CN105669660B - Nitrogen-containing heterocyclic compounds and their uses - Google Patents

Abstract

The present invention relates to nitrogen-containing hetero cyclics of a kind of structure novel and application thereof.The nitrogen-containing heterocycle compound is compound (being detailed in specification) or its acceptable salt in Pesticide Science shown in formula I.Nitrogen-containing hetero cyclics provided by the invention can be used as insecticide application.Compared with existing insecticide, the chemical stability of insecticide provided by the invention is more preferable, meanwhile, there is better killing activity for resistant insect.

Description

Nitrogen-containing heterocyclic compounds and their uses

technical field

The present invention relates to a nitrogen-containing heterocyclic compound with novel structure and its use.

technical background

In recent years, neonicotinoid insecticides have become the fastest growing class of insecticides in modern crop protection. The neonicotinoid insecticides represented by imidacloprid have high insecticidal activity, broad insecticidal spectrum, low toxicity to mammals and aquatic animals, good systemic properties, certain field stability and environmental friendliness. Traditional pesticides do not have cross-resistance. Neonicotinoids mainly act on the nicotinic acetylcholine receptors (nAChRs) of insects. The discovery of neonicotinoid insecticides is a milestone in the development of modern pesticides.

After the listing of imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram, dinotefuran, piperamid, cycloploprid, sulfluramid appeared in the neonicotinoid field. Nitrile and other high-activity, high-sales varieties provide farmers with favorable "weapons" to control piercing-sucking pests.

However, with the popularity of neonicotinoid insecticides, serious resistance problems have also arisen. At the same time, the cross-resistance between neonicotinoid insecticides due to structural similarity limits the use of these compounds to a certain extent, which has become an important problem restricting neonicotinoid insecticides. At the same time, neonicotinoid insecticides mainly control Homopteran and Coleopteran pests, show low activity against Lepidopteran pests, and the limitation in insecticidal spectrum also hinders their better development.

Therefore, it is necessary to stimulate the vitality of neonicotinoid pesticides by continuously creating new products and expanding the selection library of pesticides, and to cope with the test of nature through continuous innovation. Specifically, it is how to carry out structural modification on active nitromethylene compounds to generate new and more effective insecticides and solve the challenges faced by neonicotinoid insecticides, which is the requirement of the present invention. technical problems solved.

SUMMARY OF THE INVENTION

In the present invention, the existing active nitromethylene compounds are structurally modified, and a class of nitrogen-containing heterocyclic compounds with novel structure is designed and synthesized. Through the insecticidal activity test, the nitrogen-containing heterocyclic compounds provided by the present invention have strong insecticidal activity. Compared with existing pesticides, its chemical stability is better.

An object of the present invention is to provide a nitrogen-containing heterocyclic compound with a novel structure, the nitrogen-containing heterocyclic compound is a compound represented by formula I, or a pesticide acceptable salt thereof:

In formula I, R ₁ is hydrogen (H), C ₁ -C ₃ alkyl, halogen (F, Cl, Br or I, the same below) substituted C ₁ -C ₃ alkyl, phenyl, halogenated phenyl , 5-6 membered heterocyclic group, halogenated 5-6 membered heterocyclic group, trifluoroacetyl, or (The position marked by the curve is the substitution position, the same below);

wherein, R ₇ is a 5- to 6-membered heterocyclic group, a halogenated 5- to 6-membered heterocyclic group or a halogenated C ₁ -C ₃ alkyl group, X is O or NR ₉ , and R ₈ is a 5- to 6-membered heterocyclic group A cyclic group or a halogenated 5-6 membered heterocyclic group, Y is CH ₂ or NH, and n is 0 or 1;

The heteroatoms of the 5-6 membered heterocyclic group are selected from: one or two of N, O or S, and R ₉ is H, C ₁ -C ₃ alkyl or halogenated C ₁ -C ₃ alkyl ;

R ₂ is H, halogen (F, Cl, Br or I, the same below), C ₁ -C ₃ hydrocarbon group, halogenated C ₁ -C ₃ hydrocarbon group or C ₁ -C ₃ alkoxy group;

R ₃ and R ₄ are independently selected from: one of C ₁ -C ₄ hydrocarbon groups or halogenated C ₁ -C ₄ hydrocarbon groups; or,

The combination of R ₃ and R ₄ (abbreviated as "R ₃ +R ₄ ") and the nitrogen (N) connected to each constitute: 5-7 membered N-containing heterocycle or substituted 5-7 membered N-containing heterocycle ring;

Wherein, the substituent of the substituted 5-7 membered N-containing heterocycle is selected from: methyl, trifluoromethyl, monovalent phenyl, CH ₃ OCH ₂ , divalent cyclohexyl, substituted by trifluoromethyl One of the divalent cyclohexyl, divalent phenyl, or divalent phenyl substituted by trifluoromethyl or methoxy;

Description: The divalent cyclohexyl group, the divalent cyclohexyl group substituted by trifluoromethyl group, the divalent phenyl group, or the divalent phenyl group substituted by trifluoromethyl group or methoxy group replace the 5-7-membered group After the N-containing heterocycle is formed, it is in a "merging" relationship with the 5-7 membered N-containing heterocycle;

R ₅ and R ₆ are independently selected from: H, one of C ₁ -C ₄ hydrocarbon group, halogenated C ₁ -C ₄ hydrocarbon group or C ₁ -C ₃ oxygen-containing alkyl group;

Y is an electron withdrawing group, such as (but not limited to): nitro (NO ₂ ), cyano (CN), trifluoroacetyl or trifluoromethylsulfonyl

Z is 5-6 membered heterocyclic group, substituted 5-6 membered heterocyclic group, pyridine, pyrimidine, nitrobenzene or benzo 5-membered heterocyclic group, phenyl or substituted phenyl;

The heteroatom of the heterocyclic group is selected from: one or two of O, S or N, and the number of heteroatoms is 1 or 2;

The substituent of the substituted 5-6 membered heterocyclic group is selected from: C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halogen, NO ₂ , CN, phenyl, from methyl, methoxy group, trifluoromethyl, amino (NH ₂ ), NO ₂ , halogen, acetyl Methylsulfonyl or Substituted phenyl, pyridyl substituted by methoxy, trifluoromethyl, halogen, _NO or CN, pyrimidinyl, pyrimidinyl substituted by methyl, methylpyrrolyl substituted by methyl, thienyl, Or one or more than two (containing two) of the furyl groups substituted by trifluoromethyl;

The substituent of the substituted phenyl group is selected from: C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halogen, CN, phenyl, pyridyl, pyridyl substituted by trifluoromethyl, furyl , one or more (including two) of furyl substituted by methyl or/and trifluoromethyl, pyrrolyl or pyrrolyl substituted by methyl and acetyl.

Another object of the present invention is to disclose an application of the above nitrogen-containing heterocyclic compounds, that is, the application of the compound represented by formula I or its pesticide acceptable salt as a pesticide.

Detailed ways

In a preferred technical solution of the present invention, the nitrogen-containing heterocyclic compound of the present invention is a compound represented by formula IA, or a pesticide acceptable salt thereof:

In formula IA, R ₁ is H, halogenated C ₁ -C ₃ alkyl, phenyl, halogenated phenyl, 5- to 6-membered heterocyclic group, halogenated 5- to 6-membered heterocyclic group, trifluoroacetyl base or

Wherein, the heteroatoms of the 5-6 membered heterocyclic group are selected from: one or two of N, O or S, the number of heteroatoms is 1 or 2; R ₇ is a halogenated C ₁ -C ₃ alkyl group , X is NR ₉ , and R ₉ is H, C ₁ -C ₃ alkyl or halogenated C ₁ -C ₃ alkyl;

R ₂ is H, halogen, C ₁ -C ₃ hydrocarbon group, halogenated C ₁ -C ₃ hydrocarbon group or C ₁ -C ₃ alkoxy group;

R _3a and R _4a are independently selected from: one of C ₁ -C ₄ hydrocarbon groups or halogenated C ₁ -C ₄ hydrocarbon groups;

R ₅ and R ₆ are independently selected from: H, one of C ₁ -C ₄ hydrocarbon groups or halogenated C ₁ -C ₄ hydrocarbon groups;

Y is NO ₂ , CN, or

Z is a 5- to 6-membered heterocyclic group, a substituted 5- to 6-membered heterocyclic group, a nitrobenzene or a benzo 5-membered heterocyclic group, a phenyl group or a substituted phenyl group;

The heteroatoms of the 5-6 membered heterocyclic group are selected from: one or two of O, S or N, and the number of heteroatoms is 1 or 2;

The substituent of the substituted 5-6 membered heterocyclic group is selected from: C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halogen, NO ₂ , One or more than two (including two) of substituted phenyl or pyridyl;

The substituent of the substituted phenyl group is selected from: C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, phenyl, pyridyl, pyridyl substituted by trifluoromethyl, furyl, methyl One or more (including two) of substituted furyl groups or pyrrolyl groups substituted by methyl and acetyl groups.

Further preferred R ₁ is: H, fluorine or chlorinated C ₁ -C ₃ alkyl, phenyl, chlorophenyl, 5-6 membered heterocyclyl, chlorinated 5-6 membered heterocyclyl, tris Fluoroacetyl or

Wherein, the heteroatoms of the 5-6 membered heterocyclic group are selected from: one or two of N, O or S, the number of heteroatoms is 1 or 2; R ₇ is a fluorinated C ₁ -C ₃ alkyl group , X is NH;

Further preferred R ₁ is: H, fluoro or chloro methyl or ethyl, phenyl, chloro phenyl, 5-membered heterocyclyl, chloro 5-6 membered heterocyclyl, trifluoroacetyl or

Wherein, the heteroatom of the heterocyclic group is selected from: one or two of N, O or S, and the number of heteroatoms is 1 or 2; R ₇ is a fluorinated C ₁ -C ₃ alkyl group, and X is NH ;

Still further preferred R ₁ is: H, fluoro or chloro methyl or ethyl, phenyl, chlorophenyl, tetrahydrofuranyl, chlorothiazolyl or pyridyl, trifluoroacetyl or

Wherein, R ₇ is a fluorinated methyl group, and X is NH;

The best R ₁ is: H, CH ₂ Cl, CH ₂ CF ₃ , trifluoroacetyl, or

Further preferred R ₂ is: H, halogen, C ₁ -C ₃ hydrocarbyl, halogenated C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy;

Further preferred R ₂ is: H, Cl, (allyl), fluorine or chlorinated C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy;

The most preferred R ₂ is: H, CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH ₂ F, CH ₂ CF ₃ , allyl, OCH ₂ CH ₃ or Cl.

Further preferred R _3a and R _4a are independently selected from: one of C ₁ -C ₄ hydrocarbon groups or halogenated C ₁ -C ₄ alkyl groups;

Further preferred R _3a and R _4a are independently selected from: C ₁ -C ₄ hydrocarbon group, or one of fluorine or chlorinated C ₁ -C ₄ alkyl group;

The most preferred R _3a and R _4a are each independently selected from: CH ₃ , CH ₂ Cl, CH ₂ F, CH ₂ CH ₃ , CH ₂ CF ₃ , CH ₂ CH ₂ Cl , (CH ₃ ) ₃ C or allyl one of them.

Further preferred R ₅ and R ₆ are independently selected from: H, one of C ₁ -C ₄ hydrocarbon groups or halogenated C ₁ -C ₄ alkyl groups;

Further preferred R ₅ and R ₆ are independently selected from: H, C ₁ -C ₄ hydrocarbon group, or one of fluorine or chlorinated C ₁ -C ₄ alkyl group;

The optimal R ₅ and R ₆ are each independently selected from one of: H, CH ₃ , CH ₂ Cl, CH ₂ F, CH ₂ CH ₃ , CH ₂ CH ₂ Cl or allyl.

