CN112851665B - Novel mesoionic compounds and their use in agriculture - Google Patents

Abstract

The invention discloses a novel mesoionic compound and application thereof in agriculture, in particular to a novel mesoionic compound shown as a formula (I)Wherein X is ¹ 、X ² 、X ³ And X ⁴ Each independently is hydrogen or methyl; r is R ¹ 、R ² 、R ³ 、R ⁴ And R is ⁵ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, C _1‑6 Alkyl, halogenated C _1‑6 Alkyl groups, etc.; a is naphthyl or 9-10 membered heteroaryl; wherein the compound of formula (I) and/or the composition comprising the compound of formula (I) has excellent insecticidal activity and is used as an insecticide in agriculture, forestry and/or gardening.

Description

Novel mesoionic compounds and their use in agriculture

Technical Field

The invention relates to the field of pesticides, in particular to a novel mesoionic compound, a preparation method thereof and application thereof as a pesticide in agriculture.

Background

Pest control has been the core area of pesticide science research, and the use of pesticides in the market has resulted in effective control of a wide variety of pests. However, with the continuous expansion of the application scale of pesticides in the market, the problem of drug resistance of traditional pesticide varieties is increasingly remarkable, and the continuous occurrence of new diseases and insect pests makes the continuous research and development of new pesticides with high efficiency, safety, economy, environmental compatibility and different action modes necessary.

Disclosure of Invention

The invention provides a novel mesoionic compound which has excellent control effects on pests in agriculture, in particular to plutella xylostella, armyworm, alfalfa aphid and the like.

Specifically, in one aspect, the present invention provides a compound which is a compound having the formula (I), or a stereoisomer, a nitrogen oxide, or a salt thereof of the compound having the formula (I):

wherein:

X ¹ 、X ² 、X ³ and X ⁴ Each independently is hydrogen or methyl;

R ¹ 、R ² 、R ³ 、R ⁴ and R is ⁵ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, halogenated C _1-6 Alkyl, C _1-6 Alkyl, C _1-6 Alkoxy, halo C _1-6 Alkoxy, C _1-6 Alkylthio, halo C _1-6 Alkylthio, C _2-6 Alkenyl, C _2-6 Alkynyl, C _3-6 Cycloalkyl, C _2-6 Alkenyloxy, C _2-6 Alkynyloxy, C _3-6 Cycloalkyloxy, -SO ₂ -C _1-6 Alkyl or-C (=o) -C _1-6 An alkyl group;

a is naphthyl or 9-10 membered heteroaryl; wherein A is optionally substituted with 1,2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, C _1-6 Alkyl, halogenated C _1-6 Alkyl, C _1-6 Alkoxy, halo C _1-6 Alkoxy, C _1-6 Alkylthio or halogen C _1-6 Substituents of alkylthio groups;

the conditions are as follows: the compound of formula (I) is not:

1- ([ 1,2,4] triazol [4,3-a ] pyridin-3-ylmethyl) -4-oxo-3-phenyl-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-alkoxide; and

1- ((1H-benzo [ d ] [1,2,3] triazol-1-yl) methyl) -4-oxo-3-phenyl-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-alkoxide.

Wherein 1- ([ 1,2, 4)]Triazole [4,3-a ]]Pyridin-3-ylmethyl) -4-oxo-3-phenyl-4H-pyrido [1,2-a]The pyrimidine-1-onium-2-alkoxide has the corresponding structural formula:

1- ((1H-benzo [ d ]][1,2,3]Triazol-1-yl) methyl) -4-oxo-3-phenyl-4H-pyrido [1,2-a]The pyrimidine-1-onium-2-alkoxide has the corresponding structural formula:

in some embodiments, X ¹ 、X ² 、X ³ And X ⁴ Each independently is hydrogen.

In still other embodiments, X ² 、X ³ And X ⁴ Each independently is hydrogen, X ¹ Is methyl.

