CN105669660A

CN105669660A - Nitrogenous heterocyclic compound and use thereof

Info

Publication number: CN105669660A
Application number: CN201410667486.4A
Authority: CN
Inventors: 李忠; 徐晓勇; 袁自豪; 陆思源; 邵旭升; 须志平
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Priority date: 2014-11-20
Filing date: 2014-11-20
Publication date: 2016-06-15
Anticipated expiration: 2034-11-20
Also published as: CN105669660B

Abstract

The invention relates to a nitrogenous heterocyclic compound with a novel structure and use thereof. The nitrogenous heterocyclic compound is a compound represented by a formula I (shown in the description) or a salt thereof acceptable in pesticide science. The nitrogenous heterocyclic compound provided by the invention can serve as a pesticide. Compared with the existing pesticides, the pesticide provided by the invention has the advantages that the chemical stability is better, and meanwhile, the killing activity to resistant insects is better.

Description

Nitrogen-containing heterocycle compound and purposes thereof

Technical field

The present invention relates to the nitrogen heterocyclic ring compounds of a kind of novel structure and purposes thereof.

Technical background

In recent years, anabasine insecticide has become an insecticides with fastest developing speed in modern Crop protection. Taking Provado as the anabasine insecticide insecticidal activity height of representative, insecticidal spectrum is wide, and Mammals and hydrocoles toxicity is low, and has good interior absorption and certain field stability and environment friendly, does not have cross resistance with tradition agricultural chemicals. Anabasine insecticide acts primarily on the nAChR (nAChRs) of insect and plays a role. The discovery of anabasine insecticide is a milestone of modern agricultural chemicals development.

After Provado lists, has there is again the kind of the high reactivity such as thiacloprid, clothianidin, Diacloden, acetamiprid, Ti304, MTI-446, piperazine worm pyridine, epoxy insect pyridine, fluorine pyridine worm amine nitrile, high sales volume in neonicotine field, prevents and treats sucking pest to peasant and provides favourable " weapon ".

But, along with popularizing of anabasine insecticide, has also there is serious resistance problem in it. Meanwhile, due to the cross resistance between the neonicotinoid insecticide that structural similarity is brought, limit the use of this compounds to a certain extent, become the major issue of restriction neonicotinoid insecticide. Meanwhile, anabasine insecticide mainly prevents and treats the insect of Homoptera and Coleoptera, and lepidoptera pest is presented low activity, and the restriction on insecticidal spectrum also hinders it better to develop.

, it is necessary to by constantly formulating product innovation, thus expand the selection storehouse of agricultural chemicals, excite the vigor of neonicotinoid insecticide, deal with natural test by constantly bringing forth new ideas. Specifically, being exactly how the Nitromethylene compounds of activity is carried out structure of modification, to produce new, more effective sterilant, solve anabasine insecticide facing challenges, this is also the technical issues that need to address of the present invention.

Summary of the invention

The existing Nitromethylene compounds with activity is carried out structure of modification by the present invention, has designed and synthesized the nitrogen heterocyclic ring compounds of a class formation novelty. Through insecticidal activity test, nitrogen heterocyclic ring compounds provided by the invention has stronger insecticidal activity. Compared with existing sterilant, its chemical stability is better.

The present invention's object is, it is provided that the nitrogen heterocyclic ring compounds of a kind of novel structure, and described nitrogen heterocyclic ring compounds is compound shown in formula I, or its acceptable salt in Pesticide Science:

In formula I, R₁For hydrogen (H), C₁～C₃Alkyl, the C in halogen (F, Cl, Br or I, lower same) generation₁～C₃Alkyl, phenyl, halogenophenyl, 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in halogen generation, trifluoroacetyl base,Or(curve mark is for replacing position, lower same);

Wherein, R₇It is 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in halogen generation or the C in halogen generation₁～C₃Alkyl, X is O or NR₉, R₈Being 5～6 yuan of heterocyclic radicals in 5～6 yuan of heterocyclic radicals or halogen generation, Y is CH₂Or NH, n is 0 or 1;

The heteroatoms of described 5～6 yuan of heterocyclic radicals is selected from: a kind of or two kinds in N, O or S, R₉For H, C₁～C₃The C in alkyl or halogen generation₁～C₃Alkyl;

R₂For H, halogen (F, Cl, Br or I, lower same), C₁～C₃Alkyl, the C in halogen generation₁～C₃Alkyl or C₁～C₃Alkoxyl group;

R₃And R₄Independently it is selected from: C₁～C₄The C in alkyl or halogen generation₁～C₄One in alkyl; Or,

R₃And R₄Combination (be abbreviated as " R₃+R₄") and form with the nitrogen (N) being connected separately: 5～7 yuan containing 5～7 yuan of N heterocycle or replacement contain N heterocycle;

Wherein, the substituting group containing N heterocycle of 5～7 yuan of described replacement is selected from: methyl, trifluoromethyl, monovalent phenyl radical, CH₃OCH₂, divalence cyclohexyl, the divalence cyclohexyl replaced by trifluoromethyl, divalence phenyl, or by a kind of in the phenyl of trifluoromethyl or the divalence of methoxy substitution;

Illustrate: described divalence cyclohexyl, the divalence cyclohexyl replaced by trifluoromethyl, divalence phenyl, or by the phenyl of trifluoromethyl or the divalence of methoxy substitution replace described 5～7 yuan containing after N heterocycle, its with 5～7 yuan contain N heterocycle be " and " relation;

R₅And R₆Independently it is selected from: H, C₁～C₄Alkyl, the C in halogen generation₁～C₄Alkyl or C₁～C₃Containing a kind of in oxygen alkyl;

Y is electron-withdrawing group, such as (but being not limited to): nitro (NO₂), cyano group (CN), trifluoroacetyl baseOr trifluoromethyl sulfonyl

Z is 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals of replacement, pyridine, pyrimidine, oil of mirbane or benzo 5 yuan of heterocyclic radicals, phenyl or substituted-phenyl;

The heteroatoms of described heterocyclic radical is selected from: a kind of or two kinds in O, S or N, heteroatoms number is 1 or 2;

The substituting group of 5～6 yuan of heterocyclic radicals of described replacement is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, NO₂, CN, phenyl, by methyl, methoxyl group, trifluoromethyl, amino (NH₂)、NO₂, halogen, ethanoylMethyl sulphonylOrThe phenyl replaced, by methoxyl group, trifluoromethyl, halogen, NO₂Or the pyridyl that CN replaces, pyrimidyl, by methyl substituted pyrimidyl, by methyl substituted methylpyrrole base, thienyl, or in the furyl replaced by trifluoromethyl one or two or more kinds (containing two kinds);

The substituting group of described substituted-phenyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, CN, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, furyl, by methyl or/and the furyl that replaces of trifluoromethyl, in pyrryl or the pyrryl that replaces by methyl and ethanoyl one or two or more kinds (containing two kinds).

Another object of the present invention is, discloses above-mentioned nitrogen heterocyclic ring compounds a kind of purposes, i.e. compound shown in formula I, or its in Pesticide Science acceptable salt as the application of sterilant.

Embodiment

In the present invention's preferred technical scheme, nitrogen heterocyclic ring compounds of the present invention is compound shown in formula I A, or its acceptable salt in Pesticide Science:

In formula I A, R₁For H, the C in halogen generation₁～C₃Alkyl, phenyl, halogenophenyl, 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in halogen generation, trifluoroacetyl base or

Wherein, the heteroatoms of described 5～6 yuan of heterocyclic radicals is selected from: a kind of or two kinds in N, O or S, heteroatoms number is 1 or 2;R₇For the C in halogen generation₁～C₃Alkyl, X is NR₉, R₉For H, C₁～C₃The C in alkyl or halogen generation₁～C₃Alkyl;

R₂For H, halogen, C₁～C₃Alkyl, the C in halogen generation₁～C₃Alkyl or C₁～C₃Alkoxyl group;

R_3aAnd R_4aIndependently it is selected from: C₁～C₄The C in alkyl or halogen generation₁～C₄One in alkyl;

R₅And R₆Independently it is selected from: H, C₁～C₄The C in alkyl or halogen generation₁～C₄One in alkyl;

Y is NO₂, CN,Or

Z is 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals of replacement, oil of mirbane or benzo 5 yuan of heterocyclic radicals, phenyl or substituted-phenyl;

The heteroatoms of described 5～6 yuan of heterocyclic radicals is selected from: a kind of or two kinds in O, S or N, heteroatoms number is 1 or 2;

The substituting group of 5～6 yuan of heterocyclic radicals of described replacement is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, NO₂, CN, phenyl, by methoxyl group, trifluoromethyl or ethanoylReplace phenyl or pyridyl in one or two or more kinds (containing two kinds);

The substituting group of described substituted-phenyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, furyl, by methyl substituted furyl, or in the pyrryl replaced by methyl and ethanoyl one or two or more kinds (containing two kinds).

Preferred R further₁It is: H, the C in fluorine or chlorine generation₁～C₃Alkyl, phenyl, chlorophenyl, 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in chlorine generation, trifluoroacetyl base or

Wherein, the heteroatoms of described 5～6 yuan of heterocyclic radicals is selected from: a kind of or two kinds in N, O or S, heteroatoms number is 1 or 2; R₇For the C of fluoro₁～C₃Alkyl, X is NH;

Further preferred R₁Be: H, the methyl in fluorine or chlorine generation or ethyl, phenyl, chlorophenyl, 5 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in chlorine generation, trifluoroacetyl base or

Wherein, the heteroatoms of described heterocyclic radical is selected from: a kind of or two kinds in N, O or S, heteroatoms number is 1 or 2; R₇For the C of fluoro₁～C₃Alkyl, X is NH;

Further preferred R again₁Be: H, the methyl in fluorine or chlorine generation or ethyl, phenyl, chlorophenyl, tetrahydrofuran base, chlorine for thiazolyl or pyridyl, trifluoroacetyl base or

Wherein, R₇For the methyl of fluoro, X is NH;

Best R₁It is: H, CH₂Cl, CH₂CF₃, trifluoroacetyl base, Or

Preferred R further₂It is: H, halogen, C₁～C₃Alkyl, the C in halogen generation₁～C₃Alkyl or C₁～C₃Alkoxyl group;

Further preferred R₂It is: H, Cl,(allyl group), the C in fluorine or chlorine generation₁～C₃Alkyl or C₁～C₃Alkoxyl group;

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

Preferred R further_3aAnd R_4aIndependently it is selected from: C₁～C₄The C in alkyl or halogen generation₁～C₄One in alkyl;

Further preferred R_3aAnd R_4aIndependently it is selected from: C₁～C₄Alkyl, or the C in fluorine or chlorine generation₁～C₄One in alkyl;

Best R_3aAnd R_4aIndependently it is selected from: CH₃, CH₂Cl, CH₂F, CH₂CH₃, CH₂CF₃, CH₂CH₂Cl, (CH₃)₃In C or allyl group a kind of.