Further preferred Z is: furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, substituted furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl or pyridyl, nitrobenzene or benzothienyl, phenyl or substituted phenyl;

The substituents of the substituted furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl or pyridyl are selected from: methyl, ethyl, methoxy, phenyl, Cl, NO ₂ , CN, or by One or more than two (including two) of methoxy, trifluoromethyl or acetyl-substituted phenyl or pyridyl;

The substituent of the substituted phenyl group is selected from: methyl, methoxy, phenyl, pyridyl, pyridyl substituted by trifluoromethyl, furyl substituted by methyl, or substituted by methyl and acetyl One or more than two (including two) in the pyrrole base;

Even more preferred Z is: furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, substituted furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl or pyridyl, nitrobenzene or benzothienyl, phenyl or substituted phenyl;

The substituents of the substituted furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl or pyridyl are selected from: methyl, ethyl, methoxy, Cl, NO ₂ , CN, phenyl, or One or more than two (including two);

The substituent of the substituted phenyl group is selected from: methyl, methoxy, phenyl, or One or more than two (including two);

The nitrobenzene or benzothienyl is: or

In another preferred technical solution of the present invention, the nitrogen-containing heterocyclic compound of the present invention is a compound represented by formula IB, or a pesticide acceptable salt thereof:

In formula IB, R ₁ is H, halogen, C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkyl, phenyl, halogenated phenyl, trifluoroacetyl, 5-6 membered heterocyclic group , consisting of trifluoromethyl or halogenated 5- to 6-membered heterocyclic groups, or

wherein, R ₇ is a 5- to 6-membered heterocyclic group, a halogenated 5- to 6-membered heterocyclic group or a halogenated C ₁ -C ₃ alkyl group, X is O or NR ₉ , and R ₈ is a 5- to 6-membered heterocyclic group Cyclic group, halogenated 5- to 6-membered heterocyclic group, Y is CH ₂ or NH, and n is 0 or 1;

The heteroatoms of the 5-6 membered heterocyclic group are selected from: one or two of N, O or S, the number of heteroatoms is 1 or 2, and R ₉ is H, C ₁ -C ₃ alkyl or halogenated C ₁ -C ₃ alkyl;

R ₂ is H, C ₁ -C ₃ hydrocarbon group or halogenated C ₁ -C ₃ hydrocarbon group;

The combination of R _3b and R _4b (abbreviated as "R _3b +R _4b ") and the N connected to each constitute: a 5- to 7-membered N-containing heterocycle, a substituted 5- to 7-membered N-containing heterocycle, or A 5- to 7-membered N-containing heterocycle composed of cycloalkyl, phenyl, substituted cycloalkyl or phenyl "and" (A ring in formula IB, abbreviated as "A");

Namely: A is a 5- to 7-membered N-containing heterocycle, a substituted 5- to 7-membered N-containing heterocycle, or a 5- to 7-membered cycloalkyl, phenyl, substituted cycloalkyl or phenyl group. membered N-containing heterocycle;

Wherein, the substituted 5-7 membered N-containing heterocyclic substituent is selected from: methyl, trifluoromethyl, phenyl or One or both of them, the number of substituents is 1 or 2;

The substituent of described substituted cycloalkyl or phenyl is selected from: methyl, one or both in methoxy or trifluoromethyl, and the number of substituents is 1 or 2;

R ₅ and R ₆ are independently selected from: H, one of C ₁ -C ₄ hydrocarbon group, halogenated C ₁ -C ₄ hydrocarbon group or C ₁ -C ₃ oxygen-containing alkyl group;

Y is NO ₂ , CN, or

Z is 5-6 membered heterocyclic group, substituted 5-6 membered heterocyclic group, pyridine, pyrimidine or benzo 5-membered heterocyclic group, phenyl or substituted phenyl;

The heteroatoms of the 5-6 membered heterocyclic group are selected from: one or two of O, S or N, and the number of heteroatoms is 1 or 2;

The substituent of the substituted 5-6 membered heterocyclic group is selected from: C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halogen, NO ₂ , CN, phenyl, from methyl, methoxy group, trifluoromethyl, amino (NH ₂ ), NO ₂ , halogen, acetyl Methylsulfonyl or Substituted phenyl, pyridyl substituted by methoxy, trifluoromethyl, halogen, _NO or CN, pyrimidinyl, pyrimidinyl substituted by methyl, methylpyrrolyl substituted by methyl, thienyl or One or more than two (including two) of the furyl groups substituted by trifluoromethyl;

The substituent of the substituted phenyl group is selected from: C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halogen, CN, phenyl, pyridyl, pyridyl substituted by trifluoromethyl, furyl , one or more (including two) of furyl, pyrrolyl, or pyrrolyl substituted by methyl or/and trifluoromethyl.

Further preferred R ₁ is: H, Br, C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkyl, trifluoroacetyl, phenyl, chlorophenyl, 5-6 membered heterocyclyl , by trifluoromethyl or chloro 5-6 membered heterocyclic group, or

wherein, R ₇ is a 5- to 6-membered heterocyclic group, a chlorinated 5- to 6-membered heterocyclic group or a fluoro-substituted C ₁ -C ₃ alkyl group, X is O or NR ₉ , and R ₈ is a 5- to 6-membered heterocyclic group Cyclic or chloro-substituted 5- to 6-membered heterocyclic group, Y is CH ₂ or NH, and n is 0 or 1;

The heteroatoms of the 5-6 membered heterocyclic group are selected from: one or two of N, O or S, the number of heteroatoms is 1 or 2, and R ₉ is H, C ₁ -C ₃ alkyl or halogenated C ₁ -C ₃ alkyl;

Further preferred R ₁ is: H, Br, n-propyl, chlorine or fluorinated C ₁ -C ₃ alkyl, trifluoroacetyl, phenyl, chlorophenyl, tetrahydrofuranyl, by trifluoromethyl or chlorinated pyridyl, thienyl or thiazolyl, or

Wherein, R ₇ is trifluoromethyl, tetrahydrofuranyl, chlorothiazolyl, or chloropyridyl, X is O or NR ₉ , R ₈ is tetrahydrofuranyl, chlorothiazolyl, or chloropyridyl, and Y is CH ₂ or NH, n is 0 or 1; R ₉ is H, methyl or trifluoroethyl;

The best R ₁ is: H, trifluoroacetyl, _CH2Cl , _{CH2CF3 ,} Br,

Further preferred R ₂ is: H, C ₁ -C ₃ hydrocarbyl or halogenated C ₁ -C ₃ alkyl;

Further preferred R ₂ is: H, C ₁ -C ₃ hydrocarbyl, or C ₁ -C ₃ alkyl of fluorine or chlorine;

The best R ₂ are: H, CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH ₂ F, or CH ₂ CH ₂ Cl.

Further preferred A is a 5- to 7-membered N-containing heterocycle, a substituted 5- to 7-membered N-containing heterocycle, or a 5- to 7-membered N-containing heterocycle; that is, R _3b + R _4b is one of the following groups:

wherein, m is 0, 1 or 2, and R ₁₀ or R ₁₁ are independently selected from: H, methyl, trifluoromethyl, phenyl or one of; or, the combination of R ₁₀ and R ₁₁ (abbreviated as "R ₁₀ +R ₁₁ ") is a divalent substituted cycloalkyl or phenyl;

The substituent of the divalent substituted cycloalkyl or phenyl group is selected from: one or both of methyl, methoxy or trifluoromethyl, and the number of substituents is 1 or 2;

Still further preferred R _3b + R _4b is one of the following groups:

where m is 0, 1 or 2.

Further preferred R ₅ and R ₆ are independently selected from: H, C ₁ -C ₄ alkenyl, C ₁ -C ₄ linear or branched alkyl, halogenated C ₁ -C ₄ linear or branched One of chain alkyl groups or C ₁ -C ₃ oxyalkyl groups;

Further preferred R ₅ and R ₆ are independently selected from: one of the following groups:

_H , _CH3 , _CH2F , _CF3 , _CH2Cl , _CH2Br , _{CH2CH3 , CH2CH2Cl} , (CH ₃ ) ₃ C, or

Further preferably Z is furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyridyl, substituted

The substituents of the substituted furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl or pyridyl are selected from: C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halogen, NO ₂ , CN, phenyl, consisting of methyl, methoxy, trifluoromethyl, amino (NH ₂ ), NO ₂ , halogen, acetyl Methylsulfonyl or Substituted phenyl, pyridyl substituted by methoxy, trifluoromethyl, halogen, _NO or CN, pyrimidinyl substituted by methyl, methylpyrrolyl substituted by methyl, thienyl or substituted by trifluoro One or more than two (containing two) of methyl-substituted furyl groups;

The substituent of the substituted phenyl group is selected from: C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halogen, CN, phenyl, pyridyl, pyridyl substituted by trifluoromethyl, pyridyl substituted by methyl One or more (including two) in furyl substituted by methyl group or pyrrolyl group substituted by methyl group and acetyl group;

It is further preferred that Z is: phenyl, substituted phenyl, or substituted furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl or pyridyl;

Wherein, the substituent of the substituted phenyl group is selected from one or more than two (containing two):

Methyl, Methoxy, Phenyl, F, CN,

The substituent of described substituted furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl or pyridyl is selected from one or more than two (containing two) in the following groups:

Methyl, Methoxy, Ethyl, Phenyl, CN, _NO2 , Cl, Br,

In addition, another object of the present invention is to provide a method for preparing the compound shown in formula I, and the synthesis strategy of the method is as follows:

or (taking A as an example of N-containing heterocycle with 5-7 members)

Wherein, n is 1, 2 or 3, and the definitions of other substituents are the same as those described above.

Specifically include the following steps:

(1) An appropriate amount of acetonitrile was added to the aqueous solution of the amine compound (R _3a NH ₂ ), and the acetonitrile solution of the compound represented by formula II (abbreviated as compound II, the same below) was added dropwise under an ice bath, and the reaction progress was tracked by TLC. After the reaction, a large amount of water was added to the reaction mixture, extracted with dichloromethane, dried, suction filtered, and the solvent was evaporated to obtain compound III;

(2) Compound III and 1,1-dithiomethyl-2-Y substituted ethylene, using ethanol as a solvent, refluxed for 4 hours to 8 hours, concentrated, and separated by column chromatography to obtain product compound IV;

(3) under ice bath condition, react compound IV with amine compound (R _4a R ₆ NH) in aliphatic alcohol (reaction medium) for 4 to 8 hours, concentrate the reaction product, and separate by column chromatography to obtain compound V;

(4) First, under the catalytic condition of acid (such as hydrochloric acid, sulfuric acid or heteropolyacid, etc.), compound V reacts with the corresponding aldehyde to obtain compound VI; then, under basic conditions, compound VI is subjected to reduction reaction ( The reducing reagent can be sodium borohydride, etc.) to obtain compound IA.

or,

(1) The acetonitrile solution of compound II is added dropwise to the diamine (compound VII) solution in 5-10 times molar amount, and the reaction is carried out at 0-50°C for 5-10 hours. After removing the unreacted compound VII under reduced pressure, it was dissolved in ethyl acetate, and the solvent was spin-dried to obtain compound VIII;

(2) Compound VIII replaces ethylene with 1,1-dithiomethyl-2-Y, using ethanol as a solvent, and refluxing for 4-8 hours to obtain compound IX;

(3) First, under the catalytic condition of acid (such as hydrochloric acid, sulfuric acid or heteropolyacid, etc.), compound IX reacts with the corresponding aldehyde to obtain compound X; then, under basic conditions, compound X is subjected to reduction reaction ( The reducing reagent can be sodium borohydride, etc.) to obtain compound IB;

Insecticidal activity of the active substances according to the invention

The term "active substance of the present invention" or "active compound of the present invention" refers to a compound of the present invention, an optical isomer, cis-trans isomer or a pesticidal acceptable salt thereof, which has significantly improved insecticidal activity , and an expanded insecticidal spectrum.

