CN105017257B - Derivative of tetrahydroindeno-6-vinyl-1,3a-diazapentalene and preparation method and application thereof - Google Patents

Derivative of tetrahydroindeno-6-vinyl-1,3a-diazapentalene and preparation method and application thereof Download PDF

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CN105017257B
CN105017257B CN201410181612.5A CN201410181612A CN105017257B CN 105017257 B CN105017257 B CN 105017257B CN 201410181612 A CN201410181612 A CN 201410181612A CN 105017257 B CN105017257 B CN 105017257B
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derivative
hydrogen
independently selected
methyl
straight
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CN105017257A (en
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邵旭升
李忠
陈南阳
徐晓勇
须志平
程家高
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East China University of Science and Technology
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Abstract

The invention relates to a derivative of tetrahydroindeno-6-vinyl-1,3a-diazapentalene and a preparation method and application thereof. Based on the nitromethylene structure of an existing nitromethylene-neonicotine insecticide, substituted or non-substituted ninhydrin reacts with a nitromethylene-compound (or other analogs), and then the novel-structure derivative of tetrahydroindeno-6-vinyl-1,3a-diazapentalene is synthesized. Testing results show that the derivative has remarkable insecticidal activity and a wide insecticidal spectrum.

Description

Derivative of tetrahydrochysene indeno pyrrolo- imidazoles and its production and use
Technical field
The present invention relates to a kind of derivative of tetrahydrochysene indeno pyrrolo- imidazoles and its production and use.
Background technology
Anabasine insecticide with imidacloprid as representative is high because of insecticidal activity, and insecticidal spectrum is wide, to mammal and aquatic Animal toxicity is low, and has good system physical property and appropriate field stability and environment friendly, as New pesticides discovery Important hot fields.Develop later and in succession thiacloprid, clothianidin, Diacloden, Acetamiprid, Nitenpyram, MTI-446 etc. Serial nicotinic insecticide (European patent 247477,296453,685477,235725,235725,315826,192060, 244777th, 0386565,580553 and 1031566, Japan Patent 62292765,8259568,8291171 and 7242633).
But neonicotinoid insecticide is frequently excessively used and unavoidably causes the Environmental and ecological problems such as resistance, honeybee toxicity, The use of such compound is constrained, while anabasine insecticide controlling object is mainly Homoptera and coleoptera evil Worm, the insecticidal spectrum of its relative narrower also limit the medication selectivity in terms of pest control.
Therefore, rational molecular design is carried out, structure of modification, to produce new, more effective insecticide, solves anabasine The problems such as resistance of insecticide, honeybee toxicity and narrow insecticidal spectrum, it is applied to insecticide turns into the skill of needs solution of the invention Art problem.
The content of the invention
The present inventor's in-depth study by long-term, the nitro based on existing nitro-methylene-type neonicotinoid insecticide is sub- Methyl structural, is reacted by substituted or unsubstituted ninhydrin and nitromethylene-compound, has synthesized a kind of structure novel Tetrahydrochysene indeno pyrrolo- imidazoles derivative.After tested, the derivative has significant insecticidal activity and wider insecticidal spectrum.
A purpose of the invention is, there is provided a kind of derivative of the novel tetrahydrochysene indeno pyrrolo- imidazoles of structure.
The derivative of tetrahydrochysene indeno pyrrolo- imidazoles of the present invention be compound shown in formula I or its in Pesticide Science Acceptable salt：
In formula I, R1It is 5~6 circle heterocycles bases or 5~6 circle heterocycles bases of halo, the hetero atom of the heterocyclic radical is selected from N, O Or in S one or two or more kinds (containing two kinds)；
R2It is electron withdraw group, such as (but not limited to)：Nitro (- NO2), cyano group (- CN) or trifluoroacetyl group ( Wherein curve mark is the position of substitution, similarly hereinafter) etc.；
R3And R4It is respectively and independently selected from：Hydroxyl (- OH), C1~C4The alkoxy of straight or branched, by-OH or methoxyl group (CH3O-) the C of substitution1~C4The alkoxy of straight or branched, halogen (F, Cl, Br or I, similarly hereinafter),Or Middle one kind；
Wherein, R9 is the alkyl of C1~C3 straight or brancheds, or by electron withdraw group (such as (but not limited to)：Halogen ,-CN Or trifluoromethoxy (CF3O-) etc.) phenyl of substitution, substitution base number is 1~3 integer, and m is 0 or 1；
R10And R11It is respectively and independently selected from：Hydrogen (H), phenyl, or by halogen, C1~C3The alkyl or C of straight or branched1~C3 The fluorine-containing alkyl-substituted phenyl of straight or branched, substitution base number is 1~3 integer；
Or,
R3And R4It is oxygen containing five yuan or hexa-member heterocycle (i.e. R with the carbon atom composition that it is each respectively connected with3And R4Combination (R3+R4) beP is 1 or 2)；
R5~R8It is respectively and independently selected from：Hydrogen (H) or C1~C3It is a kind of in the alkoxy of straight or branched；N is 0 or 1.
It is another object of the present invention to provide a kind of composition, is counted with the gross weight of the composition as 100%, institute Stating composition includes：
Compound or its acceptable in Pesticide Science shown in the formula I of (a) 0.001 weight %~99.99 weight % Salt；With
Acceptable carrier and/or excipient in (b) Pesticide Science.
Further object of the present invention is to disclose the derivative and its composition of a kind of above-mentioned tetrahydrochysene indeno pyrrolo- imidazoles A kind of purposes, i.e., compound or its acceptable salt in Pesticide Science shown in formula I, or its composition (composition contains Compound or its acceptable salt in Pesticide Science shown in the formula I of (a) 0.001 weight %~99.99 weight %；(b) agriculture Pharmaceutically acceptable carrier and/or excipient) as crops insecticide application.
Additionally, a further object of the invention is, there is provided the method for compound shown in a kind of formula I.
Methods described has main steps that：As shown in formula II compound and compound shown in formula III in methyl alcohol, in 20 DEG C Under the conditions of~30 DEG C, react 2 hours to 24 hours, obtain compound (n=1) shown in a of intermediate formula I, then using prior art And hydrogen in one or two hydroxyl in compound shown in the corresponding a of reagent displaced type I, obtain the object that n in formula I is 1；Or,
Compound and compound shown in formula III under the conditions of 30 DEG C~40 DEG C, react 2 in chloromethane as shown in formula II Hour, to 24 hours, obtains compound (n=0) shown in the b of intermediate formula I, then using prior art and corresponding reagent displaced type I Hydrogen in one or two hydroxyl in compound shown in b, obtains the object that n in formula I is 0；
Wherein, R1And R2And R5~R8Definition it is identical with described previously, compound shown in formula II and chemical combination shown in formula III Thing is known compound, and it is prepared referring to following documents：
The preparation of compound shown in formula II referring to：Kagabu,S.；Moriya,K.；Shibuya,K.；Hattori,Y.； Tsuboi,S.；Shiokawa,K.1-(6-Halonicotinyl)-2-nitromethylene-imidazolidines as potential new insecticides.Biosci.Biotechnol.Biochem.1992,56,362–363；Shown in formula III The preparation of compound referring to：Reniers,J.；Meinguet,C.；Moineaux,L.；Masereel,B.；Vincent,S.P.； Frederick,R.；Wouters,J.Synthesis and inhibition study of monoamine oxidase, indoleamine2,3-dioxygenase and tryptophan 2,3-dioxygenase by3,8- substituted5H-indeno[1,2-c]pyridazin-5-one derivatives.European Journal of Medicinal Chemistry2011,46,6104-6111.
Specific embodiment
Term " active material of the invention " or " reactive compound of the invention " refer to compound shown in formula I or its Acceptable salt in Pesticide Science, it has significant insecticidal activity, and wider insecticidal spectrum.
Term " acceptable salt in Pesticide Science " means that the anion of the salt is forming insecticide pharmaceutically acceptable salt When be having appreciated that and acceptable.The salt is preferably water miscible.Suitably, the acid that the compound as shown in formula I is formed adds The salt that the salt (such as hydrochloride, phosphate, sulfate or nitrate etc.) and organic acid for including inorganic acid formation into salt are formed (such as acetate or benzoate).