In some embodiments, R ¹ 、R ² 、R ³ 、R ⁴ And R is ⁵ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, C _1-4 Alkyl, halogenated C _1-4 Alkyl, C _1-4 Alkoxy, halo C _1-4 Alkoxy, C _1-4 Alkylthio, halo C _1-4 Alkylthio, C _2-4 Alkenyl, C _2-4 Alkynyl, C _3-6 Cycloalkyl, C _2-4 Alkenyloxy, C _2-4 Alkynyloxy, C _3-6 Cycloalkyloxy, -SO ₂ -C _1-4 Alkyl or-C (=o) -C _1-4 An alkyl group.

In still other embodiments, R ¹ 、R ² 、R ³ 、R ⁴ And R is ⁵ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, -CH ₃ 、-CH ₂ CH ₃ 、-CH ₂ CH ₂ CH ₃ 、-CH(CH ₃ ) ₂ 、-CH ₂ CH ₂ CH ₂ CH ₃ 、-C(CH ₃ ) ₃ 、-CHF ₂ 、-CF ₃ 、-OCH ₃ 、-OCH ₂ CH ₃ 、-OCH ₂ CH ₂ CH ₃ 、-OCH(CH ₃ ) ₂ 、-OCH ₂ CH ₂ CH ₂ CH ₃ 、-OC(CH ₃ ) ₃ 、-OCF ₃ 、-SCH ₃ 、-SCH ₂ CH ₃ 、-SCF ₃ 、-CH＝CH ₂ Cyclopropyl, -SO ₂ -CH ₃ Or CH (CH) ₃ -C(＝O)-。

In other embodiments, R ¹ 、R ² 、R ³ 、R ⁴ And R is ⁵ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, C _1-4 Alkyl, halogenated C _1-4 Alkyl, C _1-4 Alkoxy or halo C _1-4 An alkoxy group.

In still other embodiments, R ¹ 、R ² 、R ³ 、R ⁴ And R is ⁵ Each independently is hydrogen, chlorine or-CF ₃ 。

In yet other embodiments of the present invention,the following sub-structural formula is shown as follows:

in some embodiments, A is naphthyl or 9-10 membered heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, C _1-4 Alkyl, halogenated C _1-4 Alkyl, C _1-4 Alkoxy or halo C _1-4 The substituent of the alkoxy group is substituted.

In still other embodiments, a is naphthyl, a benzo 5-membered heteroaryl, or a benzo 6-membered heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodineCyano, nitro, hydroxy, amino, C _1-4 Alkyl, halogenated C _1-4 Alkyl, C _1-4 Alkoxy or halo C _1-4 The substituent of the alkoxy group is substituted.

In still other embodiments, A is naphthyl, benzothienyl, benzofuranyl, benzothiazolyl, benzisoxazolyl, benzoxazolyl, benzimidazolyl, benzopyrazolyl, indolyl, or quinolinyl; wherein A is optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, C _1-4 Alkyl, halogenated C _1-4 Alkyl, C _1-4 Alkoxy or halo C _1-4 The substituent of the alkoxy group is substituted.

In other embodiments, A is naphthyl, benzothienyl, benzofuranyl, benzothiazolyl, benzisoxazolyl, benzoxazolyl, benzimidazolyl, benzopyrazolyl, indolyl, or quinolinyl; wherein A is optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, -CH ₃ 、-CH ₂ CH ₃ 、-CH ₂ CH ₂ CH ₃ 、-CH(CH ₃ ) ₂ 、-CH ₂ CH ₂ CH ₂ CH ₃ 、-C(CH ₃ ) ₃ 、-CHF ₂ 、-CF ₃ 、-OCH ₃ 、-OCH ₂ CH ₃ 、-OCH ₂ CH ₂ CH ₃ 、-OCH(CH ₃ ) ₂ 、-OCH ₂ CH ₂ CH ₂ CH ₃ 、-OC(CH ₃ ) ₃ or-OCF ₃ Is substituted by a substituent of (a).

In some embodiments, A is

Wherein A is optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, C _1-4 Alkyl, halogenated C _1-4 Alkyl, C _1-4 Alkoxy groupOr halogenated C _1-4 The substituent of the alkoxy group is substituted.

