CN105669660B - Nitrogen-containing heterocycle compound and application thereof - 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 heterocycle compound and application thereof

Technical field

The present invention relates to nitrogen-containing hetero cyclics of a kind of structure novel and application thereof.

Technical background

In recent years, anabasine insecticide has become an insecticides with fastest developing speed in modern crop protection.With pyrrole Worm quinoline is that the anabasine insecticide insecticidal activity of representative is high, and insecticidal spectrum is wide, low to mammal and aquatic animal toxicity, and There are good absorbability and certain field stability and environment friendly, there is no cross resistance with traditional pesticide.Anabasine Insecticide mainly acts on the nicotinic acetylcholine receptor (nAChRs) of insect and plays a role.The hair of anabasine insecticide It is now a milestone of modern development.

After imidacloprid listing, there is thiacloprid, clothianidin, Diacloden, Acetamiprid, alkene pyridine worm again in anabasine field The kind of the high activities such as amine, dinotefuran, paichongding, cycloxaprid, sulfoxaflor, high sales volume prevents and treats pierce-suck type to peasant Mouthpart insect provides advantageous " weapon ".

However, also there is serious resistance problem in popularizing with anabasine insecticide.Simultaneously as structure Cross resistance between similitude bring neonicotinoid insecticide, limits the use of such compound to a certain extent, at For the major issue for restricting neonicotinoid insecticide.Meanwhile anabasine insecticide mainly prevents and treats the evil of Homoptera and coleoptera Low activity is presented to lepidoptera pest in worm, and the limitation on insecticidal spectrum also hinders it preferably to develop.

It is, therefore, necessary to expand the selection library of pesticide, the work of Lai Jifa neonicotinoid insecticide by constantly formulating new product Power copes with natural test by constantly bringing forth new ideas.Specifically, be how to active Nitromethylene compounds into Row structure of modification solves anabasine insecticide facing challenges, this is also this to generate new, more effective insecticide Technical problem to be addressed by invention.

Summary of the invention

The present invention carries out structure of modification to existing active Nitromethylene compounds, has designed and synthesized a kind of knot The novel nitrogen-containing hetero cyclics of structure.It is tested through insecticidal activity, nitrogen-containing hetero cyclics provided by the invention have relatively strong Insecticidal activity.Compared with existing insecticide, chemical stability is more preferable.

A purpose of the invention is, provides a kind of nitrogen-containing hetero cyclics of structure novel, the nitrogen-containing heterocycle Class compound is compound or its acceptable salt in Pesticide Science shown in formula I:

In formula I, R₁For hydrogen (H), C₁~C₃Alkyl, the C in halogen (F, Cl, Br or I, similarly hereinafter) generation₁~C₃Alkyl, phenyl are halogenated Phenyl, 5~6 circle heterocyclic ring bases, 5~6 halogenated circle heterocyclic ring bases, trifluoroacetyl group,Or(curve mark is Replace position, similarly hereinafter)；

Wherein, R₇For 5~6 circle heterocyclic ring bases, halogenated 5~6 circle heterocyclic ring bases or halogenated C₁~C₃Alkyl, X are O or NR₉, R₈For 5~6 circle heterocyclic ring bases or 5~6 halogenated circle heterocyclic ring bases, Y CH₂Or NH, n are 0 or 1；

The hetero atom of 5~6 circle heterocyclic ring base is selected from: a kind of in N, O or S or two kinds, R₉For H, C₁~C₃Alkyl or halogen The C in generation₁~C₃Alkyl；

R₂For H, halogen (F, Cl, Br or I, similarly hereinafter), C₁~C₃Alkyl, halogenated C₁~C₃Alkyl or C₁~C₃Alcoxyl Base；

R₃And R₄It is respectively and independently selected from: C₁~C₄Alkyl or halogenated C₁~C₄It is a kind of in alkyl；Or,

R₃And R₄Combination (be abbreviated as " R₃+R₄") and constitute with the nitrogen (N) that is respectively connected: 5~7 yuan of heterocycle containing N or 5~7 yuan of the heterocycle containing N replaced；

Wherein, the substituent group of 5~7 yuan substituted of the heterocycle containing N is selected from: methyl, trifluoromethyl, monovalent phenyl radical, CH₃OCH₂, cyclohexyl radicals, the cyclohexyl radicals replaced by trifluoromethyl, divalent phenyl group, or taken by trifluoromethyl or methoxyl group It is a kind of in the phenyl of the divalent in generation；

Illustrate: the cyclohexyl radicals, the cyclohexyl radicals replaced by trifluoromethyl, divalent phenyl group, or by trifluoromethyl Or after the phenyl of methoxy-substituted divalent replaces 5~7 yuan of the heterocycle containing N, the heterocycle containing N with 5~7 yuan is " simultaneously " Relationship；

R₅And R₆It is respectively and independently selected from: H, C₁~C₄Alkyl, halogenated C₁~C₄Alkyl or C₁~C₃Containing in oxyalkyl one Kind；

Y is electron-withdrawing group, such as (but not limited to): nitro (NO₂), cyano (CN), trifluoroacetyl groupOr three Methyl fluoride sulfonyl

Z is 5~6 circle heterocyclic ring bases, 5~6 substituted circle heterocyclic ring bases, pyridine, 5 circle heterocyclic ring base of pyrimidine, nitrobenzene or benzo, benzene Base or substituted-phenyl；

The hetero atom of the heterocycle is selected from: a kind of in O, S or N or two kinds, hetero atom number is 1 or 2；

The substituent group of 5~6 substituted circle heterocyclic ring bases is selected from: C₁~C₃Alkyl, C₁~C₃Alkoxy, halogen, NO₂, CN, phenyl, by methyl, methoxyl group, trifluoromethyl, amino (NH₂)、NO₂, halogen, acetyl groupMethyl sulphonylOrSubstituted phenyl, by methoxyl group, trifluoromethyl, halogen, NO₂Or the pyridyl group that CN replaces, Pyrimidine radicals, by methyl substituted pyrimidine radicals, by methyl substituted methylpyrrole base, thienyl, or the furan replaced by trifluoromethyl Mutter one or two or more kinds of in base (containing two kinds)；

The substituent group of the substituted-phenyl is selected from: C₁~C₃Alkyl, C₁~C₃Alkoxy, halogen, CN, phenyl, pyridyl group, The pyridyl group replaced by trifluoromethyl, furyl, by methyl or/and the furyl of trifluoromethyl substitution, pyrrole radicals or by methyl (containing two kinds) one or two or more kinds of in the pyrrole radicals replaced with acetyl group.

Another object of the present invention is, discloses a kind of above-mentioned purposes of nitrogen-containing hetero cyclics, i.e. chemical combination shown in formula I Object or its application of acceptable salt as insecticide in Pesticide Science.

Specific embodiment

In a preferred technical solution of the invention, nitrogen-containing hetero cyclics of the present invention are I A shownization of formula Close object or its acceptable salt in Pesticide Science:

In I A of formula, R₁For H, halogenated C₁~C₃Alkyl, phenyl, halogenophenyl, 5~6 circle heterocyclic ring bases, halogenated 5~6 yuan Heterocycle, trifluoroacetyl group or

Wherein, the hetero atom of 5~6 circle heterocyclic ring base is selected from: a kind of in N, O or S or two kinds, hetero atom number is 1 or 2； R₇For halogenated C₁~C₃Alkyl, X NR₉, R₉For H, C₁~C₃Alkyl or halogenated C₁~C₃Alkyl；

R₂For H, halogen, C₁~C₃Alkyl, halogenated C₁~C₃Alkyl or C₁~C₃Alkoxy；

R_3aAnd R_4aIt is respectively and independently selected from: C₁~C₄Alkyl or halogenated C₁~C₄It is a kind of in alkyl；

R₅And R₆It is respectively and independently selected from: H, C₁~C₄Alkyl or halogenated C₁~C₄It is a kind of in alkyl；

Y is NO₂, CN,Or

Z is 5~6 circle heterocyclic ring bases, 5~6 substituted circle heterocyclic ring bases, 5 circle heterocyclic ring base of nitrobenzene or benzo, phenyl or substituted benzene Base；

The hetero atom of 5~6 circle heterocyclic ring base is selected from: a kind of in O, S or N or two kinds, hetero atom number is 1 or 2；

The substituent group of 5~6 substituted circle heterocyclic ring bases is selected from: C₁~C₃Alkyl, C₁~C₃Alkoxy, halogen, NO₂,(containing two kinds) one or two or more kinds of in substituted phenyl or pyridyl group；

The substituent group of the substituted-phenyl is selected from: C₁~C₃Alkyl, C₁~C₃Alkoxy, phenyl, pyridyl group, by fluoroform The pyridyl group that base replaces, furyl, by methyl substituted furyl, or by a kind of in methyl and the pyrrole radicals of acetyl group substitution Or two kinds or more (containing two kinds).

Further preferred R₁It is: the C of H, fluorine or chloro₁~C₃Alkyl, phenyl, chlorophenyl, 5~6 circle heterocyclic ring bases, chlorine 5~6 circle heterocyclic ring bases in generation, trifluoroacetyl group or

Wherein, the hetero atom of 5~6 circle heterocyclic ring base is selected from: a kind of in N, O or S or two kinds, hetero atom number is 1 or 2； R₇For the C of fluoro₁~C₃Alkyl, X NH；

R still more preferably₁It is: the methyl or ethyl of H, fluorine or chloro, phenyl, chlorophenyl, 5 circle heterocyclic ring bases, chlorine 5~6 circle heterocyclic ring bases in generation, trifluoroacetyl group or

Wherein, the hetero atom of the heterocycle is selected from: a kind of in N, O or S or two kinds, hetero atom number is 1 or 2； R₇For fluorine The C in generation₁~C₃Alkyl, X NH；

R still more preferably again₁It is: the methyl or ethyl of H, fluorine or chloro, phenyl, chlorophenyl, tetrahydrofuran base, Chloro-thiazole base or pyridyl group, trifluoroacetyl group or

Wherein, R₇For the methyl of fluoro, X NH；

Optimal R₁It is: H, CH₂Cl, CH₂CF₃, trifluoroacetyl group, Or

Further preferred R₂It is: H, halogen, C₁~C₃Alkyl, halogenated C₁~C₃Alkyl or C₁~C₃Alkoxy；

R still more preferably₂It is: H, Cl,The C of (allyl), fluorine or chloro₁~C₃Alkyl or C₁~C₃ Alkoxy；

Optimal R₂It is: H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂F, CH₂CF₃, allyl, OCH₂CH₃Or Cl.

Further preferred R_3aAnd R_4aIt is respectively and independently selected from: C₁~C₄Alkyl or halogenated C₁~C₄It is a kind of in alkyl；

R still more preferably_3aAnd R_4aIt is respectively and independently selected from: C₁~C₄The C of alkyl or fluorine or chloro₁~C₄One in alkyl Kind；

Optimal R_3aAnd R_4aIt is respectively and independently selected from: CH₃, CH₂Cl, CH₂F, CH₂CH₃, CH₂CF₃, CH₂CH₂Cl, (CH₃)₃C Or it is a kind of in allyl.

Further preferred R₅And R₆It is respectively and independently selected from: H, C₁~C₄Alkyl or halogenated C₁~C₄It is a kind of in alkyl；

R still more preferably₅And R₆It is respectively and independently selected from: H, C₁~C₄The C of alkyl or fluorine or chloro₁~C₄In alkyl It is a kind of；

Optimal R₅And R₆It is respectively and independently selected from: H, CH₃, CH₂Cl, CH₂F, CH₂CH₃, CH₂CH₂One in Cl or allyl Kind.

