WO2020228687A1

WO2020228687A1 - 4-aminofuran-2 (5h) one derivatives, preparation methods and applications thereof

Info

Publication number: WO2020228687A1
Application number: PCT/CN2020/089705
Authority: WO
Inventors: Yitao LI; Jian Lin; Pingyi TIAN; Junxing XU
Original assignee: Dongguan HEC Pesticides R&D Co., Ltd.
Priority date: 2019-05-13
Filing date: 2020-05-12
Publication date: 2020-11-19
Also published as: CN111925363B; CN111925364B; CN111925364A; CN111925363A

Abstract

Provided are a 4-aminofuran-2 (5H) ketone derivative having formula (I) or a stereoisomer, an N-oxide, and a salt thereof, and preparation methods of 4-aminofuran-2 (5H) ketone derivative, and their uses as pesticides in agriculture, forms of pesticide compositions thereof, and methods for controlling pests using these compounds or compositions; wherein ring A, ring B, R 1, R 2, R 3, R 4, R 5, R 6, W, W 1, R a, R b, x and y are as described in the present invention.

Description

4-AMINOFURAN-2 (5H) ONE DERIVATIVES, PREPARATION METHODS AND APPLICATIONS THEREOF

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the priority and benefits of Chinese Patent Application No. 201910394660.5, filed with the State Intellectual Property Office of China on May 13, 2019, which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to a novel 4-aminofuran-2 (5H) ketone derivative, preparation methods thereof, and its uses as a pest control agent in agriculture or horticulture.

BACKGROUND OF THE INVENTION

Infestation caused by invertebrate pests is common in agriculture, forestry, greenhouse crops, ornamental plants, nursery crops, stored food, livestock, dwellings, turf, wood products and public health, causing great losses to economic property and healthy life. Due to the increasing resistance of pests against many commercial insecticides at present, it is necessary to increase the dose to kill the pests, which places a great burden on the environment. Therefore, there is a continuing need for new compounds that are more effective, more economical, less toxic, safer to the environment, or have different sites of action to control invertebrate pests.

SUMMARY OF THE INVENTION

The present invention provides a novel 4-aminofuran-2 (5H) ketone derivative, which has excellent control effect on invertebrate pests, especially pests in agriculture.

Specifically:

In one aspect, the present invention provides a compound having Formula (I) or a stereoisomer, an N-oxide, or a salt thereof:

wherein,

each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, halogen, hydroxy, cyano, nitro, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, halo C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-;

each of R ⁵ and R ⁶ is independently hydrogen or C _1-6 alkyl;

or R ⁵ and R ⁶ together with the carbon atom to which they are attached form C _3-6 cycloalkyl;

W is N or CR ⁷;

R ⁷ is hydrogen, halogen or C _1-6 alkyl;

W ¹ is O or S;

ring A is 6-membered heteroaryl containing up to 3 nitrogen atoms;

ring B is 5-6 membered heteroaryl or 5-6 membered saturated heterocycle;

x is 0, 1, 2, 3 or 4;

each R ^a is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _2-6 alkenyl-O-, C _2-6 alkynyl-O-, halo C _1-6 alkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkyl-C _1-3 alkyl-, C _3-8 cycloalkyl-O-, C _3-8 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl -O-, C _1-6 alkyl-S (= O) _n-, C _1-6 alkyl-C (= O) -, C _1-6 alkyl-C (= O) O-, C _1-6 alkoxy-C (= O) -or -NR ^cR ^d; each R ^a is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1a;

n is 0, 1 or 2;

each R ^c and R ^d is independently hydrogen, C _1-6 alkyl, C _1-6 alkyl-C (= O) -, C _1-6 alkoxy-C (= O) -, C _1-6 alkyl-SO ₂-, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-;

each R ^1a is independently halogen, hydroxy, cyano, nitro, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, or halo C _1-6 alkoxy;

y is 0, 1, 2, 3, 4, 5 or 6;

each R ^b is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _2-6 alkenyl-O-, C _2-6 alkynyl-O-, halo C _1-6 alkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkyl-C _1-3 alkyl-, C _3-8 cycloalkyl-O-, C _3-8 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl-O-, C _1-6 alkyl-S (= O) _m-, C _1-6 alkyl-C (= O) -, C _1-6 alkyl-C (= O) O-, C _1-6 alkoxy-C (= O) -or -NR ^eR ^f; each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

m is 0, 1 or 2;

each R ^e and R ^f is independently hydrogen, C _1-6 alkyl, C _1-6 alkyl-C (= O) -, C _1-6 alkoxy-C (= O) -, C _1-6 alkyl-SO ₂-, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-;

each R ^1b is independently halogen, hydroxy, cyano, nitro, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, or halo C _1-6 alkoxy;

with the proviso that: the compound represented by formula (I) is not 4- ( ( (6-chloropyridin-3-yl) methyl) (thien-2-ylmethyl) amino) furan-2 (5H) -one.

In some embodiments, each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-.

In other embodiments, each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -C (CH ₃) ₃, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -OC (CH ₃) ₃ or -OCF ₃.

In other embodiments,

is one of the following sub-formulae:

wherein, x1 is 0, 1, 2, 3 or 4;

each x2 is independently 0, 1, 2 or 3;

each R ^a is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _2-4 alkenyl-O-, C _2-4 alkynyl-O-, halo C _1-4 alkoxy, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkyl-, C _3-6 cycloalkyl-O-, C _3-6 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl -O-, C _1-4 alkyl-S (= O) _n-, C _1-4 alkyl-C (= O) -, C _1-4 alkyl-C (= O) O-, C _1-4 alkoxy-C (= O) -or -NR ^cR ^d; each R ^a is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1a;

n is 0, 1 or 2;

each R ^c and R ^d is independently hydrogen, C _1-4 alkyl, C _1-4 alkyl-C (= O) -, C _1-4 alkoxy-C (= O) -, C _1-4 alkyl-SO ₂-, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-;

each R ^1a is independently halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, or halo C _1-4 alkoxy.

In other embodiments,

is one of the following sub-formulae:

wherein, each x1 is independently 0, 1, 2, 3, or 4;

each R ^a is independently fluorine, chlorine, bromine, iodine, hydroxy, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃ or -NH ₂; each R ^a is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1a;

each R ^1a is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CF ₃, -OCH ₃ or -OCF ₃.

In still other embodiments,

is one of the following sub-formulae:

wherein, each R ^a is independently fluorine, chlorine, bromine, iodine, hydroxyl, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃ or -NH ₂.

In some embodiments, ring B is pyrrolyl, pyrazolyl, imidazolyl, thienyl, isothiazolyl, thiazolyl, furyl, isoxazolyl, oxazolyl or tetrahydrofuryl;

y is 0, 1, 2, 3, 4, 5 or 6;

each R ^b is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-6 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _2-4 alkenyl-O-, C _2-4 alkynyl-O-, halo C _1-4 alkoxy, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkyl-, C _3-6 cycloalkyl-O-, C _3-6 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl-O-, C _1-4 alkyl-S (= O) _m-, C _1-4 alkyl-C (= O) -, C _1-4 alkyl-C (= O) O-, C _1-4 alkoxy-C (= O) -or -NR ^eR ^f; each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

m is 0, 1 or 2;

each R ^e and R ^f is independently hydrogen, C _1-4 alkyl, C _1-4 alkyl-C (= O) -, C _1-4 alkoxy-C (= O) -, C _1-4 alkyl-SO ₂-, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-;

each R ^1b is independently halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, or halo C _1-4 alkoxy.

In other embodiments,

is one of the following sub-formulae:

wherein, each y1 is independently 0, 1, 2 or 3;

each y2 is independently 0, 1 or 2;

y3 is 0, 1, 2, 3, 4, 5 or 6;

m is 0, 1 or 2;

In still other embodiments,

is one of the following sub-formulae:

m is 0, 1 or 2;

each R ^1b is independently halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, or halo C _1-4 alkoxy;

each R ^b1 is independently halogen, hydroxy, cyano, nitro, C _1-4 alkyl or halo C _1-4 alkyl.

In still other embodiments,

is one of the following sub-formulae:

wherein, each y1 is independently 0, 1, 2 or 3;

each y2 is independently 0, 1, or 2;

y3 is 0, 1, 2, 3, 4, 5 or 6;

each y4 is independently 0, 1, 2, 3, or 4;

each R ^b is independently fluorine, chlorine, bromine, iodine, hydroxy, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -C (CH ₃) ₃, -CH ₂CH ₂CH ₂CH ₂CH ₃, -CH ₂CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -CH ₂CHF ₂, -CH ₂CH ₂F, -CH ₂CH ₂Cl, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -CH=CH ₂, -CH ₂CH=CH ₂, CH ₃-CH=CH-, -C ≡CH, -CH ₂-C ≡CH, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃, -SO ₂CH ₂CH ₃, CH ₃-C (=O) , CH ₃-C (=O) O-, CH ₃O-C (=O) -or -NR ^eR ^f;

each of R ^e and R ^f is independently hydrogen, -CH ₃ or -CH ₂CH ₃;

or each R ^b is independently one of the following sub-formulae:

each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

each R ^1b is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃ or -OCF ₃.

In still other embodiments,

is one of the following sub-formulae:

each R ^b is independently fluorine, chlorine, bromine, iodine, hydroxy, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -C (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CH (CH ₃) ₃, -CH ₂CH ₂CH ₂CH ₂CH ₃, -CH ₂CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -CH ₂CHF ₂, -CH ₂CH ₂F, -CH ₂CH ₂Cl, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -CH=CH ₂, -CH ₂CH=CH ₂, CH ₃-CH=CH-, -C≡CH, -CH ₂-C ≡CH, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃, -SO ₂CH ₂CH ₃, CH ₃-C (=O) , CH ₃-C (=O) O-, CH ₃O-C (=O) -or -NR ^eR ^f;

each R ^e and R ^f is independently hydrogen, -CH ₃ or -CH ₂CH ₃;

or each R ^b is independently one of the following sub-formulae:

each R ^1b is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃ or -OCF ₃;

each R ^b1 is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃ or -CH ₂CHF ₂.