Preferred R further₅And R₆Independently it is selected from: H, C₁～C₄The C in alkyl or halogen generation₁～C₄One in alkyl;

Further preferred R₅And R₆Independently it is selected from: H, C₁～C₄Alkyl, or the C in fluorine or chlorine generation₁～C₄One in alkyl;

Best R₅And R₆Independently it is selected from: H, CH₃, CH₂Cl, CH₂F, CH₂CH₃, CH₂CH₂In Cl or allyl group a kind of.

Further preferred Z is: furyl, thienyl, pyrryl, azoles base, thiazolyl, pyridyl, the furyl of replacement, thienyl, pyrryl, azoles base, thiazolyl or pyridyl, oil of mirbane or benzothienyl, phenyl or substituted-phenyl;

The substituting group of the furyl of described replacement, thienyl, pyrryl, azoles base, thiazolyl or pyridyl is selected from: methyl, ethyl, methoxyl group, phenyl, Cl, NO₂, CN, or by the phenyl of methoxyl group, trifluoromethyl or ethanoyl replacement or pyridyl one or two or more kinds (containing two kinds);

The substituting group of described substituted-phenyl is selected from: methyl, methoxyl group, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, by methyl substituted furyl, or in the pyrryl replaced by methyl and ethanoyl one or two or more kinds (containing two kinds);

The substituting group of the furyl of described replacement, thienyl, pyrryl, azoles base, thiazolyl or pyridyl is selected from: methyl, ethyl, methoxyl group, Cl, NO₂, CN, phenyl,OrIn one or two or more kinds (containing two kinds);

The substituting group of described substituted-phenyl is selected from: methyl, methoxyl group, phenyl,OrIn one or two or more kinds (containing two kinds);

Described oil of mirbane or benzothienyl be:Or

In another preferred technical scheme of the present invention, nitrogen heterocyclic ring compounds of the present invention is compound shown in formula I B, or its acceptable salt in Pesticide Science:

In formula I B, R₁For H, halogen, C₁～C₃Alkyl, the C in halogen generation₁～C₃Alkyl, phenyl, halogenophenyl, trifluoroacetyl base, 5～6 yuan of heterocyclic radicals, by 5～6 yuan of heterocyclic radicals of trifluoromethyl or halogen generation,Or

Wherein, R₇It is 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in halogen generation or the C in halogen generation₁～C₃Alkyl, X is O or NR₉, R₈Being 5～6 yuan of heterocyclic radicals in 5～6 yuan of heterocyclic radicals, halogen generation, Y is CH₂Or NH, n is 0 or 1;

The heteroatoms of described 5～6 yuan of heterocyclic radicals is selected from: in N, O or S a kind of or two kinds, heteroatoms number be 1 or 2, R₉For H, C₁～C₃The C in alkyl or halogen generation₁～C₃Alkyl;

R₂For H, C₁～C₃The C in alkyl or halogen generation₁～C₃Alkyl;

R_3bAnd R_4bCombination (be abbreviated as " R_3b+R_4b") and form with the N being connected separately: 5～7 yuan containing N heterocycle; 5～7 yuan of replacement containing N heterocycle; or by the cycloalkyl of cycloalkyl, phenyl, replacement or phenyl " and " 5～7 yuan contain N heterocycle (in formula I B, A ring, is abbreviated as " A ");

That is: A be 5～7 yuan containing N heterocycle, 5～7 yuan of replacement containing N heterocycle, or by the cycloalkyl of cycloalkyl, phenyl, replacement or phenyl " and " 5～7 yuan containing N heterocycle;

Wherein, being selected from containing the substituting group of N heterocycle of 5～7 yuan of described replacement: methyl, trifluoromethyl, phenyl orMiddle one or two kinds, substituting group number is 1 or 2;

The cycloalkyl of described replacement or the substituting group of phenyl are selected from: a kind of or two kinds in methyl, methoxyl group or trifluoromethyl, substituting group number is 1 or 2;

Y is NO₂, CN,Or

Z is 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals of replacement, pyridine, pyrimidine or benzo 5 yuan of heterocyclic radicals, phenyl or substituted-phenyl;

The substituting group of 5～6 yuan of heterocyclic radicals of described replacement is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, NO₂, CN, phenyl, by methyl, methoxyl group, trifluoromethyl, amino (NH₂)、NO₂, halogen, ethanoylMethyl sulphonylOrThe phenyl replaced, by methoxyl group, trifluoromethyl, halogen, NO₂Or the pyridyl that CN replaces, pyrimidyl, by methyl substituted pyrimidyl, by methyl substituted methylpyrrole base, in thienyl or the furyl that replaces by trifluoromethyl one or two or more kinds (containing two kinds);

The substituting group of described substituted-phenyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, CN, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, furyl, by methyl or/and the furyl that replaces of trifluoromethyl, pyrryl, or in the pyrryl replaced by methyl and ethanoyl one or two or more kinds (containing two kinds).

Preferred R further₁It is: H, Br, C₁～C₃Alkyl, the C in halogen generation₁～C₃Alkyl, trifluoroacetyl base, phenyl, chlorophenyl, 5～6 yuan of heterocyclic radicals, by 5～6 yuan of heterocyclic radicals of trifluoromethyl or chlorine generation,Or

Wherein, R₇It is the C of 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in chlorine generation or fluoro₁～C₃Alkyl, X is O or NR₉, R₈Being 5～6 yuan of heterocyclic radicals in 5～6 yuan of heterocyclic radicals or chlorine generation, Y is CH₂Or NH, n is 0 or 1;

Further preferred R₁It is: H, Br, n-propyl, the C of chlorine or fluoro₁～C₃Alkyl, trifluoroacetyl base, phenyl, chlorophenyl, tetrahydrofuran base, by trifluoromethyl or the pyridyl in chlorine generation, thienyl or thiazolyl,Or

Wherein, R₇For trifluoromethyl, tetrahydrofuran base, chlorine are for thiazolyl or chloro-pyridine base, X is O or NR₉, R₈For tetrahydrofuran base, chlorine are for thiazolyl or chloro-pyridine base, Y is CH₂Or NH, n is 0 or 1; R₉For H, methyl or trifluoroethyl;

Best R₁It is: H, trifluoroacetyl base,CH₂Cl, CH₂CF₃,Br,

Preferred R further₂It is: H, C₁～C₃The C in alkyl or halogen generation₁～C₃Alkyl;

Further preferred R₂It is: H, C₁～C₃Alkyl, or the C of fluorine or chlorine₁～C₃Alkyl;

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

Further preferred A be 5～7 yuan containing N heterocycle, 5～7 yuan of replacement containing N heterocycle, or by the cycloalkyl of cycloalkyl, phenyl, replacement or phenyl " and " 5～7 yuan containing N heterocycle; That is, R_3b+R_4bFor a kind of in following groups:

Wherein, m is 0,1 or 2, R₁₀Or R₁₁Independently be selected from: H, methyl, trifluoromethyl, phenyl orMiddle one; Or, R₁₀And R₁₁Combination (be abbreviated as " R₁₀+R₁₁") it is the cycloalkyl of replacement of divalence or phenyl;

The cycloalkyl of the replacement of described divalence or the substituting group of phenyl are selected from: a kind of or two kinds in methyl, methoxyl group or trifluoromethyl, substituting group number is 1 or 2;

Further preferred R_3b+R_4bFor a kind of in following groups:

Wherein, m is 0,1 or 2.

Preferred R further₅And R₆Independently it is selected from: H, C₁～C₄Alkenyl, C₁～C₄The alkyl of straight or branched, the C in halogen generation₁～C₄The alkyl of straight or branched or C₁～C₃Containing a kind of in oxygen alkyl;

Further preferred R₅And R₆Independently it is selected from: a kind of in following groups:

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

Preferably Z is furyl further, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl, pyridyl, furyl, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl or the pyridyl replaced, by the furyl of pyridine, pyrimidine or benzo or thienyl, phenyl or substituted-phenyl;

The substituting group of the furyl of described replacement, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl or pyridyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, NO₂, CN, phenyl, by methyl, methoxyl group, trifluoromethyl, amino (NH₂)、NO₂, halogen, ethanoylMethyl sulphonylOrThe phenyl replaced, by methoxyl group, trifluoromethyl, halogen, NO₂Or the pyridyl that CN replaces, by methyl substituted pyrimidyl, by methyl substituted methylpyrrole base, in thienyl or the furyl that replaces by trifluoromethyl one or two or more kinds (containing two kinds);

The substituting group of described substituted-phenyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, CN, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, by methyl substituted furyl, or in the pyrryl replaced by methyl and ethanoyl one or two or more kinds (containing two kinds);

Further preferably Z is: Phenyl, substituted-phenyl, or the furyl replaced, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl or pyridyl;

Wherein, the substituting group of described substituted-phenyl be selected from one or two or more kinds (containing two kinds):

Methyl, methoxyl group, phenyl, F, CN,

The substituting group of the furyl of described replacement, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl or pyridyl is selected from following groups one or two or more kinds (containing two kinds):

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

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

Or (for A as 5～7 yuan containing N heterocycle)

Wherein, n is 1,2 or 3, and definition and the front literary composition of other substituting group are described identical.

Specifically comprise the steps:

(1) at aminated compounds (R_3aNH₂) aqueous solution adds appropriate acetonitrile, drip under ice bath and add compound shown in formula II and (be abbreviated as compound ii, acetonitrile lysate down together), TLC follows the tracks of reaction process, after reaction terminates, a large amount of water is added in reaction mixture, dichloromethane extraction, dry, take out filter, boil off solvent, obtain compound III;

(2) compound III and 1,1-bis-thiomethyl-2-Y substituted ethylene, with ethanol as solvent, backflow 4 is little of 8 hours, and concentrated, column chromatography for separation obtains product compound IV;

(3) under condition of ice bath, compound IV and aminated compounds (R_4aR₆NH) reacting 4 in fatty alcohol (reaction medium) little of 8 hours, concentration response product, column chromatography for separation obtains compound V;

(4) first, under acid (example hydrochloric acid, sulfuric acid or heteropolyacid etc.) catalytic condition, compound V and the reaction of corresponding aldehyde, obtain compound VI; More in the basic conditions, then, obtain chemical compounds I A by compound VI through reduction reaction (go back original reagent can with sodium borohydride etc.).

Or,

(1) by the acetonitrile solution dropwise of compound ii in diamines (compound VII) solution of 5-10 times of molar weight, at 0-50, DEG C reaction 5-10 hour. Decompression with acetic acid ethyl dissolution, is spin-dried for solvent, obtains compound VIII after removing unreacted compound VII;

(2) compound VIII and 1,1-bis-thiomethyl-2-Y substituted ethylene, with ethanol as solvent, backflow 4-8 hour, obtains compound Ⅸ;

(3) first, under acid (example hydrochloric acid, sulfuric acid or heteropolyacid etc.) catalytic condition, compound Ⅸ and the reaction of corresponding aldehyde, obtain compound Ⅹ; More in the basic conditions, then, obtain chemical compounds I B by compound Ⅹ through reduction reaction (go back original reagent can with sodium borohydride etc.);

The insecticidal activity of active substance of the present invention

Term " active substance of the present invention " or " active compound of the present invention " refer to acceptable salt in the compounds of this invention, its optical isomer, cis-trans-isomer or Pesticide Science, and it has the insecticidal activity significantly improved, and the insecticidal spectrum expanded.