Further preferred Z is: furyl, thienyl, pyrrole radicals, oxazolyl, thiazolyl, pyridyl group, substituted furans Base, thienyl, pyrrole radicals, oxazolyl, thiazolyl or pyridyl group, nitrobenzene or benzothienyl, phenyl or substituted-phenyl；

The substituted furyl, thienyl, pyrrole radicals, oxazolyl, thiazolyl or pyridyl group substituent group be selected from: first Base, ethyl, methoxyl group, phenyl, Cl, NO₂, CN, or the phenyl or pyridyl group that are replaced by methoxyl group, trifluoromethyl or acetyl group Middle one or two or more kinds of (containing two kinds)；

The substituent group of the substituted-phenyl is selected from: methyl, methoxyl group, phenyl, pyridyl group, the pyridine replaced by trifluoromethyl Base, by methyl substituted furyl, or by one or two or more kinds of (containing two kinds) in methyl and the pyrrole radicals of acetyl group substitution；

Z still more preferably is: furyl, thienyl, pyrrole radicals, oxazolyl, thiazolyl, pyridyl group, substituted furan It mutters base, thienyl, pyrrole radicals, oxazolyl, thiazolyl or pyridyl group, nitrobenzene or benzothienyl, phenyl or substituted-phenyl；

The substituted furyl, thienyl, pyrrole radicals, oxazolyl, thiazolyl or pyridyl group substituent group be selected from: first Base, ethyl, methoxyl group, Cl, NO₂, CN, phenyl,OrMiddle one or two or more kinds (containing two kinds)；

The substituent group of the substituted-phenyl is selected from: methyl, methoxyl group, phenyl,OrIn One or two or more kinds of (containing two kinds)；

The nitrobenzene or benzothienyl are:Or

In presently preferred technical solution, nitrogen-containing hetero cyclics of the present invention are shown in I B of formula Compound or its acceptable salt in Pesticide Science:

In I B of formula, R₁For H, halogen, C₁~C₃Alkyl, halogenated C₁~C₃Alkyl, phenyl, halogenophenyl, trifluoroacetyl Base, 5~6 circle heterocyclic ring bases, by trifluoromethyl or 5~6 halogenated circle heterocyclic ring bases,Or

Wherein, R₇For 5~6 circle heterocyclic ring bases, halogenated 5~6 circle heterocyclic ring bases or halogenated C₁~C₃Alkyl, X are O or NR₉, R₈For 5~6 circle heterocyclic ring bases, 5~6 halogenated circle heterocyclic ring bases, Y CH₂Or NH, n are 0 or 1；

The hetero atom of 5~6 circle heterocyclic ring base is selected from: it is a kind of in N, O or S or two kinds, hetero atom number be 1 or 2, R₉For H、C₁~C₃Alkyl or halogenated C₁~C₃Alkyl；

R₂For H, C₁~C₃Alkyl or halogenated C₁~C₃Alkyl；

R_3bAnd R_4bCombination (be abbreviated as " R_3b+R_4b") and constitute with the N that is respectively connected: 5~7 yuan of heterocycle containing N, substitution 5~7 yuan of heterocycle containing N, or 5~7 yuan of (formula of heterocycle containing N by naphthenic base, phenyl, substituted naphthenic base or phenyl " simultaneously " A ring in I B, is abbreviated as " A ")；

That is: the heterocycle containing N that A is 5~7 yuan, 5~7 yuan substituted of heterocycle containing N, or by naphthenic base, phenyl, substituted ring 5~7 yuan of heterocycle containing N of alkyl or phenyl " simultaneously "；

Wherein, the substituent group of 5~7 yuan substituted of the heterocycle containing N is selected from: methyl, trifluoromethyl, phenyl or Middle a kind of or two kinds, substituent group number is 1 or 2；

The substituent group of the substituted naphthenic base or phenyl is selected from: it is a kind of in methyl, methoxyl group or trifluoromethyl or two kinds, Substituent group number is 1 or 2；

R₅And R₆It is respectively and independently selected from: H, C₁~C₄Alkyl, halogenated C₁~C₄Alkyl or C₁~C₃Containing in oxyalkyl one Kind；

Y is NO₂, CN,Or

Z is 5~6 circle heterocyclic ring bases, 5~6 substituted circle heterocyclic ring bases, and 5 circle heterocyclic ring base of pyridine, pyrimidine or benzo or takes phenyl For phenyl；

The hetero atom of 5~6 circle heterocyclic ring base is selected from: a kind of in O, S or N or two kinds, hetero atom number is 1 or 2；

The substituent group of 5~6 substituted circle heterocyclic ring bases is selected from: C₁~C₃Alkyl, C₁~C₃Alkoxy, halogen, NO₂, CN, phenyl, by methyl, methoxyl group, trifluoromethyl, amino (NH₂)、NO₂, halogen, acetyl groupMethyl sulphonylOrSubstituted phenyl, by methoxyl group, trifluoromethyl, halogen, NO₂Or the pyridyl group that CN replaces, Pyrimidine radicals, by methyl substituted pyrimidine radicals, by methyl substituted methylpyrrole base, thienyl or the furan replaced by trifluoromethyl Mutter one or two or more kinds of in base (containing two kinds)；

The substituent group of the substituted-phenyl is selected from: C₁~C₃Alkyl, C₁~C₃Alkoxy, halogen, CN, phenyl, pyridyl group, The pyridyl group replaced by trifluoromethyl, furyl, the furyl replaced by methyl or/and trifluoromethyl, pyrrole radicals, or by methyl (containing two kinds) one or two or more kinds of in the pyrrole radicals replaced with acetyl group.

Further preferred R₁It is: H, Br, C₁~C₃Alkyl, halogenated C₁~C₃Alkyl, trifluoroacetyl group, phenyl, chloro Phenyl, 5~6 circle heterocyclic ring bases, by trifluoromethyl or 5~6 circle heterocyclic ring bases of chloro,Or

Wherein, R₇For 5~6 circle heterocyclic ring bases, 5~6 circle heterocyclic ring bases of chloro or the C of fluoro₁~C₃Alkyl, X are O or NR₉, R₈For 5~6 circle heterocyclic ring bases or 5~6 circle heterocyclic ring bases of chloro, Y CH₂Or NH, n are 0 or 1；

The hetero atom of 5~6 circle heterocyclic ring base is selected from: it is a kind of in N, O or S or two kinds, hetero atom number be 1 or 2, R₉For H、C₁~C₃Alkyl or halogenated C₁~C₃Alkyl；

R still more preferably₁It is: the C of H, Br, n-propyl, chlorine or fluoro₁~C₃Alkyl, trifluoroacetyl group, phenyl, Chlorophenyl, tetrahydrofuran base, by the pyridyl group of trifluoromethyl or chloro, thienyl or thiazolyl,Or

Wherein, R₇For trifluoromethyl, tetrahydrofuran base, chloro-thiazole base or chloro-pyridine base, X is O or NR₉, R₈It is four Hydrogen furyl, chloro-thiazole base or chloro-pyridine base, Y CH₂Or NH, n are 0 or 1；R₉For H, methyl or trifluoroethyl；

Optimal R₁It is: H, trifluoroacetyl group,CH₂Cl, CH₂CF₃,Br,

Further preferred R₂It is: H, C₁~C₃Alkyl or halogenated C₁~C₃Alkyl；

R still more preferably₂It is: H, C₁~C₃The C of alkyl or fluorine or chlorine₁~C₃Alkyl；

Optimal R₂It is: H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂F,Or CH₂CH₂Cl。

Further preferred A is 5~7 yuan of heterocycle containing N, 5~7 yuan substituted of heterocycle containing N, or by naphthenic base, phenyl, 5~7 yuan of heterocycle containing N of substituted naphthenic base or phenyl " simultaneously "；That is, R_3b+R_4bIt is a kind of in following groups:

Wherein, 0,1 or 2, R m₁₀Or R₁₁Be respectively and independently selected from: H, methyl, trifluoromethyl, phenyl orIn one Kind；Or, R₁₀And R₁₁Combination (be abbreviated as " R₁₀+R₁₁") be divalent substituted naphthenic base or phenyl；

The substituent group of the substituted naphthenic base or phenyl of the divalent is selected from: a kind of in methyl, methoxyl group or trifluoromethyl Or two kinds, substituent group number is 1 or 2；

R still more preferably_3b+R_4bIt is a kind of in following groups:

Wherein, 0,1 or 2 m.

Further preferred R₅And R₆It is respectively and independently selected from: H, C₁~C₄Alkenyl, C₁~C₄The alkyl of linear chain or branched chain, halogen The C in generation₁~C₄The alkyl or C of linear chain or branched chain₁~C₃Containing a kind of in oxyalkyl；

R still more preferably₅And R₆It is respectively and independently selected from: a kind of in following groups:

H, CH₃, CH₂F, CF₃, CH₂Cl, CH₂Br, CH₂CH₃, CH₂CH₂Cl, (CH₃)₃C,Or

Further preferred Z is furyl, thienyl, pyrrole radicals, oxazolyl, thiazolyl, imidazole radicals, and pyridyl group is substituted

The substituent group choosing of the substituted furyl, thienyl, pyrrole radicals, oxazolyl, thiazolyl, imidazole radicals or pyridyl group From: C₁~C₃Alkyl, C₁~C₃Alkoxy, halogen, NO₂, CN, phenyl, by methyl, methoxyl group, trifluoromethyl, amino (NH₂)、 NO₂, halogen, acetyl groupMethyl sulphonylOrSubstituted phenyl, by methoxyl group, Trifluoromethyl, halogen, NO₂Or the pyridyl group that CN replaces, by methyl substituted pyrimidine radicals, by methyl substituted methylpyrrole base, In thienyl or the furyl replaced by trifluoromethyl one or two or more kinds of (containing two kinds)；

The substituent group of the substituted-phenyl is selected from: C₁~C₃Alkyl, C₁~C₃Alkoxy, halogen, CN, phenyl, pyridyl group, The pyridyl group replaced by trifluoromethyl, by methyl substituted furyl, or by a kind of in methyl and the pyrrole radicals of acetyl group substitution Or two kinds or more (containing two kinds)；

Still more preferably Z is: Phenyl, substituted-phenyl, or the furyl, the thiophene that replace Pheno base, pyrrole radicals, oxazolyl, thiazolyl, imidazole radicals or pyridyl group；

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

Methyl, methoxyl group, phenyl, F, CN,

The substituent group choosing of the substituted furyl, thienyl, pyrrole radicals, oxazolyl, thiazolyl, imidazole radicals or pyridyl group One or two or more kinds of from following groups (containing two kinds):

Methyl, methoxyl group, ethyl, phenyl, CN, NO₂, Cl, Br,

In addition, a further object of the invention is, a kind of method of compound shown in preparation formula I, the method are provided Synthetic strategy it is as follows:

Or (by taking A is 5~7 yuan of heterocycle containing N as an example)

Wherein, 1,2 or 3 n, the definition of other substituent groups with it is described previously identical.

Specifically comprise the following steps:

(1) in aminated compounds (R_3aNH₂) appropriate acetonitrile is added in aqueous solution, compound shown in formula II is added dropwise under ice bath The acetonitrile lysate of (being abbreviated as compound ii, similarly hereinafter), TLC tracks reaction process, after reaction, into reaction mixture A large amount of water is added, methylene chloride extraction is dry, filters, boils off solvent, obtain compound III；

(2) compound III and 1,1-, bis- sulfidomethyl -2-Y substituted ethylene are flowed back 4 hours to 8 hours with ethanol as solvent, Concentration, column chromatography for separation obtain product compound IV；

(3) under condition of ice bath, compounds Ⅳ and aminated compounds (R_4aR₆NH) 4 are reacted in fatty alcohol (reaction medium) To 8 hours, reaction product was concentrated in hour, and column chromatography for separation obtains compound V；

(4) firstly, under sour (such as hydrochloric acid, sulfuric acid or heteropoly acid) catalytic condition, compound V and corresponding aldehyde reaction, Obtain compound VI；Then, then under alkaline condition, by compound VI through reduction reaction (go back original reagent can use sodium borohydride etc.) Obtain chemical compounds I A.