In some embodiments, each of R ⁵ and R ⁶ is independently hydrogen or C _1-4 alkyl;

W is N or CR ⁷;

R ⁷ is hydrogen, halogen or C _1-4 alkyl;

W ¹ is O or S.

In still other embodiments, the present invention provides a compound having Formula (II) or a stereoisomer, an N-oxide, or a salt thereof:

In other aspect, provided herein is a composition comprising the compound disclosed herein.

In still other aspect, provided herein is use of the compound of the present invention or the composition of the present invention in controlling pests.

In still other aspect, provided herein is the compound of the present invention or the composition of the present invention for use in controlling pests.

In still other aspect, provided herein is a method of controlling pests comprising administering to seeds, plants or plant parts, fruits or the soil in which the plants grow, a therapeutically effective amount of the compound of the present invention or the composition of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

DEFINITIONS AND GENERAL TERMINOLOGY

Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated in the accompanying structures and formulas. The invention is intended to cover all alternatives, modifications, and equivalents which may be included within the scope of the present invention as defined by the claims. One skilled in the art will recognize many methods and materials similar or equivalent to those described herein, which could 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 that one or more of the incorporated literature, patents, and similar materials differs from or contradicts this application, including but not limited to defined terms, term usage, described techniques, or the like, this application controls.

It is further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, can 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, can also be provided separately or in any suitable subcombination.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one skilled in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.

As used herein, the following definitions shall apply unless otherwise indicated. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, and the Handbook of Chemistry and Physics, 75th Ed. 1994. Additionally, general principles of organic chemistry are described in “Organic Chemistry” , Thomas Sorrell, University Science Books, Sausalito: 1999, 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 hereby incorporated by reference.

The grammatical articles “a” , “an” and “the” , as used herein, are intended to include “at least one” or “one or more” unless otherwise indicated herein or clearly contradicted by the context. Thus, the articles used herein refer to one or more than one (i.e., at least one) articles of the grammatical objects. By way of example, “a component” means one or more components, and thus, possibly, more than one component is contemplated and may be employed or used in an implementation of the described embodiments.

The term “comprise” is an open expression, it means comprising the contents disclosed herein, but don’t exclude other contents.

“Stereoisomers” refers to compounds which have identical chemical constitution, but differ with regard to the arrangement of the atoms or groups in space. Stereoisomers include enantiomer, diastereomers, conformer (rotamer) , geometric (cis/trans) isomer, atropisomer, etc.

“Enantiomers” refers to two stereoisomers of a compound which are non-superimposable mirror images of one another.

“Diastereomer” refers to a stereoisomer with two or more centers of chirality and whose molecules are not mirror images of one another. Diastereomers have different physical properties, e.g. melting points, boling points, spectral properties or biological activities. Mixture of diastereomers may separate under high resolution analytical procedures such as electrophoresis and chromatography such as HPLC.

Stereochemical definitions and conventions used herein 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 forms, i.e., they have the ability to rotate the plane of plane-polarized light. In describing an optically active compound, the prefixes D and L, or R and S, are used to denote the absolute configuration of the molecule about its chiral center (s) . The prefixes d and l or (+) and (-) are employed to designate the sign of rotation of plane-polarized light by the compound, with (-) or l meaning that the compound is levorotatory. A compound prefixed with (+) or d is dextrorotatory. A specific stereoisomer may be referred to as an enantiomer, and a mixture of such stereoisomers is called an enantiomeric mixture. A 50: 50 mixture of enantiomers is referred to as a racemic mixture or a racemate, which may occur where there has been no stereoselection or stereospecificity in a chemical reaction or process.

Any asymmetric atom (e.g., carbon or the like) of the compound (s) disclosed herein can be present in racemic or enantiomerically enriched, for example 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 the starting materials and procedures, the compounds can be present in the form of one of the possible stereoisomers or as mixtures thereof, such as racemates and diastereoisomer mixtures, depending on the number of asymmetric carbon atoms. Optically active (R) -and (S) -isomers may be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituent may be E or Z configuration. If the compound contains a disubstituted cycloalkyl, the cycloalkyl substituent may have a cis-or trans-configuration.

Any resulting mixtures of stereoisomers can be separated on the basis of the physicochemical differences of the constituents, into the pure or substantially pure geometric isomers, enantiomers, diastereomers, for example, by chromatography and/or fractional crystallization.

Any resulting racemates of final products or intermediates can be resolved into the optical antipodes by methods known to those skilled in the art, e.g., by separation of the diastereomeric salts thereof. Racemic products can also be resolved by chiral chromatography, e.g., high performance liquid chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.

As described herein, compounds disclosed herein may optionally be substituted with one or more substituents, such as are illustrated generally below, or as exemplified by particular classes, subclasses, and species of the invention. It will be appreciated that the phrase “optionally substituted” and “optionally substituted with... substituents” is used interchangeably with the phrase “substituted or unsubstituted” . In general, “optionally substituted” and “optionally substituted with... substituents” mean the given structure is unsubstituted or one or more hydrogen atoms in the given structure are replaced by the radical of a specified substituent. In general, the term “substituted” refers to the replacement of one or more hydrogen radicals in a given structure with the radical of a specified substituent. Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group. When more than one position in a given structure can be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at each position. Specifically, the examples of “one or more” refer to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. wherein substituents of compounds disclosed herein include, but are not limited to, deuterium, F, Cl, Br, I, CN, OH, NO ₂, NH ₂, COOH, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substitued alkyl, hydroxy-substitued alkylamino, cyano-substitued alkyl, cyano-substitued alkoxy, cyano-substitued alkylamino, amino-substitued alkyl, alkylacyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, acylamino, sulfonyl, aminosulfonyl, and the like.

Furthermore, what need to be explained is that the phrases “each…is independently” and “each of…and…is independently” , unless otherwise stated, should be broadly understood, which can mean that the specific options expressed by the same symbol are independent of each other in different groups; or the specific options expressed by the same symbol are independent of each other in same groups.

At each part of the present specification, substitutes of compounds disclosed herein are disclosed in groups or in ranges. It is specifically intended that the invention includes each and every individual subcombination of the members of such groups and ranges. For example, the term “C ₁-C ₆ alkyl” or “C _1-6 alkyl” is specifically intended to individually disclose methyl, ethyl, C ₃ alkyl, C ₄ alkyl, C ₅ alkyl, and C ₆ alkyl.

The term “alkyl” or “alkyl group” refers to a saturated linear or branched-chain monovalent hydrocarbon group of 1-20 carbon atoms, wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise stated, the alkyl group contains 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms. In one embodiment, the alkyl group contains 1-8 carbon atoms. In another embodiment, the alkyl group contains 1-6 carbon atoms. In still other embodiment, the alkyl group contains 1-4 carbon atoms. In yet other embodiment, the alkyl group contains 1-3 carbon atoms.

Examples of alkyl groups include, but are not limited to, methyl (Me, -CH ₃) , ethyl (Et, -CH ₂CH ₃) , n-propyl (n-Pr, -CH ₂CH ₂CH ₃) , isopropyl (i-Pr , -CH (CH ₃) ₂) , n-butyl (n-Bu, -CH ₂CH ₂CH ₂CH ₃) , isobutyl (i-Bu, -CH ₂CH (CH ₃) ₂) , sec-butyl (s-Bu, -CH (CH ₃) CH ₂CH ₃) , t-Bu (t-Bu, -C (CH ₃) ₃) , n-pentyl (-CH ₂CH ₂CH ₂CH ₂CH ₃) , 2-pentyl (-CH (CH ₃) CH ₂CH ₂CH ₃) , 3-pentyl (-CH (CH ₂CH ₃) ₂) , 2-methyl-2-butyl (-C (CH ₃) ₂CH ₂CH ₃) , 3-methyl-2-butyl (-CH (CH ₃) CH (CH ₃) ₂) , 3-methyl-1-butyl (-CH ₂CH ₂CH (CH ₃) ₂) , 2-methyl-1-butyl (-CH ₂CH (CH ₃) CH ₂CH ₃) , and so on.

The term “alkenyl” refers to linear or branched-chain monovalent hydrocarbon radical of 2 to 12 carbon atoms with at least one site of unsaturation, i.e., a carbon-carbon sp ² double bond, wherein the alkenyl radical may be optionally substituted by one or more substituents described herein, and includes radicals having “cis” and “trans” orientations, or alternatively, “E” and “Z” orientations. In some embodiments, the alkenyl contains 2 to 8 carbon atoms. In other embodiments, the alkenyl contains 2 to 6 carbon atoms. In still other embodiments, the alkenyl contains 2 to 4 carbon atoms. Some non-limiting examples of the alkenyl group include ethenyl or vinyl (-CH=CH ₂) , allyl (-CH ₂CH=CH ₂) , propenyl (CH ₃-CH=CH-) , oxobutenyl (CH ₃-C (=O) -CH=CH-) and the like.