The term "pesticidally acceptable salt" means that the anion of the salt is known and acceptable in forming a pesticide pharmaceutically acceptable salt. The salts are preferably water-soluble, such as hydrochloride, phosphate, sulfate, nitrate; including salts formed from organic acids, such as acetate or benzoate, and the like.

The active substances of the present invention can be used for controlling and eradicating a wide range of agricultural and forestry plant pests, stored grain pests, plant parasites, public health pests, and the like. In the present specification, "insecticide" refers to a general term for substances having the effect of controlling all the above-mentioned pests. Examples of pests include, but are not limited to: Coleopteran insects: Sitophilus zeamais, Tribolium castaneum, Potato lady beetle ( Henosepilach navigintioctomaculata ), Henosepilachna sparsa, Agriotesfuscicollis), red-footed beetle (Anomala cupripes), four-striped beetle (Popilliaquadriguttata), potato beetle (Monolepta hieroglyphica), pine beetle (Monochamusalternatus), rice root elephant (Echinocnemus squameus), Paulownia beetle (Basiprioota bisignata) , Anoplophora chinensis, Apripona germari, Scolytusschevy, or Agriotes fuscicollis. Lepidoptera: Gypsy Moth (Lymantriadispar), Sky Curtain Caterpillar (Malacosoma neustria testacea), Boxwood Borer (Diaphania perspectalis), Sack Moth (Clania variegata), Yellow Slug Moth (Cnidocampa flauescens), Masson Pine Caterpillar (Dendrolimus punctatus), Orgyia gonostigma, Paranthrenetabaniformis, Spodoptera litura, Chilo suppressalis, Ostrinia nubilalis, Ephestia cautella, Cotton roll moth ( Adoxophyes orana), chestnut worm (Laspyresia splendana), little cutworm (Agrotis fucosa), greater wax moth (Galleriamellonella), diamondback moth (Plutella xylostella), orange miner (Phyllocnistis citrella), or eastern armyworm (Mythimna separata) ). Homoptera: Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspisyanonensis, Myzus persicae, Aphis gossydii , radish aphid (Lipaphis erysimipseudobrassicae), pear bug (Stephanitis nashi), or whitefly (Bemisia tabaci). Orthoptera: Blattella germanica, Periplaneta american, Gryllotalpa africana, or Locus migratoria. Isoptera: Invasive red fire ants (Solenopsis invicta), or domestic termites (Coptotermes formosanus). Diptera: Muscadomestica, Aedes aegypti, Delia platura, Culex sp., or Anopheles sinensis. Root-knot nematodes such as Meloidogyne arenaria, Meloidogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne genera; cyst nematodes such as Globodera rostochiensis, Globodera pallida, Globodera tabacum, and Other cyst nematodes (Globodera); Heterodera such as Heterodera avenae, Heterodera glycines, Beet cyst nematode (Heteroderaschachtii), Heterodera trifolii, and other Heterodera; species of nematodes such as Anguina funesta, Anguina tritici and other Anguina; stem and leaf bud nematodes such as rice stem tip Nematodes (Aphelenchoides besseyi), Aphelenchoides fragariae, Aphelenchoides ritzemabosi and other Aphelenchoides; spiny nematodes such as Belonolaimus longicaudatus and other needle-stinging nematodes Genus Belonolaimus; pine nematodes such as Bursaphelenchus xylophilus and other Bursaphelenchus; ring nematodes such as Criconema, Criconemella, Rotifer (Criconemoides) and Mesocriconema; bulb nematodes such as Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus and other Ditylenchus; trypanosomes, trypanosomes (Dolich odorus); helical nematodes such as Helicotylenchus dihystera, Helicotylenchus multicintus and other genera Helicotylenchus; sheath nematodes such as Helicotylenchus and Hemicriconemoides ); crown nematodes, such as Hoploaimus columbus and other Hoploaimus; pseudorhizobia, such as Nacobbus aberrans and other pearl nematodes (Nacobbus); needle nematodes, such as escape long Pinworms (Longidorus elongatus) and other Longidorus (Longidorus); pinworms, such as Paratylenchus; root-rot nematodes, such as Pratylenchus brachyurus, Pratylenchus coffee , Pratylenchus zeae, Pratylenchus penetrans, and other Pratylenchus; piercing nematodes such as Radopholus similis and other Radopholus; kidney nematodes such as Rotylenchus robustus and other genera Rotylenchus; stump nematodes such as Trichodorus primitivus and other genera Trichodorus; dwarf nematodes such as gram Tylenchorhynchus claytoni, adventitious dwarf nematode (Tylenchorhynchus dubius) and other dwarf nematodes (Tylenchorhynchus); citrus nematodes such as Tylenchulus semipenetrans and other dwarf nematodes (Tylenchulus) ); Xiphinema, such as Xiphinema americanum, Xiphinema index, Xiphinema diversicaudatum and other Xiphinema.

The compounds involved in the invention have special effects on piercing-sucking and filing-sucking mouthpart pests such as aphids, leafhoppers, planthoppers, thrips, whiteflies and other agricultural and forestry pests, and at the same time, have special effects on plant parasites such as southern root-knot nematodes .

Insecticide combinations containing the active substances according to the invention

The active substances of the present invention can be prepared into insecticidal compositions by conventional methods. These active compounds can be formulated into conventional formulations. e.g. solutions, emulsions, suspensions, powders, foams, pastes, granules; aerosols, natural and synthetic materials impregnated with active substances, microcapsules in polymers, for neutrons Coated formulations of , and in combination with burning devices — formulations for use in blocks, such as smoking cartridges, smoking pots and smoking trays, as well as ULV Cold mist and Warm mist formulations.

These formulations can be produced by known methods, for example, by mixing the active compounds with extenders, which are liquid or liquefied gas or solid diluents or carriers, optionally with surfactants, ie emulsifiers and/or Dispersants and/or foam formers. For example, when water is used as an extender, organic solvents can also be used as auxiliaries.

Essentially suitable as diluents or carriers are liquid solvents such as: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or Dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffins, such as mineral oil fractions; alcohols, such as ethanol or ethylene glycol and their ethers and lipids; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or unusual polar solvents such as dimethylformamide and dimethylsulfoxide, and water.

The diluent or carrier of liquefied gas refers to a liquid that will become a gas at normal temperature and pressure, such as aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.

The solid carrier may be ground natural minerals, such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth, and ground synthetic minerals, such as highly dispersed silicic acid, Alumina and Silicates. Solid supports for granules are ground and graded natural zircon such as calcite, marble, pumice, sepiolite and dolomite, as well as granules synthesized from inorganic and organic coarse powders, and organic materials such as sawdust, coconut shells, Particles of corn cobs and tobacco stems, etc.

Nonionic and anionic emulsions can be used as emulsifiers and/or foam formers. For example, polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylarylpolyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and white protein hydrolysate. Dispersants include, for example, lignin sulfite waste liquor and methyl cellulose.

Binders such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or emulsions such as gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the formulation.

Colorants can be used, such as inorganic dyes, including iron oxide, cobalt oxide, and Prussian blue, etc.; organic dyes, such as dichloro dyes or metal phthalocyanine dyes, etc.; and trace nutrients, such as iron, manganese, boron, copper, Salts of cobalt, aluminum and zinc, etc.

These active compounds in the present invention can be mixed with other active compounds in commercial formulations, or in dosage forms prepared from these formulations, the other active compounds include but are not limited to: insecticides, baits, fungicides pesticides, acaricides, nematicides, fungicides, growth control agents, etc. Insecticides include, for example, phosphates, carbamates, (pseudo)pyrethroids, chlorinated hydrocarbons, neonicotinoids, insect growth regulators, nematoxins, pymetrozine, GABA receptors Inhibitors, fishnetin receptor inhibitors, and substances produced by microorganisms, such as abamectin, etc.

In addition, the active compounds of the present invention may also be present in their commercial formulations in admixture with synergists in dosage forms prepared from these formulations. A synergist is a compound that improves the effect of an active compound. Since the active compound itself is active, it is not necessary to add a synergist.

These formulations generally contain 0.001-99.99% by weight of the pesticidal composition, preferably 0.01-99.9% by weight, more preferably 0.05-90% by weight of the active compound of the invention. The concentration of active compound in the dosage forms prepared for use from commercial formulations can vary widely. The concentration of active compound in the dosage form used may be from 0.0000001 to 100% (g/v), preferably 0.0001 to 1%.

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. The experimental methods without specific conditions in the following examples are usually in accordance with conventional conditions, or in accordance with the conditions suggested by the manufacturer. Percentages and parts are by weight unless otherwise indicated. where r.t. stands for room temperature.

Example 1.

N-((6-Chloropyridin-3-yl)methyl)-N-ethyl-N`-methyl-2-nitro-3-(thiazol-2-yl)prop-1-enediamine ( Synthesis of compound IA-1):

(1) Synthesis of N-(6-chloropyridine-3-methylene)ethanamine (Compound III-1)

In a 250 mL three-necked round-bottomed flask with a constant pressure dropping funnel and a thermometer, add 70 g (1 mol) of 65-70% ethylamine aqueous solution, 50 mL of acetonitrile, and stir for 15 min under an ice bath to stabilize the solution temperature at around 0 °C , add 16.10g (0.10mol) of acetonitrile (25mL) solution of 6-chloro-3-chloromethylpyridine to the constant pressure dropping funnel, control the rate of addition at 3 drops/min, and the addition time at 3.5h, the reaction After completion, add water, extract with dichloromethane, collect the organic phase, and obtain 15 g of oily liquid N-(6-chloropyridine-3-methylene)ethylamine (compound III-1), with a yield of 88%.

GC-MS (m/s): 170([M] ⁺ , 20), 155(80), 126(100), 114(10), 90(12).

(2) Synthesis of N-(6-chloropyridine-3-methylene)-N-ethyl-1-thiomethyl-2-nitrovinylideneamine (Compound IV-1)

In a 100mL three-necked round bottom flask, add 17.0g (0.1mol) of N-(6-chloropyridine-3-methylene)ethylamine, 15.0g (0.09mol) of 1,1-dithiomethyl-2- Nitroethylene, 50mL of absolute ethanol, heated to reflux, refluxed for 8h. The reflux was stopped, cooled to room temperature, and concentrated to obtain a viscous liquid, which was separated by silica gel column chromatography (dichloromethane:acetone=5:1 (v/v)) to obtain 6.5 g of the product (compound IV-1), with a yield of 6.5 g. twenty three%.

GC-MS(m/s): 242([M] ⁺ -46,53), 227(15), 213(100), 169(45), 155(28), 141(29), 126(91) , 90(12).

(3) N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N`-methyl-2-nitro-3-(thiazol-2-yl)prop-1-ene Synthesis of diamine (compound V-1):

Into a 100mL round bottom flask, add 5g (0.017mol) of N-(6-chloropyridine-3-methylene)-N-ethyl-1-thiomethyl-2-nitrovinylideneamine, 1.8 g (0.017mol methylamine) in methylamine alcohol solution, 30 mL absolute ethanol, and stirring under ice bath to reduce the temperature to 0°C, and continue the reaction until the end. The solvent was evaporated under reduced pressure and concentrated to obtain a slurry, which was separated by silica gel column chromatography (dichloromethane:acetone=4:1) of compound 1.24g (compound V-1) with a yield of 27%. GC-MS (m/s): 236([M] ^+- 34,32), 207(49), 169(52), 126(49), 90(16), 67(100).