The negatively charged ion that term " in Pesticide Science acceptable salt " means this salt when forming sterilant pharmacy acceptable salt be understood with acceptable. This salt is water-soluble preferably, such as hydrochloride, phosphoric acid salt, vitriol, nitrate; Comprise the salt that organic acid is formed, such as acetate or benzoate etc.

The actives mass-energy of the present invention is used as control and eliminates the insect of agriculture and forestry plant insect, storage cereal widely, garden pest and public health insect etc.In this manual, " sterilant " refers to the general designation of the material with the effect preventing and treating the above-mentioned all insects mentioned. the example of insect includes but not limited to: coleopteron: sitophilus zea-mais (Sitophiluszeamais), red flour beetle (Triboliumcastaneum), potato bug (Henosepilachnavigintioctomaculata), potato ladybug (Henosepilachnasparsa), agriotes fussicollis (Agriotesfuscicollis), red pin green gold tortoise (Anomalacupripes), beautiful tortoise with four lines (Popilliaquadriguttata), colorado potato beetles (Monoleptahieroglyphica), ponderous borer (Monochamusalternatus), rice root weevil (Echinocnemussquameus), paulownia chrysomelid (Basiprionotabisignata), longicorn beetle (Anoplophorachinensis), mulberry borer (Apriponagermari), the little moth of navel abdomen (Scolytusschevy), or thin chest wireworm (Agriotesfuscicollis). lepidopterous insects: gypsymoth (Lymantriadispar), tent caterpillar (Malacosomaneustriatestacea), the wild snout moth's larva (Diaphaniaperspectalis) of Chinese littleleaf box thin,tough silk, Clania variegata Snellen (Claniavariegata), cnidocampa flavescens walker (Cnidocampaflauescens), dendrolimus punctatus (Dendrolimuspunctatus), orgyia antiqua (Orgyiagonostigma), white poplar clearwing moth (Paranthrenetabaniformis), prodenia litura (Spodopteralitura), striped rice borer (Chilosuppressalis), Pyrausta nubilalis (Hubern). (Ostrinianubilalis), meal moth (Ephestiacautella), lap moth (Adoxophyesorana), chestnut steinernema (Laspyresiasplendana), black cutworm (Agrotisfucosa), greater wax moth (Galleriamellonella), dish moth (Plutellaxylostella), tangerine lyonetid (Phyllocnistiscitrella), or oriental armyworm (Mythimnaseparata). Homoptera insect: rice green leafhopper (Nephotettixcincticeps), Nilaparvata lugen (brown planthopper) (Nilaparvatalugens), Kang Shi mealybug (Pseudococcuscomstocki), arrowhead scales (Unaspisyanonensis), black peach aphid (Myzuspersicae), cotten aphid (Aphisgossydii), radish aphid (Lipaphiserysimipseudobrassicae), pears class lace bug (Stephanitisnashi), or aleyrodid (Bemisiatabaci). orthopteran: Groton bug (Blattellagermanica), the big Lian of the U.S. (Periplanetaamerican), African mole cricket (Gryllotalpaafricana), or Asiatic migratory locust (Locusmigratoria). isoptera insect: S.invicta Buren (Solenopsisinvicta), or Coptotermes formosanus Shtrari． (Coptotermesformosanus). dipteral insect: housefly (Muscadomestica), Aedes aegypti (Aedesaegypti), plant fly (Deliaplatura), culex (Culexsp.), or Anopheles sinensis (Anophelessinensis). root knot nematode, such as peanut root-knot nematode (Meloidogynearenaria), Qi Shi root knot nematode (Meloidogynechitwoodi), short and small root knot nematode (Meloidogyneexigua), M hapla (Meloidogynehapla), Meloidogyne incognita (Meloidogyneincognita), javanese root knot nematode (Meloidogynejavanica), and other Meloidogyne (Meloidogyne),Cyst roundworm, such as globodera rostochiensis (Globoderarostochiensis), G.pallida (Globoderapallida), tobacco cyst roundworm (Globoderatabacum), and other cyst roundworm genus (Globodera); Golden nematode, such as cereal cyst nematode (Heteroderaavenae), soy bean cyst roundworm (Heteroderaglycines), beet cyst roundworm (Heteroderaschachtii), trifolium cyst roundworm (Heteroderatrifolii), and other Heterodera (Heterodera); Plant knurl nematode, as shear retention factor (Anguinafunesta), wheat anguina (Anguinatritici) and other nematode belong to (Anguina); Stem and leaf bud nematode, such as aphelenchoides besseyi (Aphelenchoidesbesseyi), strawberry aphelenchoides (Aphelenchoidesfragariae), chrysanthemum aphelenchoides (Aphelenchoidesritzemabosi) and other Aphelenchoides (Aphelenchoides); Thorn nematode, stings nematode (Belonolaimuslongicaudatus) such as weeds and other acupuncture nematode belongs to (Belonolaimus); Pine nematode, such as pine wood nematode (Bursaphelenchusxylophilus) and other Bursaphelenchus (Bursaphelenchus); Annular nematode, belongs to (Mesocriconema) as ring grain nematode belongs to (Criconema), little loop wire worm genus (Criconemella), Criconemoides (Criconemoides) and Middle Ring Line worm; Bulb nematode, such as rot stem nematodes (Ditylenchusdestructor), sweet potato stem nematode (Ditylenchusdipsaci), mushroom stalk nematode (Ditylenchusmyceliophagus) and other Ditylenchus (Ditylenchus); Cone nematode, as cone nematode belongs to (Dolichodorus); Helicotylenchus, as Spiral namatodes (Helicotylenchusdihystera), Pratylenchus penetrans (Helicotylenchusmulticintus) and other helicotylenchus belong to (Helicotylenchus); Sheath nematode, as sheath nematode belongs to (Hemicycliophora) and half Criconemoides (Hemicriconemoides); Hat nematode, as Colombia tie nematode (Hoploaimuscolumbus) and other tie nematode belong to (Hoploaimus); Pseudo-root nodule nematode, as abnormal pearl nematode (Nacobbusaberrans) and other pearl nematode belong to (Nacobbus); Needlework worm, as ease goes minute hand nematode (Longidoruselongatus) and other minute hand nematode to belong to (Longidorus); Nail nematode, as nail nematode belongs to (Paratylenchus); Pratylenchus, as most short-tail Pratylenchidae (Pratylenchusbrachyurus), coffee pot handle (Pratylenchuscoffee), corn lesion nematode (Pratylenchuszeae), Cobb root (Pratylenchuspenetrans) and other Pratylenchidae belong to (Pratylenchus); Similes thorne, as radopholus similes thorne (Radopholussimilis) and other similes thorne belong to (Radopholus); Kidney shape nematode, as Rotylenchulus reniformis (Rotylenchusrobustus) and other kidney shape nematode belong to (Rotylenchus); Undesirable root nematode, as original burr nematode (Trichodorusprimitivus) and other burr nematodes belong to (Trichodorus); Downgrade nematode, as Ke Laidun downgrades nematode (Tylenchorhynchusclaytoni), indefinite dwarfing nematode (Tylenchorhynchusdubius) and other Tylenchorhynchus (Tylenchorhynchus);Citrus nematode, as citrus Tylenchulus Semipenetrans (Tylenchulussemipenetrans) and other little Tylenchida belong to (Tylenchulus); Sword nematode, as X. radicicola (Xiphinemaamericanum), standard sword nematode (Xiphinemaindex), split tail sword nematode (Xiphinemadiversicaudatum) and other Xiphinema (Xiphinema).

Pierce-suck type, rasping sucking mouthparts insect are especially had special efficacy such as agriculture and forestry injurious insects such as aphid, leafhopper, plant hopper, thrips, aleyrodids by the compound that the present invention relates to, and meanwhile, the garden pests such as Meloidogyne incognita are had special efficacy.

Containing the insecticide composition of active substance of the present invention

The active substance of the present invention can be prepared into insecticides in a conventional way. These active compounds can make conventional preparation. Such as solution, emulsion, suspensoid, pulvis, foaming agent, paste, granule; Aerosol, with the natural material with synthesis of active substance dipping, microcapsule in polymer, for the dressing compound of neutron, and with combustion unit block use preparation, such as sootiness cartridge case, sootiness tank and sootiness dish, and the cold mist of ULV (Coldmist) and hot mist (Warmmist) preparation.

These preparations can be produced by known method, such as, active compound mix with expansion agent, these expansion agent be exactly liquid or liquefied gas or the diluent or carrier of solid, and tensio-active agent and emulsifying agent and/or dispersion agent and/or formation of foam agent can be selected arbitrarily. Such as when using water as expansion agent, organic solvent also can be used as auxiliary agent.

It is substantially suitable when making diluent or carrier with liquid solvent, as: arene, such as dimethylbenzene, toluene or alkylnaphthalene; The fragrance of chlorination or the fat hydrocarbon of chlorination, such as chlorobenzene, vinylchlorid or methylene dichloride; Fat hydrocarbon, such as hexanaphthene or paraffin, such as mineral oil fractions; Alcohol class, such as ethanol or ethylene glycol and their ether and lipid; Ketone class, such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone; Or not conventional polar solvent, such as dimethyl formamide and dimethyl sulfoxide (DMSO), Yi Jishui.

Such as, and the diluent or carrier of liquefied gas refers to and will become the liquid of gas at normal temperatures and pressures, aerosol propellants, such as hydrocarbon class and the butane of halogenation, propane, nitrogen and carbonic acid gas.

Solid carrier can with (ground) ground natural mineral matter ground, such as kaolin, clay, talcum, quartz, atlapulgite, polynite, or diatomite, and the synthetic mineral matter ground, the silicic acid of such as high dispersing, aluminum oxide and silicate. It is that pulverize with natural zircon that is classification for the solid carrier of particle, such as calcite, marble, float stone, sepiolite and rhombspar, and the particle of inorganic and organic meal synthesis, and organic materials such as wood sawdust, the particle etc. of Exocarpium cocois (Cocos nucifera L), corn cob and tobacco stems.

The emulsion with negatively charged ion of nonionic can be used as emulsifying agent and/or formation of foam agent. Such as polyoxyethylene-fatty acid ester, polyoxyethylene-fatty alcohol-ether class, such as alkaryl polyglycol ether class, alkyl sulfonates, alkyl sulfuric ester class, aromatic yl sulphonate class and albumin hydrolysate. Dispersion agent comprises, such as lignin sulfite waste liquor and methylcellulose gum.