The term “alkynyl” refers to a linear or branched monovalent hydrocarbon radical of 2 to 12 carbon atoms with at least a carbon-carbon, sp triple bond, wherein the alkynyl radical may be optionally substituted with one or more substituents described herein. In some embodiments, the alkynyl group contains 2-10 carbon atoms. In other embodiments, the alkynyl group contains 2-8 carbon atoms. In still other embodiments, the alkynyl group contains 2-6 carbon atoms. In yet other embodiments, the alkynyl group contains 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C≡CH, -C≡CCH ₃, -CH ₂-C≡CH, -CH ₂-C≡CCH ₃, -CH ₂CH ₂-C≡CH, -CH ₂-C≡CCH ₂CH ₃, -CH ₂CH ₂-C≡CCH ₃ and the like.

The term “alkoxy” refers to an alkyl group, as previously defined, attached to parent molecular moiety via an oxygen atom. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH ₃) , ethoxy (EtO, -OCH ₂CH ₃) , 1-propoxy (n-PrO, n-propoxy, -OCH ₂CH ₂CH ₃) , 2-propoxy (i-PrO, i-propoxy, -OCH (CH ₃) ₂) and so on.

The term “cycloalkyl” refers to a monovalent or multivalent saturated ring having 3 to 12 carbon atoms as a monocyclic, bicyclic, or tricyclic ring system. In some embodiments, the cycloalkyl group contains 3 to 10 carbon atoms. In other embodiments, the cycloalkyl group contains 3 to 8 carbon atoms. In still other embodiments, the cycloalkyl group contains 3 to 6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Some examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclohendecyl and cyclododecyl, etc.

The term “cycloalkyl-alkyl” refers to an alkyl group substituted with one or more cycloalkyl groups, wherein the alkyl and cycloalkyl groups are as defined herein. Some examples include, but are not limited to, cyclopropyl-CH ₂-, cyclobutyl-CH ₂-, cyclopentyl-CH ₂-, cyclohexyl-CH ₂-, etc.

At various places in the present specification, linking substituents are described. Where the structure clearly requires a linking group, the Markush variables listed for that group are understood to be linking groups. For example, if the structure requires a linking group and the Markush group definition for that variable lists “alkyl” or “aryl” , then it is understood that the “alkyl” or “aryl” represents a linking alkylene group or arylene group, respectively.

The term “alkylene” refers to a saturated divalent hydrocarbon group derived from a straight or branched chain saturated hydrocarbon by the removal of two hydrogen atoms. Unless otherwise specified, the alkylene group contains 1-12 carbon atoms. In some embodiments, the alkylene group contains 1-8 carbon atoms. In some embodiments, the alkylene group contains 1-6 carbon atoms. In other embodiments, the alkylene group contains 1-4 carbon atoms. In still other embodiments, the alkylene group contains 1-3 carbon atoms. In yet other embodiments, the alkylene group contains 1-2 carbon atoms. Such examples include methylene (-CH ₂-) , ethylene (-CH ₂CH ₂-) , propylene (-CH ₂CH ₂CH ₂-) , -CH (CH ₃) CH ₂-, -C (CH ₃) ₂-, -CH ₂CH ₂CH (CH ₃) -, -CH ₂CH ₂C (CH ₃) ₂-, and the like.

The term “heterocycle” , “heterocyclyl” , or “heterocyclic ring” as used interchangeably herein refers to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3-15 ring atoms, wherein the ring does not contain an aromatic ring, and in which at least one ring atom is selected from nitrogen, sulfur and oxygen. Unless otherwise specified, the heterocyclyl group may be carbon or nitrogen linked, and a -CH ₂-group can be optionally replaced by a -C (=O) -group. In which, the sulfur can be optionally oxygenized to S-oxide and the nitrogen can be optionally oxygenized to N-oxide. Examples of heterocyclyl include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (such as 2-pyrrolidinyl) , 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1, 3-dioxolanyl, dithiolanyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl) , morpholinyl, thiomorpholinyl, 1-oxidothiomorpholinyl, 1, 1-dioxidothiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thioxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, 2-oxa-5-azabicyclo [2.2.1] hept-5-yl, tetrahydropyridyl. Some non-limiting examples of heterocyclyl wherein -CH ₂-group is replaced by -C (=O) -moiety include 2-oxopyrrolidinyl, oxo-1, 3-thiazolidinyl, 2-piperidinonyl and 3, 5-dioxopiperidinyl. Some non-limited examples of heterocyclyl wherein the ring sulfur atom is oxidized is sulfolanyl, 1, 1-dioxo-thiomorpholinyl. and wherein the carbocyclyl group is optionally substituted with one or more substituents described herein.

The terms “3-12 membered heterocyclyl” , “3-10 membered heterocyclyl” , “3-8 membered heterocyclyl” or “3-6 membered heterocyclyl” , wherein “3-12 membered” , “3-10 membered” , “3-8 membered” or “3-6 membered” typically describes the number of ring-forming atoms in a molecule. For example, tetrahydrofuranyl is a 5-membered heterocyclyl, piperidinyl is an example of a 6-membered heterocyclyl.

The term “heteroatom” refers to one or more of oxygen (O) , sulfur (S) , nitrogen (N) , phosphorus (P) and silicon (Si) , including any oxidized form of nitrogen (N) , sulfur (S) , or phosphorus (P) ; the quaternized form of any basic nitrogen; or a substitutable nitrogen of a heterocyclic ring, for example, N (as in 3, 4-dihydro-2H-pyrrolyl) , NH (as in pyrrolidinyl) or NR (as in N-substituted pyrrolidinyl) .

The term “halogen” refers to fluorine (F) , chlorine (Cl) , bromine (Br) or iodine (I) .

The term “heteroaryl” refers to monocyclic, bicyclic and tricyclic carbocyclic ring systems having a total of five to twelve ring members, or five to ten ring members, or five to six ring members, wherein at least one ring in the system is aromatic, and in which at least one ring member is selected from heteroatom, and wherein each ring in the system contains 5 to 7 ring members and that has a single point or multipoint of attachment to the rest of the molecule. The term “hetreroaryl” and “heteroaromatic ring” or “heteroaromatic compound” can be used interchangeably herein. The heteroaryl group is optionally substituted by one or more substituents disclosed herein. In one embodiment, a 5-10 membered heteroaryl comprises 1, 2, 3 or 4 heteroatoms independently selected from O, S and N.

Some non-limiting examples of heteroaryl include 2-furanyl, 3-furanyl, 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, 3-triazolyl, 1, 2, 3-thiodiazolyl, 1, 3, 4-thiodiazolyl, 1, 2, 5-thiodiazolyl, pyrazinyl, 1, 3, 5-triazinyl, pyrimidonyl, pyridonyl and the following bicycles: benzimidazolyl, benzofuryl, benzotetrahydrofuryl, benzothiophenyl, indolyl (e.g., 2-indolyl) , benzopiperidinyl, etc.

The term “5-12 membered heteroaryl” , “5-10 membered heteroaryl” or “5-6 membered heteroaryl” , where “5-12 membered” , “5-10 membered” or “5-6 membered” typically describes the number of ring-forming atoms in a molety. For example, pyrrolyl, pyrazolyl, imidazolyl, thienyl, isothiazolyl, thiazolyl, furyl, isoxazolyl and oxazolyl are 5-membered heteroaryl, pyridyl, pyrimidinyl, pyrazinyl and pyridazinyl are 6-membered heteroaryl.

The term “haloalkyl” means that an alkyl group is substituted with one or more halogen atoms. Such examples include, but are not limited to, -CF ₃, -CHF ₂, -CH ₂Cl, -CH ₂CF ₃, -CH ₂CHF ₂, -CH ₂CH ₂F, -CH ₂CH ₂Cl, -CH ₂CH ₂CF ₃, and the like.

The term “haloalkoxy” means that an alkoxy group is substituted with one or more halogen atoms. Such examples include, but are not limited to, -OCF ₃, -OCHF ₂, -OCHCl ₂, -OCH ₂CHF ₂, -OCH ₂CHCl ₂, -OCH (CH ₃) CHF ₂, and the like.

The term “mercapto” refers to -SH.

The term “carboxyl” refers to -COOH.

In the present invention,

indicates that hydrogen atoms on ring A may be replaced by x R ^a, wherein when x≥2, each R ^a is the same or different; in the present invention,

indicates that hydrogen atoms on ring B may be replaced by y R ^b, wherein when y≥2, each R ^b is the same or different; for example, when

is

y1 is 0, 1, 2, or 3; wherein when y1 is 0,

is

when y1 is 1,

when y1 is 2,

is

when y1 is 3,

is

Salts of the compounds of the invention include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations having the chemical formula N ⁺ (R ^AAR ^BBR ^CCR ^DD) , wherein R ^AA, R ^BB, R ^CC and R ^DD are independently selected from hydrogen, C ₁-C ₆ alkyl, and C ₁-C ₆ hydroxyalkyl. A salt of a compound having formula (I) or formula (II) can be obtained by treating a compound having formula (I) or formula (II) with a metal hydroxide (such as sodium hydroxide) or an amine (such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine) .

When the compound of the present invention contains a basic moiety, acceptable salts can be formed from organic and inorganic acids, such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, and similarly known acceptable acids.