(4) N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N'-methyl-2-nitro-3-(thiazol-2-yl)prop-1-ene Synthesis of Diamine (Compound IA-1)

1.350g (0.005mol) of N-(6-chloropyridine-3-methylene)-N-ethyl-N'-methyl-2-nitroethylenediamine, 30mL of anhydrous acetonitrile, 0.678 g (0.006 mol) of 2-thiazolecarboxaldehyde, catalytic amount of HCl was placed in a 50 ml round bottom flask. After stirring at room temperature, a large amount of solid was precipitated after about 6 h, the reaction was stopped and filtered. The filtered solid, 25 mL methanol, 10% equiv. Ni, was placed in a 50 mL round bottom flask. Filled with hydrogen, stirred at room temperature, followed the progress of the reaction on a TLC plate, and the product had R _f =0.25 (dichloromethane:acetone=4:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IA-1 (target), which is 0.631 g of a white powdery solid with a yield of about 34%.

¹ H NMR (400MHz, DMSO)δ9.47(s,1H),8.28(s,1H),7.69(d,J=8.2Hz,1H),7.50(d,J=8.2Hz,1H),7.27( s, 1H), 6.66(s, 1H), 4.53(s, 2H), 3.93(s, 2H), 3.75–3.68(m, 2H), 3.52(s, 3H), 1.98–1.87(m, 3H) ppm. ¹³ C NMR (101MHz, DMSO) δ162.84, 149.92, 148.78, 143.65, 138.70, 132.29, 126.99, 124.71, 124.48, 124.44, 106.20, 50.92, 50.56, 42.74, 29.80, 25.22ppm.

_calcd for _{C16H18N5O2S35Cl} (M+H) ⁺ , _368.0948 ; found: _367.0955 ; _calcd for ^{C16H18N5O2S37Cl} ₍ M ₊ ^H ) ⁺ , _370.0918 ; Measured value: 369.0916.

Example 2

Synthesis of 2-((1H-pyrrol-2-yl)methyl)-3-chloromethylamino-3-(N-benzyl-N-ethylamino)acrylonitrile (Compound IIA-2):

(1) Synthesis of 3-chloromethylamino-3-(N-benzyl-N-ethylamino)acrylonitrile (Compound V-2)

Except that the chloropyridine ring is replaced by a benzene ring, a nitro group is replaced by a cyano group, and a methyl group is replaced by a chloromethyl group, other steps are the same as those in steps (1) to (3) in Example 1 to obtain compound V-2.

(2) 2-((1H-pyrrol-2-yl)methyl)-3-chloromethylamino-3-(N-benzyl-N-ethylamino)acrylonitrile (Compound IA-2) synthesis

1.24g (0.005mol) of 3-chloromethylamino-3-(N-benzyl-N-ethylamino)acrylonitrile, 30mL of anhydrous acetonitrile, 0.570g (0.006mol) of 2-pyrrolecarboxaldehyde , a catalytic amount of HCl was placed in a 50 ml round bottom flask. After stirring at room temperature, a large amount of solid was precipitated after about 7 hours, the reaction was stopped and filtered. The solids obtained by filtration, 25 mL of tetrahydrofuran, and 2x equivalents of lithium aluminum hydride were placed in a 50 mL round bottom flask. Stir at room temperature, follow the progress of the reaction on a TLC plate, and the product has R _f =0.20 (dichloromethane:acetone=3:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IA-2, which is 0.712 g of a white powdery solid, and the yield is about 38%.

¹ H NMR (400MHz, DMSO) δ 9.99(s, 1H), 9.50(s, 1H), 8.28(s, 1H), 7.39(d, J=7.2Hz, 1H), 7.25(dd, J ₁ = 7.2 Hz, J ₂ =4.0 Hz, 2H), 7.17 (d, J = 4.0 Hz, 2H), 6.88 (dd, J ₁ =4.9 Hz, J ₂ =3.6 Hz, 1H), 6.66 (d, J = 3.6 Hz, 1H), 6.23(d, J＝4.9Hz, 1H), 4.57(s, 2H), 4.23(s, 2H), 3.81(s, 2H), 3.75 –3.60(m, 2H), 1.68(t , J=4.6Hz, 3H)ppm. ¹³ C NMR (101MHz, DMSO) δ172.84, 138.54, 132.90, 128.97, 127.53, 124.38, 123.64, 120.92, 108.39, 106.20, 59.33, 53.10, 50.92, 48.2034, 3 ^.HRMS (ES+) _C18H22N435Cl (M ₊ H) ⁺ , calcd: _329.1533 ; Found: _329.1532 ; _C18H22N437Cl (M ₊ H) ⁺ , calcd: ^331.1503 ; Measured value: 331.1506.

Example 3

N-(3,3,3-Trifluoropropyl)-N-ethyl-N',N'-dimethyl-2-nitro-3-(4-cyanothiophen-2-yl)propane- Synthesis of 1-enediamine (compound IA-3):

(1) Synthesis of N-(3,3,3-trifluoropropyl)-N-ethyl-N',N'-dimethyl-2-nitroethylenediamine (compound V-3)

Except that the chloropyridine ring is replaced by trifluoromethyl methyl, and the raw material methylamine in step (3) is replaced by dimethylamine, other steps are the same as steps (1) to (3) in Example 1 to obtain compound V- 3.

1.28g (0.005mol) of N-(3,3,3-trifluoropropyl)-N-ethyl-N',N'-dimethyl-2-nitroethylenediamine, 30mL of Anhydrous acetonitrile, 0.822 g (0.006 mol) of 5-cyano-2-thiophenecarbaldehyde, catalytic amount of HCl were placed in a 50 ml round bottom flask. After stirring at room temperature, a large amount of solid was precipitated after about 14 hours, the reaction was stopped and filtered. The solid obtained by filtration, 25 mL methanol, 10% equiv. palladium on carbon, was placed in a 50 mL round bottom flask. Filled with hydrogen, stirred at room temperature, followed the progress of the reaction on a TLC plate, and the product had Rf=0.30 (dichloromethane:acetone=4:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filtration, taking the filtrate, and spin-drying the solvent to obtain the crude product, which was recrystallized with ethanol to obtain the pure product of compound IA-3, which was 0.783 g of a white powdery solid, and the yield was about 42%. ¹ H NMR(400MHz, DMSO)δ7.52(s,1H),6.43(s,1H),4.53(s,2H),3.01-2.88(m,6H),2.64-2.50(m,6H),1.52 (t, J=2.8Hz, 3H) ppm. ¹³ C NMR (101MHz, DMSO) δ 162.84, 145.92, 141.78, 126.99, 124.71 (q, J=217.3Hz), 114.48, 106.20, 85.12, 50.98, 50.10, 47.83, 43.75, 42.11, 30.12, 15.33 ppm. ¹⁹ F NMR (376 MHz, DMSO) δ-67.33 ppm. HRMS (ES+) C ₁₅ H ₂₀ N ₃ O ₂ SF ₃ (M+H) ⁺ , calcd: 377.1259; found : 377.1247.

Example 4

N-(2-Chloroethyl)-N-ethyl-N'-methyl-2-nitro-3-(5-methylfuran-2-yl)prop-1-ene-1,1-di Synthesis of Amine (Compound IA-4):

(1) Synthesis of 5-phenylfuran-2-carbaldehyde (Compound Z-4)

Under the strict protection of argon, 0.875g (0.005mol) of 5-bromo-2-furancarboxaldehyde and 0.610g (0.005mol) of phenylboronic acid were dissolved in 20mL of toluene, 20mL of ethanol and 5mL of 2mol/L potassium carbonate aqueous solution , and then add heating to reflux for 4h. After the reaction was completed, it was cooled, allowed to stand, the water layer was removed, and the water layer was washed three times with ethyl acetate. The washing solution and the reaction solution were combined, and the solvent was evaporated under reduced pressure. 97%. GC-MS (m/s): 172(100), 144(8), 99(48), 86(5).

(2) Synthesis of N-(2-chloroethyl)-N-ethyl-N'-methyl-2-nitroethene-1,1-diamine (compound V-4)

The other steps are the same as steps (1) to (3) in Example 1 except that the chloropyridine ring is replaced by chloromethyl group to obtain compound V-4.

(3) N-(2-chloroethyl)-N-ethyl-N'-methyl-2-nitro-3-(5-methylfuran-2-yl)prop-1-ene-1, Synthesis of 1-Diamine (Compound IA-4)

0.860 g (0.005 mol) of 4-phenylfuran-2-carbaldehyde was dissolved in dichloromethane, followed by dropwise addition of 1.04 g (0.005 mol) of N-(2-chloroethyl)-N-ethyl Base-N'-methyl-2-nitroethene-1,1-diamine, 30 mL of anhydrous acetonitrile, catalytic amount of HCl in a 50 mL round bottom flask. After stirring at room temperature, a large amount of bright yellow solid was precipitated after about 4 hours, the reaction was stopped and filtered. The solids obtained by filtration, 25 mL of tetrahydrofuran, and 2x equivalents of lithium aluminum hydride were placed in a 50 mL round bottom flask. Stir at room temperature, follow the progress of the reaction on a TLC plate, and the product has R _f =0.35 (dichloromethane:acetone=8:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IA-4, which is 1.213 g of white solid, and the yield is about 53%. ¹ H NMR(400MHz, DMSO)δ9.27(s,1H),7.77(d,J=8.4Hz,2H),7.43(d,J=8.4Hz,2H),7.09(d,J=7.6Hz, 1H), 6.95(d, J=7.6Hz, 1H), 4.41(s, 2H), 3.74(s, 2H), 3.79(d, J=6.8Hz, 2H), 3.70–3.56(m, 6H)ppm . ¹³ C NMR( _101MHz , DMSO) _{δ163.87,154.81,151.76,131.02,128.12,127.73,125.58,116.51,114.23,101.24,54.82,47.22,42.11,41.82,38.70,13.45ppm N3O335Cl} ( _M +H) ⁺ , calcd: _364.1428 ; found ^364.1441 ; _{C18H23N3O337Cl} ( _M +H) ⁺ , calcd: _366.1398 ; found ^366.1403 .

Example 5

Synthesis of 2-chloro-5-((2-(2-(furan-2-yl)-1-nitrovinyl)imidazolidin-1-yl)methyl)pyridine (compound IB-1):

(1) Synthesis of 2-chloro-5-(2-nitromethylene-imidazolidine-1-ylmethyl)-pyridine (Compound IX-1)

2-Chloro-5-(2-nitromethylene-imidazolidine-1-ylmethyl) was prepared according to the methods described in WO2006056108A1 and WO2007101369A1 using 0.03 mol of 2-chloro-5-chloromethylpyridine as the starting material yl)-pyridine, yield 64%; R _f =0.46 (petroleum ether:ethyl acetate=1:1); mp=157.3°C～159.9°C. GC-MS (m/s) 220(25), 126(100), 90(9).