In the formulation can with tackiness agent, such as carboxymethyl cellulose and with the polymer of the natural of powder, particle or emulsion form and synthesis, such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

Such as, with tinting material, inorganic dyestuff, ferric oxide, cobalt oxide and Prussian blue etc. can be comprised;Organic dye, such as azo dyes or metal phthalocyanine dyestuff etc.; With use trace nutrition agent, such as the salt etc. of iron, manganese, boron, copper, cobalt, aluminum and zinc.

These active compounds in the present invention can be made mixture with other active compound and be present in commercial preparation, or from, use formulation prepared by these preparations, other described active compound includes but not limited to: sterilant, bait formulation, sterilant, miticide, nematocides, mycocide, growth control agent etc. Sterilant comprises, such as phosphoric acid ester, amino formate, (plan) cinerins, chlorinated hydrocarbons, anabasine, insect growth regulator(IGR) class, neires toxin, pymetrozine, GABA acceptor inhibitor class, ryanodine receptor inhibitor class and the material produced by microorganism, such as Avrmectin etc.

In addition, these active compounds in the present invention also can be made a kind of mixture and are present in their commercial preparation to become from use formulation prepared by these preparations with synergistic agent. Synergistic agent is the compound improving active compound effect, owing to active compound itself has activity, it is possible to unlike interpolation synergistic agent.

These preparations are usually containing accounting for described insecticides 0.001-99.99 weight %, it is preferable that 0.01-99.9 weight %, it is more preferable to the active compound of the present invention of 0.05-90 weight %. Making from commercial preparation uses the concentration of the active compound formulation can change in wide scope. Use the active compound in formulation concentration can from 0.0000001-100% (g/v), preferably at 0.0001-1%.

Below in conjunction with specific embodiment, set forth the present invention further. Limit the scope of the invention it will be understood that these embodiments are only not used in for illustration of the present invention. The experimental technique of unreceipted concrete condition in the following example, usually conveniently condition, or according to the condition that manufacturer advises. Unless otherwise indicated, otherwise per-cent and part number calculate by weight. Wherein, r.t. represents room temperature.

Embodiment 1.

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

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

With in 250mL tri-mouthfuls of round-bottomed flasks of constant pressure funnel, thermometer, add the 65-70% ethylamine solution of 70g (1mol), acetonitrile 50mL, under ice bath, stir 15min, make solution temperature be stabilized in 0Closely, constant pressure funnel adds acetonitrile (25mL) solution of the chloro-3-chloromethylpyridine of 6-of 16.10g (0.10mol), control rate of addition is at 3/min, dripping and add the time at 3.5h, reaction adds water after terminating, dichloromethane extraction, collect organic phase, obtain oily liquids N-(6-chloropyridine-3-methylene radical) ethamine 15g (compound III-1), receipts rate 88%.

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

(2) synthesis of N-(6-chloropyridine-3-methylene radical)-N-ethyl-1-thiomethyl-2-nitro vinylidene amine (compound IV-1)

In 100mL tri-mouthfuls of round-bottomed flasks, add N-(6-chloropyridine-3-methylene radical) ethamine of 17.0g (0.1mol), 15.0g (0.09mol) 1,1-bis-thiomethyl-2-nitroethylene, 50mL dehydrated alcohol, is heated to backflow, backflow 8h. Stopping backflow, be cooled to room temperature, concentrate and to obtain viscous liquid, silicagel column column chromatography for separation (methylene dichloride: acetone=5:1 (v/v)) obtains product 6.5g (compound IV-1), and receipts rate is 23%.

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

(3) synthesis of N-((6-chloropyridine-3-base) methyl)-N-ethyl-N`-methyl-2-nitro-3-(thiazol-2-yl) third-1-alkene diamines (compound V-1):

To in 100mL round-bottomed flask, add N-(6-chloropyridine-3-the methylene radical)-N-ethyl-1-thiomethyl-2-nitro vinylidene amine of 5g (0.017mol), the methylamine alcohol solution of 1.8g (0.017mol first amine), 30mL dehydrated alcohol, stirring under ice bath makes temperature be down to 0, and a DEG C continuation is reacted until terminating. At pressure reducing and steaming solvent, concentrating to obtain soup compound, silicagel column column chromatography for separation (methylene dichloride: acetone=4:1) compound 1.24g (compound V-1), receipts rate is 27%. GC-MS (m/s): 236 ([M]⁺-34,32), 207 (49), 169 (52), 126 (49), 90 (16), 67 (100).

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

By N-(6-chloropyridine-3-the methylene radical)-N-ethyl-N`-methyl-2-nitro vinylidene diamines of 1.350g (0.005mol), the anhydrous acetonitrile of 30mL, the 2-thiazole carboxaldehyde of 0.678g (0.006mol), the HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 6h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the Ni of 10% equivalent, is placed in the round-bottomed flask of 50ml. Being filled with hydrogen, stir at normal temperatures, reaction process followed the tracks of by TLC plate, the R of product_f=0.25 (methylene dichloride: acetone=4:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I A-1 (target compound), be white powder solid 0.631g, product rate about 34%.

¹HNMR (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.¹³CNMR(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

The synthesis of 2-((1H-pyrroles's-2-base) methyl)-3-chloromethyl amino-3-(N-phenmethyl-N-ethylamino) vinyl cyanide (compound ii A-2):

(1) synthesis of 3-chloromethyl amino-3-(N-phenmethyl-N-ethylamino) vinyl cyanide (compound V-2)

Replacing chloropyridine ring divided by phenyl ring, cyano group substitutes nitro, and chloromethyl substitutes beyond methyl, and in other step and embodiment 1, step (1)～(3) are identical, obtain compound V-2.

(2) synthesis of 2-((1H-pyrroles's-2-base) methyl)-3-chloromethyl amino-3-(N-phenmethyl-N-ethylamino) vinyl cyanide (Compound I A-2)

By 3-chloromethyl amino-3-(N-phenmethyl-N-ethylamino) vinyl cyanide of 1.24g (0.005mol), the anhydrous acetonitrile of 30mL, the 2-pyrrole aldehyde of 0.570g (0.006mol), the HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 7h, stopped reaction, filter. By the solid that filtration obtains, 25mL tetrahydrofuran (THF), the lithium aluminium hydride of 2 times of equivalents is placed in the round-bottomed flask of 50ml. Stirring under normal temperature, reaction process followed the tracks of by TLC plate, the R of product_f=0.20 (methylene dichloride: acetone=3:1).After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I A-2, be white powder solid 0.712g, product rate about 38%.

¹HNMR (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.¹³CNMR(101MHz,DMSO)δ172.84,138.54,132.90,128.97,127.53,124.38,123.64,120.92,108.39,106.20,59.33,53.10,50.92,48.34,30.21,19.80ppm.HRMS(ES+)C₁₈H₂₂N₄ ³⁵Cl(M+H)⁺, calculated value: 329.1533; Measured value: 329.1532; C₁₈H₂₂N₄ ³⁷Cl(M+H)⁺, calculated value: 331.1503; Measured value: 331.1506.

Embodiment 3

The synthesis of N-(3,3,3-trifluoro propyl)-N-ethyl-N ', N '-dimethyl-2-nitro-3-(4-cyano thiophene-2-base) the third-1-alkene diamines (Compound I A-3):

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

Replacing chloropyridine ring divided by trifluoromethyl methyl, beyond the raw material first amine in dimethylamine alternative steps (3), in other step and embodiment 1, step (1)～(3) are identical, obtain compound V-3.

By the N-(3 of 1.28g (0.005mol), 3,3-trifluoro propyl)-N-ethyl-N ', N '-dimethyl-2-nitro vinylidene diamines, the anhydrous acetonitrile of 30mL, 5-cyano group-the 2 thiophene carboxaldehyde of 0.822g (0.006mol), the HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 14h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the palladium carbon of 10% equivalent, is placed in the round-bottomed flask of 50ml. Being filled with hydrogen, stir at normal temperatures, reaction process followed the tracks of by TLC plate, the Rf=0.30 (methylene dichloride: acetone=4:1) of product. After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I A-3, be white powder solid 0.783g, product rate about 42%.¹HNMR (400MHz, DMSO) δ 7.52 (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.¹³CNMR (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.¹⁹FNMR(376MHz,DMSO)δ-67.33ppm.HRMS(ES+)C₁₅H₂₀N₃O₂SF₃(M+H)⁺, calculated value: 377.1259; Measured value: 377.1247.

Embodiment 4

The synthesis of N-(2-chloroethyl)-N-ethyl-N '-methyl-2-nitro-3-(5-methyl furan-2-base) the third-1-alkene-1,1-diamines (Compound I A-4):

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

Under argon gas strict protection; the phenylo boric acid boric acid of the 5-bromo-2-furaldehyde of 0.875g (0.005mol), 0.610g (0.005mol) is dissolved in the wet chemical of 20mL toluene, 20mL ethanol and 5mL2mol/L, then adds reflux 4h.Reaction cools after terminating, and leaves standstill, and removes water layer, and is washed three times by water layer with ethyl acetate, merges washings and reaction solution, and pressure reducing and steaming solvent, column chromatography for separation, obtains sterling 0.836g, receipts rate about 97%. GC-MS (m/s): 172 (100), 144 (8), 99 (48), 86 (5).

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

Identical divided by step (1)～(3) in chloromethyl replacement chloropyridine ring, other step and embodiment 1, obtain compound V-4.

(3) synthesis of N-(2-chloroethyl)-N-ethyl-N '-methyl-2-nitro-3-(5-methyl furan-2-base) the third-1-alkene-1,1-diamines (Compound I A-4)

The 4-phenyl furans-2-formaldehyde of 0.860g (0.005mol) is dissolved in methylene dichloride, dropwise drip into N-(2-the chloroethyl)-N-ethyl-N '-methyl-2-nitroethylene-1 being equipped with 1.04g (0.005mol) subsequently, 1-diamines, the anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount. Stir under normal temperature, have a large amount of glassy yellow solids to precipitate out after about 4h, stopped reaction, filter. By the solid that filtration obtains, 25mL tetrahydrofuran (THF), the lithium aluminium hydride of 2 times of equivalents is placed in the round-bottomed flask of 50ml. Stirring under normal temperature, reaction process followed the tracks of by TLC plate, the R of product_f=0.35 (methylene dichloride: acetone=8:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I A-4, be white solid 1.213g, product rate about 53%.¹HNMR (400MHz, DMSO) δ 9.27 (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.¹³CNMR(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 synthesis of the chloro-5-of 2-((2-(2-(furans-2-base)-1-nitroethylene base) imidazolidine-1-base) methyl) pyridine (Compound I B-1):

(1) synthesis of the chloro-5-of 2-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine (Compound I X-1)

Taking the CCMP of 0.03mol as starting raw material, preparing the chloro-5-of 2-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine according to the method described in WO2006056108A1 and WO2007101369A1, product rate is 64%; R_f=0.46 (sherwood oil: ethyl acetate=1:1); Mp=157.3220 (25), 126 (100), 90 (9).