DESCRIPTION OF COMPOUNDS OF THE INVENTION

The present invention provides a novel 4-aminofuran-2 (5H) ketone compound and preparation methods thereof, a composition containing 4-aminofuran-2 (5H) ketone compound, and uses of such 4-aminofuran-2 (5H) ketone compounds and compositions in controlling pests.

each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, halogen, hydroxy, cyano, nitro, C _1-8 alkyl, halo C _1-8 alkyl, C _1-8 alkoxy, halo C _1-8 alkoxy, C _2-8 alkenyl, C _2-8 alkynyl, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-;

each of R ⁵ and R ⁶ is independently hydrogen or C _1-8 alkyl;

or R ⁵ and R ⁶ together with the carbon atom to which they are attached form C _3-8 cycloalkyl;

W is N or CR ⁷;

R ⁷ is hydrogen, halogen or C _1-8 alkyl;

W ¹ is O or S;

ring A is a 6-membered heteroaryl; the 6-membered heteroaryl group contains 1, 2 or 3 nitrogen atoms;

ring B is 5-6 membered heteroaryl or 5-6 membered saturated heterocycle;

x is 0, 1, 2, 3 or 4;

each R ^a is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-8 alkyl, halo C _1-8 alkyl, C _1-8 alkoxy, C _2-8 alkenyl, C _2-8 alkynyl, C _2-8 alkenyl-O-, C _2-8 alkynyl-O-, halo C _1-8 alkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkyl-C _1-3 alkyl-, C _3-8 cycloalkyl-O-, C _3-8 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl -O-, C _1-8 alkyl-S (= O) _n-, C _1-8 alkyl-C (= O) -, C _1-8 alkyl-C (= O) O-, C _1-8 alkoxy-C (= O) -or -NR ^cR ^d; each R ^a is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1a;

n is 0, 1 or 2;

each R ^c and R ^d is independently hydrogen, C _1-8 alkyl, C _1-8 alkyl-C (= O) -, C _1-8 alkoxy-C (= O) -, C _1-8 alkyl-SO ₂-, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-;

each R ^1a is independently halogen, hydroxy, cyano, nitro, C _1-8 alkyl, halo C _1-8 alkyl, C _1-8 alkoxy, or halo C _1-8 alkoxy;

y is 0, 1, 2, 3, 4, 5 or 6;

each R ^b is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-8 alkyl, halo C _1-8 alkyl, C _1-8 alkoxy, C _2-8 alkenyl, C _2-8 alkynyl, C _2-8 alkenyl-O-, C _2-8 alkynyl-O-, halo C _1-8 alkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkyl-C _1-3 alkyl-, C _3-8 cycloalkyl-O-, C _3-8 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl-O-, C _1-8 alkyl-S (= O) _m-, C _1-8 alkyl-C (= O) -, C _1-8 alkyl-C (= O) O-, C _1-8 alkoxy-C (= O) -or -NR ^eR ^f; each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

m is 0, 1 or 2;

each R ^e and R ^f is independently hydrogen, C _1-8 alkyl, C _1-8 alkyl-C (= O) -, C _1-8 alkoxy-C (= O) -, C _1-8 alkyl-SO ₂-, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-;

each R ^1b is independently halogen, hydroxy, cyano, nitro, C _1-8 alkyl, halo C _1-8 alkyl, C _1-8 alkoxy, or halo C _1-8 alkoxy;

with the proviso that: the compound represented by formula (I) is not 4- ( ( (6-chloropyridin-3-yl) methyl) (thien-2-ylmethyl) amino) furan-2 (5H) -one,

wherein, the structural formula corresponding to 4- ( ( (6-chloropyridin-3-yl) methyl) (thien-2-ylmethyl) amino) furan-2 (5H) -one is:

In some embodiments, each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, halogen, hydroxy, cyano, nitro, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, halo C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-.

In other embodiments, each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-.

In still other embodiments, each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -C (CH ₃) ₃, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -OC (CH ₃) ₃ or -OCF ₃.

In some embodiments, each of R ⁵ and R ⁶ is independently hydrogen or C _1-6 alkyl.

In other embodiments, each of R ⁵ and R ⁶ is independently hydrogen or C _1-4 alkyl.

In still other embodiments, each of R ⁵ and R ⁶ is independently hydrogen.

In some embodiments, W is N or CR ⁷;

R ⁷ is hydrogen, halogen or C _1-6 alkyl.

In other embodiments, W is N or CR ⁷;

R ⁷ is hydrogen, halogen or C _1-4 alkyl.

In still other embodiments, W is CR ⁷;

R ⁷ is hydrogen.

In some embodiments, the present invention provides a compound having Formula (II) or a stereoisomer, an N-oxide, or a salt thereof:

wherein, ring A, ring B, R ¹, R ², R ³, R ⁴, R ^a, R ^b, x and y are as described in this invention.

In other embodiments, the present invention provides a compound having Formula (III) or a stereoisomer, an N-oxide, or a salt thereof:

wherein, ring A, ring B, R ^a, R ^b, x and y are as described in this invention.

In some embodiments,

i.e., ring A, is 6-membered heteroaryl containing up to 3 nitrogen atoms.

In some embodiments, ring A is pyridyl, pyrimidinyl, pyridazinyl or pyrazinyl.

In some embodiments, x is 0, 1, 2, 3 or 4;

each R ^a is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _2-6 alkenyl-O-, C _2-6 alkynyl-O-, halo C _1-6 alkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkyl-C _1-3 alkyl-, C _3-8 cycloalkyl-O-, C _3-8 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl -O-, C _1-6 alkyl-S (= O) _n-, C _1-6 alkyl-C (= O) -, C _1-6 alkyl-C (= O) O-, C _1-6 alkoxy-C (= O) -or -NR ^cR ^d;

n is 0, 1 or 2;

each R ^c and R ^d is independently hydrogen, C _1-6 alkyl, C _1-6 alkyl-C (= O) -, C _1-6 alkoxy-C (= O) -, C _1-6 alkyl-SO ₂-, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-.

In other embodiments, x is 0, 1, 2, 3 or 4;

each R ^a is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _2-4 alkenyl-O-, C _2-4 alkynyl-O-, halo C _1-4 alkoxy, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkyl-, C _3-6 cycloalkyl-O-, C _3-6 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl -O-, C _1-4 alkyl-S (= O) _n-, C _1-4 alkyl-C (= O) -, C _1-4 alkyl-C (= O) O-, C _1-4 alkoxy-C (= O) -or -NR ^cR ^d;

n is 0, 1 or 2;

each R ^c and R ^d is independently hydrogen, C _1-4 alkyl, C _1-4 alkyl-C (= O) -, C _1-4 alkoxy-C (= O) -, C _1-4 alkyl-SO ₂-, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-.

In still other embodiments, x is 0, 1, 2, 3 or 4;

each R ^a is independently fluorine, chlorine, bromine, iodine, hydroxy, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃ or -NH ₂.

In still other embodiments, each R ^a is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1a;

each R ^1a is independently halogen, hydroxy, cyano, nitro, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy or halo C _1-6 alkoxy.

In other embodiments,

is one of the following sub-formulae:

wherein, x1 is 0, 1, 2, 3 or 4;

each x2 is independently 0, 1, 2 or 3;

each R ^a is as defined herein.

In other embodiments,

is one of the following sub-formulae:

wherein, each x1 and R ^a is as defined herein.

In other embodiments,

is one of the following sub-formulae:

wherein, each R ^a is independently fluorine, chlorine, bromine or iodine.

In other embodiments,

is one of the following sub-formulae:

In some embodiments

i.e., ring B, is 5-membered heteroaryl, 6-membered heteroaryl, 5-membered saturated heterocycle or 6-membered saturated heterocycle.

In other embodiments, ring B is pyrrolyl, pyrazolyl, imidazolyl, thienyl, isothiazolyl, thiazolyl, furyl, isoxazolyl, oxazolyl, tetrahydrofuryl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl.

In some embodiments, y is 0, 1, 2, 3, 4, 5 or 6;

m is 0, 1 or 2;

each R ^1b is independently halogen, hydroxy, cyano, nitro, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, or halo C _1-6 alkoxy.

In other embodiments, y is 0, 1, 2, 3, 4, 5 or 6;

m is 0, 1 or 2;

In still other embodiments, y is 0, 1, 2, 3, 4, 5 or 6;

each R ^b is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-5 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _2-4 alkenyl-O-, C _2-4 alkynyl-O-, halo C _1-4 alkoxy, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkyl-, C _3-6 cycloalkyl-O-, C _3-6 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl -O-, C _1-4 alkyl-S (= O) _m-, C _1-4 alkyl-C (= O) -, C _1-4 alkyl-C (= O) O-, C _1-4 alkoxy-C (= O) -or -NR ^eR ^f; each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

m is 0, 1 or 2;

In other embodiments, y is 0, 1, 2, 3, 4, 5 or 6;

each R ^b is independently fluorine, chlorine, bromine, iodine, hydroxy, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -C (CH ₃) ₃, -CH ₂CH ₂CH ₂CH ₂CH ₃, -CH ₂CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -CH ₂CHF ₂, -CH ₂CH ₂F, -CH ₂CH ₂Cl, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -CH=CH ₂, -CH ₂CH=CH ₂, CH ₃-CH=CH-, -C≡CH, -CH ₂-C≡CH, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃, -SO ₂CH ₂CH ₃, CH ₃-C (=O) , CH ₃-C (=O) O-, CH ₃O-C (=O) -or -NR ^eR ^f; each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

each of R ^e and R ^f is independently hydrogen, -CH ₃ or -CH ₂CH ₃;

In still other embodiments, each R ^b is independently one of the following sub-formulae:

wherein each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

In some embodiments,

is one of the following sub-formulae:

wherein, each y1 is independently 0, 1, 2 or 3;

each y2 is independently 0, 1, or 2;

y3 is 0, 1, 2, 3, 4, 5 or 6;

each y4 is independently 0, 1, 2, 3, or 4;

each R ^b is as defined herein.