(2) Synthesis of 2-chloro-5-((2-(2-(furan-2-yl)-1-nitrovinyl)imidazolidin-1-yl)methyl)pyridine (Compound IB-1) :

1.27g (0.005mol) of 2-chloro-5-(2-nitromethylene-imidazolidine-1-ylmethyl)-pyridine, 30mL of anhydrous acetonitrile, 0.576g (0.006mol) of furfural, A catalytic amount of HCl was placed in a 50 ml round bottom flask. After stirring at room temperature, a large amount of solid was precipitated after about 4 hours, the reaction was stopped and filtered. The solids obtained by filtration, 25 mL of tetrahydrofuran, and 2x equivalents of lithium aluminum hydride were placed in a 50 mL round bottom flask. Stir at room temperature, follow the progress of the reaction on a TLC plate, and the product has R _f =0.40 (dichloromethane:acetone=5:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-1, which is 1.060 g of white needle-like crystals, and the yield is about 64%. ¹ HNMR (400 MHz, CDCl ₃ ) δ 9.87 (s, 1H), 8.25 (s, 1H), 7.49 (d, J=5.2 Hz, 1H), 7.37 (d, J=6.0 Hz, 1H), 7.27 (d, J=12.3Hz, 1H), 6.29 (dd, J1 ₌ 3.2Hz, J2=1.8Hz, 1H ₎ , 6.15 (d, J=2.4Hz, 1H), 4.61 (s, 2H), 3.90 (s, 2H), 3.84 (t, J=8.0 Hz, 2H), 3.69 (t, J=8.0 Hz, 2H) ppm. ¹³ C NMR (101 MHz, CDCl ₃ ) δ 188.84, 162.58, 152.17, 151.44, 148.04 , 141.13, 137.05, 130.67, 124.72, 110.72, 106.73, 105.63, 51.44, 50.97, 42.19, 27.81ppm.HRMS(ES+)C ₁₅ H ₁₅ N ₄ O ₃ ³⁵ Cl(M+K) ⁺ , calculated: 373.0470; Found: _373.0468 ; calcd for _{C15H15N4O337Cl} ( _{M +} K) ⁺ , ^375.0440 ; found: 375.0444.

Example 6

2-Chloro-5-((2-(2-(5-bromo-thiophen-2-yl)-1-nitrovinyl)imidazolidine-1-yl)methyl)pyridine (Compound IB-2) synthesis:

(1) Synthesis of 2-chloro-5-(N-methyl-2-nitromethylene-imidazolidine-1-ylmethyl)-pyridine (Compound IX-2)

2-Chloro-5-(N-methyl-2-nitromethylene-imidazolidine was prepared according to the methods described in WO2006056108A1 and WO2007101369A1 using 0.03 mol of 2-chloro-5-chloromethylpyridine as starting material -1-ylmethyl)-pyridine, yield 55%; R _f =0.40 (petroleum ether:ethyl acetate=1:1); mp=160.3°C-162.9°C. GC-MS (m/s) 234(25), 126(100), 90(9).

(2) 2-Chloro-5-((2-(2-(5-bromo-thiophen-2-yl)-1-nitrovinyl)imidazolidin-1-yl)methyl)pyridine (Compound IB -2) Synthesis of

1.34g (0.005mol) of 2-chloro-5-(N-methyl-2-nitromethylene-imidazolidine-1-ylmethyl)-pyridine, 30mL of anhydrous acetonitrile, 1.146g (0.006 mol) of 5-bromo-2-thiophenecarbaldehyde, catalytic amount of HCl in a 50 ml round bottom flask. After stirring at room temperature, a large amount of solid was precipitated after about 8 hours, the reaction was stopped and filtered. The solids obtained by filtration, 25 mL of methanol, and 2 equivalents of sodium borohydride were placed in a 50 mL round bottom flask. Stir at room temperature, follow the progress of the reaction on a TLC plate, and the product has R _f =0.40 (dichloromethane:acetone=5:1). After the reaction was completed, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain a crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-2, which is 1.856 g of white needle-like crystals, and the yield is about 84%. ¹ H NMR(400MHz, DMSO)δ9.38(s,1H),8.32(s,1H),7.73(d,J=8.3Hz,1H),7.50(d,J=8.3Hz,1H),6.95( d, J＝3.5Hz, 1H), 6.48(d, J＝3.5Hz, 1H), 4.55(s, 2H), 3.85(s, 2H), 3.71(t, J＝14.6 Hz, 2H), 3.67( t, J=14.6Hz, 2H), 3.60 (s, 3H) ppm. ¹³ C NMR (101MHz, DMSO) δ162.73, 149.92, 148.80, 145.72, 138.73, 132.16, 129.83, 125.34, 124.69, 109.29, 105.36, 64.20, _50.96 , _50.61 , 42.75, 30.48 ppm. HRMS (ES+) _{C16H17N4O2S35Cl79Br} (M ₊ H) ⁺ , _calcd : _442.9944 ; found: ^442.9932 ; ^C16H17N Calcd. for _4O2S37Cl79Br (M ^+K)+ _, ^444.9924 ; found: ^444.9915 . Calcd ^. for _{C15H15N4O2S35Cl81Br} ^(M+H)+ _{, 430.9767 ;} found: ^430.9760 . Calcd ^. for _{C15H15N4O2S37Cl81Br} ^(M+K)+ _{, 432.9738 ;} found: ^432.9741 .

Example 7

Synthesis of 1-butyl-5-methyl-2-(1-nitro-2-(thiophen-3-yl)vinyl)imidazoline (compound IB-3):

(1) Synthesis of 1-butyl-5-methyl-2-(nitromethylene) imidazoline (compound IX-3)

Except that the chloropyridine ring is replaced with n-propyl group, and the raw material ethylenediamine is replaced with 1-methylethylenediamine, other steps are the same as those in step (1) in Example 5 to obtain compound IX-3.

(2) Synthesis of 1-butyl-5-methyl-2-(1-nitro-2-(thiophen-3-yl)vinyl)imidazoline (compound IB-3)

0.995g (0.005mol) of 1-butyl-5-methyl-2-(nitromethylene) imidazoline, 30mL of anhydrous acetonitrile, 0.672g (0.006mol) of 3-thiophenecarboxaldehyde, catalytic amount HCl in a 50 ml round bottom flask. After stirring at room temperature, a large amount of solid was precipitated after about 8 hours, the reaction was stopped and filtered. The solids obtained by filtration, 25 mL methanol, 10% equiv. palladium on carbon, were placed in a 50 mL round bottom flask. Filled with hydrogen and stirred at room temperature, the progress of the reaction was followed by a TLC plate, and the product had R _f =0.30 (dichloromethane:acetone=5:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-3, which is 0.758 g of a white solid, and the yield is about 52%. ¹ H NMR (400 MHz, CDCl ₃ ) δ 9.46 (s, 1H), 7.39 (d, J=8.0 Hz, 1H), 7.13 (d, J=8.0 Hz, 1H), 6.71 (s, 1H), 4.51 ( s,2H),3.82-3.75(m,1H),3.66-3.60(m,1H),3.43-3.36(m,1H),2.90-2.80(m,2H),1.82-1.77(m,2H), 1.53-1.48 (m, 2H), 1.41 (t, J=5.2Hz, 3H), 1.15 (d, J=7.2Hz, 3H) ppm. ¹³ C NMR (101 MHz, CDCl ₃ ) δ 162.42, 137.69, 129.40, 127.47 ,121.97,92.18,65.37,62.31,46.12,29.13,21.84,19.20,17.10,17.12ppm.HRMS(ES+)C ₁₄ H ₂₂ N ₃ O ₂ (M+H) ⁺ , calculated: 296.1433; found: 296.1425 .

Example 8

2-Chloro-5-((2-(3-Methyl-1-nitro-2-phenylbutenyl)-2,3-dihydro-1H-benzo[d]imidazolidine-1-yl ) methyl) thiazole (compound IB-4) synthesis:

(1) 2-Chloro-5-((2-(nitromethylene)-2,3-dihydro-1H-benzo[d]imidazol-1-yl)methyl)thiazole (Compound IX-4 ) Synthesis

Except that the chloropyridine ring is replaced by n-propyl group, and the raw material ethylenediamine is replaced by 1-methylethylenediamine, other steps are the same as step (1) in Example 5, to obtain compound IX-4.

(2) 2-Chloro-5-((2-(3-methyl-1-nitro-2-phenylbutenyl)-2,3-dihydro-1H-benzo[d]imidazolidine- Synthesis of 1-yl)methyl)thiazole (compound IB-2)

1.54 g (0.005 mol) of 2-chloro-5-((2-(nitromethylene)-2,3-dihydro-1H-benzo[d]imidazol-1-yl)methyl)thiazole , 30 mL of anhydrous acetonitrile, 0.888 g (0.006 mol) of 2-methyl-1-phenylpropan-1-one, and a catalytic amount of HCl were placed in a 50 mL round-bottomed flask. After stirring at room temperature, a large amount of solid was precipitated after about 6 h, the reaction was stopped and filtered. The filtered solid, 25 mL methanol, ₁₀ % equiv. PbO2, was placed in a 50 mL round bottom flask. Filled with hydrogen and stirred at room temperature, the progress of the reaction was followed by a TLC plate, and the product had R _f =0.35 (dichloromethane:acetone=5:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain a crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-4, which is 1.098 g of white crystals, and the yield is about 50%. ¹ H NMR(400MHz,DMSO)δ9.34(s,1H)7.80-7.21(m,10H), 4.02(s,2H),3.84(d,J=4.2Hz,2H),1.84-1.75(m, 1H), 1.07(d, J=8.2Hz, 6H)ppm. ¹³ C NMR (101MHz, DMSO)δ160.34,153.31,142.07,137.89,137.28,133.82,131,47,129.94,128.36, 125.23,120.93,118.074,1 116.32, 105.22, 60.55, 35.28, _31.63 , 19.40 ppm. HRMS (ES+) _{C22H22N4O2S35Cl} (M ₊ H) ⁺ , _calcd : _441.1152 ; found: ^441.1142 ; _C22H22N Calcd. for _4O2S37Cl (M ₊ H) ⁺ , ^441.1122 ; found: 441.1107.

Example 9

Synthesis of 2-(1-nitro-2-(thiophen-2-yl)propenyl)-1-((tetrahydrofuran-3-yl)methyl)imidazoline (compound IB-5):

(1) Synthesis of 1-((tetrahydrofuran-3-yl)methyl)-2-(nitromethylene)-1-imidazoline (compound IX-5)

7.68g (0.03mol) of 4-methylbenzenesulfonic acid (tetrahydrofuran-3-yl)methyl ester, 9.00g (0.15mol) of ethylenediamine, 8.280g (0.06mol) of potassium carbonate, 0.20g of iodine Sodium chloride and 120 mL of acetonitrile were placed in a 250 mL round-bottomed flask, heated to 70°C, reacted for 4 h, filtered, and the filtrate was collected and concentrated to obtain crude N-((tetrahydrofuran-3-yl)methyl)ethylenediamine. The obtained crude product and 4.125 g (0.025 mol) of 1,1-dithiomethyl-2-nitroethylene were dissolved in a 250 mL round-bottomed flask with 100 mL of ethanol, and reacted for 8 h under reflux conditions. Cool, wait for the solid to be precipitated, concentrate, filter and dry to obtain 5.32 g of light yellow powdery solid with a yield of 88%; GC-MS (m/s): 177(29), 99(100), 56(9).

(2) Synthesis of 2-(1-nitro-2-(thiophen-2-yl)propenyl)-1-((tetrahydrofuran-3-yl)methyl)imidazoline (compound IB-5)

1.205g (0.005mol) of 1-((tetrahydrofuran-3-yl)methyl)-2-(nitromethylene)-1-imidazoline, 30mL of anhydrous acetonitrile, 0.756g (0.006mol) of 1-Thien-2-ylethanone, catalytic amount of HCl was placed in a 50 ml round bottom flask. After stirring at room temperature, a large amount of solid was precipitated after about 5 h, the reaction was stopped and filtered. The filtered solid, 25 mL methanol, 10% equiv. Ni, was placed in a 50 mL round bottom flask. Filled with hydrogen, stirred at room temperature, followed the progress of the reaction on a TLC plate, and the product had R _f =0.30 (dichloromethane:acetone=5:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-5, which is 0.878 g of a white powdery solid with a yield of about 50%. mp=108.2～109.4℃. ¹ H NMR(400MHz, CDCl ₃ )δ10.05(s, 1H), 7.14(d, J=4.8 Hz, 1H), 6.92(d, J=4.8 Hz, 1H), 6.84 (s, 1H), 4.23 (d, J=17.7Hz, 1H), 4.16 (d, J=17.7Hz, 1H), 3.87–3.65 (m, 7H), 3.51–3.40 (m, 1H), 3.38– 3.20(m, 1H), 2.51(dt, J1 _{= 13.4Hz} , J2=6.8Hz, 1H), 2.02(td, J=13.4, 6.9Hz, 1H), 1.96(s, 3H), 1.43(td , J ₁ =13.4Hz, J ₂ =6.8Hz, 1H)ppm. ¹³ C NMR (101MHz, DMSO) δ 162.62, 143.79, 126.92, 124.68, 124.42, 105.94, 70.47, 67.13, 51.90, 50.37, 42.55, 40.12, 38. , 30.14, 29.79 ppm. HRMS (ES+) C ₁₄ H ₂₀ N ₃ O ₃ S (M+H) ⁺ , calcd: 324.1382; found: 324.1374.