In some embodiments, A is

Wherein A is optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, -CH ₃ 、-CH ₂ CH ₃ 、-CH ₂ CH ₂ CH ₃ 、-CH(CH ₃ ) ₂ 、-CH ₂ CH ₂ CH ₂ CH ₃ 、-C(CH ₃ ) ₃ 、-CHF ₂ 、-CF ₃ 、-OCH ₃ 、-OCH ₂ CH ₃ 、-OCH ₂ CH ₂ CH ₃ 、-OCH(CH ₃ ) ₂ 、-OCH ₂ CH ₂ CH ₂ CH ₃ 、-OC(CH ₃ ) ₃ or-OCF ₃ Is substituted by a substituent of (a).

In yet other embodiments, a is of the following sub-structural formula:

the inventor in the application finds that A isAnd->Is thatWhen the insecticidal composition is used, the insecticidal activity is excellent; the mortality rates of the example 12 and the example 13 on the plutella xylostella are 75 percent and 80 percent respectively under the concentration of 500 mg/L; and is carried out at the same concentration The mortality rate of example 7 to example 11 on plutella xylostella was 60% or less.

In addition, the inventor in the application finds that A is Wherein a is optionally substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine or iodine; alternatively, A isAnd->Is->When the insecticidal composition is used, the insecticidal activity is more excellent; the mortality rate of the example 1, the example 2, the example 4 and the example 5 to the plutella xylostella is 75-100% at the concentration of 500 mg/L; and the mortality rate of example 3 and example 6 on plutella xylostella is 0 at the same concentration.

In another aspect, the present invention provides a compound that is a compound having one of the following structures, or a stereoisomer, nitroxide, or salt thereof of a compound having one of the following structures:

in another aspect, the invention provides a composition comprising at least one compound of the invention.

Further, the composition of the invention comprises an agropharmaceutically acceptable adjuvant.

In another aspect, the invention provides the use of a compound of the invention and/or a composition of the invention as an insecticide in agriculture.

In yet another aspect, the present invention provides a method of controlling pests, comprising applying a compound of the present invention and/or a composition of the present invention to the pests, the pest growing medium and/or the pest growing environment.

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.

Examples of alkyl groups 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 "alkenyl" denotes a straight-chain or branched monovalent hydrocarbon radical containing 2 to 12 carbon atoms, in which there is at least one site of unsaturation, i.e. one carbon-carbon sp ² A double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group contains 2 to 8 carbon atoms; in another embodiment, the alkenyl group comprises 2 to 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-ch=ch) ₂ ) Allyl (-CH) ₂ CH＝CH ₂ ) Propenyl (CH) ₃ -ch=ch-), oxo-butenyl (CH ₃ -C (=o) -ch=ch-), and so on.

The term "alkynyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may be optionally substituted with one or more substituents described herein. In one embodiment, the alkynyl group contains 2 to 10 carbon atoms; in one embodiment, the alkynyl group contains 2 to 8 carbon atoms; in another embodiment, the alkynyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C.ident.CH, -C.ident.CCH ₃ 、-CH ₂ -C≡CH、-CH ₂ -C≡CCH ₃ 、-CH ₂ CH ₂ -C≡CH、-CH ₂ -C≡CCH ₂ CH ₃ 、-CH ₂ CH ₂ -C≡CH ₂ CH ₃ Etc.

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 ) Isopropoxy (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 "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3 to 12 carbon atoms. In one embodiment, cycloalkyl groups contain 3 to 10 carbon atoms; in another embodiment, cycloalkyl groups contain 3 to 8 carbon atoms; in yet another embodiment, cycloalkyl groups contain 3 to 6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.

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, 2-furyl, 3-furyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl), triazolyl (e.g., 2-triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 4-oxadiazolyl, 1, 2-triazolyl, 3-triazolyl, 1, 3-triazolyl, 3-thiotriazinyl, 1, 2-thiotriazinyl, 1-thiotriazinyl; the following bicyclic rings are also included, but are in no way limited to: benzimidazolyl, benzothiazolyl, benzofuranyl, benzothienyl, benzisoxazolyl, indolyl (e.g., 2-indolyl), quinolinyl, 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.