In still other embodiments,

is one of the following sub-formulae:

wherein each R ^b is independently C _1-6 alkyl, halo C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkyl-, phenyl or phenyl-C _1-3 alkyl;

In still other embodiments,

is one of the following sub-formulae:

wherein, each R ^b is independently -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -C (CH ₃) ₃, -CH ₂CH ₂CH ₂CH ₂CH ₃, -CH ₂CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -CH ₂CHF ₂, -CH ₂CH ₂F, -CH ₂CH ₂Cl, -CH=CH ₂, -CH ₂CH=CH ₂, CH ₃-CH=CH-, -C ≡CH or -CH ₂-C ≡CH;

or each R ^b is independently one of the following sub-formulae:

In other embodiments,

is one of the following sub-formulae:

In some embodiments, the present invention provides a compound having one of the following structures or a stereoisomer, an N-oxide, or a salt thereof:

In other aspect, provided herein is a composition comprising the compound of the present invention as an active ingredient.

In some embodiments, the composition disclosed herein further comprises an agrochemically acceptable surfactant and/or carrier.

In still other aspect, the present invention provides the use of the compound of the present invention or the composition of the present invention in controlling agricultural pests.

In still other aspect, the present invention provides a method for using the compound of the present invention or the composition of the present invention in controlling agricultural pests.

The pests include homopteran pests, lepidopteran pests, thysanoptera pests and coleoptera pests.

The homopteran pests include whiteflies, Aphids, Planthoppers, Leafhoppers, phylloxeras, Coccidae and Mealybug.

The lepidopteran pests include Pseudaletia separata and Plutella xylostella.

The thysanoptera pests includes Thrips.

The coleopteran pests include weevils.

According to the examples of the present invention, the pests include but are not limited to Plutella xylostella, Aphis medicaginis Koch, bemisia tabaci, Aphis gossypii Glover, Myzus persicae, and Mythimna separata.

COMPOSITIONS AND FORMULATIONS OF THE COMPOUNDS OF THE INVENTION

The compound of the present invention can generally be used as a pesticide active ingredient in compositions or preparations, and generally also include agrochemically acceptable surfactants and/or carriers.

The above surfactants may be various surfactants well known in the field of pesticide formulations, and one or more of an emulsifier, a dispersant and a wetting agent are preferably in the present invention.

Other carriers other than the above surfactants may be various carriers well known in the field of pesticide formulations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetics. Specifically, for example, one or more of silica, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine fertilizer, mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, palygorskite, mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate and mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.

The above emulsifier may be various emulsifiers known in the field of pesticide formulations. Specifically, the emulsifier may be one or more of calcium dodecylbenzene sulfonate, triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol ethoxylates, alkylphenol polyoxyethylene polyoxypropylene ethers, fatty amines, ethylene oxide adducts of fatty amides, fatty acid polyoxyethylene esters, rosin acid ethylene oxide adducts, polyol fatty acid ester and ethylene oxide adduct thereof, styryl phenyl polyoxyethylene ether, alkyl phenol formaldehyde resin polyoxyethylene ether, hydroxy-terminated polyoxyethylene polyoxypropylene ether, styryl phenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.

The above dispersing agent may be various dispersing agents known in the field of agricultural pesticide formulations. Specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxy-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and sodium p-hydroxyphenyl lignosulfonate.

The above wetting agent may be various wetting agents known in the field of pesticide formulations. Specifically, the wetting agent may be one or more of sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium dodecylbenzenesulfonate, fatty alcohol polyoxyethylene ether, alkylnaphthalenesulfonate, alkylphenol resin polyoxyethylene ether sulfate.

According to the insecticide composition of the present invention, the insecticide composition may further contain various auxiliaries for use in preparations conventionally used in the field of pesticide preparations. Specifically, the auxiliary agent to be prepared may be one or more of solvents, co-solvents, thickeners, antifreezes, capsules, protectants, antifoaming agents, disintegrants, stabilizers, preservatives and binders.

The above solvent can be known as various solvents in the field of pesticide formulations. Specifically, the solvents can 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, N-dimethyldecanoamide, N, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.

The vegetable oil includes one or more of methylated vegetable oil, rosin-based vegetable oil, turpentine oil, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil, and pine nut oil.

The mineral oil includes one or more of liquid wax, engine oil, kerosene, and lubricating oil.

At the same time, the above solvent can also be used as a co-solvent.

The above antifreeze agent may be various antifreeze agents known in the field of pesticide formulations, and the present invention is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.

The above thickener may be various thickeners known in the field of pesticide formulations. Specifically, the thickener may be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, silica, diatomite, kaolin, clay, sodium alginate, aluminum magnesium silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose, and organic bentonite.

The above-mentioned capsules may be various kinds of capsules known in the field of pesticide formulations, and one or more of polyurethane, polyurea and urea-formaldehyde resins are preferred in the present invention.

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

The above antifoaming agent may be various antifoaming agents known in the field of pesticide formulations, and the present invention is preferably one or more of organosiloxane, tributyl phosphate and silicone.

The above stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.

The above preservative is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (abbreviated as BIT) , carson and potassium sorbate.

The invention also provides a preparation prepared from the above insecticide composition, wherein the dosage forms of the preparation are emulsifiable concentrate, emulsion in water, micro-emulsion, soluble liquid agent, aqueous suspension concentrate, suspoemulsion, ultra low volume spray, oil dispersion, capsule suspension, water surface film oil agent, wettable powder, water-dispersible granule, dry flowable, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, granule, solid microcapsule preparation, effervescent tablet, effervescent granule, water floating dispersion granule or seed coating agent. The above dosage forms can be prepared by conventional methods in the art.

The preparation method of the above emulsifiable concentrate preparation may include, for example, mixing and stirring each active component, a solvent, a co-solvent, and an emulsifier to form a uniform transparent oil phase, thereby obtaining an emulsifiable concentrate preparation.

The preparation method of the above aqueous emulsion may, for example, comprise mixing an active ingredient, an emulsifier, a co-solvent with a solvent to form a homogeneous oil phase; mixing water, a thickener, an antifreeze or the like to form a uniform aqueous phase. Under high shear, the aqueous phase is added to the oil phase or the oil phase is added to the aqueous phase to form a water emulsion with good dispersibility.

The preparation method of the above microemulsion may be, for example, mixing and stirring an active ingredient, an emulsifier, and a solvent into a uniform transparent oil phase. Under agitation, water is gradually added to form a uniform transparent microemulsion.

The preparation method of the above water/oil suspension agent: for example, water or oil may be used as a medium, and an auxiliary agent such as an active component or a surfactant may be added to a sanding kettle, and after grinding to a certain particle size, the mixture may be filtered. The metered thickener is then added to the ground mother liquor, then the mixture is sheared and dispersed evenly. It is made into oil suspension or water suspension.

The preparation method of the above water-dispersible granules and soluble granules: for example, the active components, the dispersing agent, the wetting agent, the carrier, and the like may be uniformly mixed, and then pulverized to a certain particle diameter by a jet stream, and then kneaded by adding water. Finally, it is added to a granulator for granulation, and after drying, a water-dispersible granule or a soluble granule can be obtained.

The preparation method of the above-mentioned soluble powder and wettable powder: for example, the fillers of the respective active components, various auxiliary agents and other carriers may be thoroughly mixed and pulverized by an ultrafine pulverizer.

The pesticide composition of the present invention may be provided in the form of a finished preparation, that is, each substance in the composition has been mixed; it may also be provided in the form of a separate preparation, which is self-mixed in a bucket or a tank before use, and selectively mixed with water and diluted according to the concentration of the required active substance.

For additional information related to the formulation field, see “The Formulator's Toolbox-Product Forms for Modern Agriculture” by T. S. Woods, Pesticide Chemistry and Bioscience, The Food-Environment Challenge, Edited by T. Brooks and T. R. Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, column 6, line 16 to column 7, line 19 and Example 10-41; U.S. 3,309,192, column 5, lines 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's Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; Weed Control Handbook by Hance et al., 8th edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

USES OF THE COMPOUNDS AND COMPOSITIONS OF THE PRESENT INVENTION

The compounds of the present invention are particularly suitable for controlling animal pests such as arthropods, gastropods and nematodes in useful plants, including but not limited to:

Hemiptera: Planthopper (Delphacidae) such as Nilaparvata lugens, Laodelphax striatellus; Leafhopper (Deltocephalidae) such as Green rice leafhopper (Nephotettix cincticeps) ; aphid (Aphididae) such as Aphis gossypii, Aphis craccivora; Pentatomidae such as Nezara antennata; Aleyrodidae such as Trialeurodes vaporariorum; Coccidae such as Calformia red scale, Aonidiella aurantii; Tingidae; Psyllidae;

Lepidoptera: Pyralidae such as Chilo suppressalis; Noctuidae such as Spodoptera litura, Pseudaletia separata, Heliothis , Helicoverpa ; Pieridae such as Pieris rapae; Tortricidae such as Adoxophyes; Gracillariidae such as Caloptilia theivora and Phyllonorycter ringoneella; Carposinidae such as Carposina niponensis; Lyonetiidae such as Lyonetia ; Lymantriidae such as Lymantria and Euproctis ; Yponomeutidae such as Plutella xylostella; Gelechiidae such as Pectinophora gossypiella and Phthorimaea operculella; Arctiidae such as Hyphantria cunea; and Tineidae such as Tineatranslucens and Tineola bisselliella;

Thysanoptera: Frankliniella occidentalis, Thrips palmi Karny, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa and Frankliniella fusca;

Diptera: Musca domestica, Culex popiens pallens, Tabanus trigonus, Hylemya anitqua, Hylemya platura, Anopheles sinensis, Agromyza oryzae, Hydrellia griseola, Chlorops oryzae, Dacus cucurbitae, Ceratitis capitata, Liriomyza trifolii;

Coleoptera: Epilachna vigintioctopunctata, Phyllotreta striolata, Oulema oryzae, Echinocnemus squameus, Lissorhoptrus oryzophilus, Anthonomus grandis, Callosobruchus chinensis, Sphenophorus venatus, Popillia japonica, Anomala cuprea, Diabrotica , Leptinotarsa decemlineata, Agriotes , Lasioderma serricorne, Anthrenus verbasci, Tribolium castaneum, Lyctus brunneus, Anoplophora malasiaca, Tomicus piniperda;

Orthoptera: Locusta migratoria, Gryllotalpa afficana, Oxya yezoensis and Oxya japanica;

Hymenoptera: Athalia rosae, Acromyrmex and Solenopsis;

Nematodes: Aphelenchoides besseyi, Nothotylenchus acris, Heterodera glycines, Meloidogyne incognita, Pratylenchus penetrans and Nacobbus aberrans;

Blattariae: Blattella germanica, Periplaneta fuliginosa, Periplaneta Americana, Periplaneta brunnea and Blatta orientalis;

Acarina: Tetranychidae (such as Tetranychus cinnabarinus, Tetranychusurticae, Panonychus citri and Oligonychus) ; Eriophyidae (such as Aculops pelekassi) ; Tarsonemidae; Tenuipalpidae; Tuckerellidae; Acaridae; Pyroglyphidae (such as Dermatophagoides farinae and Dermatophagoides ptrenyssnus) ; Cheyletidae, (such as Cheyletus malaccensis and Cheyletus moorei) ; and Dermanyssidae.

