaccensis) and marxiana acaridae (Cheyletus moore); the family dermatophagoides (dermansidae).
Within the scope of the present invention, useful plants include the following plant species: grains (wheat, barley, rye, oats, rice, corn, sorghum and related species); beet (sugar beet); pome, stone fruit, and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, and blackberries); leguminous plants (lentils, bingo, peas, soybeans); oil crops (rape, mustard, olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts or soybeans); melon plants (pumpkin, cucumber, melon); fiber plants (cotton, flax, hemp, jute); citrus fruits (orange, lemon, grapefruit, mandarin); vegetables (spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, red pepper); laures (avocado, camphor) or plants, such as tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grape vine, hops, bananas and natural rubber plants, as well as turf, ornamental and forest plants, such as flowers, shrubs, broad-leaved trees or evergreen trees, such as conifers, and plant propagation material.
The term "plant propagation material" is understood to mean the reproductive parts of the plant, such as seeds, which parts can be used for propagation of the plant, as well as the vegetative materials, such as cuttings or tubers (e.g. potatoes).
The compounds or compositions of the present invention are pest-exterminated by an effective amount of the active agent. Wherein the effective amount of the compound of formula (I) is within 10g-5kg per hectare, and the pest control effect is good.
The invention also relates to a method for controlling pests by applying the active ingredient or composition according to the invention to the seed, the plant or the plant part, the fruit or the soil in which the plant is growing. Application may be carried out before and after the seed, plant or plant part, fruit or soil in which the plant is growing is infested with pests.
The term "effective amount" as used herein means an amount of a compound or composition of the invention sufficient to control pests on cultivated plants or in the protection of materials without causing significant damage to the treated plants. The amount can vary within wide limits and depends on various factors such as the pest species, the cultivated plant or material being treated, the climatic conditions and the particular compound used.
The compound or composition of the invention is simple to use and is applied to the pests or the growth media thereof. The dosage of the compound or composition of the present invention to be applied varies depending on weather conditions, dosage forms, application timing, application method, application area, target disease, target crop, etc.
General synthetic procedure
The following schemes describe the preparation of the compounds of the present invention. Unless otherwise indicated, the compounds of the present invention may be prepared by the methods described herein. The starting materials, reagents, and the like used in preparing the compounds of the invention are all commercially available or may be prepared by methods conventional in the art. In this specification, a structure is dominant if there is any difference between a chemical name and a chemical structure. In some embodiments, room temperature as described herein is 0-35 ℃, unless otherwise indicated. In some embodiments, the DMF is N, N-dimethylformamide.
The testing conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: nuclear magnetic instrument of 400MHz or 600MHz of Bruker (Bruker) under room temperature condition, CDC1 3 ，d 6 -DMSO，CD 3 OD or d 6 Acetone as solvent (reported in ppm) with TMS (0 ppm) or chloroform (7.26 ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (single, singlet), d (doublet ), t (triplet, quartet), q (quartet), m (multiplet ), br (broadened, broad), dd (doublet of doublets, doublet), dt (doublet of triplets, doublet). Coupling constants are expressed in hertz (Hz).
The mass spectrum test conditions used in the invention are as follows: the conditions for low resolution Mass Spectrometry (MS) data determination are: agilent 6120 Quadragole HPLC-MS (column model: zorbax SB-C18, 2.1X30 mm,3.5 μm,6min, flow rate 0.6mL/min, mobile phase 5% -95% (CH containing 0.1% formic acid) 3 CN) in (H containing 0.1% formic acid) 2 Ratio in O)) was detected with UV at 210/254nm using electrospray ionization mode (ESI).
Synthetic scheme
The target compound I can be prepared by the synthesis scheme. Reacting the intermediate A compound with the intermediate B compound under the condition of heating (80-160 ℃) to obtain a target compound I;
wherein R is 1 、R 2 And R is 3 Having the meaning described in the present invention.
Examples
Intermediate 1: synthesis of N- ((2-chlorothiazol-5-yl) methyl) pyridin-2-amine
The first step: synthesis of tert-butyl pyridin-2-ylcarbamate
2-aminopyridine (4.70 g,0.05 mol), boc anhydride (14.17 g,0.65 mol) and triethylamine (7.55 g,75 mmol) were added sequentially to dichloromethane (47 mL) and the reaction stirred at room temperature for 12 hours; the solvent was dried by spin-drying, water (45 mL), ethyl acetate extraction (50 ml×3), the organic phases were combined, the organic phase was washed with saturated brine (30 ml×3), dried, filtered, and the filtrate was concentrated, and the residue was separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) =5/1 ], to give the title compound (white solid, 2.31g, yield: 24%).