(2) synthesis of the chloro-5-of 2-((2-(2-(furans-2-base)-1-nitroethylene base) imidazolidine-1-base) methyl) pyridine (Compound I B-1):

By the chloro-5-of 2-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine of 1.27g (0.005mol), the anhydrous acetonitrile of 30mL, the furfural of 0.576g (0.006mol), the HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 4h, stopped reaction, filter. By the solid that filtration obtains, 25mL tetrahydrofuran (THF), the lithium aluminium hydride of 2 times of equivalents is placed in the round-bottomed flask of 50ml. Stirring under normal temperature, reaction process followed the tracks of by TLC plate, the R of product_f=0.40 (methylene dichloride: acetone=5:1).After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-1, be white needle-like crystals 1.060g, product rate about 64%.¹HNMR(400MHz,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.¹³CNMR(101MHz,CDCl₃)δ188.84,162.58,152.17,151.44,148.04,141.13,137.05,130.67,124.72,110.72,106.73,105.63,51.44,50.97,42.19,27.81ppm.HRMS(ES+)C₁₅H₁₅N₄O₃ ³⁵Cl(M+K)⁺, calculated value: 373.0470; Measured value: 373.0468; C₁₅H₁₅N₄O₃ ³⁷Cl(M+K)⁺, calculated value: 375.0440; Measured value: 375.0444.

Embodiment 6

The synthesis of the chloro-5-of 2-((2-(2-(5-bromo-thiophene-2-base)-1-nitroethylene base) imidazolidine-1-base) methyl) pyridine (Compound I B-2):

(1) synthesis of the chloro-5-of 2-(N-methyl-2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine (Compound I X-2)

Taking the CCMP of 0.03mol as starting raw material, preparing the chloro-5-of 2-(N-methyl-2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine according to the method described in WO2006056108A1 and WO2007101369A1, product rate is 55%; R_f=0.40 (sherwood oil: ethyl acetate=1:1); Mp=160.3234 (25), 126 (100), 90 (9).

(2) synthesis of the chloro-5-of 2-((2-(2-(5-bromo-thiophene-2-base)-1-nitroethylene base) imidazolidine-1-base) methyl) pyridine (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 HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 8h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the sodium borohydride of 2 times of equivalents is placed in the round-bottomed flask of 50ml. Stirring under normal temperature, reaction process followed the tracks of by TLC plate, the R of product_f=0.40 (methylene dichloride: acetone=5:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-2, be white needle-like crystals 1.856g, product rate about 84%.¹HNMR (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=14.6Hz, 2H), 3.67 (t, J=14.6Hz, 2H), 3.60 (s, 3H) ppm.¹³CNMR(101MHz,DMSO)δ162.73,149.92,148.80,145.72,138.73,132.16,129.83,125.34,124.69,109.29,105.36,64.20,50.96,50.61,42.75,30.48ppm.HRMS(ES+)C₁₆H₁₇N₄O₂S³⁵Cl⁷⁹Br(M+H)⁺, calculated 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) tetrahydroglyoxaline (Compound I B-3):

(1) synthesis of 1-butyl-5-methyl-2-(Nitromethylene) tetrahydroglyoxaline (Compound I X-3)

Replacing chloropyridine ring divided by n-propyl, replace beyond raw material quadrol with 1-methyl ethylenediamine, in other step and embodiment 5, step (1) is identical, obtains Compound I X-3.

(2) synthesis of 1-butyl-5-methyl-2-(1-nitro-2-(thiene-3-yl-) vinyl) tetrahydroglyoxaline (Compound I B-3)

By 1-butyl-5-methyl-2-(Nitromethylene) tetrahydroglyoxaline of 0.995g (0.005mol), the anhydrous acetonitrile of 30mL, the 3-thiophenecarboxaldehyde of 0.672g (0.006mol), the HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 8h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the palladium carbon of 10% equivalent, is placed in the round-bottomed flask of 50ml. Being filled with hydrogen, and stir at normal temperatures, reaction process followed the tracks of by TLC plate, the R of product_f=0.30 (methylene dichloride: acetone=5:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-3, be white solid 0.758g, product rate about 52%.¹HNMR(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.¹³CNMR(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 synthesis of the chloro-5-of 2-((2-(3-methyl isophthalic acid-nitro-2-phenyl butenyl)-2,3-two hydrogen-1H-benzo [d] imidazolidine-1-base) methyl) thiazole (Compound I B-4):

(1) synthesis of the chloro-5-of 2-((2-(Nitromethylene)-2,3-two hydrogen-1H-benzo [d] imidazoles-1-base) methyl) thiazole (Compound I X-4)

Replacing chloropyridine ring divided by n-propyl, replace beyond raw material quadrol with 1-methyl ethylenediamine, in other step and embodiment 5, step (1) is identical, obtains Compound I X-4.

(2) synthesis of the chloro-5-of 2-((2-(3-methyl isophthalic acid-nitro-2-phenyl butenyl)-2,3-two hydrogen-1H-benzo [d] imidazolidine-1-base) methyl) thiazole (Compound I B-2)

By the chloro-5-of the 2-((2-(Nitromethylene)-2 of 1.54g (0.005mol), 3-bis-hydrogen-1H-benzo [d] imidazoles-1-base) methyl) thiazole, the anhydrous acetonitrile of 30mL, 2-methyl isophthalic acid-phenyl third-1-ketone of 0.888g (0.006mol), the HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 6h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the PbO of 10% equivalent₂, it is placed in the round-bottomed flask of 50ml. Being filled with hydrogen, stir at normal temperatures, reaction process followed the tracks of by TLC plate, the R of product_f=0.35 (methylene dichloride: acetone=5:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-4, be white crystal 1.098g, product rate about 50%.¹HNMR (400MHz, DMSO) δ 9.34 (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.¹³CNMR(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

The synthesis of 2-(1-nitro-2-(thiophene-2-base) propenyl)-1-((tetrahydrofuran (THF)-3-base) methyl) tetrahydroglyoxaline (Compound I B-5):

(1) synthesis of 1-((tetrahydrofuran (THF)-3-base) methyl)-2-(Nitromethylene)-1-tetrahydroglyoxaline (Compound I X-5)

4-toluene sulfonic acide (tetrahydrofuran (THF)-3-base) methyl ester of 7.68g (0.03mol), 9.00g (0.15mol) quadrol, the salt of wormwood of 8.280g (0.06mol), the sodium iodide of 0.20g, 120mL acetonitrile are placed in 250mL round-bottomed flask, it is heated to 70, DEG C reaction 4h after filter, get filtrate to concentrate, obtain N-((tetrahydrofuran (THF)-3-base) methyl) quadrol crude product. With 100mL ethanol, the 1,1-bis-thiomethyl-2-nitroethylene of gained crude product, 4.125g (0.025mol) is dissolved in 250mL round-bottomed flask, under reflux conditions, reaction 8h. Cooling, wait to precipitate out solid, concentrated, filter, drying obtain pale yellow powder shape solid 5.32g, product rate is 88%; GC-MS (m/s): 177 (29), 99 (100), 56 (9).

(2) synthesis of 2-(1-nitro-2-(thiophene-2-base) propenyl)-1-((tetrahydrofuran (THF)-3-base) methyl) tetrahydroglyoxaline (Compound I B-5)

By 1-((tetrahydrofuran (THF)-3-base) methyl)-2-(the Nitromethylene)-1-tetrahydroglyoxaline of 1.205g (0.005mol), the anhydrous acetonitrile of 30mL, 1-thiophene-2-base second the ketone of 0.756g (0.006mol), the HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 5h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the Ni of 10% equivalent, is placed in the round-bottomed flask of 50ml. Being filled with hydrogen, stir at normal temperatures, reaction process followed the tracks of by TLC plate, the R of product_f=0.30 (methylene dichloride: acetone=5:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-5, be white powder solid 0.878g, product rate about 50%. M.p.=108.2～109.4 DEG C.¹HNMR(400MHz,CDCl₃) δ 10.05 (s, 1H), 7.14 (d, J=4.8Hz, 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.¹³CNMR(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-p-methoxy-phenyl) methyl)-1-nitroethylene base) hexahydropyrimidine-1-base) methyl) synthesis of pyridine (Compound I B-6):

(1) synthesis of 1-(the chloro-3-picoline base of 6-)-2-Nitromethylene hexahydropyrimidine (Compound I X-6)

Taking 2.42g (0.015mol) to chloropyridine as starting raw material, prepare 1-(the chloro-3-picoline base of 6-)-2-Nitromethylene hexahydropyrimidine according to the method described in WO2006056108A1 and WO2007101369A1, product rate is 50%; Rf=0.20 (ethanol: methylene dichloride=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-p-methoxy-phenyl) methyl)-1-nitroethylene base) hexahydropyrimidine-1-base) methyl) synthesis of pyridine (Compound I B-6)

By the chloro-5-of 2-(2-Nitromethylene-imidazolidine-1-ylmethyl) thiazole of 1.340g (0.005mol), the anhydrous acetonitrile of 30mL, the m-methoxybenzaldehyde of 0.816g (0.006mol), the HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 7h, stopped reaction, filter. By the solid that filtration obtains, 25mL tetrahydrofuran (THF), the lithium aluminium hydride of 2 times of equivalents is placed in the round-bottomed flask of 50ml. Stirring under normal temperature, reaction process followed the tracks of by TLC plate, the Rf=0.40 (methylene dichloride: acetone=5:1) of product. After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-6, be white powder solid 1.067g, product rate about 57%. 1HNMR (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=5.6Hz, 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.¹³CNMR(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; Measured value: 389.1397; C₁₉H₂₂N₄O₃ ³⁷Cl(M+H)⁺, calculated value: 391.1351; Measured value: 391.1349.

Embodiment 11

2-(synthesis of 1-(N-(2-(6-chloropyridine-3-base) 2-ethanoyl)-N '-methyl-tetrahydroglyoxaline-2-methylene)-3-(thiophene-2-base) propionitrile (Compound I B-7):

(1) synthesis of 2-(1-(2-(6-chloropyridine-3-base)-2-ethanoyl)-3-Vinylimdozoline-2-base vinyl) acetonitrile (Compound I X-7)

Replacing chloropyridine ring divided by 6-chloropyridine-3-formyl radical, replace raw material quadrol with 1-vinyl quadrol, cyano group replaces beyond nitro, and in other step and embodiment 5, step (1) is identical, obtains Compound I X 7.