Example 10

2-Chloro-5-((2-(2-(3-methoxyphenyl)methyl)-1-nitrovinyl)hexahydropyrimidin-1-yl)methyl)pyridine (Compound IB-6 ) Synthesis:

(1) Synthesis of 1-(6-chloro-3-methylpyridyl)-2-nitromethylenehexahydropyrimidine (Compound IX-6)

Using 2.42g (0.015mol) of p-chloropyridine as the starting material, 1-(6-chloro-3-methylpyridyl)-2-nitromethylenehexahydropyrimidine was prepared according to the methods described in WO2006056108A1 and WO2007101369A1 , the yield is 50%; Rf=0.20 (ethanol:dichloromethane=1:1); mp=177.9 225(100), 196(9), 154(10), 139(11), 126(31), 113(10), 99(31).

(2) 2-Chloro-5-((2-(2-(3-methoxyphenyl)methyl)-1-nitrovinyl)hexahydropyrimidin-1-yl)methyl)pyridine (compound Synthesis of IB-6)

1.340g (0.005mol) of 2-chloro-5-(2-nitromethylene-imidazolidine-1-ylmethyl)thiazole, 30mL of anhydrous acetonitrile, 0.816g (0.006mol) of 3-methyl Oxybenzaldehyde, catalytic amount of HCl was placed in a 50 ml round bottom flask. After stirring at room temperature, a large amount of solid was precipitated after about 7 hours, the reaction was stopped and filtered. The solids obtained by filtration, 25 mL of tetrahydrofuran, and 2x equivalents of lithium aluminum hydride were placed in a 50 mL round bottom flask. Stir at room temperature, follow the progress of the reaction on a TLC plate, and the product has Rf=0.40 (dichloromethane:acetone=5:1). After the reaction was completed, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain a crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-6, which is 1.067 g of a white powdery solid with a yield of about 57%. 1H NMR(400MHz, DMSO)δ9.47(s,1H),8.28(s,1H),7.69(d,J=8.2Hz,1H),7.50(d,J=8.2Hz,1H),7.28(s ,1H),7.23(d,J=3.6Hz,1H),7.18(dd,J1 ₌ 3.6Hz,J2=5.6Hz,1H),7.10(d,J=5.6Hz,1H ₎ ,4.53(s , 2H), 4.15(s, 3H), 3.93(s, 2H), 3.65–3.51(m, 2H), 3.44–3.37(m, 2H), 1.85– 1.78(m, 2H) ppm. ¹³ C NMR( 101MHz,DMSO)δ162.84,149.92,148.78,143.65,138.70, 132.29,126.99,15.89,124.71,124.48,124.44,106.20,70.81,50.92,50.56,42.74,35.18,34.67, 29.80.HRMS(ES+)C ₁₉ H _{22 N4O335Cl} ( _{M +} H) ⁺ , calcd: ^389.1380 ; found: _389.1397 ; C19H22N4O337Cl( _M +H) ⁺ , calcd: _391.1351 ; found: ^391.1349 .

Example 11

2-(1-(N-(2-(6-chloropyridin-3-yl)2-acetyl)-N'-methyl-imidazolin-2-ylmethylene)-3-(thiophene-2 Synthesis of -yl)propionitrile (compound IB-7):

(1) Synthesis of 2-(1-(2-(6-chloropyridin-3-yl)-2-acetyl)-3-vinylimidazolin-2-ylvinyl)acetonitrile (Compound IX-7)

Except that the chloropyridine ring is replaced with 6-chloropyridine-3-formyl, the raw material ethylenediamine is replaced with 1-vinylethylenediamine, and the nitro group is replaced by a cyano group, other steps are the same as in step (1) in Example 5, Compound IX-7 is obtained.

(2) 2-(1-(N-(2-(6-chloropyridin-3-yl)2-acetyl)-N'-methyl-imidazolin-2-ylmethylene)-3-( Synthesis of thiophen-2-yl)propionitrile (compound IB-7):

1.44 g (0.005 mol) of 2-(1-(2-(6-chloropyridin-3-yl)-2-acetyl)-3-vinylimidazolin-2-ylvinyl)acetonitrile, 30 mL of Anhydrous acetonitrile, 0.672 g (0.006 mol) of 2-thiophenecarbaldehyde, catalytic amount of HCl were placed in a 50 ml round bottom flask. Stir at room temperature, after about 12 hours, a large amount of solid is precipitated, stop the reaction, and filter. The solids obtained by filtration, 25 mL of methanol, and 2 equivalents of sodium borohydride were placed in a 50 mL round bottom flask. Stir at room temperature, follow the progress of the reaction on a TLC plate, and the product has R _f =0.37 (dichloromethane:acetone=5:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-7, which is 0.933 g of a white powdery solid, and the yield is about 48%. ¹ H NMR(400MHz, DMSO)δ9.42(s,1H),8.27(s,1H),7.62(d,J=8.4Hz,1H),7.50(d,J=8.4Hz,1H),7.21( d, J=4.6Hz, 1H), 6.88 (dd, J1 ₌ 4.6Hz, J2= _3.6Hz , 1H), 6.66 (d, J=3.6Hz, 1H), 6.3 (d, J=5.4Hz, ^13C NMR (101MHz, DMSO) δ162.84, _149.92 , 148.78, 143.65, 138.70, 132.29, _126.99 , 124.71, 124.48, 124.44, 120.92, 118.76, _106.20 , 55.32, 50.92, 50.8 HRMS ^OS35Cl (M+H) ⁺ , calcd: _385.0890 ; found: ^385.0900 ; _{C16H15N4S37Cl} (M ₊ H) ⁺ , calcd: 387.0860; found: 387.0877.

Example 12

2-Chloro-5-((2-(2-(5-phenylthiophen-2-yl)-1-nitrovinyl)imidazolidin-1-yl)methyl)pyridine (Compound IB-8) synthesis:

(1) Synthesis of 2-chloro-5-(2-nitromethylene-imidazolidine-1-ylmethyl)thiazole (compound IX-8)

Except for replacing the chloropyridine ring with a 5-chlorothiazole ring, other steps were the same as in step (1) in Example 5 to obtain compound IX-8.

(2) Synthesis of 5-phenylthiophene-2-carbaldehyde (Compound Z-8)

Under the strict protection of argon, 0.955g (0.005mol) of 5-bromo-2-thiophenecarboxaldehyde and 0.610g (0.005mol) of phenylboronic acid were dissolved in 20mL of toluene, 20mL of ethanol and 5mL of 2mol/L potassium carbonate aqueous solution , and added 0.289 g (0.005 mol) of tetrakis (triphenylphosphine) palladium, and heated to reflux for 4 h. After the reaction was completed, it was cooled, allowed to stand, the water layer was removed, and the water layer was washed three times with ethyl acetate. The washing solution and the reaction solution were combined, the solvent was evaporated under reduced pressure, and separated by column chromatography to obtain 902 mg of pure product with a yield of about 96%. %. GC-MS (m/s): 188(100), 160(8), 115(48), 102(5), 79(7).

(3) 2-Chloro-5-((2-(2-(5-phenylthiophen-2-yl)-1-nitrovinyl)imidazolidin-1-yl)methyl)pyridine (Compound IB- 8) Synthesis of

0.940 g (0.005 mol) of 5-phenylthiophene-2-carbaldehyde was dissolved in dichloromethane, followed by dropwise addition of 1.300 g (0.005 mol) of 2-chloro-5-(2-nitromethylene) yl-imidazolidine-1-ylmethyl)thiazole, 30 mL of anhydrous acetonitrile, catalytic amount of HCl in a 50 mL round bottom flask. After stirring at room temperature, a large amount of bright red solid was precipitated after about 3 hours, the reaction was stopped, and the solution was filtered. The filtered solid, 25 mL methanol, ₁₀ % equiv. PbO2, was placed in a 50 mL round bottom flask. Filled with hydrogen, stirred at room temperature, followed the progress of the reaction on a TLC plate, and the product had R _f =0.39 (dichloromethane:acetone=8:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain a crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-8, which is 1.049 g of a white solid, and the yield is about 49%. ¹ H NMR (400MHz, DMSO) δ9.45(s, 1H), 7.62(s, 1H), 7.56(d, J=7.5Hz, 2H), 7.38(t, J=7.5Hz, 2H), 7.27( m, 7.32–7.20, 2H), 6.67(d, J=2.5Hz, 1H), 4.56(s, 2H), 3.94(s, 2H), 3.70(t, J=8.3Hz, 2H), 3.64(t , J＝8.3Hz, 2H)ppm. ¹³ C NMR(101MHz, DMSO)δ162.96,138.82,137.51,135.21,134.47,132.52,129.49,127.64,125,80,125.41,124.67,123.43,105.9,4,350.8 ^30.36 ppm. _HRMS (ES ₊ ) _calcd for _{C20H19N3O2S235Cl} ( _M ^+H)+ _{, 432.0607} ; found: ^432.0591 _{; C20H19N3O2S237Cl} ( _M +H) ⁺ , calcd: 434.0578; found: 433.0581.

Example 13

2-Chloro-5-((2-(2-(5-(4-methoxy-phenyl)thiophen-2-yl)-1-nitrovinyl)imidazolidin-1-yl)methylamino ) Synthesis of pyridine (compound IB-9):

(1) Synthesis of 2-chloro-5-(2-nitromethylene-imidazolidine-1-ylmethylamino)-pyridine (Compound IX-9)

The other steps were the same as step (1) in Example 5, except that the chloropyridine ring was replaced by 6-chloropyridin-3-ylamino group, to obtain compound IX-9.

(2) Synthesis of 5-(4-methoxyphenyl)thiophene-2-carbaldehyde (Compound Z-9)

Under the strict protection of argon, 0.955g (0.005mol) of 5-bromo-2-thiophenecarboxaldehyde, 0.760g (0.005mol) of p-methoxyphenylboronic acid were dissolved in 20mL of toluene, 20mL of ethanol and 5mL of 2mol/L Potassium carbonate aqueous solution, heated to reflux for 4h. After the reaction, it was cooled, allowed to stand, the water layer was removed, and the water layer was washed three times with ethyl acetate. The washing solution and the reaction solution were combined, the solvent was evaporated under reduced pressure, and separated by column chromatography to obtain 1.106 g of pure product with a yield of about 1.106 g. 93%. GC-MS (m/s): 218(100), 203(52), 189(7), 175(21), 145(21), 102(10), 77(14).