Or,

(1) by diamines (compound VII) solution of the acetonitrile solution dropwise of compound ii to 5-10 times of mole, in 0- It 50 DEG C, reacts 5-10 hours.After unreacted compound VII is removed under reduced pressure, is dissolved with ethyl acetate, be spin-dried for solvent, changed Close object VIII；

(2) compound VIII and 1, bis- sulfidomethyl -2-Y substituted ethylene of 1- are flowed back 4-8 hour, are obtained with ethanol as solvent Compound Ⅸ；

(3) firstly, under sour (such as hydrochloric acid, sulfuric acid or heteropoly acid) catalytic condition, compound Ⅸ and corresponding aldehyde reaction, Obtain compound Ⅹ；Then, then under alkaline condition, by compound Ⅹ through reduction reaction (go back original reagent can use sodium borohydride etc.) Obtain chemical compounds I B；

The insecticidal activity of active material of the present invention

Term " active material of the invention " or " reactive compound of the invention " refer to that the compounds of this invention, its optics are different Acceptable salt in structure body, cis-trans-isomer or Pesticide Science has the insecticidal activity significantly improved and widened desinsection Spectrum.

Term " acceptable salt in Pesticide Science " means that the anion of the salt is forming insecticide pharmaceutically acceptable salt When be have appreciated that and it is acceptable.The salt is preferably water solubility, such as hydrochloride, phosphate, sulfate, nitrate；Packet Include the salt of organic acid formation, such as acetate or benzoate.

Active material of the invention can serve as controlling and eliminating extensive agriculture and forestry plant pest, the pest for storing cereal, plant Object helminth and public health pest etc..In the present specification, " insecticide " refers to harmful with institute mentioned above is prevented and treated The general designation of the substance of the effect of worm.The example of pest includes but is not limited to: coleopteron: sitophilus zea-mais (Sitophilus Zeamais), red flour beetle (Tribolium castaneum), potato bug (Henosepilachna Vigintioctomaculata), potato ladybug (Henosepilachna sparsa), agriotes fussicollis (Agriotes Fuscicollis), red foot green gold tortoise (Anomala cupripes), beautiful tortoise with four lines (Popillia Quadriguttata), colorado potato beetles (Monolepta hieroglyphica), ponderous borer (Monochamus Alternatus), rice root weevil (Echinocnemus squameus), paulownia are chrysomelid (Basiprionota bisignata), star Longicorn (Anoplophora chinensis), mulberry borer (Apripona germari), navel abdomen bark beetle (Scolytus ) or Agriotes subrittatus Motschulsky (Agriotes fuscicollis) schevy.Lepidopterous insects: gypsymoth (Lymantria Dispar), tent caterpillar (Malacosoma neustria testacea), Diaphania perspectalis (Diaphania Perspectalis), Clania variegata Snellen (Clania variegata), oriental moth (Cnidocampa flauescens), horse hair pine tag Worm (Dendrolimus punctatus), orgyia antiqua (Orgyia gonostigma), paranthrene tabaniformis (Paranthrene Tabaniformis), prodenia litura (Spodoptera litura), striped rice borer (Chilo suppressalis), corn borer (Ostrinia nubilalis), meal moth (Ephestia cautella), cotton roll moth (Adoxophyes orana), chestnut Steinernema (Laspyresia splendana), black cutworm (Agrotis fucosa), greater wax moth (Galleria Mellonella), diamond-back moth (Plutella xylostella), tangerine lyonetid (Phyllocnistis citrella) or east are viscous Worm (Mythimna separata).Homoptera insect: rice green leafhopper (Nephotettix cincticeps), brown plant-hopper (Nilaparvata lugens), Kang Shi mealybug (Pseudococcus comstocki), arrowhead scales (Unaspis Yanonensis), black peach aphid (Myzus persicae), cotten aphid (Aphis gossydii), radish aphid (Lipaphis erysimi Pseudobrassicae), pears class lace bug (Stephanitis nashi) or aleyrodid (Bemisia tabaci).Orthoptera elder brother Worm: Groton bug (Blattella germanica), the big Lian in the U.S. (Periplaneta american), African mole cricket (Gryllotalpa africana) or Asiatic migratory locust (Locus migratoria).Isoptera insect: S.invicta Buren (Solenopsis invicta) or coptotermes formosanus (Coptotermes formosanus).Dipteral insect: housefly (Musca Domestica), Aedes aegypti (Aedes aegypti), Hylemyia Platura Meigen (Delia platura), culex (Culex sp.), or in Magnificent anopheles (Anopheles sinensis).Root-knot nematode, such as peanut root-knot nematode (Meloidogyne arenaria), surprise Family name root-knot nematode (Meloidogyne chitwoodi), short and small root-knot nematode (Meloidogyne exigua), northern root knot Nematode (Meloidogyne hapla), Meloidogyne incognita (Meloidogyne incognita), javanese root knot nematode (Meloidogyne javanica) and other Meloidogynes (Meloidogyne)；Cyst roundworm, such as globodera rostochiensis (Globodera rostochiensis), G.pallida (Globodera pallida), tobacco cyst roundworm (Globodera tabacum) and other cyst roundworm categories (Globodera)；Golden nematode, such as cereal cyst nematode (Heterodera avenae), soy bean cyst roundworm (Heterodera glycines), beet cyst roundworm (Heterodera Schachtii), clover cyst roundworm (Heterodera trifolii) and other Heteroderas (Heterodera)； Kind tumor nematode, such as shear retention factor (Anguina funesta), wheat anguina (Anguina tritici) and other grains Turbatrix (Anguina)；Stem and leaf bud nematode, such as aphelenchoides besseyi (Aphelenchoides besseyi), the sliding sword of strawberry Nematode (Aphelenchoides fragariae), chrysanthemum aphelenchoides (Aphelenchoides ritzemabosi) and its Its Aphelenchoides (Aphelenchoides)；Nematode is pierced, as weeds pierce nematode (Belonolaimus longicaudatus) Turbatrix (Belonolaimus) is pierced with other needles；Loose ends worm, such as Bursaphelenchus xylophilus (Bursaphelenchus xylophilus) With other Bursaphelenchus (Bursaphelenchus)；Annular nematode, such as ring grain Turbatrix (Criconema), small loop wire Eimeria (Criconemella), Criconemoides (Criconemoides) and middle ring Turbatrix (Mesocriconema)；Bulb line Worm, such as rot stem nematodes (Ditylenchus destructor), sweet potato stem nematode (Ditylenchus dipsaci), mushroom Ditylenchus dipsaci (Ditylenchus myceliophagus) and other Ditylenchus (Ditylenchus)；Nematode is bored, nematode is such as bored Belong to (Dolichodorus)；Helicotylenchus, such as Spiral namatodes (Helicotylenchus dihystera), mostly with spiral Nematode (Helicotylenchus multicintus) and other helix Eimerias (Helicotylenchus)；Sheath nematode, such as Sheath Turbatrix (Hemicycliophora) and half Criconemoides (Hemicriconemoides)；It is preced with nematode, such as Colombia's knob Band nematode (Hoploaimus columbus) and other tie Turbatrixes (Hoploaimus)；Pseudo- knot nematodes, it is such as abnormal precious Pearl nematode (Nacobbus aberrans) and other pearl Turbatrixes (Nacobbus)；Needlework worm, as ease goes minute hand nematode (Longidorus elongatus) and other minute hand Turbatrixes (Longidorus)；Staple line worm, such as staple line Eimeria (Paratylenchus)；Pratylenchus, such as the shortest tail of a nematode (Pratylenchus brachyurus), the short body of coffee Nematode (Pratylenchus coffee), corn lesion nematode (Pratylenchus zeae), Cobb root (Pratylenchus penetrans) and other Pratylenchus (Pratylenchus)；Similes thorne, such as radopholus Nematode (Radopholus similis) and other perforation line Eimerias (Radopholus)；Kidney worm, such as Rotylenchulus reniformis (Rotylenchus robustus) and other kidney shape turbatrixes (Rotylenchus)；Undesirable root nematode, such as original burr nematode (Trichodorus primitivus) and other burr Turbatrixes (Trichodorus)；Species of Tylenchorhynchus Nematodes, as Clayton downgrades Nematode (Tylenchorhynchus claytoni), indefinite species of Tylenchorhynchus Nematodes (Tylenchorhynchus dubius) and other Tylenchorhynchus (Tylenchorhynchus)；Citrus nematode, such as citrus Tylenchulus Semipenetrans (Tylenchulus ) and other pulvinulus sword Turbatrixes (Tylenchulus) semipenetrans；Sword nematode, such as X. radicicola (Xiphinema Americanum), standard sword nematode (Xiphinema index), split tail sword nematode (Xiphinema ) and other Xiphinemas (Xiphinema) diversicaudatum.

Compound of the present invention is especially to pierce-suck type, rasping-sucking mouthparts pest such as aphid, leafhopper, plant hopper, thrips, powder The agriculture and forestry injurious insects such as lice have special efficacy, meanwhile, there is special efficacy to garden pests such as Meloidogyne incognitas.

Insecticide composition containing active material of the present invention

Active material of the invention can be prepared into insecticide composition in a conventional way.These reactive compounds can be done At conventional preparation.Such as solution, emulsion, suspension, pulvis, foaming agent, paste, granule；Aerosol uses active matter Natural and synthesis the material of matter dipping, the microcapsules in polymer are filled for the coating compound of neutron, and with burning Set-the preparation that uses of block, such as sootiness cylindrantherae, sootiness tank and sootiness disk and ULV harl (Cold mist) and hot mist (Warm mist) preparation.

These preparations can produce by known method, for example, reactive compound is mixed with agent is expanded, these expand agent just Liquid or liquefied gas or solid diluent or carrier, and can arbitrarily select surfactant i.e. emulsifier and/or point Powder and/or foam former.Such as when water is used as an extender, organic solvent also is used as auxiliary agent.

It is substantially suitable when making diluent or carrier with liquid solvent, such as: arene, such as dimethylbenzene, toluene Or alkylnaphthalene；The fragrance of chlorination or the fat hydrocarbon of chlorination, such as chlorobenzene, vinyl chloride or methylene chloride；Fat hydrocarbon, such as Hexamethylene or paraffin, such as mineral oil fractions；Alcohols, such as ethyl alcohol or ethylene glycol and their ether and lipid；Ketone, example Such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or cyclohexanone；Or the polar solvent being of little use, such as dimethylformamide and diformazan Base sulfoxide, Yi Jishui.

And the diluent or carrier of liquefied gas refers to that the liquid that will become gas at normal temperatures and pressures, such as aerosol promote Agent, such as the hydro carbons and butane of halogenation, propane, nitrogen and carbon dioxide.

Available (ground) ground natural minerals ground of solid carrier, such as kaolin, clay, talcum, quartz are living Property carclazyte, montmorillonite or diatomite, and the synthetic mineral matter ground, such as the silicic acid of high degree of dispersion, aluminium oxide and silicate. Solid carrier for particle is natural zircon pulverize and classification, such as calcite, marble, float stone, sepiolite and white The particle and organic material such as wood sawdust, cocoanut shell, maize cob and tobacco of marble and the synthesis of inorganic and organic coarse powder The particle etc. of stalk.

Non-ionic and anion emulsion can be used as emulsifier and/or foam former.Such as polyoxyethylene-fatty Esters of gallic acid, polyoxyethylene-fatty alcohol ethers, such as alkaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfate, Aryl sulfonates and albumin hydrolysate.Dispersing agent includes, such as lignin sulfite waste liquor and Methyl cellulose Element.

Can use adhesive in the formulation, for example, carboxymethyl cellulose and with the natural of powder, particle or emulsion form and The polymer of synthesis, such as Arabic gum, the pure and mild polyvinyl acetate of polyvinyl.

It can use colorant, such as inorganic dyestuff, including iron oxide, cobalt oxide and Prussian blue etc.；Organic dyestuff, it is such as even Chlorine dyestuff or metallized phthalocyanine dye etc.；With with trace nutrient, such as the salt of iron, manganese, boron, copper, cobalt, aluminum and zinc.