In this manual, " insecticide " is the general designation of the material of the effect of all insects for having preventing and treating mentioned above. The example of insect is included but is not limited to：Coleopteron：Sitophilus zea-mais (Sitophilus zeamais), red flour beetle (Tribolium castaneum), potato bug (Henosepilachna vigintioctomaculata), 28 stars Ladybug (Henosepilachna sparsa), agriotes fussicollis (Agriotes fuscicollis), red pin green gold tortoise (Anomala cupripes), beautiful tortoise with four lines (Popillia quadriguttata), colorado potato beetles (Monolepta Hieroglyphica), ponderous borer (Monochamus alternatus), rice root weevil (Echinocnemus squameus), bubble Paulownia is chrysomelid (Basiprionota bisignata), longicorn beetle (Anoplophora chinensis), mulberry borer (Apripona Germari), navel abdomen bark beetle (Scolytus schevy), or Agriotes subrittatus Motschulsky (Agriotes fuscicollis).
Lepidopterous insects：The malicious pretty young woman (Lymantria dispar) of dance, tent caterpillar (Malacosoma neustria Testacea), Diaphania perspectalis (Diaphania perspectalis), Clania variegata Snellen (Clania variegata), oriental moth (Cnidocampa flauescens), dendrolimus punctatus (Dendrolimus punctatus), orgyia antiqua (Orgyia Gonostigma), paranthrene tabaniformis (Paranthrene tabaniformis), prodenia litura (Spodoptera litura), Striped rice borer (Chilo suppressalis), corn borer (Ostrinia nubilalis), meal moth (Ephestia Cautella), lap moth (Adoxophyes orana), chestnut steinernema (laspyresia splendana), black cutworm (Agrotis fucosa), greater wax moth (Galleria mellonella), diamond-back moth (Plutella xylostella), tangerine lyonetid (Phyllocnistis citrella), or oriental armyworm (Mythimna separata).
Homoptera insect：Rice green leafhopper (Nephotettix cincticeps), brown plant-hopper (Nilaparvata Lugens), Kang Shi mealybugs (Pseudococcus comstocki), arrowhead scales (Unaspis yanonensis), black peach aphid (Myzus persicae), cotten aphid (Aphis gossydii), radish aphid (Lipaphis erysimi Pseudobrassicae), pears class lace bug (Stephanitis nashi), or aleyrodid (Bemisia tabaci).
Orthopteran：Groton bug (Blattella germanica), the big Lian (Periplaneta in the U.S. American), African mole cricket (Gryllotalpa africana), or Asiatic migratory locust (Locus migratoria).
Isoptera insect：S.invicta Buren (Solenopsis invicta), or coptotermes formosanus (Coptotermes formosanus)。
Dipteral insect：Housefly (Musca domestica), Aedes aegypti (Aedes aegypti), Hylemyia Platura Meigen (Delia Platura), culex (Culex sp.), or Anopheles sinensis (Anopheles sinensis).
In a preferred technical scheme of the invention, R1It is 5~6 circle heterocycles bases or 5~6 circle heterocycles bases of chloro, institute The hetero atom for stating heterocyclic radical is selected from N, O or S one or two or more kinds (containing two kinds).
Further preferred technical scheme is, R1It is tetrahydrofuran base, chloro-thiazole base or chloro-pyridine base.
Optimal R1ForOr
In presently preferred technical scheme, R2It is nitro, cyano group or trifluoroacetyl group.
In a further preferred technical solution of the present invention, R3And R4It is respectively and independently selected from：Hydroxyl, methoxyl group, ethyoxyl, Positive propoxy,N-butoxy,Cl,OrIn one Kind；
Wherein, R9It is methyl, ethyl, n-propyl, or the phenyl replaced by halogen, cyano group or trifluoromethoxy, replaces base Number is 1~3 integer, and m is 0 or 1；
R10And R11It is respectively and independently selected from：Hydrogen, phenyl, or by halogen, C1~C3The alkyl or C of straight or branched1~C3Straight chain Or the fluorine-containing alkyl-substituted phenyl of side chain, and R10And R11It is asynchronously hydrogen, substitution base number is 1~3 integer.
Further preferred technical scheme is：R3And R4It is respectively and independently selected from：Hydroxyl, methoxyl group, ethyoxyl, positive propoxy,N-butoxy,Cl,OrMiddle one kind；
Wherein, R9 is methyl, ethyl, n-propyl, or the phenyl replaced by halogen, cyano group or trifluoromethoxy, replaces base Number is 1 or 2, m are 0 or 1；
R10And R11It is respectively and independently selected from：Hydrogen, or the phenyl replaced by bromine (Br), methyl or trifluoromethyl, and R10And R11No It is simultaneously hydrogen, substitution base number is 1 or 2.
Optimal technical scheme is：R3And R4It is respectively and independently selected from：Hydroxyl, methoxyl group, ethyoxyl, positive propoxy, n-butoxy, Cl, OrMiddle one kind.
In a further preferred technical solution of the present invention, R3And R4Combination (R3+R4) beP is 2.
In a further preferred technical solution of the present invention, R5~R8It is respectively and independently selected from：It is a kind of in hydrogen (H) or methoxyl group.
Composition containing " active material of the present invention "
Counted with the gross weight of the composition as 100%, the composition includes：
(a) 0.05 weight %~90 weight % " active material of the present invention " (compound shown in formula I or its in Pesticide Science Upper acceptable salt)；Acceptable carrier and/or excipient in (b) Pesticide Science.
" active material of the invention " can be in a conventional way prepared into composition.These reactive compounds can be made often The preparation of rule, such as solution, emulsion, supensoid agent, pulvis, foaming agent, paste, granule；Aerosol, is impregnated with active material Natural and synthesis material, the microcapsules in polymer coating compound for seed and make with burner-block Preparation, such as sootiness cartridge case, sootiness tank and sootiness disk, and ULV harls (Cold mist) and hot mist (Warm mist) Preparation.
The available known method production of these preparations, for example, reactive compound is mixed with agent is expanded, these expand agent just Liquid or liquefied gas or solid diluent or carrier, and can arbitrarily from surfactant be emulsifying agent and/or point Powder and/or formation of foam agent.For example when expansion agent is made with water, organic solvent also is used as auxiliary agent.
Be substantially when making diluent or carrier with liquid flux it is suitable, such as：Arene, such as dimethylbenzene, toluene Or alkylnaphthalene；The fragrance or the fat hydrocarbon of chlorination, such as chlorobenzene, vinyl chloride or dichloromethane of chlorination；Fat hydrocarbon, such as ring Hexane or paraffin, such as mineral oil fractions；Alcohols, such as ethanol or ethylene glycol and their ether and lipid；Ketone, such as third Ketone, MEK, methyl iso-butyl ketone (MIBK) or cyclohexanone；Or the polar solvent being of little use, such as dimethylformamide and dimethyl are sub- Sulfone, Yi Jishui.The diluent or carrier of liquefied gas refers to that will turn into the liquid of gas at normal temperatures and pressures, such as aerosol propulsion The hydro carbons and butane of agent, such as halogenation, propane, nitrogen and carbon dioxide.
Solid carrier can use the natural mineral matter in ground, such as kaolin, clay, talcum, quartz, atlapulgite to cover de- Soil, or diatomite, and the mineral matter that ground synthesizes, the silicic acid of such as high degree of dispersion, aluminum oxide and silicate.For consolidating for particle Body carrier is natural announcement stone pulverize and classification, such as calcite, marble, float stone, sepiolite and dolomite, and inorganic Particle of the particle synthesized with organic meal, and organic material such as wood sawdust, cocoanut shell, maize cob and tobacco stems etc..
The emulsification row of non-ionic and anion can be used as emulsifying agent and/or formation of foam agent.Such as polyoxyethylene-fatty Esters of gallic acid, polyoxyethylene-fatty alcohol ethers, such as alkaryl polyethylene glycol ethers, alkyl sulfonates, alkylsurfuric acid esters, Aryl sulfonic acid esters and albumin hydrolysate.Dispersant includes, such as lignin sulfite waste liquor and methylcellulose.
Can use adhesive in the formulation, for example carboxymethylcellulose calcium and with the natural of powder, granule or emulsion form and The polymer of synthesis, such as Arabic gum, polyvinyl alcohol and polyvinyl acetate.Colouring agent such as inorganic dyestuff can be used, Such as iron oxide, oxidation brill and Prussian blue；Organic dyestuff, such as organic dyestuff, such as azo dyes or metal phthalcyanine；With with trace Amount nutritional agents, such as iron, suddenly, boron, copper, cobalt, the salt of aluminum and zinc etc..