Within the scope of the present invention, useful plants include the following plant species: cereals (wheat, barley, rye, oats, rice, corn, sorghum and related species) ; beets (carrots and forage beets) ; pears, stone fruits, and soft fruits (apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry) ; legumes (lentils, bin beans, peas, soybeans) ; oil crops (rapeseed, mustard, olives, sunflower, coconut, castor oil plants, cocoa beans, groundnut or soybeans) ; melons (pumpkins, cucumbers, melon) ; fiber plants (cotton, flax, hemp, jute) ; citrus fruits (orange, lemon, grapefruit, citrus) ; vegetables (spinach, lettuce, asparagus, kale, carrot, onion, tomato, potato, red pepper) ; laurel plants (avocado, cinnamomum, camphor) or plants, such as tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper , vines, hops, bananas and natural rubber plants, along with turf, ornamental and forest plants, such as flowers, shrubs, broad-leaved or evergreen trees, such as conifers, as well as plant propagation material.

The term “plant propagation material” should be understood to mean the reproductive parts of the plant, such as seeds, which can be used for the reproduction of the plant, as well as nutritional materials, such as cuttings or tubers (such as potatoes) .

The compounds or compositions of the invention can kill pests with an effective amount of the active substance. The invention therefore also relates to a method for controlling pests, which is carried out by applying the active ingredient or composition of the invention to seeds, plants or plant parts, fruits or the soil in which the plants grow. Application can take place before and after the seed, plant or plant part, fruit or plant growing soil is infested with pests.

The term “effective amount” as used means an amount of a compound of the invention sufficient to control pests on cultivated plants or in the protection of materials without causing significant damage to the treated plants. This amount can vary within a wide range and depends on various factors such as the pest species, the cultivated plant or material being treated, climatic conditions, and the specific compound used.

The compound or composition of the present invention is simple to use, and the compound or composition of the present invention is applied to the pest or a growth medium thereof. The application dose of the compound or composition of the present invention varies according to weather conditions, dosage forms, application timing, application method, application area, target disease, target crop, and the like.

GENERAL SYNTHETIC PROCEDURES

The following schemes describe the preparation of the compounds of the invention. Unless otherwise stated, the compounds of the invention can be prepared by the methods described herein. The raw materials, reagents and the like used in the preparation of the compounds of the present invention are all commercially available, or can be prepared by conventional methods in the art. In the present invention, if the chemical name of the compound doesn’t match the corresponding structure, the compound is characterized by the corresponding structure.

¹H NMR spectra of the present invention were recorded with a Bruker 400 MHz or 600 MHz spectrometer using CDCl ₃, d ⁶-DMSO, CD ₃OD, d ⁶-acetone or D ₂O as the solvent (reported in ppm) , and using TMS (0 ppm) or chloroform (7.26 ppm) as the reference standard. When peak multiplicities are reported, the following abbreviations are used: s (singlet) , d (doublet) , t (triplet) , q (quartet) , m (multiplet) , br (broadened) , dd (doublet of doublets) , dt (doublet of triplets) . Coupling constants, when given, were reported in Hertz (Hz) .

The mass spectrometry test conditions used in the present invention are: low-resolution mass spectral (MS) data were determined on an Agilent 6120 Quadrupole HPLC-MS spectrometer equipped with an Agilent Zorbax SB-C18 (2.1 x 30 mm, 3.5 μm) . The flow rate was 0.6 mL/min; the mobile phases consisted of a combination of A (0.1%formic acid in CH ₃CN) and B (0.1%formic acid in H ₂O) in gradient mode (5%to 95%) , and an ESI source was used, the peak of HPLC was recorded with UV-Vis detection at 210/254 nm.

Synthesis scheme

Synthesis scheme 1

Intermediate compound d can be prepared by synthesis scheme 1. Compound a and compound b can undergo substitution reaction to obtain compound c; compound c can undergo intramolecular ring closure in a sodium methoxide /methanol system to obtain intermediate compound d.

Synthesis scheme 2

Intermediate compound g can be prepared by synthesis scheme 2. Compound e and compound f are subjected to an amine-aldehyde condensation reaction to obtain a compound, which can be reduced by a reducing agent (e.g., sodium borohydride) to obtain intermediate compound g. wherein, ring A, ring B, R ^a, R ^b, x and y have the meanings described in the present invention.

Synthesis scheme 3

The target compound represented by formula (III) can be prepared by synthesis scheme 3. The intermediate compound g and the intermediate compound d together can be heated, dehydrated and decarboxylated to obtain the target compound represented by formula (III) . wherein, ring A, ring B, R ^a, R ^b, x and y have the meanings described in the present invention.

Examples

Intermediate O: synthesis of 4- (methoxycarbonyl) -5-oxo-2, 5-dihydrofuran-3-olate sodium

Step 1: synthesis of methyl 2-methoxy-2-oxoethylmalonate

Potassium monomethyl malonate (30.0 g, 0.19 mol) was dissolved in N, N-dimethylformamide (180 mL) at room temperature and the mixture was heated to 45 ℃. Then to the mixture was dropwise added methyl bromoacetate (35.3 g, 0.23 mol) . After the dropwise addition was completed, the mixture was further stirred at 45 ℃ for 8 hours. After the reaction was completed, the mixture was directly concentrated in vacuo to remove the solvent. Then the resulting mixture was added with water (45 mL) and extracted with ethyl acetate (30 mL x 3) . The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated in vacuo to obtain colorless liquid 29.5 g with a yield of 80.8%.

Step 2: synthesis of 4- (methoxycarbonyl) -5-oxo-2, 5-dihydrofuran-3-olate sodium

Methyl 2-methoxy-2-oxoethylmalonate (29.5 g, 0.16 mol) was dissolved in 100 mL of methanol. The mixture was heated to 50 ℃, and then a solution of 30%sodium methoxide (30.7 g, 0.17 mol) in methanol was added dropwise. After the dropwise addition was completed, the obtained mixture was heated to 70 ℃ and stirred under reflux for 3 hours. The mixture was cooled to 0 ℃ and filtered by suction. The filter cake was washed with methanol (30 mL x 3) , and dried at 50 ℃ under vacuum to obtain a white solid 21.3 g with a yield of 76.2%.

¹H NMR (400 MHz, D ₂O) δ (ppm) : 3.73 (s, 3H) , 4.42 (s, 2H) .

Example 1: synthesis of 4- ( ( (6-chloropyridin-3-yl) methyl) ( (1-methyl-1H-pyrazol-3-yl) methyl) amino) furan-2 (5H) -one

Step 1: synthesis of 1- (6-chloropyridin-3-yl) -N- ( (1-methyl-1H-pyrazol-3-yl) methyl) methylamine

To a 100 mL single-necked flask were added 5-aminomethyl-2-chloropyridine (0.20 g, 1.40 mmol) and 1-methyl-1H-pyrazole-3-carboxaldehyde (0.17 g, 1.54 mmol) , then methanol (20 mL) was added and the resulting mixture was stirred at room temperature for 12 hours. Sodium borohydride (0.13 g, 3.51 mmol) was slowly added. The mixture was stirred at room temperature for 30 minutes. Then a yellow clear solution was obtained and was concentrated in vacuo to remove the solvent. The residue was added with water (45 mL) and extracted with ethyl acetate (15 mL x 3) . The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether /ethyl acetate (v /v) = 3/1) to obtain yellow oil 0.28 g with a yield of 84.3%.

MS (ES-API, pos. ion) m/z: 237.70 [M + 1] ⁺.

Step 2: synthesis of 4- ( ( (6-chloropyridin-3-yl) methyl) ( (1-methyl-1H-pyrazol-3-yl) methyl) amino) furan-2 (5H) -one

To a 50 mL single-necked flask were added 1- (6-chloropyridin-3-yl) -N- ( (1-methyl-1H-pyrazol-3-yl) methyl) methylamine (0.28 g, 1.18 mmol) , 4- (methoxycarbonyl) -5-oxo-2, 5-dihydrofuran-3-olate sodium (0.28 g, 1.54 mmol) and butyronitrile (12 mL) in turn at room temperature, then potassium hydrogen sulfate (0.40 g, 2.96 mmol) was added. The resulting mixture was heated to 95 ℃ and stirred for 10 hours. After cooling to room temperature, the mixture was poured into water (45 mL) , extracted with ethyl acetate (15 mL x 3) . The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether /ethyl acetate (v /v) = 1/3) to obtain light yellow oil 0.19 g with a yield of 50.4%.