These reactive compounds in the present invention can be made mixture with other reactive compounds and be present in commercial preparation, Or among the dosage forms prepared from these preparations, other reactive compounds include but is not limited to: insecticide, kills at bait formulation Microbial inoculum, acaricide, nematicide, fungicide, growth control agent etc..Insecticide includes, such as phosphoric acid ester, carbamic acid Esters, (quasi-) cinerins, chlorinated hydrocarbons, anabasine, insect growth regulator, IGR class, neires toxin, pymetrozine, GABA acceptor inhibitor class, ryanodine receptor inhibitor class and the substance generated by microorganism, such as avermectin.

In addition, the quotient that a kind of mixture is present in them can also be made in these reactive compounds in the present invention with synergist At among the dosage forms prepared from these preparations in product preparation.Synergist is the compound for improving reactive compound effect, due to Reactive compound itself is active, can also be unlike addition synergist.

These preparations, which usually contain, accounts for the insecticide composition 0.001-99.99 weight %, preferably 0.01-99.9 weight Measure %, the reactive compound of the invention of more preferable 0.05-90 weight %.It is made from commercial preparation using the activity in dosage form The concentration of compound can change in wide range.It can be from 0.0000001- using the concentration of the reactive compound in dosage form 100% (g/v), preferably in 0.0001-1%.

Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.Wherein, R.t. room temperature is represented.

Embodiment 1.

N- ((6- chloropyridine -3- base) methyl)-N- ethyl-N`- methyl -2- nitro -3- (thiazol-2-yl) propyl- 1- alkene two The synthesis of amine (chemical compounds I A-1):

(1) synthesis of N- (6- chloropyridine -3- methylene) ethamine (compound III -1)

In the 250mL three neck round bottom flask with constant pressure funnel, thermometer, the 65-70% of 70g (1mol) is added Ethylamine solution, acetonitrile 50mL stir 15min under ice bath, stablize solution temperature near 0 DEG C, in constant pressure funnel It is middle be added 16.10g (0.10mol) the chloro- 3- chloromethylpyridine of 6- acetonitrile (25mL) solution, control rate of addition 3 drip/ Min, time for adding is in 3.5h, after reaction, adds water, methylene chloride extraction collects organic phase, obtains oily liquids N- (6- chlorine Pyridine -3- methylene) ethamine 15g (compound III -1), yield 88%.

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

(2) N- (6- chloropyridine -3- methylene)-N- ethyl -1- sulfidomethyl -2- nitro ethenylidene amine (compounds Ⅳ -1) Synthesis

In 100mL three neck round bottom flask, N- (6- chloropyridine -3- methylene) ethamine of 17.0g (0.1mol) is added, Bis- sulfidomethyl -2- nitroethylene of 15.0g (0.09mol) 1,1-, 50mL dehydrated alcohol are heated to flowing back, and flow back 8h.Stop back Stream, is cooled to room temperature, is concentrated to give viscous liquid, silicagel column column chromatography for separation (methylene chloride: acetone=5:1 (v/v)) must produce Object 6.5g (compounds Ⅳ -1), yield 23%.

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- chloropyridine -3- base) methyl)-N- ethyl-N`- methyl -2- nitro -3- (thiazol-2-yl) propyl- 1- alkene The synthesis of diamines (compound V -1):

Into 100mL round-bottomed flask, N- (6- chloropyridine -3- the methylene)-N- ethyl -1- sulphur of 5g (0.017mol) is added Methyl -2- nitro ethenylidene amine, the methylamine alcohol solution of 1.8g (0.017mol methylamine), 30mL dehydrated alcohol stir under ice bath Mixing makes temperature be down to 0 DEG C, and the reaction was continued until terminating.Solvent is boiled off in decompression, is concentrated to give slurry, silicagel column column chromatography point From (methylene chloride: acetone=4:1) compound 1.24g (compound V -1), yield 27%.GC-MS(m/s):236([M]⁺- 34,32), 207 (49), 169 (52), 126 (49), 90 (16), 67 (100).

(4) N- ((6- chloropyridine -3- base) methyl)-N- ethyl-N '-methyl -2- nitro -3- (thiazol-2-yl) propyl- 1- alkene The synthesis of diamines (chemical compounds I A-1)

By N- (6- chloropyridine -3- methylene)-N- ethyl-N`- methyl -2- nitro Asia ethylene of 1.350g (0.005mol) The HCl of base diamines, the anhydrous acetonitrile of 30mL, the 2- thiazole carboxaldehyde of 0.678g (0.006mol), catalytic amount is placed in the round bottom of 50ml In flask.It is stirred under room temperature, there is a large amount of solid to be precipitated after about 6h, stop reaction, filtering.The solid that will be obtained by filtration, 25mL methanol, the Ni of 10% equivalent, is placed in the round-bottomed flask of 50ml.It is filled with hydrogen, is stirred at normal temperature, the tracking of TLC plate is anti- Answer process, the R of product_f=0.25 (methylene chloride: acetone=4:1).To which after reaction, solvent is spin-dried for, glutinous shape object is remained Three times with methylene chloride and water extraction, dichloromethane layer is taken, NaCl saturated solution washs three times, uses Na₂SO₄It is dried overnight.It crosses Filter, take filtrate, be spin-dried for solvent, obtain crude product, with ethyl alcohol recrystallize compound IA-1 (object) sterling, for white Pulverulent solids 0.631g, yield about 34%.

¹H NMR (400MHz, DMSO) δ 9.47 (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.¹³C 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. HRMS(ES+)

C₁₆H₁₈N₅O₂S³⁵Cl(M+H)⁺, calculated value: 368.0948；Measured value: 367.0955；C₁₆H₁₈N₅O₂S³⁷Cl(M+H)⁺, Calculated value: 370.0918；Measured value: 369.0916.

Embodiment 2

2- ((1H- pyrroles -2- base) methyl) -3- chloromethyl amino -3- (N- benzyl-N- ethylamino) acrylonitrile (is changed Close II A-2 of object) synthesis:

(1) synthesis of 3- chloromethyl amino -3- (N- benzyl-N- ethylamino) acrylonitrile (compound V -2)

Chloropyridine ring is replaced divided by phenyl ring, cyano substitutes nitro, and chloromethyl substitutes other than methyl, other steps and embodiment Step (1)~(3) are identical in 1, obtain compound V -2.

(2) 2- ((1H- pyrroles -2- base) methyl) -3- chloromethyl amino -3- (N- benzyl-N- ethylamino) acrylonitrile The synthesis of (compound IA-2)

By 3- chloromethyl amino -3- (N- benzyl-N- ethylamino) acrylonitrile of 1.24g (0.005mol), 30mL's Anhydrous acetonitrile, the 2- pyrrole aldehyde of 0.570g (0.006mol), the HCl of catalytic amount are placed in the round-bottomed flask of 50ml.Under room temperature It stirs, there is a large amount of solid to be precipitated after about 7h, stop reaction, filtering.The solid that will be obtained by filtration, 25mL tetrahydrofuran, 2 The lithium aluminium hydride of times equivalent is placed in the round-bottomed flask of 50ml.It is stirred under room temperature, TLC plate tracks reaction process, the R of product_f= 0.20 (methylene chloride: acetone=3:1).To which after reaction, solvent is spin-dried for, glutinous shape object methylene chloride and water extraction are remained It takes three times, takes dichloromethane layer, NaCl saturated solution washs three times, uses Na₂SO₄It is dried overnight.Filtering, takes filtrate, is spin-dried for molten Agent obtains crude product, with ethyl alcohol recrystallize compound IA-2 sterling, be white powdery solids 0.712g, yield is about 38%.

¹H 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,J₁=7.2Hz, J₂=4.0Hz, 2H), 7.17 (d, J=4.0Hz, 2H), 6.88 (dd, J₁=4.9Hz, J₂ =3.6Hz, 1H), 6.66 (d, J=3.6Hz, 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.¹³C NMR(101MHz,DMSO)δ 172.84,138.54, 132.90,128.97,127.53,124.38,123.64,120.92,108.39,106.20,59.33, 53.10,50.92,48.34,30.21, 19.80ppm.HRMS(ES+)C₁₈H₂₂N₄ ³⁵Cl(M+H)⁺, calculated value: 329.1533；It is real Measured value: 329.1532； C₁₈H₂₂N₄ ³⁷Cl(M+H)⁺, calculated value: 331.1503；Measured value: 331.1506.

Embodiment 3

N- (3,3,3- trifluoro propyl)-N- ethyl-N ', N '-dimethyl -2- nitro -3- (4- cyano thiophene -2- base) propyl- The synthesis of 1- alkene diamines (compound IA-3):

(1) N- (3,3,3- trifluoro propyl)-N- ethyl-N ', N '-dimethyl -2- nitro ethenylidene diamines (compound V -3) synthesis

Chloropyridine ring is replaced divided by trifluoromethyl methyl, it is other other than the raw material methylamine in dimethylamine alternative steps (3) Step is identical as step (1)~(3) in embodiment 1, obtains compound V -3.

By N- (3,3,3- trifluoro propyl)-N- ethyl-N ' of 1.28g (0.005mol), N '-dimethyl -2- nitro Asia second Alkenyl diamines, the anhydrous acetonitrile of 30mL, 5- cyano -2 thiophene carboxaldehyde of 0.822g (0.006mol), the HCl of catalytic amount are placed in In the round-bottomed flask of 50ml.It is stirred under room temperature, there is a large amount of solid to be precipitated after about 14h, stop reaction, filtering.It will filter The solid arrived, 25mL methanol, the palladium carbon of 10% equivalent are placed in the round-bottomed flask of 50ml.It is filled with hydrogen, is stirred at normal temperature, TLC plate tracks reaction process, the Rf=0.30 (methylene chloride: acetone=4:1) of product.To which after reaction, solvent is revolved It is dry, it remains glutinous shape object methylene chloride and water extraction three times, takes dichloromethane layer, NaCl saturated solution is washed three times, used Na₂SO₄It is dried overnight.Filtering, take filtrate, be spin-dried for solvent, obtain crude product, with ethyl alcohol recrystallize compound I A-3 it is pure Product are white powdery solids 0.783g, yield about 42%.¹H 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.¹³C 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, 50.10,47.83,43.75,42.11,30.12,15.33ppm.¹⁹F NMR(376MHz, DMSO)δ-67.33ppm. HRMS(ES+)C₁₅H₂₀N₃O₂SF₃(M+H)⁺, calculated value: 377.1259；Measured value: 377.1247.