The term "alkenyloxy" means that the alkenyl group is attached to the remainder of the molecule through an oxygen atom, wherein the alkenyl group has the meaning as described herein.

The term "alkynyloxy" means an alkynyl group attached to the remainder of the molecule through an oxygen atom, wherein the alkynyl group has the meaning as described herein.

The term "cycloalkyloxy" means that the cycloalkyl group is attached to the remainder of the molecule through an oxygen atom, wherein the cycloalkyl group has the meaning as described herein.

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 the invention may be prepared by treating the compounds of the invention 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 compounds of the present invention are generally useful as pesticide active ingredients in compositions or formulations, and generally also include agropharmaceutically acceptable adjuvants including surfactants and/or carriers.

The surfactant may be any of various surfactants known in the art of agricultural chemical 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 agricultural chemical 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 may be various emulsifiers known in the field of pesticide formulation, and specifically, the emulsifier may be 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, rosin acid ethylene oxide adduct, 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 formulation 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 can be various wetting agents known in the pesticide formulation field, and concretely, the wetting agent can be one or more of sodium dodecyl sulfate, secondary sodium alkyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl naphthalene sulfonate and alkylphenol 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 dosage forms, and specifically, the adjuvants for formulation may be one or more of solvents, co-solvents, thickeners, antifreezes, encapsulating materials, protectants, antifoaming agents, disintegrants, stabilizers, preservatives and binders.

The above solvent may be various solvents well known in the field of agricultural chemical formulation, and specifically, the solvent may be 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 above antifreezing agent may be various antifreezing agents known in the field of agricultural chemical formulation, and the present invention is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.

The thickener may be various thickeners known in the field of pesticide dosage forms, and specifically, the thickener may be one or more of xanthan gum, polyvinyl alcohol, polyacrylate alcohol, polyethylene glycol, white carbon black, diatomaceous earth, kaolin, clay, sodium alginate, aluminum magnesium silicate, aluminum sodium silicate, carboxymethyl cellulose, hydroxypropyl cellulose sodium, and organic bentonite.

The capsule wall material can be various capsule wall materials known in the pesticide formulation field, and the invention is preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.

The protective agent may be any of various protective agents known in the field of agricultural chemical formulations, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.

The above defoamer may be various defoamers known in the field of pesticide formulation, and the present invention is preferably one or more of organosiloxane, tributyl phosphate and silicone.

The stabilizer is one or more selected from 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 above dosage forms can 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 above aqueous emulsion preparation method may include, for example, mixing the active ingredient, the emulsifier, the cosolvent and the solvent to form 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 by mixing and stirring the active ingredient, the emulsifier and the solvent into a uniform 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. The invention therefore 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.

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).

"room temperature" in the present invention refers to the natural temperature around the location of the object, which may vary depending on the region, season, time of day, typically between-20 c and 45 c or about 18 c to 30 c or about 20 c to 25 c or about 22 c, unless otherwise specified. DMF is N, N-dimethylformamide.

Synthetic scheme

Synthesis scheme one

The target compound represented by the formula (I) can be prepared by a first synthesis scheme. The intermediate compound M reacts with the intermediate compound N under the heating condition (60-180 ℃) to obtain the target compound shown in the formula (I).

Examples

Intermediate M1: synthesis of N- (benzo [ d ] thiazol-2-ylmethyl) pyridin-2-amine

The compound pyridin-2-ylcarbamate (0.97 g,5.00 mmol) was dissolved in DMF (15 mL) and the reaction was stirred at 0deg.C for 15 min, then sodium hydride (0.36 g,15.00 mmol) was added three times and after the addition was complete, the stirring reaction was continued for 30 min at 0deg.C; the reaction was warmed to room temperature and then slowly dropped into a solution of 2- (bromomethyl) benzo [ d ] thiazole (1.15 g,5.04 mmol) in DMF (10 mL); after the addition, the reaction is carried out for 12 hours at room temperature; after completion of the reaction, ice water (25 mL) was added to the reaction, extraction was performed with ethyl acetate (60 ml×3), the organic phases were combined, the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give 0.9g of a yellow oil.