¹H NMR (400 MHz, DMSO-d ₆) δ (ppm) : 8.32 (d, J = 1.7 Hz, 1H) , 7.74 (d, J = 7.2 Hz, 1H) , 7.63 (s, 1H) , 7.50 (d, J = 8.2 Hz, 1H) , 6.20 (s, 1H) , 4.95 (d, J = 47.8 Hz, 2H) , 4.73 (d, J = 11.4 Hz, 1H) , 4.49 (s, 2H) , 4.32 (s, 2H) , 3.79 (s, 3H) ;

MS (ES-API, pos. ion) m/z: 319.76 [M + 1] ⁺.

An aminomethyl-substituted pyridine derivative is reacted with a formaldehyde-substituted 5-membered heteroaryl derivative or a 5-6 membered saturated heterocyclic derivative according to the synthetic method of the step 1 of Example 1 or referring to the prior art synthesis method. Then, the intermediate compounds in Table 1 were obtained.

Table 1

The intermediate compound in Table 1 is reacted with the intermediate O (structure is:

) according to the synthesis method of the step 2 of Example 1 to obtain the target compound in Table 2.

Table 2

Activity test

1) Test method-Test target: Aphis craccivora Koch

Spray method: cowpea leaves that growed uniformly were chosen and made into leaf dishes by using a hole punch, with two leaf dishes per dish. A wet sponge block was placed in a petri dish and the leaf dish was placed on the sponge, and water was added to level the leaf dish for use. 2-3 Instar Aphis craccivora Koch raised indoors was inoculated to the prepared leaf dishes, with more than 15 numbers per dish. Each dish was sprayed with 0.5 mL of medicinal liquid by using spray tower. The test samples after treatment was placed in the observation room, and the results were observed 2 days later. The insect body was touched with a writing brush. If there was no response, the insect was considered to be dead. The test concentration was 100 mg /L.

The test results showed that the lethal rates of compounds of Example 1, Example 2, Example 5, Example 9, Example 12, Example 15, Example 16, Example 24, Example 27 and Example 36 for Aphis craccivora Koch were ≥80%.

2) Test method-Test target: bemisia tabaci

Spray method: eggplant seedlings that growed uniformly were placed in a bemisia tabaci breeding cage. After 24 hours, the egg-laying plants were transferred to an insect-free cage for normal cultivation. When the nymphs reached 3rd instar, a 12 mm diameter punch was used to take samples and leaf dishes were made. The leaf dishes were placed in a 9 cm petri dish (hydrated with agar) , and the number of nymphs in each leaf dish was counted under a stereo microscope, and then leaf dishes were sequentially sprayed with medicinal liquids from low concentration to high concentration by using a potter spray tower. After being dried naturally in the shade, leaf dishes in a 9 cm petri dish were placed in an artificial climate chamber. After 3 days, the number of dead and live nymphs was counted under a stereo microscope, and the lethal rates were calculated. The test concentrations were 10 mg /L, 30 mg /L, 50 mg /L, 100 mg /L and 200 mg /L.

The test results showed that: at a test concentration of 100 mg /L, the lethal rates of compounds of Example 9, Example 27, Example 34, Example 35, Example 38, Example 39, Example 42, Example 43, Example 44, Example 45, Example 46, Example 47 and Example 48 for bemisia tabaci were ≥80%, the lethal rate of compounds of flupyradifurone for bemisia tabaci was only 50%;

at a test concentration of 50 mg /L, the lethal rates of compounds of Example 9, Example 27, Example 34, Example 39, Example 42, Example 44, Example 46 and Example 48 for bemisia tabaci were ≥80%, the lethal rates of compounds of Example 49 for bemisia tabaci was below 10%.

3) Test method-Test target: Aphis gossypii

Spray method: cowpea leaves that growed uniformly were chosen and made into leaf dishes by using a hole punch, with two leaf dishes per dish. A wet sponge block was placed in a petri dish and the leaf dish was placed on the sponge, and water was added to level the leaf dish for use. 2-3 Instar Aphis gossypii raised indoors was inoculated to the prepared leaf dishes, with more than 15 numbers per dish. Each dish was sprayed with 0.5 mL of medicinal liquid by using spray tower. The test samples after treatment was placed in the observation room, and the results were observed 2 days later. The insect body was touched with a writing brush. If there was no response, the insect was considered to be dead. The test concentration were 100 mg /L and 200 mg /L.

The test results showed that at a test concentration of 100 mg /L, the lethal rates of compounds of Example 1, Example 2, Example 34, Example 42, Example 44, Example 46 and Example 48 for Aphis gossypii were ≥80%.

4) Test method-Test target: Plutella xylostella

Leaf immersion method: an appropriate amount of fresh corn leaves or cabbage leaves were naturally dried in the shade after being fully infiltrated in the prepared medicinal solution, and then they were placed in a petri dish lined with a filter paper. 2-3 Instar Plutella xylostella was inoculated with 10 numbers per dish and were observed and cultivated indoors at 24～27 ℃, and the results were observed 3 days later. The insect body was touched with a writing brush. If there was no response, the insect was considered to be dead. The test concentration was 100 mg /L.

The test results showed that the lethal rate of compound of Example 22 for Plutella xylostella was ≥80%.

5) Test method-Test target: Myzus persicae

Spray method: cowpea leaves that growed uniformly were chosen and made into leaf dishes by using a hole punch, with two leaf dishes per dish. A wet sponge block was placed in a petri dish and the leaf dish was placed on the sponge, and water was added to level the leaf dish for use. 2-3 Instar Myzus persicae raised indoors was inoculated to the prepared leaf dishes, with more than 15 numbers per dish. Each dish was sprayed with 0.5 mL of medicinal liquid by using spray tower. The test samples after treatment was placed in the observation room, and the results were observed 2 days later. The insect body was touched with a writing brush. If there was no response, the insect was considered to be dead. The test concentration was 100 mg /L.

The test results showed that the lethal rate of compound of Example 2, Example 15 and Example 16 for Myzus persicae were ≥80%.

6) Test method-Test target: Pseudaletia separata

Leaf immersion method: an appropriate amount of fresh corn leaves or cabbage leaves were naturally dried in the shade after being fully infiltrated in the prepared medicinal solution, and then they were placed in a petri dish lined with a filter paper. 2-3 Instar Pseudaletia separata was inoculated with 10 numbers per dish and were observed and cultivated indoors at 24～27 ℃, and the results were observed 3 days later. The insect body was touched with a writing brush. If there was no response, the insect was considered to be dead. The test concentration was 100 mg /L.

The test results showed that the lethal rate of compound of Example 2, Example 8, Example 23, Example 24 and Example 26 for Pseudaletia separata were ≥80%.

The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

Claims

A compound having Formula (I) or a stereoisomer, an N-oxide, or a salt thereof,

wherein,

each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, halogen, hydroxy, cyano, nitro, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, halo C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-;

each of R ⁵ and R ⁶ is independently hydrogen or C _1-6 alkyl;

or R ⁵ and R ⁶ together with the carbon atom to which they are attached form C _3-6 cycloalkyl;

W is N or CR ⁷;

R ⁷ is hydrogen, halogen or C _1-6 alkyl;

W ¹ is O or S;

ring A is 6-membered heteroaryl containing up to 3 nitrogen atoms;

ring B is 5-6 membered heteroaryl or 5-6 membered saturated heterocycle;

x is 0, 1, 2, 3 or 4;

each R ^a is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _2-6 alkenyl-O-, C _2-6 alkynyl-O-, halo C _1-6 alkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkyl-C _1-3 alkyl-, C _3-8 cycloalkyl-O-, C _3-8 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl-O-, C _1-6 alkyl-S (= O) _n-, C _1-6 alkyl-C (= O) -, C _1-6 alkyl-C (= O) O-, C _1-6 alkoxy-C (= O) -or -NR ^cR ^d; each R ^a is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1a;

n is 0, 1 or 2;

each R ^c and R ^d is independently hydrogen, C _1-6 alkyl, C _1-6 alkyl-C (= O) -, C _1-6 alkoxy-C (= O) -, C _1-6 alkyl-SO ₂-, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-;

each R ^1a is independently halogen, hydroxy, cyano, nitro, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, or halo C _1-6 alkoxy;

y is 0, 1, 2, 3, 4, 5 or 6;

each R ^b is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _2-6 alkenyl-O-, C _2-6 alkynyl-O-, halo C _1-6 alkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkyl-C _1-3 alkyl-, C _3-8 cycloalkyl-O-, C _3-8 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl -O-, C _1-6 alkyl-S (= O) _m-, C _1-6 alkyl-C (= O) -, C _1-6 alkyl-C (= O) O-, C _1-6 alkoxy-C (= O) -or -NR ^eR ^f; each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

m is 0, 1 or 2;

each R ^e and R ^f is independently hydrogen, C _1-6 alkyl, C _1-6 alkyl-C (= O) -, C _1-6 alkoxy-C (= O) -, C _1-6 alkyl-SO ₂-, C _3-8 cycloalkyl or C _3-8 cycloalkyl-C _1-3 alkyl-;

each R ^1b is independently halogen, hydroxy, cyano, nitro, C _1-6 alkyl, halo C _1-6 alkyl, C _1-6 alkoxy, or halo C _1-6 alkoxy;

with the proviso that: the compound represented by formula (I) is not 4- ( ( (6-chloropyridin-3-yl) methyl) (thien-2-ylmethyl) amino) furan-2 (5H) -one.
The compound of claim 1, wherein,

each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-.
The compound of claim 1 or 2, wherein,

each of R ¹, R ², R ³ and R ⁴ is independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -C (CH ₃) ₃, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -OC (CH ₃) ₃ or -OCF ₃.
The compound of any one of claims 1 to 3, wherein,