And a second step of: synthesis of N- ((2-chlorothiazol-5-yl) methyl) pyridin-2-amine
Tert-butyl pyridin-2-ylcarbamate (1.94 g,0.01 mol) was dissolved in DMF (30 mL) at room temperature, sodium hydride (0.36 g,15 mmol) was added in portions at 0℃over 30 minutes, and after the addition was completed, stirring was continued for 30 minutes at 0℃the reaction temperature was raised to room temperature, and a solution of 2-chloro-5-chloromethylthiazole (1.68 g,0.01 mol) in DMF (10 mL) was slowly added dropwise, followed by reaction at room temperature for 8 hours. To the reaction solution was added 25mL of ice water, extracted with ethyl acetate (40 ml×3), and the organic phases were combined, washed with saturated brine (20 ml×3), dried over magnesium sulfate, filtered, and concentrated to give an oil. The oily substance obtained above was dissolved in methylene chloride (20 mL), and trifluoroacetic acid (2.3 g,0.01 mol) was slowly added dropwise at room temperature, and after the addition was completed, the reaction was allowed to rise to 40 ℃, and after the reflux reaction was carried out for 8 hours; the reaction was concentrated, aqueous potassium carbonate was added, ph=8, ethyl acetate (30 ml×3) was added, the mixture was extracted, and the organic phase was washed with water (10 ml×3), dried, filtered, and the filtrate was concentrated, and the residue was separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) =7/3 ], to give the title compound (yellow oil, 0.78g, yield: 34%).
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.19(d,1H),7.45-7.42(m,2H),7.65(t,1H),6.42(d,1H),4.80(s,1H),4.68(d,2H)；
MS(ES-API,pos.ion)m/z:226.10[M+1] + 。
The intermediate compounds in table 1 can be prepared according to the above-described synthetic method of intermediate 1 using the corresponding starting materials.
TABLE 1
Intermediate 4: synthesis of N- ((6- (methylthio) pyridin-3-yl) methyl) pyridin-2-amine
The first step: synthesis of 6- (methylthio) pyridine-3-carbaldehyde
6-chloronicotinaldehyde (7.05 g,50.00 mmol), sodium methyl mercaptan (17.5 g,250 mmol) and DMF (100 mL) were added to a 250mL single port bottle and heated at 70deg.C under reflux with stirring for 12 hr. After the reaction was completed, the reaction was stopped, cooled to room temperature, poured into ice water (300 mL), and stirred vigorously at room temperature for 10 minutes. The precipitate was separated from the solution, and the precipitate was filtered off and washed with 50mL of water to give the title compound (off-white solid, 4.8g, yield: 62.7%).
And a second step of: synthesis of N- ((6- (methylthio) pyridin-3-yl) methyl) pyridin-2-amine
6- (methylthio) pyridine-3-carbaldehyde (2.4 g,16.00 mmol), anthranilate (1.5 g,16.00 mmol) and methylene chloride (20 mL) were added to a 100mL single-necked flask, and the mixture was stirred at room temperature for 10 minutes, concentrated by distillation under reduced pressure, and the residual solution was heated in an oil bath at 90℃while stirring under vacuum for 4 hours. After completion of the reaction, tetrahydrofuran (10 mL) and methanol (20 mL) were added and dissolved, and the mixture was stirred at room temperature, followed by slow addition of sodium borohydride (608 mg,16.00 mmol) in portions over 30 minutes, and after completion of the addition, the reaction was stirred at room temperature for 12 hours. The reaction mixture was concentrated by distillation under the reduced pressure, washed with water (100 mL), extracted with ethyl acetate (100 mL. Times.3), and the organic phases were combined and dried over anhydrous magnesium sulfate for 1 hour. The filtrate was filtered and distilled under reduced pressure, followed by column chromatography separation [ petroleum ether/ethyl acetate (v/v) =2/1 ] to give the title compound (white solid, 2g, yield: 54%).
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.58(s,1H),8.24(d,J＝7.3Hz,1H),7.85-7.65(m,2H),7.42(s,1H),7.13(dd,J＝7.3Hz,4.6Hz,1H),6.62(s,1H),4.36(s,2H),4.0(s,1H),2.55(s,3H)；
MS(ES-API,pos.ion)m/z:232.30[M+1] + 。
The intermediate compounds in table 2 can be prepared according to the above described synthetic method of intermediate 4 using the corresponding starting materials.