The oil obtained above was dissolved in dichloromethane (30 mL) and stirred at room temperature; then, trifluoroacetic acid (1.8 mL) is slowly dripped, and after the dripping is finished, the reaction is heated to 40 ℃ and the reflux reaction is carried out for 12 hours; the reaction was then concentrated, saturated aqueous potassium carbonate was added, ph=8, ethyl acetate extraction (60 ml×3), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the filtrate concentrated under reduced pressure, and separated by column chromatography [ petroleum ether/ethyl acetate (v/v) =2/1 ] to give 0.41g of yellow solid, yield: 34%.

¹ H NMR(400MHz,CDCl ₃ )δ8.17(d,J＝4.9Hz,1H),8.01(d,J＝8.1Hz,1H),7.85(d,J＝7.9Hz,1H),7.47(d,J＝27.9Hz,2H),7.38(d,J＝16.1Hz,1H),6.68(d,J＝12.2Hz,1H),6.54(d,J＝8.4Hz,1H),5.37(s,1H),5.02(d,J＝6.1Hz,2H).

MS(ES-API,pos.ion)m/z:242.12[M+1] ⁺ .

The intermediate compounds in table 1 were prepared using the corresponding starting materials, with reference to a similar synthetic method to example M1, or with reference to synthetic methods in the prior art.

TABLE 1

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Intermediate N1: synthesis of bis (2, 4, 6-trichlorophenyl) -2- (3-trifluoromethylphenyl) malonate

The first step: synthesis of methyl 2- (3- (trifluoromethyl) phenyl) acetate

3-Trifluoromethylphenylacetic acid (4.08 g,20 mmol) was dissolved in methanol (60 mL), concentrated sulfuric acid (2 mL) was added, the reaction temperature was increased to 60℃and reacted at 60℃for 10 hours; after completion of the reaction, the resulting mixture was concentrated under reduced pressure, and the resulting residue was dissolved with ethyl acetate (100 mL), then washed with water (30 ml×3), dried over anhydrous sodium sulfate for 1 hour, filtered, and the filtrate was concentrated and separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) =30/1 ], to give 4.0g of a colorless liquid, yield: 91.7%.

And a second step of: synthesis of dimethyl 2- (3- (trifluoromethyl) phenyl) malonate

Methyl 2- (3- (trifluoromethyl) phenyl) acetate (2.9 g,17.5 mmol) was dissolved in tetrahydrofuran (40 mL) and then 60% sodium hydride (1.70 g,42 mmol) was added in portions at room temperature, and after the addition was completed, the reaction was carried out at room temperature for 30 minutes; dimethyl carbonate (8.1 g,90 mmol) was then added dropwise to the reaction, and after completion of the addition, the reaction was warmed to 60℃and refluxed for 18 hours. After completion of the reaction, the reaction was quenched by addition of 15mL of saturated ammonium chloride solution, followed by extraction with ethyl acetate (50 ml×3), drying the combined organic phases over sodium sulfate for 1 hour, filtering, concentrating the filtrate, and separating the filtrate by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) =10/1 ] to give the objective product as a colorless liquid: 3.0g, yield 75.8%.

And a third step of: synthesis of 2- (3- (trifluoromethyl) phenyl) malonic acid

Dimethyl 2- (3- (trifluoromethyl) phenyl) malonate (5.52 g,20.00 mmol) was added slowly to a 100mL reaction flask, an aqueous solution (40 mL) of sodium hydroxide (4.00 g,100.00 mmol) was stirred under reflux at 60℃with heating in an oil bath for 3h. After the reaction was completed, the reaction was moved to 0 ℃ with stirring under ice bath, and concentrated hydrochloric acid (10 mL) was slowly added to make the solution ph=1. Ethyl acetate (50 ml×3) was added to extract the aqueous phase, the organic phases were combined, and after drying the organic phase over anhydrous sodium sulfate for 1h, the organic solvent was removed by filtration and distillation under reduced pressure, 4.41g of a yellow solid was obtained in the yield: 90%.