(2) 2-(synthesis of 1-(N-(2-(6-chloropyridine-3-base) 2-ethanoyl)-N '-methyl-tetrahydroglyoxaline-2-methylene)-3-(thiophene-2-base) propionitrile (Compound I B-7):

By 2-(1-(2-(6-chloropyridine-3-base)-2-the ethanoyl)-3-Vinylimdozoline-2-base vinyl) acetonitrile of 1.44g (0.005mol); the anhydrous acetonitrile of 30mL; the 2 thiophene carboxaldehyde of 0.672g (0.006mol), the HCl of catalytic amount is placed in the round-bottomed flask of 50ml. Stir under normal temperature, have a large amount of solids to precipitate out after about 12h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the sodium borohydride of 2 times of equivalents is placed in the round-bottomed flask of 50ml. Stirring under normal temperature, reaction process followed the tracks of by TLC plate, the R of product_f=0.37 (methylene dichloride: acetone=5:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-7, be white powder solid 0.933g, product rate about 48%.¹HNMR (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.¹³CNMR(101MHz,DMSO)δ162.84,149.92,148.78,143.65,138.70,132.29,126.99,124.71,124.48,124.44,120.92,118.76,106.20,55.32,50.92,50.56,42.74.HRMS(ES+)C₁₉H₁₈N₄OS³⁵Cl(M+H)⁺, calculated value: 385.0890;Measured value: 385.0900; C₁₆H₁₅N₄S³⁷Cl(M+H)⁺, calculated value: 387.0860; Measured value: 387.0877.

Embodiment 12

The synthesis of the chloro-5-of 2-((2-(2-(5-phenyl thiophene-2-base)-1-nitroethylene base) imidazolidine-1-base) methyl) pyridine (Compound I B-8):

(1) synthesis of the chloro-5-of 2-(2-Nitromethylene-imidazolidine-1-ylmethyl) thiazole (Compound I X-8)

Replacing beyond chloropyridine ring divided by 5-chlorine thiazole ring, in other step and embodiment 5, step (1) is identical, obtains Compound I X 8.

(2) synthesis of 5-phenyl thiophene-2-formaldehyde (compound Z-8)

Under argon gas strict protection; the phenylo boric acid of the bromo-2 thiophene carboxaldehyde of 5-of 0.955g (0.005mol), 0.610g (0.005mol) is dissolved in the wet chemical of 20mL toluene, 20mL ethanol and 5mL2mol/L; and add the tetrakis triphenylphosphine palladium of 0.289g (0.005mol), reflux 4h. Reaction cools after terminating, and leaves standstill, and removes water layer, and is washed three times by water layer with ethyl acetate, merges washings and reaction solution, and pressure reducing and steaming solvent, column chromatography for separation, obtains sterling 902mg, receipts rate about 96%. GC-MS (m/s): 188 (100), 160 (8), 115 (48), 102 (5), 79 (7).

(3) synthesis of the chloro-5-of 2-((2-(2-(5-phenyl thiophene-2-base)-1-nitroethylene base) imidazolidine-1-base) methyl) pyridine (Compound I B-8)

The 5-phenyl thiophene-2-formaldehyde of 0.940g (0.005mol) is dissolved in methylene dichloride, dropwise drip into the chloro-5-of 2-(2-Nitromethylene-imidazolidine-1-ylmethyl) thiazole being equipped with 1.300g (0.005mol) subsequently, the anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount. Stir under normal temperature, have a large amount of shiny red solids to precipitate out after about 3h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the PbO of 10% equivalent₂, it is placed in the round-bottomed flask of 50ml. Being filled with hydrogen, stir at normal temperatures, reaction process followed the tracks of by TLC plate, the R of product_f=0.39 (methylene dichloride: acetone=8:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-8, be white solid 1.049g, product rate about 49%.¹HNMR (400MHz, DMSO) δ 9.45 (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.¹³CNMR(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)⁺, calculated value: 434.0578; Measured value: 433.0581.

Embodiment 13

The synthesis of the chloro-5-of 2-((2-(2-(5-(4-methoxyl group-phenyl) thiophene-2-base)-1-nitroethylene base) imidazolidine-1-base) methylamino) pyridine (Compound I B-9):

(1) synthesis of the chloro-5-of 2-(2-Nitromethylene-imidazolidine-1-ylmethyl amino)-pyridine (Compound I X-9)

Replacing beyond chloropyridine ring divided by 6-chloropyridine-3-base amino, in other step and embodiment 5, step (1) is identical, obtains Compound I X 9.

(2) synthesis of 5-(4-p-methoxy-phenyl) thiophene-2-formaldehyde (compound Z-9)

Under argon gas strict protection; by in the wet chemical that methoxyphenylboronic acid is dissolved in 20mL toluene, 20mL ethanol and 5mL2mol/L of the bromo-2 thiophene carboxaldehyde of 5-of 0.955g (0.005mol), 0.760g (0.005mol), reflux 4h.Reaction cools after terminating, and leaves standstill, and removes water layer, and is washed three times by water layer with ethyl acetate, merges washings and reaction solution, and pressure reducing and steaming solvent, column chromatography for separation, obtains sterling 1.106g, receipts rate about 93%. GC-MS (m/s): 218 (100), 203 (52), 189 (7), 175 (21), 145 (21), 102 (10), 77 (14).

(3) synthesis of the chloro-5-of 2-((2-(2-(5-(4-methoxyl group-phenyl) thiophene-2-base)-1-nitroethylene base) imidazolidine-1-base) methylamino) pyridine (Compound I B-9)

5-(4-p-methoxy-phenyl) thiophene-2-formaldehyde of 1.090g (0.005mol) is dissolved in methylene dichloride, dropwise drip into the chloro-5-of 2-(2-Nitromethylene-imidazolidine-1-ylmethyl amino)-pyridine being equipped with 1.345g (0.005mol) subsequently, the anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount. Stir under normal temperature, have a large amount of orange solids to precipitate out after about 4h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the PbO of 10% equivalent₂, it is placed in the round-bottomed flask of 50ml. Being filled with hydrogen, stir at normal temperatures, reaction process followed the tracks of by TLC plate, the R of product_f=0.32 (methylene dichloride: acetone=8:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-9, be white solid 1.394g, product rate about 59%.¹HNMR (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.¹³CNMR(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-(synthesis of 2-(1-((6-chloropyridine-3-base) methyl) tetrahydroglyoxaline-2-base-vinyl)-2-(2-(trifluoromethyl sulfonyl) ethyl)-4-(3-p-methoxy-phenyl) thiazole (Compound I B-10):

(1) synthesis of the chloro-5-of 2-(2-trifyl methylene radical-imidazolidine-1-ylmethyl)-pyridine (Compound I X-10)

Replacing beyond nitros divided by three fluorosulfonyls, in other step and embodiment 5, step (1) is identical, obtains Compound I X 10.

(2) synthesis of 5-(4-p-methoxy-phenyl) thiophene-2-formaldehyde (compound Z-10)

Under argon gas strict protection; 6-methoxyl group-2-the pyridine boronic acid of bromo-for the 4-of 0.950g (0.005mol) 2-thiazole carboxaldehyde, 0.765g (0.005mol) is dissolved in the wet chemical of 20mL toluene, 20mL ethanol and 5mL2mol/L, then adds reflux 4h. Reaction cools after terminating, and leaves standstill, and removes water layer, and is washed three times by water layer with ethyl acetate, merges washings and reaction solution, and pressure reducing and steaming solvent, column chromatography for separation, obtains sterling 1.006g, receipts rate about 91%. GC-MS (m/s): 220 (100), 205 (65), 177 (40), 147 (12), 116 (8), 78 (5).

(3) 2-(synthesis of 2-(1-((6-chloropyridine-3-base) methyl) tetrahydroglyoxaline-2-base-vinyl)-2-(2-(trifluoromethyl sulfonyl) ethyl)-4-(3-p-methoxy-phenyl) thiazole (Compound I B-10)

4-(6-methoxypyridine-2-base) thiazole-2-formaldehyde of 1.100g (0.005mol) is dissolved in methylene dichloride; dropwise drip into the chloro-5-of 2-(2-trifyl methylene radical-imidazolidine-1-ylmethyl)-pyridine being equipped with 1.71g (0.005mol) subsequently; the anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount.Stir under normal temperature, have a large amount of glassy yellow solids to precipitate out after about 4h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the palladium carbon of 10% equivalent, is placed in the round-bottomed flask of 50ml. Being filled with hydrogen, stir at normal temperatures, reaction process followed the tracks of by TLC plate, the R of product_f=0.35 (methylene dichloride: acetone=8:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-10, be white solid 1.213g, product rate about 53%.¹HNMR (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.¹³CNMR (101MHz, 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.¹⁹FNMR(376MHz,DMSO)δ-67.33ppm.HRMS(ES+)C₂₂H₂₁N₄O₃S₂ ³⁵ClF₃(M+H)⁺, calculated value: 545.0696; Measured value: 545.0702; C₂₂H₂₁N₄O₃S₂ ³⁷ClF₃(M+H)⁺, calculated value: 547.0666; Measured value: 547.0664.

Embodiment 15

3-(1-((6-chloropyridine-3-base) methyl) tetrahydroglyoxaline-2-base vinyl)-1, the synthesis of the fluoro-4-of 1,1-tri-(4-(4-(trifluoromethyl) phenyl) thienyl-2-base) fourth-2-ketone (Compound I B-11):

(1) synthesis of 3-(1-((6-chloropyridine-3-base) methyl) tetrahydroglyoxaline-2-base vinyl)-1,1,1-trifluoropropyl-2 ketone (Compound I X-11)

Replacing beyond nitro divided by fluoroform acyl group, in other step and embodiment 5, step (1) is identical, obtains Compound I X 11.

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

Under argon gas strict protection; by in the wet chemical that trifluoromethylbenzene boronic acid is dissolved in 20mL toluene, 20mL ethanol and 5mL2mol/L of the bromo-2 thiophene carboxaldehyde of 4-of 0.955g (0.005mol), 0.950g (0.005mol), reflux 4h. Reaction cools after terminating, and leaves standstill, and removes water layer, and is washed three times by water layer with ethyl acetate, merges washings and reaction solution, and pressure reducing and steaming solvent, column chromatography for separation, obtains sterling 1.204g, receipts rate about 94%. GC-MS (m/s): 255 (100), 203 (64), 175 (40), 145 (12), 115 (8).

(3) 3-(1-((6-chloropyridine-3-base) methyl) tetrahydroglyoxaline-2-base vinyl)-1, the synthesis of the fluoro-4-of 1,1-tri-(4-(4-(trifluoromethyl) phenyl) thienyl-2-base) fourth-2-ketone (Compound I B-11)

4-(4-trifluoromethyl) thiophene-2-formaldehyde of 1.280g (0.005mol) is dissolved in methylene dichloride, dropwise drip into the 3-(1-((6-chloropyridine-3-base) methyl) tetrahydroglyoxaline-2-base vinyl)-1 being equipped with 1.53g (0.005mol) subsequently, 1,1-trifluoropropyl-2 ketone, the anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount. Stir under normal temperature, have a large amount of orange solids to precipitate out after about 4h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the sodium borohydride of 2 times of equivalents is placed in the round-bottomed flask of 50ml. Stirring under normal temperature, reaction process followed the tracks of by TLC plate, the R of product_f=0.36 (methylene dichloride: acetone=8:1).After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na2SO4 dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-11, be white solid 1.851g, product rate about 68%.