TABLE 2
Intermediate 8: synthesis of bis (2, 4, 6-trichlorophenyl) 2- (2-nitro-1-phenylethyl) malonate
The first step: synthesis of (2-nitroethylene) benzene
Benzaldehyde (4.24 g,40 mmol) and nitromethane (7.32 g,120 mmol) were dissolved in methanol (8 mL), and 10mL of 48% aqueous sodium hydroxide (4.80 g,120 mmol) was added dropwise at-8deg.C, the temperature was controlled below 15deg.C, the reaction was completed for 15 minutes, and a precipitate was formed. 50mL of ice water is added, and the mixture is reacted for 20 minutes at the temperature of 0 ℃; the reaction solution was slowly added to hydrochloric acid (6 m,30 ml), the temperature was controlled at 0 ℃ and stirred for 5 minutes to generate yellow precipitate; suction filtration, washing of the filter cake with ice water (20 mL. Times.2) and drying gave the title compound (yellow solid, 3.38g, yield: 57%).
And a second step of: synthesis of dimethyl 2- (2-nitro-1-phenylethyl) malonate
(2-nitroethylene) benzene (3.28 g,22 mmol) and dimethyl malonate (1.64 g,11 mmol) were dissolved in toluene (20 mL), and triethylamine (2.22 g,22 mmol) was added thereto and reacted at room temperature for 8 hours. To the reaction solution was added 50mL of water, stirred, extracted with ethyl acetate (30 mL x 2), and the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated, and the residue was separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) =4/1 ], to give the title compound (yellow oil, 3.56g, yield: 58%).
And a third step of: synthesis of 2- (2-nitro-1-phenylethyl) malonic acid
Sodium hydroxide (1.60 g,40 mmol) was dissolved in 10mL of water, a solution of dimethyl 2- (2-nitro-1-phenylethyl) malonate (1.41 g,5 mmol) in methanol (10 mL) was added, the reaction temperature was raised to 60℃and the reaction was stirred for 2 hours. Cooled to room temperature, the reaction solution was poured into ice water (20 mL), stirred, ph=1 was adjusted with dilute hydrochloric acid, insoluble matter was formed, ethyl acetate (30 ml×2) was extracted, and the organic phases were combined and then evaporated in vacuo to give the title compound (yellow solid, 1.09g, yield: 86%).
Fourth step: synthesis of bis (2, 4, 6-trichlorophenyl) 2- (2-nitro-1-phenylethyl) malonate
2- (2-Nitro-1-phenylethyl) malonic acid (1.26 g,5 mmol) was dissolved in 20mL of methylene chloride, 0.2mL of DMF was added dropwise, the reaction temperature was lowered to-5℃and oxalyl chloride (1.27 g,10 mmol) was added dropwise slowly, and the reaction was carried out at 0℃for 10 hours after the addition. 2,4, 6-trichlorophenol (0.39 g,2 mmol) was added to the reaction mixture, and the reaction was continued with stirring at 0℃for 12 hours. The reaction mixture was concentrated, cooled to room temperature, methanol (15 mL) was added, the precipitate was separated out, and the filtrate was washed with methanol (10 mL. Times.2) and dried to give the title compound (white solid, 1.06g, yield: 35%).
1 H NMR(400MHz,CDCl3)δ(ppm):7.40(s,4H),7.38-7.26(m,3H),7.18(t,J＝7.3Hz,2H),5.24(dd,J＝13.4,9.8Hz,1H),5.07(dd,J＝13.5,3.8Hz,1H),4.73(d,J＝8.7Hz,1H),4.55(td,J＝9.2,3.8Hz,1H)；
MS(ES-API,pos.ion)m/z:612.87[M+1] + 。
The intermediate compounds in table 3 can be prepared according to the above-described synthetic method of intermediate 8 using the corresponding starting materials.
TABLE 3 Table 3
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Example 1: synthesis of 1- ((2-chlorothiazol-5-yl) methyl) -3- (2-nitro-1-phenylethyl) -4-oxo-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-alkoxide
N- ((2-chlorothiazol-5-yl) methyl) pyridin-2-amine (0.24 g,0.5 mmol) and bis (2, 4, 6-trichlorophenyl) 2- (2-nitro-1-phenylethyl) malonate (0.31 g,0.5 mmol) were dissolved in 15mL of toluene solution and reacted at 110℃for 12 hours. After the reaction was stopped, the reaction mixture was concentrated, and [ petroleum ether/ethyl acetate (v/v) =1/3 ] was separated by silica gel column chromatography to give the objective compound (yellow solid, 0.120g, yield: 54%).