Embodiment 4

N- (2- chloroethyl)-N- ethyl-N '-methyl -2- nitro -3- (5- methylfuran -2- base) propyl- 1- alkene -1,1- two The synthesis of amine (compound IA-4):

(1) synthesis of 5- benzofurane -2- formaldehyde (compound Z-4)

Under argon gas strict protection, by the 5-bromo-2-furaldehyde of 0.875g (0.005mol), 0.610g (0.005mol) Phenyl boric acid boric acid be dissolved in the wet chemical of 20mL toluene, 20mL ethyl alcohol and 5mL 2mol/L, add and be heated to reflux 4h.Cool down after reaction, stand, remove water layer, and with ethyl acetate by water layer wash three times, merge cleaning solution with react Liquid, decompression boil off solvent, and column chromatography for separation obtains sterling 0.836g, yield about 97%.GC-MS(m/s):172(100),144 (8),99(48), 86(5)。

(2) N- (2- chloroethyl)-N- ethyl-N '-methyl -2- nitroethylene -1,1- diamines (compound V -4) synthesis

Chloropyridine ring is replaced divided by chloromethyl, other steps are identical as step (1)~(3) in embodiment 1, obtain compound Ⅴ-4。

(3) N- (2- chloroethyl)-N- ethyl-N '-methyl -2- nitro -3- (5- methylfuran -2- base) propyl- 1- alkene -1,1- The synthesis of diamines (compound IA-4)

4- benzofurane -2- the formaldehyde of 0.860g (0.005mol) is dissolved in methylene chloride, then instills and is equipped with dropwise N- (2- chloroethyl)-N- ethyl-N '-methyl -2- nitroethylene -1,1- diamines of 1.04g (0.005mol), the anhydrous second of 30mL Nitrile, in the round-bottomed flask of the 50ml of the HCl of catalytic amount.It is stirred under room temperature, there is a large amount of bright yellow solid to be precipitated after about 4h, Stop reaction, filtering.The lithium aluminium hydride of the solid that will be obtained by filtration, 25mL tetrahydrofuran, 2 times of equivalents is placed in the round bottom of 50ml In flask.It is stirred under room temperature, TLC plate tracks reaction process, the R of product_f=0.35 (methylene chloride: acetone=8:1).To anti- After answering, solvent is spin-dried for, glutinous shape object methylene chloride and water extraction is remained three times, takes dichloromethane layer, NaCl saturation is molten Liquid washs three times, uses Na₂SO₄It is dried overnight.Filtering, takes filtrate, is spin-dried for solvent, obtain crude product, recrystallizes to change with ethyl alcohol The sterling of object IA-4 is closed, is white solid 1.213g, yield about 53%.¹H 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.¹³C 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.HRMS(ES+)C₁₈H₂₃N₃O₃ ³⁵Cl(M+ H)⁺, calculated value: 364.1428；Measured value 364.1441；C₁₈H₂₃N₃O₃ ³⁷Cl(M+H)⁺, calculated value: 366.1398；Measured value: 366.1403。

Embodiment 5

The chloro- 5- of 2- ((2- (2- (furans -2- base) -1- nitroethenyl group) imidazolidine -1- base) methyl) pyridine (compound IB-1 synthesis):

(1) synthesis of the chloro- 5- of 2- (2- Nitromethylene-imidazolidine -1- ylmethyl)-pyridine (compound IX-1)

Using the 2-vhloro-5-chloromethylpyridine of 0.03mol as starting material, according to WO2006056108A1 and Method described in WO2007101369A1 prepares the chloro- 5- of 2- (2- Nitromethylene-imidazolidine -1- ylmethyl)-pyridine, and yield is 64%；R_f=0.46 (petroleum ether: ethyl acetate=1:1)；Mp=157.3 DEG C~159.9 DEG C.GC-MS (m/s) 220 (25), 126 (100), 90 (9).

(2) the chloro- 5- of 2- ((2- (2- (furans -2- base) -1- nitroethenyl group) imidazolidine -1- base) methyl) pyridine (chemical combination Object IB-1) synthesis:

By the chloro- 5- of 2- (2- Nitromethylene-imidazolidine -1- ylmethyl)-pyridine of 1.27g (0.005mol), 30mL's Anhydrous acetonitrile, the furfural of 0.576g (0.006mol), the HCl of catalytic amount are placed in the round-bottomed flask of 50ml.It is stirred under room temperature, There is a large amount of solid to be precipitated after about 4h, stops reaction, filtering.The solid that will be obtained by filtration, 25mL tetrahydrofuran, 2 times of equivalents Lithium aluminium hydride be placed in the round-bottomed flask of 50ml.It is stirred under room temperature, TLC plate tracks reaction process, the R of product_f=0.40 (methylene chloride: acetone=5:1).To which after reaction, solvent is spin-dried for, glutinous shape object methylene chloride and water extraction three are remained It is secondary, dichloromethane layer is taken, NaCl saturated solution washs three times, uses Na₂SO₄It is dried overnight.Filtering, takes filtrate, is spin-dried for solvent, obtain Crude product, with ethyl alcohol recrystallize compound IB-1 sterling, be white needle-like crystals 1.060g, yield about 64%.¹H NMR(400 MHz,CDCl₃) δ 9.87 (s, 1H), 8.25 (s, 1H), 7.49 (d, J=5.2Hz, 1H), 7.37 (d, J=6.0Hz, 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=8.0Hz, 2H), 3.69 (t, J=8.0Hz, 2H) ppm.¹³C NMR (101MHz,CDCl₃)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+)C₁₅H₁₅N₄O₃ ³⁵Cl (M+K)⁺, calculated value: 373.0470；Measured value: 373.0468；C₁₅H₁₅N₄O₃ ³⁷Cl(M+K)⁺, calculated value: 375.0440；It is real Measured value: 375.0444.

Embodiment 6

The chloro- 5- of 2- ((2- (2- (the bromo- thiophene -2- base of 5-) -1- nitroethenyl group) imidazolidine -1- base) methyl) pyridine (is changed Close object IB-2) synthesis:

(1) conjunction of the chloro- 5- of 2- (N- methyl -2- Nitromethylene-imidazolidine -1- ylmethyl)-pyridine (compound IX-2) At

Using the 2-vhloro-5-chloromethylpyridine of 0.03mol as starting material, according to WO2006056108A1 and Method described in WO2007101369A1 prepares the chloro- 5- of 2- (N- methyl -2- Nitromethylene-imidazolidine -1- ylmethyl)-pyrrole Pyridine, yield 55%；R_f=0.40 (petroleum ether: ethyl acetate=1:1)；Mp=160.3 DEG C~162.9 DEG C.GC-MS(m/s) 234 (25), 126 (100), 90 (9).

(2) the chloro- 5- of 2- ((2- (2- (the bromo- thiophene -2- base of 5-) -1- nitroethenyl group) imidazolidine -1- base) methyl) pyridine The synthesis of (compound I B-2)

By the chloro- 5- of 2- (N- methyl -2- Nitromethylene-imidazolidine -1- ylmethyl)-pyridine of 1.34g (0.005mol), The anhydrous acetonitrile of 30mL, the bromo- 2 thiophene carboxaldehyde of 5- of 1.146g (0.006mol), the round bottom that the HCl of catalytic amount is placed in 50ml are burnt In bottle.It is stirred under room temperature, there is a large amount of solid to be precipitated after about 8h, stop reaction, filtering.The solid that will be obtained by filtration, 25mL The sodium borohydride of methanol, 2 times of equivalents is placed in the round-bottomed flask of 50ml.It is stirred under room temperature, TLC plate tracks reaction process, product R_f=0.40 (methylene chloride: acetone=5:1).To which after reaction, solvent is spin-dried for, glutinous shape object methylene chloride is remained Three times with water extraction, dichloromethane layer is taken, NaCl saturated solution washs three times, uses Na₂SO₄It is dried overnight.Filtering, takes filtrate, Be spin-dried for solvent, obtain crude product, with ethyl alcohol recrystallize compound IB-2 sterling, be white needle-like crystals 1.856g, yield About 84%.¹H NMR (400MHz, DMSO) δ 9.38 (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.¹³C NMR(101MHz,DMSO)δ 162.73, 149.92,148.80,145.72,138.73,132.16,129.83,125.34,124.69,109.29, 105.36,64.20,50.96, 50.61,42.75,30.48ppm.HRMS(ES+)C₁₆H₁₇N₄O₂S³⁵Cl⁷⁹Br(M+H)⁺, calculate Value: 442.9944；Measured value: 442.9932；C₁₆H₁₇N₄O₂S³⁷Cl⁷⁹Br(M+K)⁺, calculated value: 444.9924；Measured value: 444.9915。 C₁₅H₁₅N₄O₂S³⁵Cl⁸¹Br(M+H)⁺, calculated value: 430.9767；Measured value: 430.9760. C₁₅H₁₅N₄O₂S³⁷Cl⁸¹Br (M+K)⁺, calculated value: 432.9738；Measured value: 432.9741.

Embodiment 7

The synthesis of 1- butyl -5- methyl -2- (1- nitro -2- (thiene-3-yl) vinyl) imidazoline (compound IB-3):

(1) synthesis of 1- butyl -5- methyl -2- (Nitromethylene) imidazoline (compound IX-3)

Chloropyridine ring is replaced divided by n-propyl, is replaced other than raw material ethylenediamine with 1- methyl ethylenediamine, other steps and reality It applies in example 5 that step (1) is identical, obtains compound IX-3.

(2) conjunction of 1- butyl -5- methyl -2- (1- nitro -2- (thiene-3-yl) vinyl) imidazoline (compound IB-3) At

By 1- butyl -5- methyl -2- (Nitromethylene) imidazoline of 0.995g (0.005mol), the anhydrous second of 30mL Nitrile, the 3- thiophenecarboxaldehyde of 0.672g (0.006mol), the HCl of catalytic amount are placed in the round-bottomed flask of 50ml.It is stirred under room temperature, There is a large amount of solid to be precipitated after about 8h, stops reaction, filtering.The solid that will be obtained by filtration, 25mL methanol, 10% equivalent Palladium carbon is placed in the round-bottomed flask of 50ml.It is filled with hydrogen, and is stirred at normal temperature, TLC plate tracks reaction process, product R_f=0.30 (methylene chloride: acetone=5:1).To which after reaction, solvent is spin-dried for, glutinous shape object methylene chloride and water are remained Extraction three times, takes dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄It is dried overnight.Filtering, takes filtrate, is spin-dried for Solvent obtains crude product, with ethyl alcohol recrystallize compound I B-3 sterling, be white solid 0.758g, yield about 52%.¹H NMR(400MHz,CDCl₃) δ 9.46 (s, 1H), 7.39 (d, J=8.0Hz, 1H), 7.13 (d, J=8.0Hz, 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.¹³C NMR(101MHz,CDCl₃)δ162.42,137.69,129.40,127.47,121.97,92.18,65.37, 62.31, 46.12,29.13,21.84,19.20,17.10,17.12ppm.HRMS(ES+)C₁₄H₂₂N₃O₂(M+H)⁺, calculated value: 296.1433；Measured value: 296.1425.

Embodiment 8

The chloro- 5- of 2- ((2- (3- methyl-1-nitro-2- phenylbutene base)-2,3- dihydro-1H- benzo [d] imidazolidine-1- Base) methyl) thiazole (compound IB-4) synthesis:

(1) the chloro- 5- of 2- ((2- (Nitromethylene) -2,3- dihydro -1H- benzo [d] imidazoles -1- base) methyl) thiazole (is changed Close object IX-4) synthesis

Chloropyridine ring is replaced divided by n-propyl, is replaced other than raw material ethylenediamine with 1- methyl ethylenediamine, other steps and reality It applies in example 5 that step (1) is identical, obtains compound IX-4.

(2) the chloro- 5- of 2- ((2- (3- methyl-1-nitro-2- phenylbutene base)-2,3- dihydro-1H- benzo [d] imidazolidine- 1- yl) methyl) thiazole (compound IB-2) synthesis

By the chloro- 5- of 2- ((2- (Nitromethylene) -2,3- dihydro -1H- benzo [d] imidazoles -1- of 1.54g (0.005mol) Base) methyl) thiazole, the anhydrous acetonitrile of 30mL, 2- methyl-1-phenyl propyl- 1- ketone of 0.888g (0.006mol), catalytic amount HCl is placed in the round-bottomed flask of 50ml.It is stirred under room temperature, there is a large amount of solid to be precipitated after about 6h, stop reaction, filtering.It will The solid being obtained by filtration, 25mL methanol, the PbO of 10% equivalent₂, it is placed in the round-bottomed flask of 50ml.It is filled with hydrogen, in room temperature Lower stirring, TLC plate track reaction process, the R of product_f=0.35 (methylene chloride: acetone=5:1).To after reaction, incite somebody to action Solvent is spin-dried for, and remains glutinous shape object methylene chloride and water extraction three times, takes dichloromethane layer, and NaCl saturated solution washs three times, Use Na₂SO₄It is dried overnight.Filtering, takes filtrate, is spin-dried for solvent, obtain crude product, recrystallizes to obtain compound I B-4 with ethyl alcohol Sterling is white crystal 1.098g, yield about 50%.¹H 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.¹³C NMR (101MHz,DMSO)δ160.34,153.31,142.07,137.89,137.28,133.82,131,47, 129.94,128.36, 125.23,120.93,118.74,117.05,116.32,105.22,60.55,35.28,31.63, 19.40ppm.HRMS(ES+) C₂₂H₂₂N₄O₂S³⁵Cl(M+H)⁺, calculated value: 441.1152；Measured value: 441.1142； C₂₂H₂₂N₄O₂S³⁷Cl(M+H)⁺, calculated value: 441.1122；Measured value: 441.1107.