These reactive compounds of the invention can with other reactive compounds be made mixture be present in commercial preparation or In the use formulation prepared from these preparations, other reactive compounds are included but is not limited to：Insecticide, closes bait, sterilized Agent, acaricide kills line, fungicide, growth control agent etc..Insecticide includes that such as phosphoric acid ester, carbamates is removed Worm chrysanthemum esters, chlorinated hydrocarbons, benzoyl area kind, neires toxin and the material produced by microorganism, such as AVM.
Additionally, these reactive compounds of the invention also can be made a kind of mixture with synergist is present in their commodity Into in the use formulation prepared from these preparations in preparation.Synergist is the compound for improving reactive compound effect, due to work Property compound is active in itself, can also add synergist.
Understand after tested：Compound shown in formula I or its acceptable salt (" active material of the present invention ") in Pesticide Science Especially to agriculture and forestry injurious insects such as pierce-suck type, rasping-sucking mouthparts (such as：Aphid, leafhopper, plant hopper, thrips and aleyrodid etc.) there is special efficacy.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip Part, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage and number is calculated by weight.Wherein, R.t. room temperature (20 DEG C~30 DEG C) is represented.
Embodiment 1
1- ((6- chloropyridine -3- bases) methyl) -4a, 9a- dihydroxy -10- nitros -2,3,4a, 9a- tetrahydroindenes [2', 1': 4,5] and pyrroles [1,2-a] and imidazoles -9 (1H) -one (chemical compounds I -1) synthesis
By the chloro- 5- of 2- (2- Nitromethylenes-imidazolidine -1- ylmethyls)-pyridine of 1.27g (0.005mol), 30ml's Absolute methanol, the ninhydrin of 0.890g (0.005mol), is placed in the round-bottomed flask of 100ml.Under normal temperature stir, TLC with Track reacts to raw material point and disappears.Stop reaction, filtering obtains 1.863g solids (chemical compounds I -1), and yield is 90%.
1H NMR(400MHz,DMSO-d6) δ 8.34 (s, 1H), 7.89-7.71 (m, 4H), 7.66 (t, J=6.9Hz, 1H), 7.52 (d, J=8.0Hz, 1H), 7.09 (s, 1H), 6.43 (s, 1H), 5.09 (dd, J=249.9,15.4Hz, 2H), 4.02- 3.71(m,3H),3.72–3.49(m,1H)ppm.
13C NMR(100MHz,DMSO-d6)δ196.56,156.75,150.02,149.62,146.44,139.70, 136.25,134.70,132.43,131.18,125.62,124.73,124.36,104.25,89.13,86.52,54.47, 48.71,40.00ppm.
HRMS (ES+) calculated values C19H15 35ClN4O5Na(M+Na)+,437.0629；Measured value, 437.0623.
Calculated value C19H15 37ClN4O5Na(M+Na)+,439.0599；Measured value, 439.0613.
Embodiment 2
1- ((6- chloropyridine -3- bases) methyl) -4a, 9b- dihydroxy -10- nitros -2,3,4a, 9b- tetrahydroindenes [1', 2': 4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -2) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9a- dihydroxy -10- nitro -2,3, 4a, 9a- tetrahydroindene [2', 1':4,5] and pyrroles [1,2-a] and imidazoles -9 (1H) -one, the dichloromethane of 10ml is placed in 25ml's In round-bottomed flask.Stir under reflux conditions, TLC tracking reaction to raw material point disappears.Stop reaction, product is through silicagel column post layer Analysis separates (pure ethyl acetate makees eluant, eluent), obtains 0.311g white solids (chemical compounds I -2), and yield is 75%.
1H NMR(400MHz,DMSO-d6) δ 8.36 (s, 1H), 8.28 (d, J=7.8Hz, 1H), 7.84 (t, J=7.5Hz, 1H), 7.81-7.71 (m, 2H), 7.59 (t, J=7.4Hz, 1H), 7.51 (d, J=8.2Hz, 1H), 7.10 (s, 1H), 6.44 (s, 1H), 5.11 (dd, J=251.7,15.5Hz, 2H), 3.97-3.79 (m, 2H), 3.71 (dd, J=17.6,9.7Hz, 1H), 3.56 (dd, J=17.5,9.5Hz, 1H) ppm.
13C NMR(100MHz,DMSO-d6)δ195.75,156.75,153.31,149.98,149.60,139.68, 137.00,132.88,132.51,130.12,128.41,124.68,123.94,107.46,88.12,84.20,54.22, 48.63,40.02ppm.
HRMS (ES+) calculated values C19H15 35ClN4O5Na(M+Na)+,437.0629；Measured value, 437.0617.
Calculated value C19H15 37ClN4O5Na(M+Na)+,439.0599；Measured value, 439.0601.
Embodiment 3
1- ((6- chloropyridine -3- bases) methyl) -9b- hydroxyl -4a- methoxyl group -10- nitros -2,3,4a, 9b- tetrahydroindenes [1',2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -3) synthesis：
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the anhydrous tetrahydro furan of 10ml is placed in In the round-bottomed flask of 25ml.0.036g (0.0015mol) NaH is added, is stirred to gas no longer release at room temperature, added enough Iodomethane, TLC tracking reaction to raw material point disappear.Stop reaction, be evaporated, crude on silica gel post column chromatography for separation (pure second Acetoacetic ester makees eluant, eluent), 0.364g white solids (chemical compounds I -3) are obtained, yield is 85%.
1H NMR(400MHz,DMSO-d6) δ 8.35 (s, 1H), 8.27 (d, J=7.7Hz, 1H), 7.87 (t, J=7.3Hz, 1H), 7.77 (d, J=7.0Hz, 2H), 7.60 (t, J=7.2Hz, 1H), 7.51 (d, J=8.0Hz, 1H), 6.66 (s, 1H), 5.09 (dd, J=212.3,15.6Hz, 2H), 4.09-3.94 (m, 2H), 3.93-3.81 (m, 1H), 3.75-3.64 (m, 1H), 3.61–3.49(m,1H),3.45(s,3H)ppm.
13C NMR(100MHz,DMSO-d6)δ193.95,156.35,153.93,149.96,149.60,139.67, 137.41,132.61,132.40,130.22,128.10,124.69,123.95,107.26,90.84,84.83,54.44, 52.70,48.75,40.00ppm.
HRMS (ES+) calculated values C20H18 35ClN4O5(M+H)+429.0966；Measured value, 429.0951.
Calculated value C20H18 37ClN4O5(M+H)+,431.0936；Measured value, 431.0933.
Embodiment 4
1- ((6- chloropyridine -3- bases) methyl) -4a- hydroxyl -9b- methoxyl group -10- nitros -2,3,4a, 9b- tetrahydroindenes [1',2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -4) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the absolute methanol of 10ml is placed in 25ml's In round-bottomed flask.Add 0.0172g (0.0001mol) p-methyl benzenesulfonic acid to make catalyst, stir at room temperature, TLC tracking reaction is extremely Raw material point disappears.Question response terminates, and is evaporated, and it is white that crude by column chromatography separation (pure ethyl acetate makees eluant, eluent) obtains 0.364g Color solid (chemical compounds I -4), yield is 85%.
1H NMR(400MHz,DMSO-d6) δ 8.35 (s, 1H), 8.20 (d, J=7.8Hz, 1H), 7.84 (t, J=7.5Hz, 1H), 7.78 (d, J=7.7Hz, 2H), 7.62 (t, J=7.4Hz, 1H), 7.53 (d, J=3.8Hz, 2H), 5.12 (dd, J= 153.9,15.6Hz, 2H), 3.99-3.84 (m, 2H), 3.77 (dd, J=15.8,9.5Hz, 1H), 3.57 (q, J=9.5Hz, 1H),3.35(s,3H)ppm.
13C NMR(100MHz,DMSO-d6)δ195.82,157.06,151.46,149.96,149.50,139.59, 136.87,133.44,132.51,130.42,128.68,124.74,124.12,103.97,89.40,88.27,54.46, 53.72,48.83,40.33ppm.
HRMS (ES+) calculated values C20H18 35ClN4O5(M+H)+,429.0966；Measured value, 429.0964. calculated values C20H18 37ClN4O5(M+H)+,431.0936；Measured value, 431.0943.
Embodiment 5
1- ((6- chloropyridine -3- bases) methyl) -9b- ethyoxyl -4a- hydroxyl -10- nitros -2,3,4a, 9b- tetrahydroindenes [1',2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -5) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the absolute ethyl alcohol of 10ml is placed in 25ml's In round-bottomed flask.Add 0.0172g (0.0001mol) p-methyl benzenesulfonic acid to make catalyst, stir at room temperature, TLC tracking reaction is extremely Raw material point disappears.Question response terminates, and is evaporated, and it is white that crude by column chromatography separation (pure ethyl acetate makees eluant, eluent) obtains 0.376g Color solid (chemical compounds I -5), yield is 85%.