MS(ES-API,pos.ion)m/z:442.9[M+1] + ；
1 H NMR(400MHz,CDCl 3 )δ(ppm):9.08(d,J＝7.1Hz,1H),7.88–7.79(m,1H),7.63(s,1H),7.57(d,J＝8.8Hz,1H),7.47(d,J＝7.2Hz,2H),7.32–7.29(m,1H),7.28–7.16(m,3H),5.63(s,2H),5.61–5.57(m,1H),5.32–5.24(m,1H),5.21–5.16(m,1H).
Intermediate compounds 1 to 7 were prepared by the similar preparation method as in example 1 with the corresponding intermediate compounds 8 to 11, respectively, to give the objective compounds in table 4.
TABLE 4 Table 4
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Test case
1) Test target: plutella xylostella
Leaf dipping method: and (3) fully soaking a proper amount of cabbage leaves in the prepared liquid medicine, naturally drying in the shade, putting the cabbage leaves into a culture dish filled with filter paper, inoculating 10 heads of 2-3-year medium-term larvae of plutella xylostella per dish, culturing the cabbage leaves in an observation room at 24-27 ℃, and investigating the result after 3 d. The writing brush is used for touching the insect bodies, no reaction is regarded as dead insects, and the test concentration is 200mg/L.
2) Test target: armyworm
Leaf dipping method: and (3) fully soaking a proper amount of corn leaves in the prepared liquid medicine, naturally drying in the shade, placing the corn leaves in a culture dish filled with filter paper, inoculating 10 heads/dish of the myxoma 3-year middle-stage larvae, placing the corn leaves in an observation room at 24-27 ℃ for culture, investigating the result after 72 hours, and testing the concentration of 200mg/L.
3) Test target: aphis Medicago
Spraying method: selecting cowpea leaves with consistent growth, making leaf discs by using a puncher, placing wet sponge blocks in each dish, placing the leaf discs on the sponge, and adding water to be flush with the leaf discs for later use. The Aphis Medicago sativa (2-3 years old) raised indoors is inoculated on prepared leaf discs, and more than 15 heads of each disc are inoculated. The treatment is carried out by adopting a spray tower, and the spraying liquid amount is 0.5mL for each treatment. The test material after the medicament treatment is placed in an observation chamber, and the result is observed after 48 hours. The writing brush is used for touching the insect bodies, no reaction is regarded as dead insects, and the test concentration is 200mg/L.
4) Test target: brown planthopper 2-3 years old
Stem and leaf spray method: selecting healthy plants with roots (2-3 leaf stage of rice seedlings), carefully cleaning the roots, fixing the plants in a culture dish by quartz sand, spraying the rice seedlings with different concentrations of medicaments under a Potter spraying tower, airing, inoculating insects on the plants, and covering a plastic cup. The blank was treated and then the above procedure was repeated in trial dose order, with no less than 2 replicates per treatment. Each treated seedling is about 5, and the number of insects is 15. The reagent-treated test material is placed in an observation chamber, water is dripped into a culture dish for moisturizing at regular time, and the result is observed after 96 hours. The writing brush is used for touching the insect bodies, no reaction is regarded as dead insects, and the test concentration is 200mg/L.
The test results show that: at 200mg/L, the mortality rate of the example 5, the example 12, the example 14 and the example 18 to the plutella xylostella is above 90%;
at a concentration of 200mg/L, the mortality rate of the example 11 and the example 14 to the green peach aphids is more than 80%;
at a concentration of 200mg/L, the mortality rate of example 4 and example 9 for brown planthoppers was 100%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Claims (7)
1. A compound which is a compound having the formula (I) or a salt of a compound having the formula (I):
wherein:
R 1 is hydrogen or CH 3 -；
R 2 Thiazol-5-yl, pyridin-3-yl or pyrimidin-5-yl; wherein said thiazol-5-yl, pyridin-3-yl and pyrimidin-5-yl are optionally substituted with one or moreSelected from fluorine, chlorine, bromine, iodine or CH 3 S-substituent substitution;
R 3 phenyl or thienyl; wherein said phenyl and thienyl are optionally substituted with one or more groups selected from fluorine, chlorine, bromine, iodine or CF 3 -substituent substitution.
2. A compound according to claim 1, wherein:
R 2 is that
3. A compound according to claim 1, wherein:
R 3 is that
4. A compound according to any one of claims 1 to 3 which is a compound having one of the following structures or a salt of a compound having one of the following structures:
5. a composition comprising a compound of any one of claims 1-4.
6. Use of a compound according to any one of claims 1 to 4 or a composition according to claim 5 as an insecticide in agriculture.
7. A method of killing plutella xylostella and/or brown planthopper in agriculture with a compound according to any one of claims 1 to 4 or a composition according to claim 5.
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