is one of the following sub-formulae:

wherein, x1 is 0, 1, 2, 3 or 4;

each x2 is independently 0, 1, 2 or 3;

each R ^a is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _2-4 alkenyl-O-, C _2-4 alkynyl-O-, halo C _1-4 alkoxy, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkyl-, C _3-6 cycloalkyl-O-, C _3-6 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl -O-, C _1-4 alkyl-S (= O) _n-, C _1-4 alkyl-C (= O) -, C _1-4 alkyl-C (= O) O-, C _1-4 alkoxy-C (= O) -or -NR ^cR ^d; each R ^a is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1a;

n is 0, 1 or 2;

each R ^c and R ^d is independently hydrogen, C _1-4 alkyl, C _1-4 alkyl-C (= O) -, C _1-4 alkoxy-C (= O) -, C _1-4 alkyl-SO ₂-, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-;

each R ^1a is independently halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, or halo C _1-4 alkoxy.
The compound of any one of claims 1 to 4, wherein,

is one of the following sub-formulae:

wherein, each x1 is independently 0, 1, 2, 3, or 4;

each R ^a is independently fluorine, chlorine, bromine, iodine, hydroxy, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃ or -NH ₂;

each R ^a is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1a;

each R ^1a is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CF ₃, -OCH ₃ or -OCF ₃.
The compound of any one of claims 1 to 5, wherein

is one of the following sub-formulae:

wherein, each R ^a is independently fluorine, chlorine, bromine, iodine, hydroxyl, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃ or -NH ₂.
The compound of any one of claims 1 to 6, wherein,

ring B is pyrrolyl, pyrazolyl, imidazolyl, thienyl, isothiazolyl, thiazolyl, furyl, isoxazolyl, oxazolyl or tetrahydrofuryl;

y is 0, 1, 2, 3, 4, 5 or 6;

each R ^b is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-6 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _2-4 alkenyl-O-, C _2-4 alkynyl-O-, halo C _1-4 alkoxy, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkyl-, C _3-6 cycloalkyl-O-, C _3-6 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl -O-, C _1-4 alkyl-S (= O) _m-, C _1-4 alkyl-C (= O) -, C _1-4 alkyl-C (= O) O-, C _1-4 alkoxy-C (= O) -or -NR ^eR ^f; each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

m is 0, 1 or 2;

each R ^e and R ^f is independently hydrogen, C _1-4 alkyl, C _1-4 alkyl-C (= O) -, C _1-4 alkoxy-C (= O) -, C _1-4 alkyl-SO ₂-, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-;

each R ^1b is independently halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, or halo C _1-4 alkoxy.
The compound of any one of claims 1 to 7, wherein,

is one of the following sub-formulae:

wherein, each y1 is independently 0, 1, 2 or 3;

each y2 is independently 0, 1 or 2;

y3 is 0, 1, 2, 3, 4, 5 or 6;

each R ^b is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-6 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _2-4 alkenyl-O-, C _2-4 alkynyl-O-, halo C _1-4 alkoxy, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkyl-, C _3-6 cycloalkyl-O-, C _3-6 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl-O-, C _1-4 alkyl-S (= O) _m-, C _1-4 alkyl-C (= O) -, C _1-4 alkyl-C (= O) O-, C _1-4 alkoxy-C (= O) -or -NR ^eR ^f; each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

m is 0, 1 or 2;

each R ^e and R ^f is independently hydrogen, C _1-4 alkyl, C _1-4 alkyl-C (= O) -, C _1-4 alkoxy-C (= O) -, C _1-4 alkyl-SO ₂-, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-;

each R ^1b is independently halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, or halo C _1-4 alkoxy.
The compound of any one of claims 1 to 8, wherein,

is one of the following sub-formulae:

each R ^b is independently halogen, hydroxy, mercapto, cyano, nitro, carboxyl, C _1-6 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkenyl, C _2-4 alkynyl, C _2-4 alkenyl-O-, C _2-4 alkynyl-O-, halo C _1-4 alkoxy, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkyl-, C _3-6 cycloalkyl-O-, C _3-6 cycloalkyl-C _1-3 alkyl-O-, phenyl, phenoxy, phenyl-C _1-3 alkyl-, phenyl-C _1-3 alkyl-O-, C _1-4 alkyl-S (= O) _m-, C _1-4 alkyl-C (= O) -, C _1-4 alkyl-C (= O) O-, C _1-4 alkoxy-C (= O) -or -NR ^eR ^f; each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

m is 0, 1 or 2;

each R ^e and R ^f is independently hydrogen, C _1-4 alkyl, C _1-4 alkyl-C (= O) -, C _1-4 alkoxy-C (= O) -, C _1-4 alkyl-SO ₂-, C _3-6 cycloalkyl or C _3-6 cycloalkyl-C _1-3 alkyl-;

each R ^1b is independently halogen, hydroxy, cyano, nitro, C _1-4 alkyl, halo C _1-4 alkyl, C _1-4 alkoxy, or halo C _1-4 alkoxy;

each R ^b1 is independently halogen, hydroxy, cyano, nitro, C _1-4 alkyl or halo C _1-4 alkyl.
The compound of any one of claims 1 to 8, wherein,

is one of the following sub-formulae:

wherein, each y1 is independently 0, 1, 2 or 3;

each y2 is independently 0, 1, or 2;

y3 is 0, 1, 2, 3, 4, 5 or 6;

each R ^b is independently fluorine, chlorine, bromine, iodine, hydroxy, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -C (CH ₃) ₃, -CH ₂CH ₂CH ₂CH ₂CH ₃, -CH ₂CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -CH ₂CHF ₂, -CH ₂CH ₂F, -CH ₂CH ₂Cl, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -CH=CH ₂, -CH ₂CH=CH ₂, CH ₃-CH=CH-, -C ≡CH, -CH ₂-C ≡CH, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃, -SO ₂CH ₂CH ₃, CH ₃-C (=O) , CH ₃-C (=O) O-, CH ₃O-C (=O) -or -NR ^eR ^f;

each R ^e and R ^f is independently hydrogen, -CH ₃ or -CH ₂CH ₃;

or each R ^b is independently one of the following sub-formulae:

each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

each R ^1b is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃ or -OCF ₃.
The compound of any one of claims 1 to 9, wherein,

is one of the following sub-formulae:

each R ^b is independently fluorine, chlorine, bromine, iodine, hydroxy, mercapto, cyano, nitro, carboxyl, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -C (CH ₃) ₃, -CH ₂CH ₂CH ₂CH ₂CH ₃, -CH ₂CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -CH ₂CHF ₂, -CH ₂CH ₂F, -CH ₂CH ₂Cl, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃, -CH=CH ₂, -CH ₂CH=CH ₂, CH ₃-CH=CH-, -C ≡CH, -CH ₂-C ≡CH, -OCF ₃, -SCH ₃, -SCH ₂CH ₃, -SO ₂CH ₃, -SO ₂CH ₂CH ₃, CH ₃-C (=O) -, CH ₃-C (=O) O-, CH ₃O-C (=O) -or -NR ^eR ^f;

each R ^e and R ^f is independently hydrogen, -CH ₃ or -CH ₂CH ₃;

or each R ^b is independently one of the following sub-formulae:

each R ^b is independently and optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R ^1b;

each R ^1b is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃, -OCH ₃, -OCH ₂CH ₃, -OCH ₂CH ₂CH ₃, -OCH (CH ₃) ₂, -OCH ₂CH ₂CH ₂CH ₃, -OCH (CH ₃) CH ₂CH ₃, -OCH ₂CH (CH ₃) CH ₃ or -OCF _3;

each R ^b1 is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH ₃, -CH ₂CH ₃, -CH ₂CH ₂CH ₃, -CH (CH ₃) ₂, -CH ₂CH ₂CH ₂CH ₃, -CH (CH ₃) CH ₂CH ₃, -CH ₂CH (CH ₃) CH ₃, -CHF ₂, -CF ₃ or -CH ₂CHF ₂.
The compound of any one of claims 1 to 11, wherein,

each of R ⁵ and R ⁶ is independently hydrogen or C _1-4 alkyl; preferably, each of R ⁵ and R ⁶ is independently hydrogen;

W is N or CR ⁷;

R ⁷ is hydrogen, halogen or C _1-4 alkyl; preferably, R ⁷ is hydrogen;

W ¹ is O or S.
The compound of any one of claims 1 to 12 having formula (II) or a stereoisomer, an N-oxide, or a salt thereof:
A compound having one of the following structures or a stereoisomer, an N-oxide, or a salt thereof:
A composition comprising the compound of any one of claims 1 to 14.
Use of the compound of any one of claims 1 to 14 or the composition of claim 15 in controlling pests.
The use of claim 16, wherein the pests include at least one selected from Aphis medicaginis Koch, bemisia tabaci, Aphis gossypii Glover, Plutella xylostella, Myzus persicae and Mythimna separata.
The compound of any one of claims 1 to 14 or the composition of claim 15 for use in controlling pests.
The compound or the composition of claim 18, wherein the pests include at least one selected from Aphis craccivora Koch, bemisia tabaci, Aphis gossypii, Plutella xylostella, Myzus persicae and Pseudaletia separata.
A method of controlling pests comprising administering to seeds, plants or plant parts, fruits or the soil in which the plants grow, a therapeutically effective amount of the compound according to any one of claims 1 to 14 or the composition according to claim 15.
The method of claim 20, wherein wherein the pests include at least one selected from Aphis craccivora Koch, bemisia tabaci, Aphis gossypii, Plutella xylostella, Myzus persicae and Pseudaletia separata.