1H NMR(400MHz,DMSO-d6) δ 8.35 (s, 1H), 8.23 (d, J=7.7Hz, 1H), 7.84 (t, J=7.4Hz, 1H), 7.78 (d, J=7.6Hz, 2H), 7.61 (t, J=7.2Hz, 1H), 7.52 (d, J=8.2Hz, 1H), 7.48 (s, 1H), 5.11 (dd, J=151.6,15.6Hz, 2H), 4.03-3.83 (m, 2H), 3.83-3.72 (m, 1H), 3.72-3.62 (m, 1H), (t, J=6.6Hz, the 3H) ppm. of 3.57 (dd, J=18.8,9.3Hz, 1H), 3.50-3.45 (m, 1H), 1.16
13C NMR(100MHz,DMSO-d6)δ195.88,156.98,151.69,149.95,149.51,139.59, 136.83,133.35,132.52,130.33,128.72,124.71,124.05,104.65,89.21,88.24,61.45, 54.45,48.84,40.30,15.88ppm.
HRMS (ES+) calculated values C21H20 35ClN4O5(M+H)+,443.1122；Measured value, 443.1118. calculated values C21H20 37ClN4O5(M+H)+,445.1093；Measured value, 445.1100.
Embodiment 6
1- ((6- chloropyridine -3- bases) methyl) -4a- hydroxyl -10- nitro -9b- propoxyl group -2,3,4a, 9b- tetrahydroindenes [1',2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -6) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the propyl alcohol of 10ml is placed in the round bottom of 25ml In flask.Add 0.0172g (0.0001mol) p-methyl benzenesulfonic acid to make catalyst, stir at room temperature, TLC tracking reaction to raw material Point disappears.Question response terminates, and is evaporated, and crude by column chromatography separates (pure ethyl acetate makees eluant, eluent) and obtains 0.365g whites admittedly Body (chemical compounds I -6), yield is 80%.
1H NMR(400MHz,DMSO-d6) δ 8.35 (s, 1H), 8.22 (d, J=7.7Hz, 1H), 7.84 (t, J=7.3Hz, 1H), 7.77 (d, J=7.7Hz, 2H), 7.61 (t, J=7.2Hz, 1H), 7.51 (d, J=8.1Hz, 1H), 7.45 (s, 1H), 5.11 (dd, J=145.5,15.6Hz, 2H), 4.00-3.84 (m, 2H), 3.83-3.70 (m, 1H), 3.66-3.48 (m, 2H), (t, J=7.2Hz, the 3H) ppm. of 3.34-3.25 (m, 1H), 1.56 (q, J=13.8,6.8Hz, 2H), 0.88
13C NMR(100MHz,DMSO-d6)δ195.92,157.03,151.71,149.96,149.51,139.59, 136.79,133.39,132.52,130.32,128.77,124.71,124.03,104.64,89.05,88.34,67.40, 54.51,48.83,40.31,23.27,10.94ppm.
HRMS (ES+) calculated values C22H22 35ClN4O5(M+H)+,457.1279；Measured value, 457.1275. calculated values C22H22 37ClN4O5(M+H)+,459.1249；Measured value, 459.1250.
Embodiment 7
9b- butoxy -1- ((6- chloropyridine -3- bases) methyl) -4a- hydroxyl -10- nitros -2,3,4a, 9b- tetrahydroindenes [1',2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -7) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the butanol of 10ml is placed in the round bottom of 25ml In flask.Add 0.0172g (0.0001mol) p-methyl benzenesulfonic acid to make catalyst, TLC tracking reaction to raw material point is stirred at room temperature Disappear.Question response terminates, and is evaporated, and crude by column chromatography separates (pure ethyl acetate makees eluant, eluent) and obtains 0.334g white solids (chemical compounds I -7), yield is 71%.
1H NMR(400MHz,DMSO-d6) δ 8.35 (s, 1H), 8.21 (d, J=7.8Hz, 1H), 7.84 (t, J=7.5Hz, 1H), 7.77 (d, J=7.8Hz, 2H), 7.61 (t, J=7.5Hz, 1H), 7.51 (d, J=8.2Hz, 1H), 7.44 (s, 1H), 5.11 (dd, J=146.4,15.6Hz, 2H), 4.01-3.84 (m, 2H), 3.77 (dd, J=15.8,9.3Hz, 1H), 3.65- 3.50 (m, 2H), 3.42-3.36 (m, 1H), 1.60-1.44 (m, 2H), 1.39-1.31 (m, 2H), 0.87 (t, J=7.0Hz, 3H)ppm.
13C NMR(100MHz,DMSO-d6)δ195.92,157.02,151.73,149.96,149.50,139.58, 136.77,133.39,132.52,130.30,128.76,124.69,124.02,104.63,89.07,88.34,65.39, 54.52,48.83,40.31,32.12,19.23,14.31ppm.
HRMS (ES+) calculated values C23H24 35ClN4O5(M+H)+,471.1435；Measured value, 471.1423. calculated values C23H24 37ClN4O5(M+H)+,473.1406；Measured value, 473.1403.
Embodiment 8
1- ((6- chloropyridine -3- bases) methyl) -4a, 9b- dimethoxy -10- nitros -2,3,4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -8) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the anhydrous tetrahydro furan of 10ml is placed in In the round-bottomed flask of 25ml.0.072g (0.003mol) NaH is added, is stirred to gas no longer release at room temperature, added enough Iodomethane, TLC tracking reaction to raw material point disappear.Question response terminates, and is evaporated, and crude by column chromatography separates (pure acetic acid second Ester makees eluant, eluent) 0.376g white solids (chemical compounds I -8) are obtained, yield is 85%.
1H NMR(400MHz,DMSO-d6) δ 8.35 (q, 1H), 8.20 (d, J=7.8Hz, 1H), 7.89 (t, J=7.5Hz, 1H), 7.84 (d, J=7.6Hz, 1H), 7.78 (d, J=7.1Hz, 1H), 7.65 (t, J=7.4Hz, 1H), 7.51 (d, J= 8.2Hz, 1H), 5.10 (dd, J=134.7,15.7Hz, 2H), 4.00 (q, J=9.8Hz, 1H), 3.89 (dt, J=15.4, 7.6Hz, 1H), 3.81-3.69 (m, 1H), 3.57 (q, J=9.7Hz, 1H), 3.38 (s, 3H), 3.36 (s, 3H) ppm.
13C NMR(100MHz,DMSO-d6)δ194.15,156.69,151.58,149.95,149.52,139.59, 137.34,133.87,132.37,130.68,128.35,124.72,124.14,103.92,91.17,89.69,54.63, 53.73,53.48,48.94,41.09ppm.
HRMS (ES+) calculated values C21H20 35ClN4O5(M+H)+,443.1122；Measured value, 443.1113. calculated values C21H20 37ClN4O5(M+H)+,445.1093；Measured value, 445.1101.
Embodiment 9
1- ((6- chloropyridine -3- bases) methyl) -9b- ethyoxyl -4a- methoxyl group -10- nitros -2,3,4a, 9b- tetrahydroindenes [1',2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -9) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the absolute ethyl alcohol of 10ml is placed in 25ml's In round-bottomed flask.Add 0.0172g (0.0001mol) p-methyl benzenesulfonic acid to make catalyst, stir at room temperature, TLC tracking reactions.Treat Reaction terminates, and the extraction that adds water is evaporated, and is subsequently adding the anhydrous tetrahydro furan of 10ml.It is eventually adding 0.036g (0.0015mol) NaH, stirs to gas no longer release at room temperature, adds enough iodomethane, and TLC tracking reaction to raw material point disappears.Treat anti- Should terminate, be evaporated, crude by column chromatography separate (pure ethyl acetate makees eluant, eluent) obtain 0.319g white solids (chemical compounds I- 9), yield is 70%.
1H NMR(400MHz,DMSO-d6) δ 8.35 (s, 1H), 8.23 (d, J=7.8Hz, 1H), 7.88 (t, J=7.5Hz, 1H), 7.83 (d, J=7.6Hz, 1H), 7.77 (d, J=8.0Hz, 1H), 7.64 (t, J=7.4Hz, 1H), 7.50 (d, J= 8.2Hz, 1H), 5.10 (dd, J=133.9,15.6Hz, 2H), 4.00 (q, J=9.9Hz, 1H), 3.90 (m, 1H), 3.76 (m, 1H), (t, J=6.8Hz, the 3H) ppm. of 3.67-3.52 (m, 2H), 3.52-3.42 (m, 1H), 3.38 (s, 3H), 1.18
13C NMR(100MHz,DMSO-d6)δ194.21,156.58,151.85,149.96,149.53,139.59, 137.29,133.78,132.37,130.58,128.40,124.69,124.07,104.56,91.17,89.31,61.84, 54.63,53.62,48.94,41.08,15.88ppm.