(3) 2-Chloro-5-((2-(2-(5-(4-methoxy-phenyl)thiophen-2-yl)-1-nitrovinyl)imidazolidin-1-yl) Synthesis of Methylamino)pyridine (Compound IB-9)

1.090 g (0.005 mol) of 5-(4-methoxyphenyl)thiophene-2-carbaldehyde was dissolved in dichloromethane, followed by dropwise addition of 1.345 g (0.005 mol) of 2-chloro-5- (2-Nitromethylene-imidazolidine-1-ylmethylamino)-pyridine, 30 mL of anhydrous acetonitrile, catalytic amount of HCl in a 50 mL round bottom flask. After stirring at room temperature, a large amount of orange-red solid was precipitated after about 4 hours, the reaction was stopped, and the mixture was filtered. The filtered solid, 25 mL methanol, ₁₀ % equiv. PbO2, was placed in a 50 mL round bottom flask. Filled with hydrogen and stirred at room temperature, the progress of the reaction was followed by a TLC plate, and the product had R _f =0.32 (dichloromethane:acetone=8:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-9, which is 1.394 g of white solid, and the yield is about 59%. ¹ H NMR (400MHz, DMSO) δ9.45(s, 1H), 8.33(s, 1H), 7.73(d, J=7.1Hz, 1H), 7.55-7.40(m, 3H), 7.12(s, 1H) ), 6.95(d, J=7.7Hz, 2H), 6.61(s, 1H), 5.23(s, 1H), 4.57(s, 2H), 3.91(s, 2H), 3.77(s, 3H), 3.70 (s,2H),3.67(s,2H) ppm. ¹³ C NMR(101MHz,DMSO)δ162.85,155.88,153.66,149.89,148.79,138.72,132.37,124.71,118.96,112.80,109.01,108.60,107.492 _51.06 , _50.53 , 42.68, 28.61 ppm. HRMS(ES+) calcd for _{C22H21N5O3S35Cl} ( _M +H) ⁺ , _{472.1210 ;} found: _{472.1196 ;} ^{C22H21N5O3S 37} Cl(M+H) ⁺ , calcd: 474.1181; found: 474.1174.

Example 14

2-(2-(1-((6-Chloropyridin-3-yl)methyl)imidazolin-2-yl-vinyl)-2-(2-(trifluoromethylsulfonyl)ethyl)- Synthesis of 4-(3-methoxyphenyl)thiazole (compound IB-10):

(1) Synthesis of 2-chloro-5-(2-trifluoromethanesulfonylmethylene-imidazolidine-1-ylmethyl)-pyridine (Compound IX-10)

The other steps were the same as step (1) in Example 5 except that the nitro group was replaced by a trifluorosulfonyl group to obtain compound IX-10.

(2) Synthesis of 5-(4-methoxyphenyl)thiophene-2-carbaldehyde (Compound Z-10)

Under the strict protection of argon, 0.950g (0.005mol) of 4-bromo-2-thiazolecarboxaldehyde, 0.765g (0.005mol) of 6-methoxy-2-pyridineboronic acid were dissolved in 20mL of toluene, 20mL of ethanol and 5mL of 2mol/L potassium carbonate aqueous solution was added and heated to reflux for 4h. After the reaction was completed, it was cooled, allowed to stand, the water layer was removed, and the water layer was washed three times with ethyl acetate. The washing solution and the reaction solution were combined, the solvent was evaporated under reduced pressure, and separated by column chromatography to obtain 1.006 g of pure product with a yield of about 91%. GC-MS (m/s): 220(100), 205(65), 177(40), 147(12), 116(8), 78(5).

(3) 2-(2-(1-((6-chloropyridin-3-yl)methyl)imidazolin-2-yl-vinyl)-2-(2-(trifluoromethylsulfonyl)ethane Synthesis of yl)-4-(3-methoxyphenyl)thiazole (compound IB-10)

1.100 g (0.005 mol) of 4-(6-methoxypyridin-2-yl)thiazole-2-carbaldehyde was dissolved in dichloromethane, followed by dropwise addition of 1.71 g (0.005 mol) of 2-chloromethane -5-(2-Trifluoromethanesulfonylmethylene-imidazolidin-1-ylmethyl)-pyridine, 30 mL of anhydrous acetonitrile, catalytic amount of HCl in a 50 mL round bottom flask. After stirring at room temperature, a large amount of bright yellow solid was precipitated after about 4 h, the reaction was stopped and filtered. The solids obtained by filtration, 25 mL methanol, 10% equiv. palladium on carbon, were placed in a 50 mL round bottom flask. Filled with hydrogen, stirred at room temperature, followed the progress of the reaction on a TLC plate, and the product had R _f =0.35 (dichloromethane:acetone=8:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-10, which is 1.213 g of white solid, and the yield is about 53%. ¹ H NMR(400MHz,DMSO)δ9.47(s,1H),8.32(s,1H),7.72(d,J=8.0Hz,1H),7.52(d,J=8.0Hz,2H),7.49( d, J=9.6Hz, 1H), 6.95(d, J=9.6Hz, 2H), 4.58(s, 2H), 3.94(s, 2H), 3.78(s, 3H), 3.71(d, J=6.3 Hz, 2H), 3.68 (d, J = 6.3 Hz, 2H) ppm. ¹³ C NMR (101 MHz, DMSO) δ 162.87, 158.81, 149.90, 148.76, 144.57, 140.69, 138.70, 128.51, 127.43, 124.23 (q, J = 203.9Hz), 123.35, 117.88, 114.63, 105.93, 55.58, 50.95, 50.61, 42.78, 30.13ppm. ¹⁹ F NMR(376MHz, DMSO)δ-67.33ppm.HRMS(ES+) C ₂₂ H ₂₁ N ₄ O ₃ S ₂ ^35ClF3 ( _{M +} H) ⁺ , _calcd : _545.0696 ; found: ^545.0702 ; _{C22H21N4O3S237ClF3} ( _M +H) ⁺ , calcd: _547.0666 ; found: 547.0664.

Example 15

3-(1-((6-Chloropyridin-3-yl)methyl)imidazolin-2-ylvinyl)-1,1,1-trifluoro-4-(4-(4-(trifluoromethyl) Synthesis of yl)phenyl)thienyl-2-yl)butan-2-one (compound IB-11):

(1) 3-(1-((6-chloropyridin-3-yl)methyl)imidazolin-2-ylvinyl)-1,1,1-trifluoropropan-2one (Compound IX-11) Synthesis

The other steps were the same as in step (1) in Example 5 except that the nitro group was replaced by a trifluoroformyl group to obtain compound IX-11.

(2) Synthesis of 4-(4-trifluoromethylphenyl)thiophene-2-carbaldehyde (Compound Z-11)

Under the strict protection of argon, 0.955g (0.005mol) of 4-bromo-2-thiophenecarboxaldehyde, 0.950g (0.005mol) of p-trifluoromethylphenylboronic acid were dissolved in 20mL of toluene, 20mL of ethanol and 5mL of 2mol/L of potassium carbonate aqueous solution, heated to reflux for 4h. After the reaction, it was cooled, allowed to stand, the water layer was removed, and the water layer was washed three times with ethyl acetate. The washing solution and the reaction solution were combined, the solvent was evaporated under reduced pressure, and separated by column chromatography to obtain 1.204 g of pure product with a yield of about 94%. GC-MS (m/s): 255(100), 203(64), 175(40), 145(12), 115(8).

(3) 3-(1-((6-chloropyridin-3-yl)methyl)imidazolin-2-ylvinyl)-1,1,1-trifluoro-4-(4-(4-( Synthesis of trifluoromethyl)phenyl)thienyl-2-yl)butan-2-one (compound IB-11)

1.280 g (0.005 mol) of 4-(4-trifluoromethylphenyl)thiophene-2-carbaldehyde was dissolved in dichloromethane, followed by dropwise addition of 1.53 g (0.005 mol) of 3-(1- ((6-chloropyridin-3-yl)methyl)imidazolin-2-ylvinyl)-1,1,1-trifluoropropan-2-one, 30 mL of anhydrous acetonitrile, 50 mL of catalytic HCl in a round bottom flask. After stirring at room temperature, a large amount of orange-red solid was precipitated after about 4 hours, the reaction was stopped, and the mixture was filtered. The solids obtained by filtration, 25 mL of methanol, and 2 equivalents of sodium borohydride were placed in a 50 mL round bottom flask. Stir at room temperature, follow the progress of the reaction on a TLC plate, and the product has R _f =0.36 (dichloromethane:acetone=8:1). After the reaction, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na2SO4 overnight. Filtration, taking the filtrate, and spin-drying the solvent to obtain the crude product, which was recrystallized with ethanol to obtain the pure product of compound IB-11, which was 1.851 g of white solid, and the yield was about 68%.

¹ H NMR (400MHz, DMSO) δ9.47(s, 1H), 8.30(s, 1H), 7.83-7.79(m, 3H), 7.77-7.65(m, 3H), 7.47(d, J=8.2Hz ,1H),7.13(d,J=1.1Hz,1H),4.58(s,2H),3.97(s,2H),3.80–3.70(m,2H),3.70–3.64(m,2H).

¹³ C NMR(101MHz, DMSO)δ176.23,162.83,149.89,148.74,145.39,139.30,138.68,132.33,126.18(q,J=212.8Hz),124.67,123.40,121.88,115.8(q,J=193.4Hz) 105.78,51.00,50.58, 40.63,40.42,40.21,40.00,39.80,39.59,39.38,30.16ppm.

¹⁹ F NMR (376 MHz, DMSO) δ-60.83, -55.90 ppm. HRMS (ES+) C ₂₄ H ₁₉ N ₃ OS ³⁵ ClF ₆ (M+H) ⁺ , calcd: 546.0842; found: 546.0844; C ₂₄ H _19N3OS37ClF6 ( _M +H) ⁺ , calcd: ^548.0812 _; found: 548.0819.

Example 16

Synthesis of 2-chloro-5-((2-(1-nitro-2-(benzofuran-2-yl)vinyl)imidazolin-1-yl)ethyl)pyridine (compound IB-12):

(1) Synthesis of 2-chloro-5-((2-nitromethylene-imidazolidin-1-yl)ethyl)-pyridine (Compound IX-12)

Except that 2-chloro-5-(1-chloroethyl)pyridine was used as the starting material instead of 6-chloro-3-chloromethylpyridine, other steps were the same as step (1) in Example 5 to obtain compound IX-12.

(2) 2-Chloro-5-((2-(1-nitro-2-(benzofuran-2-yl)vinyl)imidazolin-1-yl)ethyl)pyridine (Compound IB-12) Synthesis

0.730 g (0.005 mol) of benzofuran-2-carbaldehyde was dissolved in dichloromethane, followed by dropwise addition of 1.34 g (0.005 mol) of 2-chloro-5-((2-nitromethylene) - Imidazolidine-1-yl)ethyl)-pyridine, 30 mL of anhydrous acetonitrile, catalytic amount of HCl in a 50 mL round bottom flask. After stirring at room temperature, a large amount of bright yellow solid was precipitated after about 4 hours, the reaction was stopped and filtered. The filtered solid, 25 mL methanol, 10% equiv. Ni, was placed in a 50 mL round bottom flask. Filled with hydrogen, stirred at room temperature, followed the progress of the reaction on a TLC plate, and the product had R _f =0.30 (dichloromethane:acetone=7:1). After the reaction was completed, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na2SO4 overnight. Filtration, taking the filtrate, and spin-drying the solvent to obtain a crude product, which was recrystallized with ethanol to obtain the pure product of compound IB-12, which was 1.231 g of a white solid, and the yield was about 64%. ¹ H NMR (400MHz, DMSO) δ9.22(s, 1H), 8.65(s, 1H), 7.91(d, J=6.0Hz, 1H), 7.80(d, J=5.4Hz, 1H), 7.63( d, J=6.8Hz, 1H), 7.55 (s, 1H), 7.38–7.31 (m, 3H), 4.39 (s, 2H), 3.98 (q, J=7.8Hz, 1H), 3.69–3.60 (m ,4H)1.90(q,J＝7.8Hz,3H)ppm. ¹³ C NMR (101MHz,DMSO)δ162.41,153.77,151.20,150.86,142.39,137.55,131.72,127.53,124.89, 123.88,123.90,120.42,1 106.73, 56.84, 48.27, 47.93, 31.68, 22.41 ppm. HRMS (ES+) C ₂₀ H ₂₀ N ₄ O ₃ ³⁵ Cl(M+H) ⁺ calcd: 399.1224; found 399.1220; C ₂₀ H ₂₀ N ₄ O Calcd. for _337Cl (M+H) ⁺ : ^401.1194 ; found: 401.1190.