¹HNMR (400MHz, DMSO) δ 9.47 (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).

¹³CNMR (101MHz, DMSO) δ 176.23,162.83,149.89,148.74,145.39,139.30,138.68,132.33,126.18 (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.

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

Embodiment 16

The synthesis of the chloro-5-of 2-((2-(1-nitro-2-(cumarone-2-base) vinyl) tetrahydroglyoxaline-1-base) ethyl) pyridine (Compound I B-12):

(1) synthesis of the chloro-5-of 2-((2-Nitromethylene-imidazolidine-1-base) ethyl)-pyridine (Compound I X-12)

Replacing the chloro-3-chloromethylpyridine of 6-as beyond raw material divided by the chloro-5-of 2-(1-chloroethyl) pyridine, in other step and embodiment 5, step (1) is identical, obtains Compound I X 12.

(2) synthesis of the chloro-5-of 2-((2-(1-nitro-2-(cumarone-2-base) vinyl) tetrahydroglyoxaline-1-base) ethyl) pyridine (Compound I B-12)

Cumarone-2-the formaldehyde of 0.730g (0.005mol) is dissolved in methylene dichloride, dropwise drip into the chloro-5-of 2-((2-Nitromethylene-imidazolidine-1-base) the ethyl)-pyridine being equipped with 1.34g (0.005mol) subsequently, the anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount. Stir under normal temperature, have a large amount of glassy yellow solids to precipitate out after about 4h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the Ni of 10% equivalent, is placed in the round-bottomed flask of 50ml. Being filled with hydrogen, stir at normal temperatures, reaction process followed the tracks of by TLC plate, the R of product_f=0.30 (methylene dichloride: acetone=7:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na2SO4 dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-12, be white solid 1.231g, product rate about 64%.¹HNMR (400MHz, DMSO) δ 9.22 (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.¹³CNMR(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-(synthesis of 3-(2-(1-(1-bromo-4,4,4-triRuorobutyl-2-base) tetrahydroglyoxaline-2-base alkene base)-2-nitro-ethyl) phenylpyridine (Compound I B-13):

(1) synthesis of 1-(1-bromo-4,4,4-triRuorobutyl-2-base)-2-(nitroethylene base) tetrahydroglyoxaline (Compound I X-13)

Replacing the chloro-3-chloromethylpyridine of 6-as beyond raw material divided by the bromo-3-of 4-chloro-1,1,1-trifluorobutane, in other step and embodiment 5, step (1) is identical, obtains Compound I X 13.

(2) 3-(synthesis of 3-(2-(1-(1-bromo-4,4,4-triRuorobutyl-2-base) tetrahydroglyoxaline-2-base alkene base)-2-nitro-ethyl) phenylpyridine (Compound I B-13)

4-(pyridin-3-yl) phenyl aldehyde of 0.915g (0.005mol) is dissolved in methylene dichloride, dropwise drip into the 1-(1-bromo-4 being equipped with 1.58g (0.005mol) subsequently, 4,4-triRuorobutyl-2-base)-2-(nitroethylene base) tetrahydroglyoxaline, the anhydrous acetonitrile of 30mL, in the round-bottomed flask of the 50ml of the HCl of catalytic amount. Stir under normal temperature, have a large amount of glassy yellow solids to precipitate out after about 4h, stopped reaction, filter. By the solid that filtration obtains, 25mL methyl alcohol, the sodium borohydride of 2 times of equivalents is placed in the round-bottomed flask of 50ml. Stirring under normal temperature, reaction process followed the tracks of by TLC plate, the R of product_f=0.25 (methylene dichloride: acetone=7:1). After question response terminates, being spin-dried for by solvent, the glutinous shape thing methylene dichloride of residual and water extract three times, get dichloromethane layer, and NaCl saturated solution washs three times, uses Na₂SO₄Dried overnight. Filter, get filtrate, be spin-dried for solvent, obtain thick product, do, with ethanol, the sterling that recrystallization obtains Compound I B-13, be white solid 1.626g, product rate about 67%.¹HNMR (400MHz, DMSO) δ 9.27 (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.¹³CNMR (101MHz, DMSO) δ 162.18,153.57,151.29,148.63,137.35,136.39,130.08, (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; C₂₀H₂₀N₄O₂F₃ ⁸¹Br(M+H)⁺, calculated value: 486.0701; Measured value: 486.0702.

According to the instruction of embodiment 1～4 and embodiment 5～16, those skilled in the art without the need to creative work, also can compound listed by preparation table 1 and table 2, concrete steps repeat no longer one by one.

Table 1 (shown in formula I A compound)

Continued 1

Table 2 (shown in formula I B compound)

Continued 2

Embodiment 17

The insecticidal activity test of the compounds of this invention

(1) to the insecticidal activity of aphid

Aphid belongs to homoptera pest, has piercing-sucking mouthparts, is a kind of common crop pests. Taking beans aphid (Aphiscracivora) as tested object, adopt pickling process test.

Operating process: the various sample of precise, adds N respectively, and dinethylformamide is configured to 10g/L mother liquor, is diluted to the concentration of 500ppm with the aqueous solution containing 0.2mL/LTritonX-100 during experiment. Until aptery one-tenth aphid on bean sprouts stable suck after, immerse in the liquid that concentration is 500ppm together with bean sprouts, take out after 5s, suck unnecessary liquid with thieving paper, move in clean vessel in 23Temperature is raised. Every concentration establishes 3 repetitions, and control group is the aqueous solution containing 0.2mL/LTritonX-100. Processing after 24 hours, statistics tries the dead worm number of aphid, and according to formulae discovery mortality ratio (%): mortality ratio (%)=(comparison worm number-process alive worm number alive)/comparison worm number × 100% alive.The results are shown in following table.

(2) to the insecticidal activity of mythimna separata

Mythimna separata belongs to lepidoptera pest, has chewing mouthparts, is a kind of common crop pests. Taking oriental armyworm (Mythimnaseparata) as tested object, adopt the test of immersion liquid feeding method.

Working method: be that solution is accurately mixed with 500ppm solution taking acetone by testing compound, and make blank with aqueous acetone solution process. Fresh corn blade is flooded 3 seconds in the solution, then at room temperature dries, take food for examination worm, check after 24 hours and calculate mortality ratio (%) (formula is the same) of trying worm. Often group uses 10 examination worms, if 3 times are repeated. The results are shown in following table.

(3) to the insecticidal activity of nematode

Root knot nematode belongs to nematode door, pad sword order (Tylenchida), pad sword suborder, different skin Superfamily, different dermatological department (Heteroderidea), root knot nematode subfamily (Meloidogyninae), Meloidogyne, is a kind of endanger serious plant nematode.

Taking Meloidogyne incognita (Meloidogyneincongnita) as tested object, it is for examination host taking cucumber seedling, adopts the test of test tube planting method.

Operating process: will treat that test agent is made into liquid by desired concn stand-by, and get out enough root knot nematode second instar larvaes. The cucumber seedling in one week age is planted after in test tube, in test tube, adds the liquid prepared in right amount, and to often propping up, test tube accesses about 2000 larvas. Test tube is placed in 20～25 DEG C, cultivates under 10h illumination, and 20d " Invest, Then Investigate " result, counts the root knot number on every strain plant root. Each sample revision test 3 times, each sample of test does 4 re-treatments every time.

Taking distilled water as blank, it is negative control that distilled water adds root knot nematode, taking fenamiphos and abamectin solution as positive control.

Classification (classification obtains submeter in table 3), statistics inhibiting rate is carried out by root knot quantity. Statistics sees the following form 4.

Inhibiting rate (%)=(negative control obtains mark-test group and obtains mark)/negative control obtains mark × 100%

Table 3

Table 4

Continued 4

Claims

1. a nitrogen-containing heterocycle compound, it is characterised in that, described nitrogen-containing heterocycle compound is compound shown in formula I, or its acceptable salt in Pesticide Science:

In formula I, R₁For hydrogen, C₁～C₃Alkyl, the C in halogen generation₁～C₃Alkyl, phenyl, halogenophenyl, 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in halogen generation, trifluoroacetyl base,

R₃And R₄Combination and form with the nitrogen being connected separately: 5～7 yuan containing 5～7 yuan of N heterocycle or replacement contain N heterocycle;

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

The substituting group of 5～6 yuan of heterocyclic radicals of described replacement is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, NO₂, CN, phenyl, by methyl, methoxyl group, trifluoromethyl, amino, NO₂, halogen, ethanoyl, methyl sulphonyl,The phenyl replaced, by methoxyl group, trifluoromethyl, halogen, NO₂Or CN replace pyridyl, pyrimidyl, by methyl substituted pyrimidyl, by methyl substituted methylpyrrole base, thienyl, or in the furyl replaced by trifluoromethyl one or two or more kinds;

The substituting group of described substituted-phenyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, CN, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, furyl, by methyl or/and the furyl that replaces of trifluoromethyl, in pyrryl or the pyrryl that replaces by methyl and ethanoyl one or two or more kinds.

2. nitrogen-containing heterocycle compound as claimed in claim 1, it is characterised in that, described nitrogen-containing heterocycle compound is compound shown in formula I A, or its acceptable salt in Pesticide Science:

Wherein, the heteroatoms of described 5～6 yuan of heterocyclic radicals is selected from: a kind of or two kinds in N, O or S, heteroatoms number is 1 or 2; R₇For the C in halogen generation₁～C₃Alkyl, X is NR₉, R₉For H, C₁～C₃The C in alkyl or halogen generation₁～C₃Alkyl;

Y is NO₂, CN,

The substituting group of 5～6 yuan of heterocyclic radicals of described replacement is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, NO₂, in CN, phenyl, the phenyl replaced by methoxyl group, trifluoromethyl or ethanoyl or pyridyl one or two or more kinds;

The substituting group of described substituted-phenyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, furyl, by methyl substituted furyl, or in the pyrryl replaced by methyl and ethanoyl one or two or more kinds.

3. nitrogen-containing heterocycle compound as claimed in claim 2, it is characterised in that, wherein R₁It is: H, the C in fluorine or chlorine generation₁～C₃Alkyl, phenyl, chlorophenyl, 5～6 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in chlorine generation, trifluoroacetyl base or

Wherein, the heteroatoms of described 5～6 yuan of heterocyclic radicals is selected from: a kind of or two kinds in N, O or S, heteroatoms number is 1 or 2; R₇For the C of fluoro₁～C₃Alkyl, X is NH.

4. nitrogen-containing heterocycle compound as claimed in claim 3, it is characterised in that, wherein R₁Be: H, the methyl in fluorine or chlorine generation or ethyl, phenyl, chlorophenyl, 5 yuan of heterocyclic radicals, 5～6 yuan of heterocyclic radicals in chlorine generation, trifluoroacetyl base or

Wherein, the heteroatoms of described heterocyclic radical is selected from: a kind of or two kinds in N, O or S, heteroatoms number is 1 or 2;

R₇For the C of fluoro₁～C₃Alkyl, X is NH.