HRMS (ES+) calculated values C22H22 35ClN4O5(M+H)+,457.1279；Measured value, 457.1281. calculated values C22H22 37ClN4O5(M+H)+,459.1249；Measured value, 459.1251.
Embodiment 10
1- ((6- chloropyridine -3- bases) methyl) -4a- methoxyl group -10- nitro -9b- propoxyl group -2,3,4a, 9b- tetrahydroindenes [1',2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -10) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the absolute ethyl alcohol of 10ml is placed in 25ml's In round-bottomed flask.Add 0.0172g (0.0001mol) p-methyl benzenesulfonic acid to make catalyst, stir at room temperature, TLC tracking reactions.Treat Reaction terminates, and the extraction that adds water is evaporated, and is subsequently adding the anhydrous tetrahydro furan of 10ml.It is eventually adding 0.036g (0.0015mol) NaH, stirs to gas no longer release at room temperature, adds enough iodomethane, and TLC tracking reaction to raw material point disappears.Treat anti- Should terminate, be evaporated, crude by column chromatography separate (pure ethyl acetate makees eluant, eluent) obtain 0.287g white solids (chemical compounds I- 10), yield is 61%.
1H NMR(400MHz,DMSO-d6) δ 8.34 (s, 1H), 8.22 (d, J=7.9Hz, 1H), 7.88 (t, J=7.5Hz, 1H), 7.83 (d, J=7.7Hz, 1H), 7.77 (d, J=8.2Hz, 1H), 7.65 (t, J=7.6Hz, 1H), 7.50 (d, J= 8.2Hz, 1H), 5.09 (dd, J=125.9,15.7Hz, 2H), 4.01 (m, 1H), 3.90 (m, 1H), 3.81-3.70 (m, 1H), (t, J=7.5Hz, the 3H) ppm. of 3.62-3.45 (m, 2H), 3.35-3.40 (m, 4H), 1.63-1.52 (m, 2H), 0.90
13C NMR(100MHz,DMSO-d6)δ194.27,156.63,151.87,149.96,149.53,139.60, 137.27,133.80,132.39,130.58,128.42,124.70,124.05,104.52,91.27,89.23,67.69, 54.67,53.58,48.93,41.08,23.35,11.03ppm.
HRMS (ES+) calculated values C23H24 35ClN4O5(M+H)+,471.1435；Measured value, 471.1432. calculated values C23H24 37ClN4O5(M+H)+,473.1406；Measured value, 473.1408.
Embodiment 11
1- ((6- chloropyridine -3- bases) methyl) -4a- hydroxyls -9b- (2- hydroxyl-oxethyls) -10- nitros -2,3,4a, 9b- Tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -11) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the ethylene glycol of 10ml is placed in the circle of 25ml In the flask of bottom.Add 0.0172g (0.0001mol) p-methyl benzenesulfonic acid to make catalyst, stir at room temperature, TLC tracking reaction to original Shots disappear.Question response terminates, and is evaporated, and crude by column chromatography separates (pure ethyl acetate makees eluant, eluent) and obtains 0.399g whites Solid (chemical compounds I -11), yield is 87%.
1H NMR(400MHz,DMSO-d6) δ 8.36 (s, 1H), 8.22 (d, J=7.8Hz, 1H), 7.85 (t, J=7.5Hz, 1H), 7.78 (d, J=7.8Hz, 2H), 7.62 (t, J=7.5Hz, 1H), 7.51 (d, J=8.4Hz, 1H), 7.49 (s, 1H), 5.12 (dd, J=126.2,15.5Hz, 2H), 4.97 (s, 1H), 4.00-3.85 (m, 2H), 3.79 (m, 1H), 3.70 (m, 1H), 3.67–3.52(m,4H)ppm.
13C NMR(100MHz,DMSO-d6)δ195.59,157.14,151.46,149.97,149.54,139.61, 136.74,133.47,132.45,130.41,128.87,124.73,124.07,104.49,89.21,88.16,67.52, 60.76,54.56,48.89,40.55ppm.
HRMS (ES+) calculated values C21H20 35ClN4O6(M+H)+,459.1071；Measured value, 459.1070. calculated values C21H20 37ClN4O6(M+H)+,461.1042；Measured value, 461.1042.
Embodiment 12
1- ((6- chloropyridine -3- bases) methyl) -4a- hydroxyls -9b- (2- methoxyethoxies) -10- nitros -2,3,4a, 9b- Tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -12) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the glycol monomethyl ether of 10ml is placed in In the round-bottomed flask of 25ml.Add 0.0172g (0.0001mol) p-methyl benzenesulfonic acid to make catalyst, stir at room temperature, TLC tracking Reaction to raw material point disappears.Question response terminates, and is evaporated, and crude by column chromatography separates (pure ethyl acetate makees eluant, eluent) and obtains 0.391g white solids (chemical compounds I -12), yield is 83%.
1H NMR(400MHz,DMSO-d6) δ 8.36 (s, 1H), 8.21 (d, J=7.9Hz, 1H), 7.85 (t, J=7.5Hz, 1H), 7.78 (d, J=7.4Hz, 2H), 7.62 (t, J=7.4Hz, 1H), 7.52 (d, J=8.2Hz, 1H), 7.40 (s, 1H), 5.11 (dd, J=127.8,15.6Hz, 2H), 4.01-3.83 (m, 2H), 3.82-3.71 (m, 2H), 3.63-3.48 (m, 4H), 3.34(s,3H)ppm.
13C NMR(100MHz,DMSO-d6)δ195.65,157.08,151.42,149.94,149.53,139.62, 136.83,133.42,132.50,130.43,128.78,124.72,124.08,104.26,89.26,88.20,71.68, 64.97,58.47,54.53,48.87,40.40ppm.
HRMS (ES+) calculated values C22H22 35ClN4O6(M+H)+,473.1228；Measured value, 473.1213. calculated values C22H22 37ClN4O6(M+H)+,475.1198；Measured value, 475.1198.
Embodiment 13
1- ((6- chloropyridine -3- bases) methyl) -4a, 9b- diethoxy -10- nitros -2,3,4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -13) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the anhydrous tetrahydro furan of 10ml is placed in In the round-bottomed flask of 25ml.0.036g (0.0015mol) NaH is added, is stirred to gas no longer release at room temperature, added enough Iodoethane, TLC tracking reaction.Question response terminates, and being evaporated and adding water is spin-dried for, is subsequently adding with dichloromethane extraction, organic phase The absolute ethyl alcohol of 10ml, 0.0172g (0.0001mol) p-methyl benzenesulfonic acid makees catalyst, stirs at room temperature, and TLC tracking reaction is extremely Raw material point disappears.Question response terminates, and is evaporated, and it is white that crude by column chromatography separation (pure ethyl acetate makees eluant, eluent) obtains 0.273g Color solid (chemical compounds I -13), yield is 58%.
1H NMR(400MHz,DMSO-d6) δ 8.34 (s, 1H), 8.21 (d, J=7.9Hz, 1H), 7.87 (t, J=7.6Hz, 1H), 7.81 (d, J=7.7Hz, 1H), 7.77 (dd, J=8.2,1.9Hz, 1H), 7.64 (t, J=7.5Hz, 1H), 7.51 (d, J =8.2Hz, 1H), 5.09 (dd, J=134.2,15.6Hz, 2H), 4.05-3.94 (m, 1H), 3.94-3.84 (m, 1H), 3.81- 3.71(m,1H),3.70–3.61(m,2H),3.61–3.52(m,2H),3.52–3.44(m,1H),1.22–1.11(m,6H) ppm.
13C NMR(100MHz,DMSO-d6)δ194.55,156.56,151.91,149.94,149.51,139.57, 137.16,133.71,132.38,130.51,128.41,124.68,123.97,104.46,91.19,89.28,61.65, 61.48,54.58,48.93,41.18,15.84,15.73ppm.
HRMS (ES+) calculated values C23H24 35ClN4O5(M+H)+,471.1435；Measured value, 471.1419. calculated values C23H24 37ClN4O5(M+H)+,473.1406；Measured value, 473.1405.