Fourth step: synthesis of bis (2, 4, 6-trichlorophenyl) -2- (3-trifluoromethylphenyl) malonate

2- (3-trifluoromethylphenyl) malonic acid (4.41 g,18.00 mmol), N-dimethylformamide (1 mL) and methylene chloride (50 mL) were added to a 250mL single-necked flask and stirred in an ice bath at 0 ℃. Oxalyl chloride (8 mL,95 mmol) was then slowly added dropwise to the reaction at 0deg.C, after which the reaction was allowed to return to room temperature and continued for 6h. After completion of the reaction, 2,4, 6-trichlorophenol (8.00 g,40.00 mmol) was added to the reaction mixture, and the reaction was continued for 12 hours. The reaction was closed, the reaction mixture was concentrated, methanol (40 mL) was added, and the mixture was allowed to stand at room temperature for 3 hours, a large amount of white precipitate was precipitated from the reaction mixture, and the mixture was filtered, and the cake was washed with methanol (20 mL) to give 6.64g of a white solid, yield: 61%.

¹ H NMR(400MHz,CDCl ₃ )δ(ppm):7.94(s,1H),7.87(d,J＝7.8Hz,1H),7.73(d,J＝7.8Hz,1H),7.62(t,J＝7.8Hz,1H),7.49(s,2H),7.41(s,2H),5.40(s,1H)。

MS(ES-API,pos.ion)m/z:607.85[M+1] ⁺ 。

The preparation was carried out using the corresponding materials with reference to the synthesis of intermediate N1, or with reference to the synthesis of the prior art, giving the intermediate compounds in table 2.

TABLE 2

Example 1: synthesis of 1- (benzo [ d ] thiazol-2-ylmethyl) -4-oxo-3- (3- (trifluoromethyl) phenyl) -4H-pyrido [1,2-a ] pyrimidin-1-ium-2-alkoxide

Bis (2, 4, 6-trichlorophenyl) -2- (3-trifluoromethylphenyl) malonate (0.35 g,0.58 mmol) and N- (benzo [ d ] thiazol-2-ylmethyl) pyridin-2-amine (0.14 g,0.58 mmol) were dissolved in 8mL of toluene and reacted at 110℃for 48 hours. Concentrated under reduced pressure, and the residue was separated by column chromatography [ petroleum ether/ethyl acetate (v/v) =1/4 ] to give 80mg of a yellow solid, yield: 30%.

¹ H NMR(400MHz,CDCl ₃ )δ9.54(d,J＝6.8Hz,1H),8.10(d,J＝62.4Hz,5H),7.88(d,J＝8.0Hz,1H),7.53(d,J＝21.3Hz,3H),7.42(d,J＝20.4Hz,2H),5.97(s,2H).

MS(ES-API,pos.ion)m/z:454.4[M+1] ⁺ .

The target compounds in Table 3 were obtained by carrying out the preparation using intermediates M1 to M8 and the corresponding intermediates N1 to N3 as starting materials, by analogy with the synthesis of example 1 or by reference to the preparation methods of the prior art.

TABLE 3 Table 3

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Activity test case

Test target: plutella xylostella

Leaf dipping method: the method comprises the steps of 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 500mg/L.

Test target: armyworm

Leaf dipping method: the target to be tested is myxoworm, a proper amount of corn leaves are fully soaked in the prepared liquid medicine and then naturally dried in the shade, the corn leaves are placed in a culture dish filled with filter paper, 10 heads/dish of myxoworm middle-stage larvae of 3 years old are connected, the corn leaves are placed in an observation room at 24-27 ℃ for culture, and after 72 hours, the investigation result is carried out, and the test concentration of the sample is 500mg/L.

The test results show that: the mortality rate of the example 1, the example 2, the example 4, the example 5, the example 12 and the example 13 to the plutella xylostella is 75-100% at the concentration of 500 mg/L;

at a concentration of 500mg/L, the mortality rate of the armyworms in example 4 and example 5 is 80-100%.

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 (3)

1. A compound which is a compound having one of the following structures, or a salt of a compound having one of the following structures:

2. a composition comprising the compound of claim 1.

3. Use of a compound according to claim 1 or a composition according to claim 2 as an insecticide in agriculture.