Embodiment 9

2- (1- nitro -2- (thiophene -2- base) acrylic) -1- ((tetrahydrofuran -3- base) methyl) imidazoline (compound I B-5 synthesis):

(1) synthesis of 1- ((tetrahydrofuran -3- base) methyl) -2- (Nitromethylene) -1- imidazoline (compound IX-5)

By 4- toluenesulfonic acid (tetrahydrofuran -3- base) methyl ester, 9.00g (0.15mol) second of 7.68g (0.03mol) Diamines, the potassium carbonate of 8.280g (0.06mol), the sodium iodide of 0.20g, 120mL acetonitrile are placed in 250mL round-bottomed flask, heating To 70, is filtered after DEG C reaction 4h, take filtrate to be concentrated, obtain N- ((tetrahydrofuran -3- base) methyl) ethylenediamine crude product.With 100mL second 1,1-, the bis- sulfidomethyl -2- nitroethylene of gained crude product, 4.125g (0.025mol) are dissolved in 250mL round-bottomed flask by alcohol, Under counterflow condition, 8h is reacted.Cooling, solid to be precipitated, is concentrated, filters, being dried to obtain pale yellow powder shape solid 5.32g, produces Rate is 88%；GC-MS (m/s): 177 (29), 99 (100), 56 (9).

(2) 2- (1- nitro -2- (thiophene -2- base) acrylic) -1- ((tetrahydrofuran -3- base) methyl) imidazoline (chemical combination Object IB-5) synthesis

By 1- ((tetrahydrofuran -3- base) methyl) -2- (Nitromethylene) -1- imidazoline of 1.205g (0.005mol), The anhydrous acetonitrile of 30mL, the 1- thiophene -2- base ethyl ketone of 0.756g (0.006mol), the round bottom that the HCl of catalytic amount is placed in 50ml are burnt In bottle.It is stirred under room temperature, there is a large amount of solid to be precipitated after about 5h, stop reaction, filtering.The solid that will be obtained by filtration, 25mL Methanol, the Ni of 10% equivalent, is placed in the round-bottomed flask of 50ml.Be filled with hydrogen, stir at normal temperature, TLC plate tracking react into Journey, the R of product_f=0.30 (methylene chloride: acetone=5:1).To which after reaction, solvent is spin-dried for, glutinous shape object is remained with two Chloromethanes and water extraction three times, take dichloromethane layer, and NaCl saturated solution washs three times, use Na₂SO₄It is dried overnight.Filtering, takes Filtrate is spin-dried for solvent, obtains crude product, with ethyl alcohol recrystallize compound IB-5 sterling, be white powdery solids 0.878g, yield about 50%.M.p.=108.2~109.4 DEG C¹H NMR(400MHz,CDCl₃)δ10.05(s,1H),7.14 (d, J=4.8 Hz, 1H), 6.92 (d, J=4.8Hz, 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, J₁=13.4Hz, J₂=6.8Hz, 1H) ppm.¹³C NMR(101MHz,DMSO)δ162.62,143.79,126.92,124.68,124.42, 105.94,70.47,67.13,51.90, 50.37,42.55,40.12,38.48,30.14,29.79ppm.HRMS(ES+) C₁₄H₂₀N₃O₃S(M+H)⁺, calculated value: 324.1382；Measured value: 324.1374.

Embodiment 10

The chloro- 5- of 2- ((2- (2- (3- methoxyphenyl) methyl) -1- nitroethenyl group) hexahydropyrimidine -1- base) methyl) pyrrole The synthesis of pyridine (compound IB-6):

(1) synthesis of 1- (the chloro- 3- picolyl of 6-) -2- Nitromethylene hexahydropyrimidine (compound IX-6)

Using 2.42g (0.015mol) to chloropyridine as starting material, according to WO2006056108A1 and Method described in WO2007101369A1 prepares 1- (the chloro- 3- picolyl of 6-) -2- Nitromethylene hexahydropyrimidine, yield It is 50%；Rf=0.20 (ethyl alcohol: methylene chloride=1:1)；Mp=177.9225 (100), 196 (9), 154 (10), 139 (11), 126 (31), 113 (10), 99 (31).

(2) the chloro- 5- of 2- ((2- (2- (3- methoxyphenyl) methyl) -1- nitroethenyl group) hexahydropyrimidine -1- base) methyl) The synthesis of pyridine (compound IB-6)

By the chloro- 5- of 2- (2- Nitromethylene-imidazolidine -1- ylmethyl) thiazole of 1.340g (0.005mol), 30mL's Anhydrous acetonitrile, the m-methoxybenzaldehyde of 0.816g (0.006mol), the HCl of catalytic amount are placed in the round-bottomed flask of 50ml.Often Temperature is lower to be stirred, and has a large amount of solid to be precipitated after about 7h, stops reaction, filtering.The solid that will be obtained by filtration, 25mL tetrahydro furan It mutters, the lithium aluminium hydride of 2 times of equivalents is placed in the round-bottomed flask of 50ml.It is stirred under room temperature, TLC plate tracks reaction process, product Rf=0.40 (methylene chloride: acetone=5:1).To which after reaction, solvent is spin-dried for, remain glutinous shape object methylene chloride and Water extracts three times, takes dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄It is dried overnight.Filtering, takes filtrate, revolves Dry solvent, obtains crude product, with ethyl alcohol recrystallize compound IB-6 sterling, be white powdery solids 1.067g, yield About 57%.1H NMR (400MHz, DMSO) δ 9.47 (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=5.6 Hz, 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.¹³C 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+)C₁₉H₂₂N₄O₃ ³⁵Cl(M+H)⁺, calculated value: 389.1380；It is real Measured value: 389.1397； C₁₉H₂₂N₄O₃ ³⁷Cl(M+H)⁺, calculated value: 391.1351；Measured value: 391.1349.

Embodiment 11

2- (1- (N- (2- (6- chloropyridine -3- base) 2- acetyl group)-N '-methyl-imidazoles quinoline -2- methylene) -3- (thiophene Pheno -2- base) propionitrile (compound IB-7) synthesis:

(1) 2- (1- (2- (6- chloropyridine -3- base) -2- acetyl group) -3- Vinylimdozoline -2- base vinyl) acetonitrile The synthesis of (compound IX-7)

Chloropyridine ring is replaced divided by 6- chloropyridine -3- formoxyl, raw material ethylenediamine, cyano are replaced with 1- vinyl ethylenediamine Replace other than nitro, other steps are identical as step (1) in embodiment 5, obtain compound IX -7.

(2) 2- (1- (N- (2- (6- chloropyridine -3- base) 2- acetyl group)-N '-methyl-imidazoles quinoline -2- methylene) -3- The synthesis of (thiophene -2- base) propionitrile (compound IB-7):

By 2- (1- (2- (6- chloropyridine -3- base) -2- acetyl group) -3- Vinylimdozoline-of 1.44g (0.005mol) 2- base vinyl) acetonitrile, the anhydrous acetonitrile of 30mL, the 2 thiophene carboxaldehyde of 0.672g (0.006mol), the HCl of catalytic amount is placed in In the round-bottomed flask of 50ml.It is stirred under room temperature, there is a large amount of solid to be precipitated after about 12h, stop reaction, filtering.It will filter The sodium borohydride of the solid arrived, 25mL methanol, 2 times of equivalents is placed in the round-bottomed flask of 50ml.It is stirred under room temperature, the tracking of TLC plate Reaction process, the R of product_f=0.37 (methylene chloride: acetone=5:1).To which after reaction, solvent is spin-dried for, glutinous shape is remained Object methylene chloride and water extraction three times, take dichloromethane layer, and NaCl saturated solution washs three times, use Na₂SO₄It is dried overnight. Filtering, take filtrate, be spin-dried for solvent, obtain crude product, with ethyl alcohol recrystallize compound IB-7 sterling, be white powder Solid 0.933g, yield about 48%.¹H NMR (400MHz, DMSO) δ 9.42 (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, 2H), 4.62 (s, 2H), 4.31 (s, 2H), 3.68- 3.64 (m, 2H), 3.42-3.34 (m, 2H), 2.83 (t, J=5.4Hz, 1H) ppm.¹³C NMR(101MHz,DMSO)δ 162.84,149.92, 148.78,143.65,138.70,132.29,126.99,124.71,124.48,124.44, 120.92,118.76,106.20,55.32, 50.92,50.56,42.74.HRMS(ES+)C₁₉H₁₈N₄OS³⁵Cl(M+H)⁺, calculate Value: 385.0890；Measured value: 385.0900；C₁₆H₁₅N₄S³⁷Cl(M+H)⁺, calculated value: 387.0860；Measured value: 387.0877。

Embodiment 12

The chloro- 5- of 2- ((2- (2- (5- tolylthiophene -2- base) -1- nitroethenyl group) imidazolidine -1- base) methyl) pyridine (is changed Close object IB-8) synthesis:

(1) synthesis of the chloro- 5- of 2- (2- Nitromethylene-imidazolidine -1- ylmethyl) thiazole (compound IX-8)

It is replaced other than chloropyridine ring divided by 5- chlorine thiazole ring, other steps are identical as step (1) in embodiment 5, changed Close object IX -8.

(2) synthesis of 5- tolylthiophene -2- formaldehyde (compound Z-8)

Under argon gas strict protection, by the bromo- 2 thiophene carboxaldehyde of 5- of 0.955g (0.005mol), 0.610g (0.005mol) Phenyl boric acid be dissolved in the wet chemical of 20mL toluene, 20mL ethyl alcohol and 5mL 2mol/L, and 0.289g is added The tetrakis triphenylphosphine palladium of (0.005mol), is heated to reflux 4h.It cools down, stands after reaction, remove water layer, and with acetic acid second Ester washs water layer three times, merges cleaning solution and reaction solution, and decompression boils off solvent, and column chromatography for separation obtains sterling 902mg, yield About 96%. GC-MS(m/s):188(100),160(8),115(48),102(5),79(7).

(3) the chloro- 5- of 2- ((2- (2- (5- tolylthiophene -2- base) -1- nitroethenyl group) imidazolidine -1- base) methyl) pyridine The synthesis of (compound IB-8)

5- tolylthiophene -2- the formaldehyde of 0.940g (0.005mol) is dissolved in methylene chloride, then instills and is equipped with dropwise The chloro- 5- of 2- (2- Nitromethylene-imidazolidine -1- ylmethyl) thiazole of 1.300g (0.005mol), the anhydrous acetonitrile of 30mL are urged In the round-bottomed flask of the 50ml of the HCl of change amount.It is stirred under room temperature, there is a large amount of shiny red solid to be precipitated after about 3h, stopped anti- It answers, filters.The solid that will be obtained by filtration, 25mL methanol, the PbO of 10% equivalent₂, it is placed in the round-bottomed flask of 50ml.It is filled with hydrogen Gas stirs at normal temperature, and TLC plate tracks reaction process, the R of product_f=0.39 (methylene chloride: acetone=8:1).Wait react knot Solvent is spin-dried for by Shu Hou, is remained glutinous shape object methylene chloride and water extraction three times, is taken dichloromethane layer, NaCl saturated solution is washed It washs three times, uses Na₂SO₄It is dried overnight.Filtering, takes filtrate, is spin-dried for solvent, obtain crude product, recrystallize to obtain compound with ethyl alcohol The sterling of IB-8 is white solid 1.049g, yield about 49%.¹H 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.¹³C NMR(101MHz,DMSO)δ162.96,138.82,137.51,135.21,134.47,132.52,129.49, 127.64, 125.80,125.41,124.67,123.43,105.93,50.98,50.55,43.43,30.36ppm.HRMS(ES +) C₂₀H₁₉N₃O₂S₂ ³⁵Cl(M+H)⁺, calculated value: 432.0607；Measured value: 432.0591；C₂₀H₁₉N₃O₂S₂ ³⁷Cl(M+H)⁺, meter Calculation value: 434.0578；Measured value: 433.0581.