Embodiment 14
1- ((6- chloropyridine -3- bases) methyl) -10- nitro -5- carbonyls -1,2,3,4a, 5,9b- hexahydro indenes [1', 2':4, 5] and pyrroles [1,2-a] and imidazoles e-4a, 9b- dibutyl ester (chemical compounds I -14) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the dichloromethane of 10ml is placed in 25ml's In round-bottomed flask.N, the N '-diisopropylethylamine of 2eq are added, 0.212g (0.002mol) butyl chloride is added, stirred at room temperature Mix, TLC tracking reaction to raw material point disappears.Question response terminates, and is evaporated, and (pure ethyl acetate is washed for crude by column chromatography separation De- agent) 0.499g white solids (chemical compounds I -14) are obtained, yield is 90%.
1H NMR(400MHz,DMSO-d6) δ 8.35 (s, 1H), 8.19 (d, J=7.7Hz, 1H), 7.94-7.81 (m, 2H), 7.76 (d, J=8.1Hz, 1H), 7.68 (t, J=7.2Hz, 1H), 7.53 (d, J=8.1Hz, 1H), 5.14 (dd, J=346.8, 15.5Hz,2H),4.10–3.98(m,1H),3.97–3.87(m,1H),3.86–3.72(m,1H),3.71–3.55(m,1H), 2.47-2.34 (m, 2H), 2.33-2.18 (m, 2H), 1.55 (q, J=14.3,7.1Hz, 2H), 1.46 (q, J=14.2, 7.1Hz, 2H), 0.91 (t, J=7.1Hz, 3H), 0.86 (t, J=7.1Hz, 3H) ppm.
13C NMR(100MHz,DMSO-d6)δ188.96,171.04,170.69,154.92,149.58,149.08, 147.64,139.06,136.85,132.44,131.67,130.47,126.25,124.19,124.09,103.37,89.28, 87.54,54.14,48.22,39.92,35.25,34.25,17.89,17.58,13.36,13.10ppm.
HRMS (ES+) calculated values C27H28 35ClN4O7(M+H)+,555.1647；Measured value, 555.1631. calculated values C27H28 37ClN4O7(M+H)+,557.1617；Measured value, 557.1619.
Embodiment 15
The chloro- 1- of 9b- ((6- chloropyridine -3- bases) methyl) -4a- hydroxyl -10- nitros -2,3,4a, 9b- tetrahydroindenes [1', 2': 4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -15) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the chloroform of 10ml is placed in the round bottom of 25ml Boiling is heated in flask.The thionyl chloride of 3eq is added dropwise, TLC tracking reaction to raw material point disappears.Question response terminates, and is evaporated, thick to produce Thing obtains 0.346g white solids (chemical compounds I -15) through column chromatography for separation (pure ethyl acetate makees eluant, eluent), and yield is 80%.
1H NMR(400MHz,DMSO-d6) δ 8.37 (s, 1H), 8.28 (d, J=7.8Hz, 1H), 7.93 (t, J=7.5Hz, 1H), 7.83 (d, J=7.6Hz, 1H), 7.80 (d, J=8.2Hz, 1H), 7.66 (t, J=7.5Hz, 1H), 7.53 (d, J= 8.2Hz, 1H), 7.21 (s, 1H), 5.10 (dd, J=193.1,15.5Hz, 2H), 4.02-3.91 (m, 1H), 3.86 (dd, J= 18.0,9.3Hz, 1H), 3.71 (dd, J=17.5,9.2Hz, 1H), 3.67-3.57 (m, 1H) ppm.
13C NMR(100MHz,DMSO-d6)δ189.84,155.08,152.06,150.04,149.66,139.74, 137.96,132.16,131.31,130.90,128.43,124.87,124.71,107.08,89.28,87.03,54.28, 48.77,40.62ppm.
HRMS (ES+) calculated values C19H15 35Cl2N4O4(M+H)+,433.0470；Measured value, 433.0462. calculated values C19H15 35Cl37ClN4O4(M+H)+,435.0441；Measured value, 435.0430.
Embodiment 16
The chloro- 1- of 9b- ((6- chloropyridine -3- bases) methyl) -4a- methoxyl group -10- nitros -2,3,4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -16) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the chloroform of 10ml is placed in the round bottom of 25ml Boiling is heated in flask.The thionyl chloride of 3eq is added dropwise, TLC tracking reaction to raw material point disappears.Question response terminates, and adds 1ml first Alcohol, stirs 5min, is evaporated, and crude product obtains 0.346g white solids and (changes through column chromatography for separation (pure ethyl acetate makees eluant, eluent) Compound I -16), yield is 80%.
1H NMR(400MHz,DMSO-d6) δ 8.39 (s, 1H), 8.20 (d, J=7.9Hz, 1H), 7.92 (t, J=7.5Hz, 1H), 7.86 (d, J=7.6Hz, 1H), 7.82 (d, J=8.2Hz, 1H), 7.69 (t, J=7.5Hz, 1H), 7.52 (d, J= 7.8Hz, 1H), 5.14 (dd, J=70.1,15.8Hz, 2H), 4.10-3.97 (m, 1H), 3.97-3.77 (m, 2H), 3.77- 3.67(m,1H),3.43(s,3H)ppm.
13C NMR(100MHz,DMSO-d6)δ189.45,156.19,150.25,150.01,149.58,139.67, 137.63,132.15,131.79,131.17,128.76,125.08,124.70,103.41,92.33,86.86,54.70, 54.05,49.11,41.08ppm.
HRMS (ES+) calculated values C20H17 35Cl2N4O4(M+H)+,447.0627；Measured value, 447.0622. calculated values C20H17 35Cl37ClN4O4(M+H)+,449.0597；Measured value, 449.0597.
Embodiment 17
The chloro- 1- of 9b- ((6- chloropyridine -3- bases) methyl) -10- nitros -4a- (para-totuidine) -2,3,4a, 9b- tetrahydroindene [1',2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -17) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a of 0.414g (0.001mol), 9b- dihydroxy -10- nitro -2,3, 4a, 9b- tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one, the chloroform of 10ml is placed in the round bottom of 25ml Boiling is heated in flask.The thionyl chloride of 3eq is added dropwise, TLC tracking reaction to raw material point disappears.Question response terminates, and adds 1.2eq Para-totuidine, stirs 5min, is evaporated, and it is solid that crude product obtains 0.417g whites through column chromatography for separation (pure ethyl acetate makees eluant, eluent) Body (chemical compounds I -17), yield is 80%.
1H NMR(400MHz,DMSO-d6) δ 8.35 (s, 1H), 8.30 (d, J=7.7Hz, 1H), 8.00-7.88 (m, 2H), 7.79-7.65 (m, 2H), 7.51 (d, J=8.2Hz, 1H), 6.83 (d, J=8.0Hz, 2H), 6.60 (d, J=7.3Hz, 2H), 6.47 (s, 1H), 5.10 (dd, J=310.1,15.7Hz, 2H), 4.16-3.99 (m, 1H), 3.99-3.79 (m, 2H), 3.76- 3.61(m,1H),2.17(s,3H)ppm.
13C NMR(100MHz,DMSO-d6)δ189.56,154.96,151.78,149.98,149.58,143.80, 139.54,137.94,132.36,131.43,130.96,128.98,128.57,126.54,125.32,124.65,116.05, 104.14,89.81,77.51,54.44,48.89,41.07,20.60ppm.
HRMS(ES+)calcd for C26H22 35Cl2N5O3(M+H)+,522.1100；found,522.1105.calcd forC26H22 35Cl37ClN5O3(M+H)+,524.1070；found,524.1066.
Embodiment 18
1- ((2- diuril azoles -5- bases) methyl) -4a, 9a- dihydroxy -10- nitros -2,3,4a, 9a- tetrahydroindenes [2', 1': 4,5] and pyrroles [1,2-a] and imidazoles -9 (1H) -one (chemical compounds I -18) synthesis
By the chloro- 5- of (E) -2- ((2- (Nitromethylene) imidazolidine -1- bases) methyl) thiazole of 1.425g (0.005mol), The absolute methanol of 30ml, the ninhydrin of 0.890g (0.005mol), is placed in the round-bottomed flask of 100ml.Stirred under normal temperature, TLC tracking reaction to raw material disappears.After question response terminates, sterling (chemical compounds I -18) is filtrated to get, yield is 88%.