Example 17

3-(3-(2-(1-(1-Bromo-4,4,4-trifluorobutyl-2-yl)imidazolin-2-ylalkenyl)-2-nitroethyl)phenyl Synthesis of Pyridine (Compound IB-13):

(1) Synthesis of 1-(1-bromo-4,4,4-trifluorobutyl-2-yl)-2-(nitrovinyl)imidazoline (compound IX-13)

Except for replacing 6-chloro-3-chloromethylpyridine with 4-bromo-3-chloro-1,1,1-trifluorobutane as the raw material, other steps are the same as in step (1) in Example 5 to obtain the compound IX–13.

(2) 3-(3-(2-(1-(1-Bromo-4,4,4-trifluorobutyl-2-yl)imidazolin-2-ylalkenyl)-2-nitroethyl ) Synthesis of Phenylpyridine (Compound IB-13)

0.915g (0.005mol) of 4-(pyridin-3-yl)benzaldehyde was dissolved in dichloromethane, followed by dropwise addition of 1.58g (0.005mol) of 1-(1-bromo-4,4, 4-Trifluorobutyl-2-yl)-2-(nitrovinyl)imidazoline, 30 mL of anhydrous acetonitrile, catalytic amount of HCl in a 50 mL round bottom flask. After stirring at room temperature, a large amount of bright yellow solid was precipitated after about 4 hours, the reaction was stopped and filtered. The solids obtained by filtration, 25 mL of methanol, and 2 equivalents of sodium borohydride were placed in a 50 mL round bottom flask. Stir at room temperature, follow the progress of the reaction on a TLC plate, and the product has R _f =0.25 (dichloromethane:acetone=7:1). After the reaction was completed, the solvent was spin-dried, the residual sticky substance was extracted three times with dichloromethane and water, the dichloromethane layer was taken, washed three times with a saturated NaCl solution, and dried with Na ₂ SO ₄ overnight. Filter, take the filtrate, spin dry the solvent to obtain the crude product, which is recrystallized with ethanol to obtain the pure product of compound IB-13, which is 1.626 g of white solid, and the yield is about 67%. ¹ H NMR (400MHz, DMSO) δ9.27(s, 1H), 8.70(s, 1H), 8.53(d, J=5.6Hz, 1H), 8.17(d, J=6.8Hz, 1H), 7.69( dd, J ₁ =8.4 Hz, J ₂ =5.4 Hz, 2H), 7.47–7.40 (m, 3H), 7.29–7.23 (m, 2H), 7.01 (dd, J ₁ =5.6 Hz, J ₂ =8.4 Hz ,1H),4.51(s,2H),4.20(s,2H),3.69-3.60(m,4H)3.15-3.08(m,1H),2.87(d,J＝4.8Hz,2H),2.56(d , J=6.8Hz, 2H) ppm. ¹³ C NMR (101MHz, DMSO) δ162.18, 153.57, 151.29, 148.63, 137.35, 136.39, 130.08, 127.88, 125.43 (q, J=203.3Hz), 124.85, 123.48, 120.83, 104.49, 51.36, 47.81, 45.74, 41.33, 37.27, 33.19, 23.84 ppm. HRMS(ES+) C ₂₀ H ₂₀ N ₄ O ₂ F ₃ ⁷⁹ Br(M+H) ⁺ , calcd: 484.0072; found 484.0078; C Calcd ^{. for 20H20N4O2F381Br(M+H)+} _{, 486.0701 ; found :} ^486.0702 .

According to the teachings of Examples 1 to 4 and Examples 5 to 16, those skilled in the art can also prepare the compounds listed in Table 1 and Table 2 without creative efforts, and the specific steps will not be repeated one by one.

Table 1 (compounds represented by formula IA)

Continued from Table 1

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Table 2 (compounds represented by formula IB)

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Example 17

Insecticidal activity test of the compounds of the present invention

(1) Insecticidal activity against aphids

Aphids belong to the order Homoptera with piercing-sucking mouthparts and are common crop pests. Taking bean aphid (Aphiscracivora) as the test object, the dipping method was used to test.

Operation process: Accurately weigh various samples, add N,N-dimethylformamide respectively to prepare a 10g/L mother liquor, and dilute it to a concentration of 500ppm with an aqueous solution containing 0.2mL/L Triton X-100 during the experiment. After the wingless adult aphid is stably sucking on the bean sprouts, immerse the bean sprouts in the liquid with a concentration of 500ppm, take it out after 5s, absorb the excess liquid with absorbent paper, and move it into a clean container for 23 hours. Warm feeding. Each concentration was repeated three times, and the control group was an aqueous solution containing 0.2 mL/L Triton X-100. After 24 hours of treatment, the number of dead worms of the test aphids was counted, and the mortality rate (%) was calculated according to the formula: mortality rate (%)=(number of live worms in control-number of live worms treated)/number of live worms in control×100%. The results are shown in the table below.

(2) Insecticidal activity against armyworms

Armyworms belong to the order Lepidoptera with chewing mouthparts and are common crop pests. The oriental armyworm (Mythimna separata) was used as the test object, and the test was carried out by immersion feeding method.

Operation method: The compound to be tested is accurately prepared into a 500 ppm solution with acetone as a solution, and treated with an aqueous acetone solution as a blank control. The fresh corn leaves were dipped in the solution for 3 seconds, then air-dried at room temperature for feeding by the test insects, and the mortality (%) of the test insects was checked and calculated after 24 hours (the formula is the same as above). 10 test worms were used in each group with 3 repetitions. The results are shown in the table below.

(3) Insecticidal activity against nematodes

Root-knot nematodes belong to the phylum Nematoda, Tylenchida, Tylenchida, Heteroderidea, Meloidogyninae, and the genus Meloidogyninae. of plant parasitic nematodes.

Taking Meloidogyne incongnita as the test object and cucumber seedlings as the test host, the test was carried out by in vitro planting method.

Operation process: prepare the sample to be tested into a liquid medicine according to the required concentration, and prepare a sufficient amount of the second instar larvae of root knot nematodes. After planting one-week-old cucumber seedlings into test tubes, add an appropriate amount of the prepared medicinal liquid to the test tubes, and put about 2,000 larvae into each test tube. The test tube was placed at 20-25°C and cultivated under the light of 10h. After 20d, the results were investigated and the number of root knots on the root system of each plant was counted. Each sample was replicated 3 times, and each sample was subjected to 4 replicates in each experiment.

Take distilled water as blank control, add root knot nematode in distilled water as negative control, and take fenamiphos and abamectin solution as positive control.

Grading according to the number of root knots (see Table 3 for the grading score table), and statistical inhibition rate. The statistical results are shown in Table 4 below.

Inhibition rate (%) = (score of negative control - score of test group)/score of negative control × 100%

table 3

Table 4

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Claims (14)

1. a nitrogen-containing heterocyclic compound is characterized in that, described nitrogen-containing heterocyclic compound is a compound shown in formula I, or its pesticide acceptable salt: In formula I, R ₁ is: H, fluoro or chloro methyl or ethyl, phenyl, chlorophenyl, tetrahydrofuranyl, chlorothiazolyl or pyridyl, trifluoroacetyl or R ₇ is a fluorinated methyl group, and X is NH; R ₂ is H, halogen, C ₁ -C ₃ hydrocarbon group, halogenated C ₁ -C ₃ hydrocarbon group or C ₁ -C ₃ alkoxy group; R ₃ and R ₄ are independently selected from: one of C ₁ -C ₄ hydrocarbon groups or halogenated C ₁ -C ₄ hydrocarbon groups; R ₅ and R ₆ are independently selected from: H, one of C ₁ -C ₄ hydrocarbon group, halogenated C ₁ -C ₄ hydrocarbon group or C ₁ -C ₃ oxygen-containing alkyl group; Y is: nitro, cyano, trifluoroacetyl or trifluoromethylsulfonyl; Z is: furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, substituted furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl or pyridyl, phenyl, substituted phenyl, The substituents of the substituted furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl or pyridyl are selected from: methyl, ethyl, methoxy, phenyl, Cl, NO ₂ , CN, or by One or more of phenyl or pyridyl substituted with methoxy, trifluoromethyl or acetyl; The substituent of the substituted phenyl group is selected from: methyl, methoxy, phenyl, pyridyl, pyridyl substituted by trifluoromethyl, furyl substituted by methyl, or substituted by methyl and acetyl One or more of the pyrrole groups. 2. The nitrogen-containing heterocyclic compound of claim 1, wherein R ₁ is: H, CH ₂ Cl, CH ₂ CF ₃ , trifluoroacetyl, 3. The nitrogen-containing heterocyclic compound of claim 1, wherein R ₂ is: H, halogen, C ₁ -C ₃ hydrocarbyl, halogenated C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy. 4. The nitrogen-containing heterocyclic compound of claim 3, wherein R ₂ is: H, Cl, allyl, fluorine or chlorinated C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy. 5. The nitrogen-containing heterocyclic compound of claim 4, wherein R ₂ is: H, CH ₂ F, CH ₂ CF ₃ , allyl or Cl. 6 . The nitrogen-containing heterocyclic compound of claim 1 , wherein R ₃ and R ₄ are independently selected from: one of C ₁ -C ₄ hydrocarbon groups or halogenated C ₁ -C ₄ alkyl groups. 7 . . 7. The nitrogen-containing heterocyclic compound according to claim 6, wherein R ₃ and R ₄ are independently selected from: C ₁ -C ₄ hydrocarbon group, or fluorine or chlorinated C ₁ -C ₄ alkyl group one of them. 8. The nitrogen-containing heterocyclic compound of claim 7, wherein R ₃ and R ₄ are independently selected from: CH ₃ , CH ₂ Cl, CH ₂ F, CH ₂ CH ₃ , CH ₂ CF ₃ , one of CH ₂ CH ₂ Cl, (CH ₃ ) ₃ C or allyl. 9 . The nitrogen-containing heterocyclic compound according to claim 1 , wherein R ₅ and R ₆ are independently selected from: H, C ₁ -C ₄ hydrocarbon group or halogenated C ₁ -C ₄ alkyl group. 10 . A sort of. 10. The nitrogen-containing heterocyclic compound according to claim 9, wherein R ₅ and R ₆ are independently selected from: H, C ₁ -C ₄ hydrocarbon group, or fluorine or chlorinated C ₁ -C ₄ One of the alkyl groups. 11. The nitrogen-containing heterocyclic compound of claim 10, wherein R ₅ and R ₆ are independently selected from: H, CH ₃ , CH ₂ Cl, CH ₂ F, CH ₂ CH ₃ , CH ₂ One of CH ₂ Cl or allyl. 12. The nitrogen-containing heterocyclic compound of claim 1, wherein the substituent of the substituted furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl or pyridyl is selected from: methyl , ethyl, methoxy, Cl, NO ₂ , CN, phenyl, one or more of them. 13. The nitrogen-containing heterocyclic compound of claim 1, wherein the substituent of the substituted phenyl group is selected from the group consisting of: methyl, methoxy, phenyl, one or more of them. 14. The use of the nitrogen-containing heterocyclic compound according to any one of claims 1 to 13 in the preparation of an insecticide for killing aphids, armyworms or nematodes.