Embodiment 13

The chloro- 5- of 2- ((2- (2- (5- (4- methoxyl group-phenyl) thiophene -2- base) -1- nitroethenyl group) imidazolidine -1- base) Methylamino) pyridine (compound IB-9) synthesis:

(1) synthesis of the chloro- 5- of 2- (2- Nitromethylene-imidazolidine -1- vlmethyl)-pyridine (compound IX-9)

It is replaced other than chloropyridine ring divided by 6- chloropyridine -3- base amino, other steps are identical as step (1) in embodiment 5, Obtain compound IX -9.

(2) synthesis of 5- (4- methoxyphenyl) thiophene -2-formaldehyde (compound Z-9)

Under argon gas strict protection, by the bromo- 2 thiophene carboxaldehyde of 5- of 0.955g (0.005mol), 0.760g (0.005mol) Methoxyphenylboronic acid is dissolved in the wet chemical of 20mL toluene, 20mL ethyl alcohol and 5mL 2mol/L, be heated to reflux 4h.Cool down after reaction, stand, remove water layer, and with ethyl acetate by water layer wash three times, merge cleaning solution with react Liquid, decompression boil off solvent, and column chromatography for separation obtains sterling 1.106g, yield about 93%.GC-MS(m/s):218(100),203 (52),189(7), 175(21),145(21),102(10),77(14)。

(3) the chloro- 5- of 2- ((2- (2- (5- (4- methoxyl group-phenyl) thiophene -2- base) -1- nitroethenyl group) imidazolidine -1- Base) methylamino) pyridine (compound IB-9) synthesis

5- (4- methoxyphenyl) thiophene -2-formaldehyde of 1.090g (0.005mol) is dissolved in methylene chloride, then dropwise Instillation is equipped with the chloro- 5- of 2- (2- Nitromethylene-imidazolidine -1- vlmethyl)-pyridine of 1.345g (0.005mol), The anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount.It is stirred under room temperature, there is a large amount of Exocarpium Citri Rubrum after about 4h Color solid is precipitated, and stops reaction, filtering.The solid that will be obtained by filtration, 25mL methanol, the PbO of 10% equivalent₂, it is placed in 50ml's In round-bottomed flask.It is filled with hydrogen, is stirred at normal temperature, TLC plate tracks reaction process, the R of product_f=0.32 (methylene chloride: Acetone=8:1).To which after reaction, solvent is spin-dried for, remains glutinous shape object methylene chloride and water extraction three times, take dichloromethane Alkane layer, NaCl saturated solution wash three times, use Na₂SO₄It is dried overnight.Filtering, takes filtrate, is spin-dried for solvent, obtain crude product, use second Alcohol recrystallize compound IB-9 sterling, be white solid 1.394g, yield about 59%.¹H NMR(400MHz,DMSO) δ 9.45 (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.¹³C NMR(101MHz,DMSO)δ162.85,155.88,153.66,149.89,148.79, 138.72,132.37, 124.71,118.96,112.80,109.01,108.60,107.92,102.49,51.06,50.53, 42.68,28.61ppm. HRMS(ES+)C₂₂H₂₁N₅O₃S³⁵Cl(M+H)⁺, calculated value: 472.1210；Measured value: 472.1196； C₂₂H₂₁N₅O₃S³⁷Cl(M+H)⁺, calculated value: 474.1181；Measured value: 474.1174.

Embodiment 14

2- (2- (1- ((6- chloropyridine -3- base) methyl) imidazoline -2- base-vinyl) -2- (2- (trimethyl fluoride sulfonyl Base) ethyl) -4- (3- methoxyphenyl) thiazole (compound IB-10) synthesis:

(1) the chloro- 5- of 2- (2- trifyl methylene-imidazolidine -1- ylmethyl)-pyridine (compound IX-10) Synthesis

It is replaced other than nitro divided by three fluorosulfonyls, other steps are identical as step (1) in embodiment 5, obtain compound IX–10。

(2) synthesis of 5- (4- methoxyphenyl) thiophene -2-formaldehyde (compound Z-10)

Under argon gas strict protection, by the bromo- 2- thiazole carboxaldehyde of the 4- of 0.950g (0.005mol), 0.765g (0.005mol) 6- methoxyl group -2- pyridine boronic acid be dissolved in the wet chemical of 20mL toluene, 20mL ethyl alcohol and 5mL 2mol/L, then plus Enter to be heated to reflux 4h.It cools down, stands after reaction, remove water layer, and wash water layer three times with ethyl acetate, merging is washed Liquid and reaction solution are washed, decompression boils off solvent, and column chromatography for separation obtains sterling 1.006g, yield about 91%.GC-MS(m/s):220 (100),205(65), 177(40),147(12),116(8),78(5)。

(3) 2- (2- (1- ((6- chloropyridine -3- base) methyl) imidazoline -2- base-vinyl) -2- (2- (trifluoromethyl sulphur Acyl group) ethyl) -4- (3- methoxyphenyl) thiazole (compound IB-10) synthesis

4- (6- methoxypyridine -2- base) thiazole -2- formaldehyde of 1.100g (0.005mol) is dissolved in methylene chloride, then The chloro- 5- of 2- (2- trifyl methylene-imidazolidine -1- ylmethyl)-for being equipped with 1.71g (0.005mol) is instilled dropwise Pyridine, the anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount.It stirs, has after about 4h a large amount of under room temperature Bright yellow solid be precipitated, stop reaction, filtering.The solid that will be obtained by filtration, 25mL methanol, the palladium carbon of 10% equivalent are placed in In the round-bottomed flask of 50ml.It is filled with hydrogen, is stirred at normal temperature, TLC plate tracks reaction process, the R of product_f=0.35 (dichloro Methane: acetone=8:1).To which after reaction, solvent is spin-dried for, remains glutinous shape object methylene chloride and water extraction three times, take Dichloromethane layer, NaCl saturated solution wash three times, use Na₂SO₄It is dried overnight.Filtering, takes filtrate, is spin-dried for solvent, obtain and slightly produce Product, with ethyl alcohol recrystallize compound IB-10 sterling, be white solid 1.213g, yield about 53%.¹H NMR (400MHz, DMSO) δ 9.47 (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=6.3Hz, 2H), 3.68 (d, J=6.3Hz, 2H) ppm.¹³C NMR(101MHz,DMSO)δ162.87, 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.¹⁹F NMR (376MHz,DMSO)δ-67.33ppm.HRMS(ES+) C₂₂H₂₁N₄O₃S₂ ³⁵ClF₃(M+H)⁺, calculated value: 545.0696；Actual measurement Value: 545.0702； C₂₂H₂₁N₄O₃S₂ ³⁷ClF₃(M+H)⁺, calculated value: 547.0666；Measured value: 547.0664.

Embodiment 15

Three fluoro- 4- (4- (4- (trifluoro of 3- (1- ((6- chloropyridine -3- base) methyl) imidazoline -2- base vinyl) -1,1,1- Methyl) phenyl) thienyl -2- base) and butyl- 2- ketone (compound IB-11) synthesis:

(1) 2 ketone (chemical combination of 3- (1- ((6- chloropyridine -3- base) methyl) imidazoline -2- base vinyl) -1,1,1- trifluoro propyl- Object IX-11) synthesis

It is replaced other than nitro divided by trifluoro formoxyl, other steps are identical as step (1) in embodiment 5, obtain compound IX–11。

(2) synthesis of 4- (4- trifluoromethyl) thiophene -2-formaldehyde (compound Z-11)

Under argon gas strict protection, by the bromo- 2 thiophene carboxaldehyde of 4- of 0.955g (0.005mol), 0.950g (0.005mol) Trifluoromethylbenzene boronic acid is dissolved in the wet chemical of 20mL toluene, 20mL ethyl alcohol and 5mL 2mol/L, be heated to reflux 4h.Cool down after reaction, stand, remove water layer, and with ethyl acetate by water layer wash three times, merge cleaning solution with react Liquid, decompression boil off solvent, and column chromatography for separation obtains sterling 1.204g, yield about 94%.GC-MS(m/s):255(100),203 (64),175(40), 145(12),115(8)。

(3) three fluoro- 4- (4- (4- of 3- (1- ((6- chloropyridine -3- base) methyl) imidazoline -2- base vinyl) -1,1,1- (trifluoromethyl) phenyl) thienyl -2- base) butyl- 2- ketone (compound IB-11) synthesis

4- (4- trifluoromethyl) thiophene -2-formaldehyde of 1.280g (0.005mol) is dissolved in methylene chloride, then by Drop instills the 3- (1- ((6- chloropyridine -3- base) methyl) imidazoline -2- base vinyl) -1,1 for being equipped with 1.53g (0.005mol), 2 ketone of 1- trifluoro propyl-, the anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount.It is stirred under room temperature, about 4h After there is a large amount of Chinese red solid to be precipitated, stop reaction, filtering.The solid that will be obtained by filtration, 25mL methanol, the boron of 2 times of equivalents Sodium hydride is placed in the round-bottomed flask of 50ml.It is stirred under room temperature, TLC plate tracks reaction process, the R of product_f=0.36 (dichloro Methane: acetone=8:1).To which after reaction, solvent is spin-dried for, remains glutinous shape object methylene chloride and water extraction three times, take Dichloromethane layer, NaCl saturated solution are washed three times, are dried overnight with Na2SO4.Filtering, takes filtrate, is spin-dried for solvent, obtain and slightly produce Product, with ethyl alcohol recrystallize compound I B-11 sterling, be white solid 1.851g, yield about 68%.

¹H 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).

¹³C 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.

¹⁹F NMR(376MHz,DMSO)δ-60.83,-55.90ppm.HRMS(ES+)C₂₄H₁₉N₃OS³⁵ClF₆(M+H)⁺, meter Calculation value: 546.0842；Measured value: 546.0844；C₂₄H₁₉N₃OS³⁷ClF₆(M+H)⁺, calculated value: 548.0812；Measured value: 548.0819。

Embodiment 16

The chloro- 5- of 2- ((2- (1- nitro -2- (benzofuran -2- base) vinyl) imidazoline -1- base) ethyl) pyridine (chemical combination Object IB-12) synthesis:

(1) synthesis of the chloro- 5- of 2- ((2- Nitromethylene-imidazolidine -1- base) ethyl)-pyridine (compound IX-12)

Divided by the chloro- 5- of 2- (1- chloroethyl) pyridine replacement the chloro- 3- chloromethylpyridine of 6- as raw material other than, other steps and Step (1) is identical in embodiment 5, obtains compound IX -12.

(2) the chloro- 5- of 2- ((2- (1- nitro -2- (benzofuran -2- base) vinyl) imidazoline -1- base) ethyl) pyridine The synthesis of (compound IB-12)

Benzofuran -2- the formaldehyde of 0.730g (0.005mol) is dissolved in methylene chloride, then instills dropwise and is equipped with 1.34g The chloro- 5- of the 2- of (0.005mol) ((2- Nitromethylene-imidazolidine -1- base) ethyl)-pyridine, the anhydrous acetonitrile of 30mL, catalysis In the round-bottomed flask of the 50ml of the HCl of amount.It is stirred under room temperature, there is a large amount of bright yellow solid to be precipitated after about 4h, stopped anti- It answers, filters.The solid that will be obtained by filtration, 25mL methanol, the Ni of 10% equivalent are placed in the round-bottomed flask of 50ml.It is filled with hydrogen Gas stirs at normal temperature, and TLC plate tracks reaction process, the R of product_f=0.30 (methylene chloride: acetone=7:1).Wait react After, solvent is spin-dried for, glutinous shape object methylene chloride and water extraction is remained three times, takes dichloromethane layer, NaCl saturated solution Washing three times, is dried overnight with Na2SO4.Filtering, takes filtrate, is spin-dried for solvent, obtain crude product, recrystallize to obtain chemical combination with ethyl alcohol The sterling of object IB-12 is white solid 1.231g, yield about 64%.¹H 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.¹³C NMR (101MHz,DMSO)δ162.41,153.77,151.20,150.86,142.39, 137.55,131.72,127.53,124.89, 123.88,123.90,120.42,118.61,106.73,56.84,48.27, 47.93,31.68,22.41ppm.HRMS(ES+) C₂₀H₂₀N₄O₃ ³⁵Cl(M+H)⁺, calculated value: 399.1224；Measured value 399.1220；C₂₀H₂₀N₄O₃ ³⁷Cl(M+H)⁺, calculated value: 401.1194；Measured value: 401.1190.