1H NMR(400MHz,DMSO-d6) δ 7.85 (t, J=7.4Hz, 1H), 7.78 (t, J=7.1Hz, 2H), 7.71- 7.61 (m, 2H), 7.14 (s, 1H), 6.46 (s, 1H), 5.15 (dd, J=224.8,15.5Hz, 2H), 4.04-3.73 (m, 3H), 3.69–3.53(m,1H)ppm.
13C NMR(100MHz,DMSO-d6)δ196.42,156.15,152.22,146.27,141.72,136.63, 136.29,134.68,131.25,125.68,124.36,104.57,89.65,89.19,86.41,54.22,44.56, 39.85ppm.
HRMS (ES+) calculated values C17H13 35ClN4O5SNa(M+Na)+,443.0193；Measured value, 443.0189. calculated values C17H13 37ClN4O5SNa(M+Na)+,445.0163；Measured value, 445.0160.
Embodiment 19
1- ((2- diuril azoles -5- bases) methyl) -4a, 9b- dihydroxy -10- nitros -2,3,4a, 9b- tetrahydroindenes [1', 2': 4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -19) synthesis
By 1- ((2- diuril azoles -5- bases) methyl) -4a of 0.445g (0.001mol), 9a- dihydroxy -10- nitro -2,3, 4a, 9a- tetrahydroindene [2', 1':4,5] and pyrroles [1,2-a] and imidazoles -9 (1H) -one, the dichloromethane of 10ml is placed in 25ml's In round-bottomed flask.Stirred at reflux, TLC tracking reactions.Question response time long enough, crude product is through column chromatography for separation (pure acetic acid Ethyl ester makees eluant, eluent) 0.356g white solids (chemical compounds I -19) are obtained, yield is 80%.
1H NMR(400MHz,DMSO-d6) δ 8.28 (d, J=7.8Hz, 1H), 7.85 (t, J=7.5Hz, 1H), 7.74 (d, J=7.6Hz, 1H), 7.66 (s, 1H), 7.58 (t, J=7.4Hz, 1H), 7.14 (s, 1H), 6.45 (s, 1H), 5.16 (dd, J= 177.8,15.6Hz, 2H), 3.97 (dd, J=17.9,10.2Hz, 1H), 3.87 (dd, J=17.8,10.1Hz, 1H), 3.69 (dd, J=17.5,9.8Hz, 1H), 3.53 (dd, J=17.4,9.7Hz, 1H) ppm.
13C NMR(100MHz,DMSO-d6)δ195.1,155.6,152.7,151.6,141.1,136.6,136.2, 132.3,129.7,127.9,123.5,107.3,87.7,83.5,53.5,44.0,39.4ppm.
HRMS (ES+) calculated values C17H13 35ClN4O5SNa(M+Na)+,443.0193；Measured value, 443.0195. calculated values C17H13 37ClN4O5SNa(M+Na)+,445.0163；Measured value, 445.0161.
Embodiment 20
1- ((6- chloropyridine -3- bases) methyl) -4a, 9a- dihydroxy -10- (2,2,2- trifluoroacetyl groups) -2,3,4a, 9a- Tetrahydroindene [2', 1':4,5] and pyrroles [1,2-a] and imidazoles -9 (1H) -one (chemical compounds I -20) synthesis
By 3- (1- ((6- chloropyridine -3- bases) methyl) imidazolidinone -2- alkenyls) -1,1,1- of 1.525g (0.005mol) Trifluoro propane -2- ketone, the absolute methanol of 30ml, the ninhydrin of 0.890g (0.005mol) is placed in the round-bottomed flask of 100ml In.Stirred under normal temperature, TLC tracking reaction to raw material point disappears.After question response terminates, sterling (chemical compounds I -20) is filtrated to get, Yield is 90%.
1H NMR(400MHz,DMSO-d6) δ 8.34 (s, 1H), 7.89-7.71 (m, 4H), 7.66 (t, J=6.9Hz, 1H), 7.52 (d, J=8.0Hz, 1H), 7.09 (s, 1H), 6.43 (s, 1H), 5.09 (dd, J=249.9,15.4Hz, 2H), 4.02- 3.71(m,3H),3.72–3.49(m,1H)ppm.
13C NMR(100MHz,DMSO-d6) δ 196.56,176.50,156.75,150.02,149.62,146.44, 139.70,136.25,134.70,132.43,131.18,125.62,124.73,124.36,116.01,104.25,89.13, 86.52,54.47,48.71,40.00ppm.
HRMS (ES+) calculated values C19H15 35ClN4O5Na(M+Na)+,465.0703；Measured value, 465.0706. calculated values C19H15 37ClN4O5Na(M+Na)+,467.0674；Measured value, 467.0677.
Embodiment 21
1- ((6- chloropyridine -3- bases) methyl) -4a, 9b- dihydroxy -10- (2,2,2- trifluoroacetyl groups) -2,3,4a, 9b- Tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -21) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a, 9a- dihydroxy -10- (2,2,2- tri- of 0.465g (0.001mol) Acetyl fluoride base) -2,3,4a, 9a- tetrahydroindenes [2', 1':4,5] and pyrroles [1,2-a] and imidazoles -9 (1H) -one, the dichloro of 10ml Methane, is placed in the round-bottomed flask of 25ml.Stirred at reflux, TLC tracking reactions.Question response time long enough, is evaporated, crude product 0.353g white solids (chemical compounds I -21) are obtained through column chromatography for separation (pure ethyl acetate makees eluant, eluent), yield is 76%.
1H NMR(400MHz,DMSO-d6) δ 8.36 (s, 1H), 8.28 (d, J=7.8Hz, 1H), 7.84 (t, J=7.5Hz, 1H), 7.81-7.71 (m, 2H), 7.59 (t, J=7.4Hz, 1H), 7.51 (d, J=8.2Hz, 1H), 7.10 (s, 1H), 6.44 (s, 1H), 5.11 (dd, J=251.7,15.5Hz, 2H), 3.97-3.79 (m, 2H), 3.71 (dd, J=17.6,9.7Hz, 1H), 3.56 (dd, J=17.5,9.5Hz, 1H) ppm.
13C NMR(100MHz,DMSO-d6) δ 195.75,176.50,156.75,153.31,149.98,149.60, 139.68,137.00,132.88,132.51,130.12,128.41,124.68,123.94,115.20,107.46,88.12, 84.20,54.22,48.63,40.02ppm.
HRMS (ES+) calculated values C19H15 35ClN4O5Na(M+Na)+,465.0703；Measured value, 465.0708. calculated values C19H15 37ClN4O5Na(M+Na)+,467.0674；Measured value, 467.0679.
Embodiment 22
1- ((6- chloropyridine -3- bases) methyl) -4a, 9a- dihydroxy -6,7- dimethoxy -10- nitros -2,3,4a, 9a- Tetrahydroindene [2', 1':4,5] and pyrroles [1,2-a] and imidazoles -9 (1H) -one (chemical compounds I -22) synthesis
By the chloro- 5- of 2- (2- Nitromethylenes-imidazolidine -1- ylmethyls)-pyridine of 1.27g (0.005mol), 30ml's Absolute methanol, 5, the 6- dimethoxy ninhydrins of 1.190g (0.005mol), is placed in the round-bottomed flask of 100ml.Normal temperature Lower stirring, TLC tracking reaction to raw material disappears.After question response terminates, sterling (chemical compounds I -22) is filtrated to get, yield is 83%.
1H NMR(400MHz,DMSO-d6)δ8.36(s,1H),7.77–7.52(m,3H),7.14(s,1H),6.99(s, 1H), 6.34 (s, 1H), 5.10 (dd, J=257.8,15.3Hz, 2H), 4.15-3.75 (m, 8H), 3.75-3.61 (m, 1H), 3.61–3.45(m,1H)ppm.
13C NMR(101MHz,DMSO-d6)δ193.05,155.21,156.06,151.66,148.46,146.07, 147.35,136.16,133.05,127.18,125.18,106.58,105.18,101.68,85.65,80.16,56.92, 55.80,54.60,46.10,38.39ppm.
HRMS (ES+) calculated values C21H19 35ClN4O7Na(M+Na)+,497.0840；Measured value, 497.0846. calculated values C21H19 37ClN4O7Na(M+Na)+,499.0810；Measured value, 499.0815.