5. nitrogen-containing heterocycle compound as claimed in claim 4, it is characterised in that, wherein R₁Be: H, the methyl in fluorine or chlorine generation or ethyl, phenyl, chlorophenyl, tetrahydrofuran base, chlorine for thiazolyl or pyridyl, trifluoroacetyl base or

Wherein, R₇For the methyl of fluoro, X is NH.

6. nitrogen-containing heterocycle compound as claimed in claim 4, it is characterised in that, wherein R₁It is: H, CH₂Cl, CH₂CF₃, trifluoroacetyl base,

7. nitrogen-containing heterocycle compound as claimed in claim 2, it is characterised in that, wherein R₂It is: H, halogen, C₁～C₃Alkyl, the C in halogen generation₁～C₃Alkyl or C₁～C₃Alkoxyl group.

8. nitrogen-containing heterocycle compound as claimed in claim 7, it is characterised in that, wherein R₂It is: H, Cl, allyl group, the C in fluorine or chlorine generation₁～C₃Alkyl or C₁～C₃Alkoxyl group.

9. nitrogen-containing heterocycle compound as claimed in claim 8, it is characterised in that, wherein R₂It is: H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂F, CH₂CF₃, allyl group, OCH₂CH₃Or Cl.

10. nitrogen-containing heterocycle compound as claimed in claim 2, it is characterised in that, wherein R_3aAnd R_4aIndependently it is selected from: C₁～C₄The C in alkyl or halogen generation₁～C₄One in alkyl.

11. nitrogen-containing heterocycle compounds as claimed in claim 10, it is characterised in that, wherein R_3aAnd R_4aIndependently it is selected from: C₁～C₄Alkyl, or the C in fluorine or chlorine generation₁～C₄One in alkyl.

12. nitrogen-containing heterocycle compounds as claimed in claim 11, it is characterised in that, wherein R_3aAnd R_4aIndependently it is selected from: CH₃, CH₂Cl, CH₂F, CH₂CH₃, CH₂CF₃, CH₂CH₂Cl, (CH₃)₃In C or allyl group a kind of.

13. nitrogen-containing heterocycle compounds as claimed in claim 2, it is characterised in that, wherein R₅And R₆Independently it is selected from: H, C₁～C₄The C in alkyl or halogen generation₁～C₄One in alkyl.

14. nitrogen-containing heterocycle compounds as claimed in claim 13, it is characterised in that, wherein R₅And R₆Independently it is selected from: H, C₁～C₄Alkyl, or the C in fluorine or chlorine generation₁～C₄One in alkyl.

15. nitrogen-containing heterocycle compounds as claimed in claim 14, it is characterised in that, wherein R₅And R₆Independently it is selected from: H, CH₃, CH₂Cl, CH₂F, CH₂CH₃, CH₂CH₂In Cl or allyl group a kind of.

16. nitrogen-containing heterocycle compounds as claimed in claim 2, it is characterized in that, wherein Z is: furyl, thienyl, pyrryl, azoles base, thiazolyl, pyridyl, the furyl of replacement, thienyl, pyrryl, azoles base, thiazolyl or pyridyl, oil of mirbane or benzothienyl, phenyl or substituted-phenyl;

The substituting group of the furyl of described replacement, thienyl, pyrryl, azoles base, thiazolyl or pyridyl is selected from: methyl, ethyl, methoxyl group, phenyl, Cl, NO₂, CN, or in the phenyl replaced by methoxyl group, trifluoromethyl or ethanoyl or pyridyl one or two or more kinds;

The substituting group of described substituted-phenyl is selected from: methyl, methoxyl group, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, by methyl substituted furyl, or in the pyrryl replaced by methyl and ethanoyl one or two or more kinds.

17. nitrogen-containing heterocycle compounds as claimed in claim 16, it is characterised in that, wherein said oil of mirbane or benzothienyl be:

18. nitrogen-containing heterocycle compounds as claimed in claim 16, it is characterised in that, the substituting group of the furyl of wherein said replacement, thienyl, pyrryl, azoles base, thiazolyl or pyridyl is selected from: methyl, ethyl, methoxyl group, Cl, NO₂, CN, phenyl,In one or two or more kinds.

19. nitrogen-containing heterocycle compounds as claimed in claim 16, it is characterised in that, the substituting group of wherein said substituted-phenyl is selected from: methyl, methoxyl group, phenyl,In one or two or more kinds.

20. nitrogen-containing heterocycle compounds as claimed in claim 1, it is characterised in that, described nitrogen-containing heterocycle compound is compound shown in formula I B, or its acceptable salt in Pesticide Science:

In formula I B, R₁For H, halogen, C₁～C₃Alkyl, the C in halogen generation₁～C₃Alkyl, phenyl, halogenophenyl, trifluoroacetyl base, 5～6 yuan of heterocyclic radicals, by 5～6 yuan of heterocyclic radicals of trifluoromethyl or halogen generation,

R₂For H, C₁～C₃The C in alkyl or halogen generation₁～C₃Alkyl;

R_3bAnd R_4bCombination and form with the N being connected separately: 5～7 yuan containing N heterocycle, 5～7 yuan of replacement containing N heterocycle, or by the cycloalkyl of cycloalkyl, phenyl, replacement or phenyl " and " 5～7 yuan contain N heterocycle; That is:

A be 5～7 yuan containing N heterocycle, 5～7 yuan of replacement containing N heterocycle, or by the cycloalkyl of cycloalkyl, phenyl, replacement or phenyl " and " 5～7 yuan containing N heterocycle;

Y is NO₂, CN,

The substituting group of 5～6 yuan of heterocyclic radicals of described replacement is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, NO₂, CN, phenyl, by methyl, methoxyl group, trifluoromethyl, amino, NO₂, halogen, ethanoyl, methyl sulphonyl,The phenyl replaced, by methoxyl group, trifluoromethyl, halogen, NO₂Or the pyridyl that CN replaces, pyrimidyl, by methyl substituted pyrimidyl, by methyl substituted methylpyrrole base, in thienyl or the furyl that replaces by trifluoromethyl one or two or more kinds;

The substituting group of described substituted-phenyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, CN, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, furyl, by methyl or/and the furyl that replaces of trifluoromethyl, pyrryl, or in the pyrryl replaced by methyl and ethanoyl one or two or more kinds.

21. nitrogen-containing heterocycle compounds as claimed in claim 20, it is characterised in that, wherein R₁It is: H, Br, n-propyl, the C of chlorine or fluoro₁～C₃Alkyl, trifluoroacetyl base, phenyl, chlorophenyl, tetrahydrofuran base, by trifluoromethyl or the pyridyl in chlorine generation, thienyl or thiazolyl,

Wherein, R₇For trifluoromethyl, tetrahydrofuran base, chlorine are for thiazolyl or chloro-pyridine base, X is O or NR₉, R₈For tetrahydrofuran base, chlorine are for thiazolyl or chloro-pyridine base, Y is CH₂Or NH, n is 0 or 1;R₉For H, methyl or trifluoroethyl.

22. nitrogen-containing heterocycle compounds as claimed in claim 21, it is characterised in that, wherein R₁It is a kind of in following groups: H, trifluoroacetyl base,CH₂Cl, CH₂CF₃,Br,

23. nitrogen-containing heterocycle compounds as claimed in claim 20, it is characterised in that, wherein R₂It is: H, C₁～C₃The C in alkyl or halogen generation₁～C₃Alkyl.

24. nitrogen-containing heterocycle compounds as claimed in claim 23, it is characterised in that, wherein R₂It is: H, C₁～C₃Alkyl, or the C of fluorine or chlorine₁～C₃Alkyl.

25. nitrogen-containing heterocycle compounds as claimed in claim 24, it is characterised in that, wherein R₂It is: H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂F,

26. nitrogen-containing heterocycle compounds as claimed in claim 20, it is characterised in that, wherein R_3bAnd R_4bTo be combined as in following groups a kind of:

Wherein, m is 0,1 or 2, R₁₀Or R₁₁Independently be selected from: H, methyl, trifluoromethyl, phenyl orMiddle one; Or, R₁₀And R₁₁The cycloalkyl of the replacement being combined as divalence or phenyl;

The cycloalkyl of the replacement of described divalence or the substituting group of phenyl are selected from: a kind of or two kinds in methyl, methoxyl group or trifluoromethyl, substituting group number is 1 or 2.

27. nitrogen-containing heterocycle compounds as claimed in claim 26, it is characterised in that, wherein R_3bAnd R_4bTo be combined as in following groups a kind of:

Wherein, m is 0,1 or 2.

28. nitrogen-containing heterocycle compounds as claimed in claim 20, it is characterised in that, wherein R₅And R₆Independently it is selected from: H, C₁～C₄Alkenyl, C₁～C₄The alkyl of straight or branched, the C in halogen generation₁～C₄The alkyl of straight or branched or C₁～C₃Containing a kind of in oxygen alkyl.

29. nitrogen-containing heterocycle compounds as claimed in claim 28, it is characterised in that, wherein R₅And R₆It is a kind of to be independently selected from following groups:

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

30. nitrogen-containing heterocycle compounds as claimed in claim 20, it is characterized in that, wherein Z is furyl, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl, pyridyl, furyl, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl or the pyridyl replaced, by the furyl of pyridine, pyrimidine or benzo or thienyl, phenyl or substituted-phenyl;

The substituting group of the furyl of described replacement, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl or pyridyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, NO₂, CN, phenyl, by methyl, methoxyl group, trifluoromethyl, amino, NO₂, halogen, ethanoyl, methyl sulphonyl,The phenyl replaced, by methoxyl group, trifluoromethyl, halogen, NO₂Or the pyridyl that CN replaces, by methyl substituted pyrimidyl, by methyl substituted methylpyrrole base, in thienyl or the furyl that replaces by trifluoromethyl one or two or more kinds;

The substituting group of described substituted-phenyl is selected from: C₁～C₃Alkyl, C₁～C₃Alkoxyl group, halogen, CN, phenyl, pyridyl, the pyridyl replaced by trifluoromethyl, by methyl substituted furyl, or in the pyrryl replaced by methyl and ethanoyl one or two or more kinds.

31. nitrogen-containing heterocycle compounds as claimed in claim 30, it is characterised in that, wherein Z is: Phenyl, substituted-phenyl, or the furyl replaced, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl or pyridyl;

Wherein, the substituting group of described substituted-phenyl be selected from following groups one or two or more kinds:

Methyl, methoxyl group, phenyl, F, CN,

The substituting group of the furyl of described replacement, thienyl, pyrryl, azoles base, thiazolyl, imidazolyl or pyridyl be selected from following groups one or two or more kinds:

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

32. if nitrogen-containing heterocycle compound as described in any one in claims 1 to 31 is as the application of sterilant.