Embodiment 17

3- (3- (2- (1- (the bromo- 4,4,4- triRuorobutyl -2- base of 1-) imidazoline -2- base alkenyl) -2- nitro-ethyl) phenyl The synthesis of pyridine (compound IB-13):

(1) conjunction of 1- (the bromo- 4,4,4- triRuorobutyl -2- base of 1-) -2- (nitroethenyl group) imidazoline (compound IX-13) At

Divided by the bromo- 3- of 4- chloro- 1, other than 1,1- trifluorobutane replaces the chloro- 3- chloromethylpyridine of 6- as raw material, Qi Tabu Suddenly identical as step (1) in embodiment 5, obtain compound IX -13.

(2) 3- (3- (2- (1- (the bromo- 4,4,4- triRuorobutyl -2- base of 1-) imidazoline -2- base alkenyl) -2- nitro-ethyl) The synthesis of phenylpyridine (compound IB-13)

4- (pyridin-3-yl) benzaldehyde of 0.915g (0.005mol) is dissolved in methylene chloride, then instills and is equipped with dropwise 1- (bromo- 4,4,4- triRuorobutyl -2- base of 1-) -2- (nitroethenyl group) imidazoline of (1.58g 0.005mol), 30mL's is anhydrous Acetonitrile, in the round-bottomed flask of the 50ml of the HCl of catalytic amount.It is stirred under room temperature, there is a large amount of bright yellow solid to analyse after about 4h Out, stop reaction, filtering.The solid that will be obtained by filtration, 25mL methanol, the round bottom that the sodium borohydride of 2 times of equivalents is placed in 50ml are burnt In bottle.It is stirred under room temperature, TLC plate tracks reaction process, the R of product_f=0.25 (methylene chloride: acetone=7:1).Wait react After, solvent is spin-dried for, glutinous shape object methylene chloride and water extraction is remained three times, takes dichloromethane layer, NaCl saturated solution Washing three times, uses Na₂SO₄It is dried overnight.Filtering, takes filtrate, is spin-dried for solvent, obtain crude product, recrystallize to obtain chemical combination with ethyl alcohol The sterling of object IB-13 is white solid 1.626g, yield about 67%.¹H 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, J₁=8.4Hz, J₂= 5.4Hz,2H),7.47–7.40 (m,3H),7.29–7.23(m,2H),7.01(dd,J₁=5.6Hz, J₂=8.4Hz, 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.¹³C 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, 104.49,51.36,47.81,45.74,41.33,37.27,33.19,23.84ppm. HRMS(ES+)C₂₀H₂₀N₄O₂F₃ ⁷⁹Br(M +H)⁺, calculated value: 484.0072；Measured value 484.0078；C₂₀H₂₀N₄O₂ F₃ ⁸¹Br(M+H)⁺, calculated value: 486.0701；Actual measurement Value: 486.0702.

According to the introduction of Examples 1 to 4 and embodiment 5~16, those skilled in the art are not necessarily to creative work, can also make Compound listed by standby Tables 1 and 2, specific steps no longer repeat one by one.

Table 1 (compound shown in I A of formula)

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Table 2 (compound shown in I B of formula)

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Embodiment 17

The insecticidal activity of the compounds of this invention is tested

(1) to the insecticidal activity of aphid

Aphid belongs to homoptera pest, has sucking mouth parts, is a kind of common crop pests.With bean aphid (Aphis Cracivora it is) test object, is tested using infusion process.

Operating process: the various samples of precise are separately added into n,N-Dimethylformamide and are configured to 10g/L mother liquor, real The concentration of 500ppm is diluted to when testing with the aqueous solution of the X-100 of Triton containing 0.2mL/L.To aptery adult aphid in bean sprouts After upper stabilization is sucked, immerses in the medical fluid that concentration is 500ppm, taken out after 5s, it is extra to be sucked with blotting paper together with bean sprouts Medical fluid moves into clean vessel in 23Temperature raising.Every concentration sets 3 repetitions, and control group is the X- of Triton containing 0.2mL/L 100 aqueous solution.After processing 24 hours, the dead borer population of statistics examination aphid, and the death rate (%) is calculated according to formula: the death rate (%)=(compareing borer population-processing living borer population living)/compares borer population × 100% living.As a result it see the table below.

(2) to the insecticidal activity of mythimna separata

Mythimna separata belongs to lepidoptera pest, has biting mouthparts, is a kind of common crop pests.With oriental armyworm (Mythimna separata) is test object, is tested using immersion liquid feeding method.

Operating method: untested compound is accurately configured to 500ppm solution as solution using acetone, and with aqueous acetone solution Blank control is made in processing.Fresh corn blade is impregnated 3 seconds in the solution, is then dried at room temperature, for test worm feeding, 24 The death rate (%) (formula is same as above) of test worm is checked and calculated after hour.Every group uses 10 test worms, if 3 repetitions.As a result it sees below Table.

(3) to the insecticidal activity of nematode

Root-knot nematode belongs to Nematoda, Tylenchida (Tylenchida), pad sword suborder, different skin Superfamily, Heteroderidae (Heteroderidea), root-knot nematode subfamily (Meloidogyninae), Meloidogyne are a kind of serious plants of harm Parasitic nematode.

With Meloidogyne incognita (Meloidogyne incongnita) be test object, with cucumber seedling be for try host, It is tested using test tube planting method.

Operating process: will be made into that medical fluid is stand-by to test agent by required concentration, and get out enough two ages of root-knot nematode Larva.After the cucumber seedling of one week old is planted into test tube, it is added the medical fluid prepared in right amount into test tube, and to every test tube About 2000 larvas of middle access.Test tube is placed in 20~25 DEG C, cultivates under 10h illumination, investigation result after 20d, counts every plant of plant Root knot number on root system.Each sample repeats test 3 times, tests each sample every time and does 4 reprocessings.

Using distilled water as blank control, distilled water adds root-knot nematode to be negative control, with fenamiphos and abamectin solution For positive control.

(classification Score Lists are shown in Table 3), statistics inhibiting rate are classified by root knot quantity.Statistical result see the table below 4.

Inhibiting rate (%)=(negative control goals for-test group goals for)/negative control goals for × 100%

Table 3

Table 4

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Claims (14)

1. a kind of nitrogen-containing heterocycle compound, which is characterized in that the nitrogen-containing heterocycle compound be Formulas I shown in compound or its Acceptable salt in Pesticide Science:

In Formulas I, R₁It is: the methyl or ethyl of H, fluorine or chloro, phenyl, chlorophenyl, tetrahydrofuran base, chloro-thiazole base or pyrrole Piperidinyl, trifluoroacetyl group orR₇For the methyl of fluoro, X NH；

R₂For H, halogen, C₁~C₃Alkyl, halogenated C₁~C₃Alkyl or C₁~C₃Alkoxy；

R₃And R₄It is respectively and independently selected from: C₁~C₄Alkyl or halogenated C₁~C₄It is a kind of in alkyl；

R₅And R₆It is respectively and independently selected from: H, C₁~C₄Alkyl, halogenated C₁~C₄Alkyl or C₁~C₃Containing a kind of in oxyalkyl；

Y is: nitro, cyano, trifluoroacetyl group or trifluoromethyl sulfonyl；

Z is: furyl, thienyl, pyrrole radicals, oxazolyl, thiazolyl, pyridyl group, substituted furyl, thienyl, pyrrole radicals, Oxazolyl, thiazolyl or pyridyl group, phenyl, substituted-phenyl,

The substituted furyl, thienyl, pyrrole radicals, oxazolyl, thiazolyl or pyridyl group substituent group be selected from: methyl, second Base, methoxyl group, phenyl, Cl, NO₂, CN, or by a kind of in the phenyl or pyridyl group of the substitution of methoxyl group, trifluoromethyl or acetyl group Or two kinds or more；

The substituent group of the substituted-phenyl is selected from: methyl, methoxyl group, phenyl, pyridyl group, the pyridyl group replaced by trifluoromethyl, By methyl substituted furyl, or by one or two or more kinds of in methyl and the pyrrole radicals of acetyl group substitution.

2. nitrogen-containing heterocycle compound as described in claim 1, which is characterized in that wherein R₁It is: H, CH₂Cl, CH₂CF₃, trifluoro second Acyl group,

3. nitrogen-containing heterocycle compound as described in claim 1, which is characterized in that wherein R₂It is: H, halogen, C₁~C₃Alkyl, halogen The C in generation₁~C₃Alkyl or C₁~C₃Alkoxy.

4. nitrogen-containing heterocycle compound as claimed in claim 3, which is characterized in that wherein R₂It is: H, Cl, allyl, fluorine or chloro C₁~C₃Alkyl or C₁~C₃Alkoxy.

5. nitrogen-containing heterocycle compound as claimed in claim 4, which is characterized in that wherein R₂It is: H, CH₂F, CH₂CF₃, allyl Or Cl.

6. nitrogen-containing heterocycle compound as described in claim 1, which is characterized in that wherein R₃And R₄It is respectively and independently selected from: C₁~C₄ Alkyl or halogenated C₁~C₄It is a kind of in alkyl.

7. nitrogen-containing heterocycle compound as claimed in claim 6, which is characterized in that wherein R₃And R₄It is respectively and independently selected from: C₁~C₄ The C of alkyl or fluorine or chloro₁~C₄It is a kind of in alkyl.

8. nitrogen-containing heterocycle compound as claimed in claim 7, which is characterized in that wherein R₃And R₄It is respectively and independently selected from: CH₃, CH₂Cl, CH₂F, CH₂CH₃, CH₂CF₃, CH₂CH₂Cl, (CH₃)₃It is a kind of in C or allyl.

9. nitrogen-containing heterocycle compound as described in claim 1, which is characterized in that wherein R₅And R₆It is respectively and independently selected from: H, C₁~ C₄Alkyl or halogenated C₁~C₄It is a kind of in alkyl.

10. nitrogen-containing heterocycle compound as claimed in claim 9, which is characterized in that wherein R₅And R₆It is respectively and independently selected from: H, C₁ ~C₄The C of alkyl or fluorine or chloro₁~C₄It is a kind of in alkyl.

11. nitrogen-containing heterocycle compound as claimed in claim 10, which is characterized in that wherein R₅And R₆It is respectively and independently selected from: H, CH₃, CH₂Cl, CH₂F, CH₂CH₃, CH₂CH₂It is a kind of in Cl or allyl.

12. nitrogen-containing heterocycle compound as described in claim 1, which is characterized in that the wherein substituted furyl, thiophene Base, pyrrole radicals, oxazolyl, thiazolyl or pyridyl group substituent group be selected from: methyl, ethyl, methoxyl group, Cl, NO₂, CN, phenyl,Middle one or two or more kinds.

13. nitrogen-containing heterocycle compound as described in claim 1, which is characterized in that the wherein substituent group choosing of the substituted-phenyl From: methyl, methoxyl group, phenyl,Middle one or two or more kinds.

14. nitrogen-containing heterocycle compound is aphid, mythimna separata or nematode are killed in preparation as described in any one of claim 1~13 Application in insecticide.