Embodiment 23
1- ((6- chloropyridine -3- bases) methyl) -4a, 9b- dihydroxy -7,8- dimethoxy -10- nitros -2,3,4a, 9b- Tetrahydroindene [1', 2':4,5] and pyrroles [1,2-a] and imidazoles -5 (1H) -one (chemical compounds I -23) synthesis
By 1- ((6- chloropyridine -3- bases) methyl) -4a, 9a- dihydroxy -6,7- dimethoxies of 0.474g (0.001mol) Base -10- nitros -2,3,4a, 9a- tetrahydroindene [2', 1':4,5] and pyrroles [1,2-a] and imidazoles -9 (1H) -one, the dichloro of 10ml Methane, is placed in the round-bottomed flask of 25ml.Stirred at reflux, TLC tracking reactions.Question response time long enough, is evaporated, crude product 0.370g white solids (chemical compounds I -23) are obtained through column chromatography for separation (pure ethyl acetate makees eluant, eluent), yield is 78%.
1H NMR(400MHz,DMSO-d6) δ 8.36 (s, 1H), 7.77 (s, 2H), 7.52 (d, J=7.1Hz, 1H), 7.14 (s, 1H), 6.99 (s, 1H), 6.34 (s, 1H), 5.10 (dd, J=257.8,15.3Hz, 2H), 4.15-3.75 (m, 8H), 3.75–3.61(m,1H),3.61–3.45(m,1H)ppm.
13C NMR(101MHz,DMSO-d6)δ193.05,156.21,156.06,150.66,149.46,149.07, 148.35,139.16,132.05,125.18,124.18,108.58,107.18,103.68,87.65,83.16,55.92, 55.80,53.60,48.10,39.39ppm.
HRMS (ES+) calculated values C21H19 35ClN4O7Na(M+Na)+,497.0840；Measured value 497.0846.
Calculated value C21H19 37ClN4O7Na(M+Na)+,499.0810；Measured value 499.0815.
With reference to the preparation method of chemical compounds I -1~chemical compounds I -23 above, the present invention is also prepared for compound listed by table 1 (its preparation process is repeated no more).
Table 1
Continued 1
Continued 1
Continued 1
Continued 1
Continued 1
Continued 1
Continued 1
Continued 1
Embodiment 24.
The insecticidal activity test of the compounds of this invention
(1) to the insecticidal activity of aphid
Aphid belongs to homoptera pest, is a kind of common crop pests with piercing mouth parts.With bean aphid (Aphis Craccivora) it is test object, is tested using infusion process.
Operating process：The various samples of precise, are separately added into DMF and are configured to 10g/L mother liquors, real The concentration of 500ppm is diluted to when testing with the aqueous solution of the X-100 of Triton containing 0.2mL/L.Treat aptery adult aphid on bean sprouts After stabilization is sucked, immersed in the liquid that concentration is 500ppm together with bean sprouts, taken out after 5s, unnecessary medicine is sucked with blotting paper Liquid, raises in the clean vessel of immigration in 23 DEG C of constant temperature.3 repetitions are set per concentration, control group is the X- of Triton containing 0.2mL/L 100 aqueous solution.After treatment 24 hours, the dead borer population of statistics examination aphid, and the death rate (%) is calculated according to formula：The death rate (%)=(control borer population living-treatment work borer population)/control borer population × 100% living, the results are shown in Table 2.
(2) to the insecticidal activity of plant hopper
Plant hopper belongs to homoptera pest, is a kind of common crop pests with piercing mouth parts.With brown paddy plant hopper (Nilaparvata lugens) is test object, is tested using spray-on process.
Operating process：Testing compound is accurately configured to 500,250,100,50 with acetone as solvent, 25,12.5, 6.25th, 3.13,1.57,0.79ppm solution, and processed with aqueous acetone solution and make blank.Each treatment repeats 3 glasss and (weighs It is multiple 3 times).With every glass of even spraying 2ml of small manual sprayer.Planthopper 10 is connect per basin within 6 hours before dispenser.Successively carry out altogether 3 batch experiments.After treatment 24 hours, count the dead borer population of test worm, and calculate the death rate (%) (formula is ibid).Result is shown in Table 2.
(3) to the insecticidal activity of mythimna separata
Using leaching leaf feeding method.Testing compound is accurately configured to 500,250,100,50 with acetone as solvent, 25, 12.5th, 6.25,3.13,1.57ppm solution, and processed with aqueous acetone solution and make blank.By fresh maize leaf molten Impregnated in liquid 3 seconds, then airing at room temperature, takes food for test worm, the death rate of test worm is checked and calculated after 24h, and (%, formula is same On), often treatment uses 10 test worms, if 3 repetitions.The results are shown in Table 2.
(4) to the insecticidal activity of diamondback moth
Using leaching leaf feeding method.Fresh Cabbage leaf is impregnated 3 seconds in above-mentioned solution, it is then cool at room temperature It is dry, taken food for test worm, the death rate (%, formula is ibid) of test worm is checked and calculated after 24h, often treatment uses 10 test worms, if 3 times Repeat.Processed with clear water and make blank.The results are shown in Table 2.
Table 2
Continued 2
Continued 2
Continued 2

Claims (8)

1. a kind of derivative of tetrahydrochysene indeno pyrrolo- imidazoles, it is characterised in that the derivative be compound shown in Formulas I or Its acceptable salt in Pesticide Science：
In Formulas I, R1It is tetrahydrofuran base, chloro-thiazole base or chloro-pyridine base；R2It is nitro, cyano group or trifluoroacetyl group；R3With R4It is respectively and independently selected from：Hydroxyl, C1~C4The alkoxy of straight or branched, by hydroxyl or the C of methoxy substitution1~C4Straight chain or branch The alkoxy of chain, halogen,Middle one kind；Or R3And R4Be combined as
R5~R8It is respectively and independently selected from：Hydrogen or C1~C3It is a kind of in the alkoxy of straight or branched；N is 0 or 1；
Wherein, R9It is C1~C3The alkyl of straight or branched, or the phenyl replaced by halogen, cyano group or trifluoromethoxy, replace base Number is 1~3 integer, and m is 0 or 1；
R10And R11It is respectively and independently selected from：Hydrogen, phenyl, or by halogen, C1~C3The alkyl or C of straight or branched1~C3Straight chain or branch The fluorine-containing alkyl-substituted phenyl of chain, substitution base number is 1~3 integer；P is 1 or 2.
2. derivative as claimed in claim 1, it is characterised in that wherein, R1For
3. derivative as claimed in claim 1, it is characterised in that wherein, R3And R4It is respectively and independently selected from：Hydroxyl, methoxyl group, second Epoxide, positive propoxy,N-butoxy, Middle one kind；
Wherein, R9It is methyl, ethyl, n-propyl, or the phenyl replaced by halogen, cyano group or trifluoromethoxy, substitution base number is 1~3 integer, m is 0 or 1；
R10And R11It is respectively and independently selected from：Hydrogen, phenyl, or by halogen, C1~C3The alkyl or C of straight or branched1~C3Straight chain or branch The fluorine-containing alkyl-substituted phenyl of chain, substitution base number is 1~3 integer；And R10And R11It is asynchronously hydrogen.
4. derivative as claimed in claim 3, it is characterised in that wherein, R10And R11It is respectively and independently selected from：Hydrogen, or by bromine, first Base or the phenyl of trifluoromethyl substitution, substitution base number is 1 or 2；And R10And R11It is asynchronously hydrogen.
5. derivative as claimed in claim 4, it is characterised in that wherein, R3And R4It is respectively and independently selected from：Hydroxyl, methoxyl group, Ethyoxyl, positive propoxy, n-butoxy, Cl, In one Kind.
6. derivative as claimed in claim 1, it is characterised in that wherein, R5~R8It is respectively and independently selected from：In hydrogen or methoxyl group It is a kind of.
7. a kind of method for preparing the derivative as described in any one in claim 1~6, it is characterised in that methods described Have main steps that：Compound and compound shown in formula III in methyl alcohol, under the conditions of 20 DEG C~30 DEG C, react 2 as shown in Formula II Hour, to 24 hours, obtains compound shown in intermediate Formulas I a, then using in compound shown in corresponding reagent displaced type Ia one Hydrogen in individual or two hydroxyls, obtains the object that n in Formulas I is 1；Or,
In chloromethane, under the conditions of 30 DEG C~40 DEG C, reaction 2 is small for compound and compound shown in formula III as shown in Formula II Up to 24 hours, compound shown in intermediate Formulas I b is obtained, then using one in compound shown in corresponding reagent displaced type Ib Or hydrogen in two hydroxyls, obtain the object that n in Formulas I is 0；
Wherein, R1And R2And R5~R8Definition it is identical with described in any one in claim 1~6.
8. derivative described in any one or comprising derivative described in any one in claim 1~6 in claim 1~6 With the composition of acceptable carrier in Pesticide Science and/or excipient as the insecticide of crops application.
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